H A N D B O O K O F

SOIL SCIENCES
PROPERTIES AND PROCESSES
SECOND EDITION
 Handbook of Soil Sciences

Handbook of Soil Sciences: Properties and Processes, Second Edition

Handbook of Soil Sciences: Resource Management and Environmental Impacts, Second Edition
H A N D B O O K O F
SOIL SCIENCES
PROPERTIES AND PROCESSES
SECOND EDITION

Edited by
Pan Ming Huang
Yuncong Li
Malcolm E. Sumner

Boca Raton London New York

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 To
Pan Ming Huang (1934–2009)
Editor in Chief
Dr. Pan Ming Huang died on September 13, 2009, after a short illness. He was a towering leader in the field of soil science, and
soil chemistry in particular, having served the profession for over 44 years formerly as professor of soil science at the University of
Saskatchewan, Saskatoon, Saskatchewan, Canada. He was a dedicated teacher and author of over 300 journal articles published in
the most prestigious journals. In the midst of the revision of the Handbook of Soil Sciences, having developed and approved the
outline, set the standards for the contributions, and solicited the cooperation of all the associate editors, he unexpectedly fell
ill. One of his strengths was his ability to involve, organize, and inspire colleagues to cooperate in pursuing scientific endeavors as
was evidenced by his initial inputs into this work. Unfortunately, he passed away before being able to see any of the fruits of his
labors, the completed manuscripts. Dr. Huang is survived by his wife, Yun Yin, who was gracious in the handover of all the materi-
als required for us to complete the handbook in a timely manner. We dedicate this book to Dr. Huang as a lasting memorial to his
many contributions to soil science.
 Contents

Preface........................................................................................................................................................... xi
Editors.. ........................................................................................................................................................ xiii
Associate Editors...........................................................................................................................................xv
Contributors............................................................................................................................................... xvii
Introduction.............................................................................................................................................. xxiii

Part I  Soil Physics

Introduction  Markus Tuller������������������������������������������������������������������������������������������������������������������������������������������������������������ I-1
1 Physical Properties of Primary Particles ............................................................................................................1-1
Joseph M. Skopp
2 Soil Structure . ........................................................................................................................................................... 2-1
Teamrat A. Ghezzehei
3 Mechanics of Unsaturated Soils for Agricultural Applications .................................................................. 3-1
Rainer Horn and Stephan Peth
4 Soil Water Content and Water Potential Relationships ................................................................................. 4-1
Dani Or, Jon M. Wraith, David A. Robinson, and Scott B. Jones
5 Water Flow in Soils .................................................................................................................................................. 5-1
David E. Radcliffe and Jirka Šimůnek
6 Water and Energy Balances in the Soil–Plant–Atmosphere Continuum . ................................................ 6-1
Steven R. Evett, John H. Prueger, and Judy A. Tolk
7 Solute Transport ........................................................................................................................................................7-1
Feike J. Leij and Antonella Sciortino
8 Gas Transport in Soils ............................................................................................................................................ 8-1
Dennis E. Rolston and Per Møldrup
9 Soil Thermal Regime ............................................................................................................................................... 9-1
Robert Horton and Tyson Ochsner
10 Soil Spatial Variability .......................................................................................................................................... 10-1
Ole Wendroth, Sylvia Koszinski, and Vicente Vasquez

vii
viii Contents

Part II  Soil Chemistry

Introduction  Donald L. Sparks����������������������������������������������������������������������������������������������������������������������������������������������������� II-1
11 Soil Organic Matter ............................................................................................................................................... 11-1
Jeffrey A. Baldock and Kris Broos
12 Soil Solution . ........................................................................................................................................................... 12 -1
Paul Schwab
13 Kinetics and Mechanisms of Soil Chemical Reactions . .............................................................................. 13 -1
Donald L. Sparks
14 Oxidation–Reduction Phenomena . ................................................................................................................... 14 -1
Bruce R. James and Dominic A. Brose
15 Soil Colloidal Behavior ......................................................................................................................................... 15 -1
Sabine Goldberg, Inmaculada Lebron, John C. Seaman, and Donald L. Suarez
16 Ion Exchange Phenomena .................................................................................................................................... 16 -1
Ian C. Bourg and Garrison Sposito
17 Chemisorption and Precipitation Reactions . ................................................................................................. 17-1
Robert G. Ford
18 Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids,
and Other Inorganics ............................................................................................................................................ 18 -1
Pan Ming Huang (Deceased) and A.G. Hardie
19 Soil pH and pH Buffering .................................................................................................................................... 19 -1
Paul R. Bloom and Ulf Skyllberg

Part III  Soil Mineralogy

Introduction  Joseph W. Stucki������������������������������������������������������������������������������������������������������������������������������������������������������III-1
20 Alteration, Formation, and Occurrence of Minerals in Soils .................................................................... 20 -1
G. Jock Churchman and David J. Lowe
21 Phyllosilicates . ........................................................................................................................................................ 21-1
Hideomi Kodama
22 Oxide Minerals in Soils ........................................................................................................................................ 22 -1
Nestor Kämpf, Andreas C. Scheinost, and Darrell G. Schulze
23 Poorly Crystalline Aluminosilicate Clay Minerals .. ..................................................................................... 23 -1
James Harsh

Part IV  Soil Biology and Biochemistry: Soil Biology in Its Second Golden Age
Introduction  E.A. Paul and Paolo Nannipieri���������������������������������������������������������������������������������������������������������������������������� IV-1
24 Microbiota ................................................................................................................................................................ 24 -1
Raffaella Balestrini, Valeria Bianciotto, Paola Bonfante, Michael Schloter, Sharath Srinivasiah,
R. Greg Thorn, Kurt E. Williamson, and K. Eric Wommack
25 Soil Fauna ................................................................................................................................................................. 25 -1
Michael Bonkowski, M.A. Callaham, Jr., Marianne Clarholm, David C. Coleman, D.A. Crossley, Jr.,
Bryan Griffiths, Paul F. Hendrix, Robert McSorley, Mark G. St. John, and P.C.J. van Vliet
Contents ix

26 Microbially Mediated Processes . ....................................................................................................................... 26 -1

Susumu Asakawa, Else K. Bünemann, Emmanuel Frossard, E.G. Gregorich, Jan Jansa, H.H. Janzen,
Michael A. Kertesz, Makoto Kimura, Loretta Landi, David Long, Terence L. Marsh, Paolo Nannipieri,
Astrid Oberson, Giancarlo Renella, and Thomas Voice
27 Nitrogen Transformations ................................................................................................................................... 27-1
Richa Anand, Jean-Claude Germon, Peter M. Groffman, Jeanette M. Norton, Laurent Philippot,
James I. Prosser, and Joshua P. Schimel
28 Molecular Techniques .................................................................................................................................................................... 28-1
Judith Ascher, Maria Teresa Ceccherini, Yin Chen, Guo-Chun Ding, Holger Heuer, Jiri Jirout, Deepak Kumaresan,
J. Colin Murrell, Giacomo Pietramellara, and Kornelia Smalla

Part V  Pedology
Introduction  Larry T. West and Larry P. Wilding������������������������������������������������������������������������������������������������������������������������V-1
29 Geomorphology of Soil Landscapes ............................................................................................................................ 29-1
Douglas A. Wysocki, Philip J. Schoeneberger, Daniel R. Hirmas, and Hannan E. LaGarry
30 Pedogenic Processes .......................................................................................................................................................... 30-1
Judith K. Turk, Oliver A. Chadwick, and Robert C. Graham
31 Soil Taxonomy .......................................................................................................................................................................31-1
Robert J. Ahrens and Richard W. Arnold
32 Other Systems of Soil Classification ........................................................................................................................... 32-1
Erika Michéli and Otto C. Spaargaren
33 Classification of Soils ........................................................................................................................................................ 33-1
Olafur Arnalds, Fredrich H. Beinroth, J.C. Bell, J.G. Bockheim, Janis L. Boettinger, M.E. Collins, R.G. Darmody,
Steven G. Driese, Hari Eswaran, Delvin S. Fanning, D.P. Franzmeier, C.T. Hallmark, Willie Harris, Wayne H.
Hudnall, Randall K. Kolka, David J. Lowe, Paul A. McDaniel, D.G. McGahan, H. Curtis Monger, Lee C. Nordt,
Chien-Lu Ping, Martin C. Rabenhorst, Paul F. Reich, Randall Schaetzl, Joey N. Shaw, Christopher W. Smith,
Randal J. Southard, David Swanson, C. Tarnocai, Goro Uehara, Larry T. West, and Larry P. Wilding
34 Land Evaluation for Landscape Units ........................................................................................................................ 34-1
J. Bouma, J.J. Stoorvogel, and M.P.W. Sonneveld
35 Hydropedology .................................................................................................................................................................... 35-1
Phillip Owens, Henry Lin, and Zamir Libohova
36 Subaqueous Soils ................................................................................................................................................................. 36-1
Mark H. Stolt and Martin C. Rabenhorst
37 Digital Soil Mapping ..........................................................................................................................................................37-1
Alex B. McBratney, Budiman Minasny, Robert A. MacMillan, and Florence Carré
38 Soil Change in the Anthropocene: Bridging Pedology, Land Use and Soil Management ................... 38-1
Daniel deB. Richter, Jr. and Arlene J. Tugel
39 Noninvasive Geophysical Methods Used in Soil Science .................................................................................. 39-1
James A. Doolittle
 Preface

Handbook of Soil Sciences is the second edition of a comprehen- Handbook of Soil Sciences: Resource Management and Environ­
sive reference work on the discipline of soil science as practiced mental Interactions
today. The new edition has been completely revised and rewrit-
Part I: Soil Physical, Chemical, and Biological Interfacial
ten to reflect the current state of knowledge. It contains defini-
Interactions
tive descriptions of each major area in the discipline, including
Part II: Soil Fertility and Plant Nutrition
its fundamental principles, appropriate methods to measure
Part III: Interdisciplinary Aspects of Soil Science
each property, many examples of the variations in properties
Part IV: Soil Databases
in different soils throughout the world, and guidelines for the
interpretation of the data for various applications (agricultural, The subdivision of each part into a series of chapters was made
engineering, and environmental). by the associate editors and, in some cases, may appear to be
This handbook assembles the core of knowledge from all somewhat arbitrary. The chapters have been arranged in such a
fields encompassed within the discipline of soil science. It is way as to produce a thread running through each part. A com-
a resource rich in data, which will provide professional soil plete table of contents, which is provided at the beginning of
scientists, agronomists, engineers, ecologists, biologists, natu- each book, gives a general outline of the scope of the covered
ralists, and students with their point of first entry into a par- subject material. In addition, a comprehensive subject index and
ticular aspect of soil science. The contributions serve those an assemblage of units in common usage in soil science are pro-
professionals seeking factual reference information on a par- vided at the end.
ticular aspect. The handbook provides a thorough understand- When the revision of this work was started, Dr. Pan Ming
ing of soil science principles and practices based on a rigorous, Huang, who was the associate editor for the soil chemistry part
complete, and up-to-date treatment of the subject matter in the first edition, took on the role of editor in chief. Tragically
compiled by the leaders in each field. In general, the follow- and unexpectedly, he passed away in September 2009 in the
ing critical elements are present in each part: description of midst of overseeing this expansive work. At short notice, the
concepts and theories, definitions, approaches, methodologies publisher approached us to complete this massive task to which
and procedures, data in tabular and figure forms, and exten- we agreed in November 2009. Posthumously, we wish to recog-
sive references. nize the vision, hard work, and dedication of our friend and col-
The handbook is organized into two books comprising nine league, Dr. Huang, in developing the revised outline of the book
parts, covering the six traditional areas of soil science together and soliciting the participation of all the associate editors and,
with a new part dealing with interfacial interactions among the in turn, the authors.
physical, chemical, and biological regimes within the soil, a part The chapters of this handbook have been written by many
on the interdisciplinary aspects, and a final part on databases. authors, all experts in their own fields, and peer-reviewed by
The two books are organized as follows: independent reviewers. The nine parts have been carefully edited
and integrated by the associate editors, all distinguished soil sci-
Handbook of Soil Sciences: Properties and Processes entists in their own fields. This handbook is a tribute to the dedi-
Part I: Soil Physics cation of the authors, associate editors, and the publisher and its
Part II: Soil Chemistry editorial associates. We wish to thank all the authors for their
Part III: Soil Mineralogy valuable contributions, the many nameless reviewers for their
Part IV: Soil Biology and Biochemistry useful and helpful comments and criticisms, and the associate
Part V: Pedology editors for all their hard work that they willingly contributed.

xi
xii Preface

We also wish to recognize John Sulzycki who was highly effec- students, and visiting scientists, especially Helena Ren, Gaelan
tive in twisting our arms to pick up the threads and continue Jones, and David Li at the Tropical Research and Education
with the project after Dr. Huang’s death, Randy Brehm who con- Center, University of Florida, helped us in the editorial process
tinued with the management of this project, and Jill Jurgensen, for which we are duly grateful. Finally, we would like to thank
Vinithan Sethumadhavan, and Suganthi Thirunavukarasu our wives, Priscilla and Zhitong, for their patience, sacrifice,
who dealt with the minutiae of the editorial process. In addi- understanding, support, and encouragement without which this
tion, several research associates, graduate and undergraduate project would not have been possible.
 Editors

Dr. Pan Ming Huang (deceased) was the professor emeritus Agricultural University, China; his MS (1990) in agronomy from
of soil science at the University of Saskatchewan, Saskatoon, the University of Georgia; and his PhD (1993) in environmental
Saskatchewan, Canada, and served for 44 years in that insti- science from the University of Maryland. He is also an affili-
tution. He received his BSc (1957) from the National Chung ated professor at the University of Florida’s Center for Tropical
Hsing University, Taiwan; his MSc (1962) from the University of Agriculture, Hydrologic Sciences Academic Cluster, School of
Manitoba; and his PhD (1966) from the University of Wisconsin, Natural Resources and Environment, and Water Institute, and a
Madison, Wisconsin. His research work significantly advanced courtesy professor at the Shandong Agricultural University. He
the frontiers of knowledge on the formation, chemistry, nature, has received many awards and distinctions including a fellow of
and surface reactivity of mineral colloids, organic matter, and both the American Society of Agronomy and the Soil Science
organomineral complexes in soils and sediments and their role Society of America, Food and Agriculture Organization (FAO)
in the dynamics, transformations, and fate of nutrients, toxic Fellow, Wilson Popenoe Award (InterAmerican Society for
metals, and xenobiotics in terrestrial and aquatic environments. Tropical Horticulture), Outstanding Paper Award (Florida State
His research findings, embodied in well over 300 refereed scien- Horticultural Society), Jim App Award (University of Florida),
tific publications, are fundamental to the development of sound Junior Faculty Research Award (Sigma Xi, the international
strategies for managing land and water resources in the Earth’s honor society of science and engineering), Senior Faculty Award
critical zone. In addition to developing and teaching courses in (Gamma Sigma Delta, the honor society of agriculture), Research
soil physical chemistry and mineralogy, soil analytical chemis- Innovation Award (University of Florida), Wachovia Extension
try, and ecological toxicology, he trained and inspired MSc and Professional Award (Extension Association of Florida), and
PhD students and postdoctoral fellows, and received visiting sci- Research Foundation Professor Award (University of Florida).
entists from all over the world. He served on numerous national His research and extension program focuses on water and soil
and international scientific and academic committees. He quality monitoring, assessment and remediation, manage-
also served as a member of editorial boards, including the Soil ment practices to improve nutrient use efficiency, and nutrient
Science Society of America Journal. He served the International cycling in soils/sediments. He has authored or coauthored over
Union of Pure and Applied Chemistry and the International 160 research papers, 70 extension articles, and 15 book chapters.
Union of Soil Sciences in a number of capacities. He received He recently edited a book, Water Quality Concepts, Sampling,
the Distinguished Researcher Award from the University of and Analyses (Taylor & Francis). He serves as an associate edi-
Saskatchewan, the Soil Science Research Award from the Soil tor for Critical Reviews in Environmental Science and Technology
Science Society of America, the Distinguished Alumnus Award and Communications in Soil Science and Plant Analysis.
and the Chair Professorship Award from the National Chung Additionally, he has chaired or cochaired 20 graduate students,
Hsing University, and the Y. Q. Tang Chair Professorship Award served as a committee member for 24 other graduate students,
from Zhejiang University. He was a fellow of the Canadian and ­supervised 15 postdoctoral fellows and many international
Society of Soil Science, the Soil Science Society of America, visiting scientists.
the American Society of Agronomy, the American Association
Dr. Malcolm E. Sumner is the Regents’ professor emeritus
for the Advancement of Science, and the World Innovation
of environmental soil science in the Department of Crop and
Foundation.
Soil Sciences at the University of Georgia, Athens, Georgia. He
Dr. Yuncong Li is the University of Florida Research Foundation received his BSc Agriculture (1954) in chemistry and soil ­science
(UFRF) professor of soil science in the Department of Soil and and his MSc Agriculture (cum laude) (1957) in soil physics
Water Science at the Tropical Research and Education Center, from the University of Natal, South Africa, and his DPhil (1961)
Institute of Food and Agricultural Sciences (IFAS), University in soil chemistry from the University of Oxford, Oxford, United
of Florida in Homestead, Florida. He received his BS (1982) Kingdom. His alma mater, the University of Natal, awarded him
in soil science and agricultural chemistry from the Shandong an honorary doctor of science degree in recognition of his career

xiii
xiv Editors

contributions to soil science. Before coming to the University Visiting Fellowship (Australia) and the D. W. Brooks Faculty
of Georgia, he was professor and head of the Department of Awards for Excellence in Research and International Agriculture
Soil Science and Agrometeorology at the University of Natal, (University of Georgia). He has presented addresses at more than
South Africa. He has spent sabbatical leaves at the Agricultural 100 universities and research institutions throughout the world
University (Wageningen, the Netherlands), University of on his research findings. He has also served as associate editor
Missouri (Columbia), University of Wisconsin (Madison), for the Soil Science Society of America Journal and is a member
University of Newcastle-upon-Tyne (United Kingdom), Vista of editorial boards of many other journals. His published works
University (South Africa), University of Adelaide (Australia), cover a wide range of topics, including subsoil acidity, the agri-
and the Commonwealth Scientific and Industrial Research cultural uses of gypsum, diagnosis of yield-limiting factors, ben-
Organization (CSIRO) (Australia). Over 90 graduate students eficial use of anthropogenic wastes, and transport of nutrients
and postdoctoral associates have studied under his guidance in in soils. A widely respected author, Dr. Sumner’s works include
South Africa and the United States where he taught courses in Soil Acidity (Springer-Verlag, 1991), Soil Crusting: Chemical
soil chemistry, soil physics, and soil fertility. In addition to being and Physical Processes (Lewis Publishers, 1992), Suelos de la
a fellow of both the American Society of Agronomy and the Soil Agroindustria Cafetalera de Guatemala (University of Georgia,
Science Society of America, he holds the Agronomic Research 1994), Distribution, Properties and Management of Australian
Award and the Werner L. Nelson Award for Diagnosis of Yield Sodic Soils (CSIRO Publications, 1995), Sodic Soils: Distribution,
Limiting Factors from the American Society of Agronomy and Properties, Management, and Environmental Consequences
the Soil Science Research Award, International Soil Science (Oxford University Press, 1998), and the Handbook of Soil
Award, and the Soil Science Distinguished Service Award from Science (CRC Press, 1999). He has authored or coauthored over
the Soil Science Society of America. He is the holder of many other 350 scientific papers, including 220 refereed journal articles, and
awards and distinctions including the Sir Frederick McMasters has contributed chapters to over 30 books.
 Associate Editors

Dr. Paolo Nannipieri (Soil Biology and Biochemistry) received served as president of the Soil Science Society of America and
his BSc and MSc biology degrees from Pisa University and his the International Union of Soil Sciences.
PhD (soil biochemistry) from the University of Pisa. He is a
member of the Soil Science Society of America, the Italian Dr. Joseph W. Stucki (Soil Mineralogy) is professor of environ-
Society of Soil Science, and the Italian Society of Agricultural mental soil physical chemistry in the Department of Natural
Chemistry. He is currently professor of agricultural bio- Resources and Environmental Sciences at the University of
chemistry and head of the Department of Plant, Soil and Illinois, Urbana-Champaign, Illinois. He is a fellow of both the
Environmental Sciences at University of Firenze, Firenze, Italy. American Society of Agronomy and the Soil Science Society of
He served as president of the Italian Society of Agricultural America and holds the Marion L. and Chrystie M. Jackson Soil
Chemistry and is currently serving as the president of the Science Award from the Soil Science Society of America. He
Commission 2.3 Soil Biology of the International Union of Soil served as associate editor of the Soil Science Society of America
Societies (IUSS). He is also the editor in chief of Biology and Journal and chaired the Soil Mineralogy Division of the Soil
Fertility of Soils. He holds several distinctions for his global Science Society of America. He also received the Marion L. and
contributions to soil science. Chrystie M. Jackson Mid-Career Clay Scientist Award from the
Clay Minerals Society, where he served as president in 1997–1998.
Dr. Donald L. Sparks (Soil Chemistry) is the S. Hallock du Pont
Chair in soil and environmental chemistry, Francis Alison pro- Dr. Markus Tuller (Soil Physics) received his MS and PhD in
fessor, and director of the Delaware Institute for the Environment civil engineering and water management from the University
at the University of Delaware (UD). Dr. Sparks is internationally of Natural Resources and Applied Life Sciences (BOKU) in
recognized for his research in the areas of kinetics of geochemi- Vienna, Austria. He is currently an associate professor of soil
cal processes and mechanisms of metal/oxyanion/nutrient reac- and environmental physics in the Department of Soil, Water,
tions at biogeochemical interfaces using in situ spectroscopic and and Environmental Science at the University of Arizona in
microscopic techniques. He is the author or coauthor of 281 pub- Tucson, Arizona, with adjunct appointment in hydrology and
lications and 2 soil chemistry textbooks. He has given plenary water resources. He is the recipient of the Soil Science Society
and keynote presentations at scientific conferences throughout of America Soil Physics Early Career Award. His general area
the world and been a lecturer at 80 universities and institutes of research is focused on modeling and measurement of mass
and serves on the editorial boards of eight scholarly journals. and energy transport and distribution in porous media. Specific
He has received numerous awards and honors, including fellow research interests include hydraulic behavior of swelling soils
of the American Society of Agronomy, the Soil Science Society and liner materials, interfacial pore-scale phenomena, liquid
of America, the American Association for the Advancement of behavior in porous media in reduced gravity, and the application
Science, the Geochemical Society, and the European Association of x-ray computed tomography (CT) for porous media research.
of Geochemistry; the M. L. and Chrystie M. Jackson Soil Science
Award and the Soil Science Research Award from the Soil Dr. Larry T. West (Pedology) received his BSc and MSc in soil
Science Society of America; the Environmental Quality Research science from the University of Arkansas and his PhD (soil sci-
Award from the American Society of Agronomy; the Francis ence) from Texas A&M University. He served on the faculty
Alison Award, the UD’s highest faculty award; UD’s Doctoral at the University of Georgia for 20 years and is currently with
Student Advising and Mentoring Award; Distinguished Alumni the USDA-Natural Resources Conservation Service as National
Awards from the University of Kentucky and Virginia Tech; Leader for Soil Survey Research and Laboratory at the National
Honorary Membership in the Polish Soil Science Society; and Soil Survey Center, Lincoln, Nebraska. Dr. West has served as
the Geoffrey Marshall Mentoring Award. Dr. Sparks has also chair of Division S-5 of the Soil Science Society of America.

xv
 Contributors

Robert J. Ahrens Raffaella Balestrini Paola Bonfante

National Soil Survey Center Consiglio Nazionale delle Ricerche Consiglio Nazionale delle Ricerche
Natural Resources Conservation Service Istituto per la Protezione delle Piante Istituto per la Protezione delle Piante
United States Department of Agriculture and and
Lincoln, Nebraska Dipartimento di Biologia Vegetale Dipartimento di Biologia Vegetale
Università di Torino Università di Torino
Richa Anand Turin, Italy Turin, Italy
Faculty of Land and Food Sciences
Department of Soil Science Fredrich H. Beinroth
Department of Agronomy and Soils Michael Bonkowski
The University of British Columbia
University of Puerto Rico Department of Terrestrial Ecology
Vancouver, British Columbia, Canada
San Juan, Puerto Rico Institute of Zoology
University of Cologne
Olafur Arnalds
J.C. Bell Koln, Germany
Agricultural University of Iceland
Department of Soil, Water, and Climate
Reykjavik, Iceland
University of Minnesota
J. Bouma
St. Paul, Minnesota
Richard W. Arnold Environmental Sciences Group
Soil Survey Division Valeria Bianciotto Wageningen University and Research
Natural Resources Conservation Service Consiglio Nazionale delle Ricerche Centre
United States Department of Agriculture Istituto per la Protezione delle Piante Wageningen, the Netherlands
Washington, District of Columbia and
Dipartimento di Biologia Vegetale
Ian C. Bourg
Susumu Asakawa Università di Torino
Earth Sciences Division
Soil Biology and Chemistry Turin, Italy
Lawrence Berkeley National Laboratory
Graduate School of Bioagricultural
Paul R. Bloom and
Sciences
Department of Soil, Water, and Climate Geochemistry Department
Nagoya University
College of Food, Agricultural and University of California, Berkeley
Nagoya, Japan
Natural Resource Sciences Berkeley, California
University of Minnesota
Judith Ascher
St. Paul, Minnesota Kris Broos
Department of Plant, Soil and
Environmental Science Flemish Institute for Technological
J.G. Bockheim
University of Florence Research
Department of Soil Science
Florence, Italy Boeretang, Belgium
University of Wisconsin-Madison
Madison, Wisconsin
Jeffrey A. Baldock Dominic A. Brose
Land and Water Division Janis L. Boettinger Department of Environmental Science
Commonwealth Scientific and Industrial Plants, Soils, and Climate Department and Technology
Research Organisation Utah State University University of Maryland
Glen Osmond, South Australia, Australia Logan, Utah College Park, Maryland

xvii
xviii Contributors

Else K. Bünemann D.A. Crossley, Jr. D.P. Franzmeier

Institute of Plant, Animal and Department of Entomology Department of Agronomy
Agroecosystem Sciences University of Georgia Purdue University
Eidgenössische Technische Hochschule Athens, Georgia West Lafayette, Indiana
Zürich
Zürich, Switzerland R.G. Darmody Emmanuel Frossard
Department of Natural Resources and Institute of Plant, Animal and
M.A. Callaham, Jr. Environmental Sciences Agroecosystem Sciences
Southern Research Station University of Illinois Eidgenössische Technische Hochschule
United States Department Urbana and Champaign, Illinois Zürich
of Agriculture-Forest Service Zürich, Switzerland
Athens, Georgia Guo-Chun Ding
Federal Research Centre for Cultivated Jean-Claude Germon
Florence Carré Plants Department of Soil and Environmental
Institute for Environment and Sustainability Julius Kühn-Institut Microbiology
European Commission Joint Research Institute for Epidemiology and Pathogen Institut National de la Recherche
Centre Diagnostics Agronomique
Ispra, Italy Messeweg, Germany Dijon, France
Maria Teresa Ceccherini James A. Doolittle
Department of Plant, Soil and National Soil Survey Center Teamrat A. Ghezzehei
Environmental Science Natural Resources Conservation Service School of Natural Sciences
University of Florence United States Department of Agriculture University of California, Merced
Florence, Italy Newton Square, Pennsylvania Merced, California

Oliver A. Chadwick Steven G. Driese Sabine Goldberg

Department of Geography Department of Geology United States Salinity Laboratory
University of California, Santa Barbara Baylor University Agricultural Research Service
Santa Barbara, California Waco, Texas United States Department of Agriculture
Riverside, California
Yin Chen Hari Eswaran
Department of Biological Sciences Soil Survey Division
University of Warwick Natural Resources Conservation Service Robert C. Graham
Coventry, United Kingdom United States Department of Agriculture Department of Environmental Science
Washington, District of Columbia University of California, Riverside
G. Jock Churchman Riverside, California
School of Agriculture, Food and Wine Steven R. Evett
University of Adelaide Soil and Water Management Research Unit E.G. Gregorich
Glen Osmond, South Australia, Australia Conservation and Production Research Agriculture and Agri-Food Canada
Laboratory Ottawa, Ontario, Canada
Marianne Clarholm
Agricultural Research Service
Department of Forest Mycology and
United States Department of Agriculture Bryan Griffiths
Pathology
Bushland, Texas Teagasc
Swedish University of Agricultural
Sciences Environment Research Centre
Delvin S. Fanning
Uppsala, Sweden Wexford, Ireland
Department of Agronomy
David C. Coleman University of Maryland
College Park, Maryland Peter M. Groffman
Department of Zoology
Cary Institute of Ecosystem Studies
University of Georgia
Robert G. Ford University of Georgia
Athens, Georgia
National Risk Management Research Millbrook, New York
M.E. Collins Laboratory
Department of Soil and Water Science Office of Research and Development C.T. Hallmark
Institute of Food and Agricultural Sciences United States Environmental Protection Department of Soil and Crop Sciences
University of Florida Agency Texas A&M University
Gainesville, Florida Cincinnati, Ohio College Station, Texas
Contributors xix

A.G. Hardie Bruce R. James Randall K. Kolka

Department of Soil Science Environmental Science and Technology Northern Research Station
Stellenbosch University University of Maryland United States Department of Agriculture
Stellenbosch, Western Cape, South Africa College Park, Maryland Forest Service
Grand Rapids, Minnesota
Willie Harris Jan Jansa
Department of Soil and Water Sciences Institute of Plant, Animal and Sylvia Koszinski
Institute of Food and Agricultural Sciences Agroecosystem Sciences Institute of Soil Landscape Research
University of Florida Eidgenössische Technische Hochschule Leibniz Centre for Agricultural
Gainesville, Florida Zürich Landscape Research (ZALF)
Zürich, Switzerland Müncheberg, Germany
James Harsh
Department of Crop and Soil Sciences H.H. Janzen Deepak Kumaresan
Washington State University Agriculture and Agri-Food Canada Department of Biological Sciences
Pullman, Washington Lethbridge, Alberta, Canada University of Warwick
Coventry, United Kingdom
Paul F. Hendrix Jiri Jirout
Department of Crop and Soil Sciences Faculty of Science
Odum School of Ecology Hannan E. LaGarry
Institute of Soil Biology
University of Georgia Department of Physical and Life Sciences
Biology Centre
Athens, Georgia Chadron State College
University of South Bohemia
Chadron, Nebraska
České Budějovice, Czech Republic
Holger Heuer
Federal Research Centre for Cultivated Loretta Landi
Scott B. Jones
Plants Department of Soil Science and Plant
Department of Plants, Soils, and Climate
Julius Kühn-Institut Nutrition
Utah State University
Institute for Epidemiology and Pathogen Institute of Biological Chemistry
Logan, Utah
Diagnostics University of Florence
Messeweg, Germany Florence, Italy
Nestor Kämpf
Daniel R. Hirmas Departamento de Solos
Inmaculada Lebron
Department of Geography Universidade Federal do Rio Grande do
Environment Centre Wales
University of Kansas Sul
Centre for Ecology & Hydrology
Lawrence, Kansas Porto Alegre, Rio Grande do Sul, Brazil
Bangor, United Kingdom

Rainer Horn
Michael A. Kertesz Feike J. Leij
Institut für Pflanzenernährung und
SUNFix Centre for Nitrogen Fixation Department of Civil Engineering and
Bodenkunde
Food and Natural Resources Construction Management
Christian-Albrechts-Universität zu Kiel
The University of Sydney California State University, Long Beach
Kiel, Germany
Sydney, New South Wales, Australia Long Beach, California

Robert Horton
Yuncong Li
Department of Agronomy Makoto Kimura
Department of Soil and Water Science
Iowa State University Laboratory of Soil Biology and
Tropical Research and Education
Ames, Iowa Chemistry
Center
Graduate School of Bioagricultural
Institute of Food and Agriculture Sciences
Pan Ming Huang (Deceased) Sciences
University of Florida
Department of Soil Science Nagoya University
Homestead, Florida
University of Saskatchewan Chikusa, Nagoya, Japan
Saskatoon, Saskatchewan, Canada
Hideomi Kodama Zamir Libohova
Wayne H. Hudnall Centre for Land and Biological Resources National Soil Survey Center
Department of Plant and Soil Science Research National Resources Conservation Service
Texas Tech University Agriculture and Agri-Food Canada United States Department of Agriculture
Lubbock, Texas Ottawa, Ontario, Canada Lincoln, Nebraska
xx Contributors

Henry Lin Budiman Minasny Phillip Owens

Department of Crop and Soil Sciences Department of Agriculture, Food and Department of Agronomy
Pennsylvania State University Natural Resources Purdue University
University Park, Pennsylvania The University of Sydney West Lafayette, Indiana
Sydney, New South Wales, Australia
David Long E.A. Paul
Department of Geological Sciences Per Møldrup Natural Resource Ecology Laboratory
Michigan State University Department of Biotechnology, Chemistry Colorado State University
East Lansing, Michigan and Environmental Engineering Fort Collins, Colorado
Aalborg University
David J. Lowe Aalborg, Denmark Stephan Peth
Department of Earth and Ocean Sciences Institut für Pflanzenernährung und
University of Waikato H. Curtis Monger Bodenkunde
Hamilton, New Zealand Department of Plant and Environmental Christian-Albrechts-Universität zu Kiel
Sciences Kiel, Germany
Robert A. MacMillan New Mexico State University
World Soil Information Las Cruces, New Mexico Laurent Philippot
International Soil Reference and Department of Soil and Environmental
Information Centre J. Colin Murrell
Microbiology
Wageningen, the Netherlands Department of Biological Sciences
Institut National de la Recherche
University of Warwick
Agronomique
Terence L. Marsh Coventry, United Kingdom
Dijon, France
Department of Microbiology and
Molecular Genetics and Center for Paolo Nannipieri
Giacomo Pietramellara
Microbial Ecology Department of Soil Science and Plant
Department of Plant, Soil and
Michigan State University Nutrition
Environmental Science
East Lansing, Michigan University of Florence
University of Florence
Florence, Italy
Florence, Italy
Alex B. McBratney
Department of Agriculture, Food and Lee C. Nordt
Department of Geology Chien-Lu Ping
Natural Resources
Baylor University School of Natural Resources and
The University of Sydney
Waco, Texas Agricultural Sciences
Sydney, New South Wales, Australia
University of Alaska
Jeanette M. Norton Palmer, Alaska
Paul A. McDaniel
Soil Science Division Department of Plants, Soils and Climate
Utah State University James I. Prosser
University of Idaho
Logan, Utah Institute of Biological and
Moscow, Idaho
Environmental Sciences
D.G. McGahan Astrid Oberson University of Aberdeen
Department of Agribusiness, Agronomy, Institute of Plant, Animal and Aberdeen, United Kingdom
Horticulture and Range Management Agroecosystem Sciences
Tarleton State University Eidgenössische Technische Hochschule John H. Prueger
Stephenville, Texas Zürich Soil, Water, and Air Resources Research
Zürich, Switzerland Unit
Robert McSorley National Laboratory for Agriculture and
Department of Entomology and Tyson Ochsner the Environment
Nematology Department of Plant and Soil Sciences Agricultural Research Service
University of Florida Oklahoma State University United States Department of Agriculture
Gainesville, Florida Stillwater, Oklahoma Ames, Iowa

Erika Michéli Dani Or Martin C. Rabenhorst

Department of Soil Science and Department of Environmental Sciences Department of Environmental Science
Agricultural Chemistry Eidgenössische Technische Hochschule and Technology
Szent István University Zürich University of Maryland
Godollo, Hungary Zürich, Switzerland College Park, Maryland
Contributors xxi

David E. Radcliffe Philip J. Schoeneberger Christopher W. Smith

Department of Crop and Soil Sciences National Soil Survey Center Soil Survey Division
University of Georgia Natural Resource Conservation Service Natural Resources Conservation Service
Athens, Georgia United States Department of Agriculture United States Department of Agriculture
Lincoln, Nebraska Washington, District of Columbia
Paul F. Reich
Soil Survey Division Darrell G. Schulze M.P.W. Sonneveld
Natural Resources Conservation Service Department of Agronomy Department of Environmental Sciences
United States Department of Agriculture Purdue University Land Dynamics Group
Washington, District of Columbia West Lafayette, Indiana Wageningen University and Research
Centre
Giancarlo Renella Paul Schwab Wageningen, the Netherlands
Department of Soil Science and Plant Department of Agronomy
Nutrition Purdue University Randal J. Southard
University of Florence West Lafayette, Indiana Department of Land, Air and Water
Florence, Italy
Resources
Antonella Sciortino
Daniel deB. Richter, Jr. University of California, Davis
Department of Civil Engineering and
Nicholas School of the Environment Davis, California
Construction Management
Duke University California State University, Long Beach
Durham, North Carolina Otto C. Spaargaren
Long Beach, California Taxonomy of Soils
David A. Robinson World Reference and Information Centre
John C. Seaman
Environment Centre Wales Wageningen, the Netherlands
Savannah River Ecology Laboratory
Centre for Ecology & Hydrology
University of Georgia
Bangor, United Kingdom Donald L. Sparks
Athens, Georgia
Department of Plant and Soil Sciences
Dennis E. Rolston and
Joey N. Shaw
Department of Land, Air and Water Delaware Environmental Institute
Department of Agronomy and Soils
Resources University of Delaware
Auburn University
University of California Newark, Delaware
Auburn, Alabama
Davis, California
Jirka Šimůnek Garrison Sposito
Randall Schaetzl
Department of Environmental Sciences Division of Ecosystem Sciences
Department of Geography
University of California, Riverside University of California, Berkeley
and
Riverside, California Berkeley, California
Department of Geology
Michigan State University Sharath Srinivasiah
East Lansing, Michigan Joseph M. Skopp
School of Natural Resources Department of Plant and Soil Sciences
University of Nebraska University of Delaware
Andreas C. Scheinost
Lincoln, Nebraska Newark, Delaware
Helmholtz-zentrum Dresden-Rossendorf
Institute of Radiochemistry
Ulf Skyllberg Mark G. St. John
Dresden, Germany
Department of Forest Ecology and Landcare Research
Management Lincoln, New Zealand
Joshua P. Schimel
Department of Ecology, Evolution and Swedish University of Agricultural
Marine Biology Sciences Mark H. Stolt
University of California, Davis Umeå, Sweden Department of Natural Resources Science
Santa Barbara, California University of Rhode Island
Kornelia Smalla Kingston, Rhode Island
Michael Schloter Federal Research Centre for Cultivated
Department of Terrestrial Ecogenetics Plants J.J. Stoorvogel
German Research Center for Julius Kühn-Institut Laboratory of Soil Science and Geology
Environmental Health Institute for Epidemiology and Pathogen Wageningen University and Research
Institute of Soil Ecology Diagnostics Centre
Neuherberg, Germany Messeweg, Germany Wageningen, the Netherlands
xxii Contributors

Joseph W. Stucki Arlene J. Tugel Ole Wendroth

Department Natural Resources and Natural Resources Conservation Service Department of Plant and Soil Sciences
Environmental Sciences United States Department of Agriculture University of Kentucky
University of Illinois Las Cruces, New Mexico Lexington, Kentucky
Urbana, Illinois
Markus Tuller Larry T. West
Donald L. Suarez Department of Soil, Water and National Soil Survey Center
United States Salinity Laboratory Environmental Science Natural Resources Conservation Service
Agricultural Research Service The University of Arizona United States Department of Agriculture
United States Department of Agriculture Tucson, Arizona Lincoln, Nebraska
Forest Service
Riverside, California Judith K. Turk Larry P. Wilding
Department of Environmental Sciences Department of Soil and Crop Sciences
University of California, Riverside Texas A&M University
David Swanson
Riverside, California College Station, Texas
Natural Resources Conservation Service
United States Department of Agriculture
Goro Uehara Kurt E. Williamson
Palmer, Alaska
Department of Tropical Plant and Soil Integrated Science Center
Sciences The College of William and Mary
C. Tarnocai
University of Hawaii at Manoa Williamsburg, Virginia
Agriculture and Agri-Food Canada
Honolulu, Hawaii
Ottawa, Ontario, Canada
K. Eric Wommack
P.C.J. van Vliet Department of Plant and Soil Sciences
R. Greg Thorn Blgg AgroXpertus University of Delaware
Department of Biology Wageningen, the Netherlands Newark, Delaware
University of Western Ontario
London, Ontario, Canada Vicente Vasquez Jon M. Wraith
Department of Plant and Soil Sciences College of Life Sciences and Agriculture
Judy A. Tolk University of Kentucky University of New Hampshire
Soil and Water Management Research Lexington, Kentucky Durham, New Hampshire
Unit
Conservation and Production Research Thomas Voice
Douglas A. Wysocki
Laboratory Department of Civil and Environmental
National Soil Survey Center
Agricultural Research Service Engineering
Natural Resources Conservation Service
United States Department of Agriculture Michigan State University
United States Department of Agriculture
Bushland, Texas East Lansing, Michigan
Lincoln, Nebraska
 Introduction

Malcolm E. Sumner soil has been the source from which great antidotes to disease
University of Georgia and infection, the antibiotics, have been developed.
In ancient times, soil and water degradation, resulting in
Yuncong Li
University of Florida unsustainable crop production often due to the accumulation of
salts, led to the downfall of civilizations. Directly or indirectly,
Larry P. Wilding (Retired) the soil resource impacts, undergirds, and transcends all of soci-
Texas A&M University
ety’s urban, industrial, and agrarian interests. Current local to
global policies and issues on conservation and sustainability,
What Is Soil? land use, energy, environmental quality, taxation, and food,
feed, and fiber production are derived largely from the quality
Soil, the extremely thin but precious skin covering our planet, and extent of the available soil resource.
supports all terrestrial life forms and contributes nutrients to Despite the clearly pivotal role that soil plays in supporting life
aquatic and marine environments. This covering of the unweath- on Earth, a precise definition of soil is elusive. At this stage, one
ered and partially weathered geological formations at the Earth’s can say that soil is an evolving, living organic/inorganic covering
surface is a unique, fragile veneer. No longer rock nor geological of the Earth’s surface, which is in dynamic equilibrium with the
sediment, soil has been altered during the process of soil forma- atmosphere above, the biosphere within, and the geology below.
tion by geological, topographical, climatic, physical, chemical, Soil acts as an anchor for roots, a purveyor of water and nutrients,
and biological factors to form a living entity, which inextrica- a residence for a vast and still largely unidentified community
bly links inorganic or mineral particles with organic matter and of microorganisms and animals, a sanitizer of the environment,
biota bathed in a milieu of liquid water and gases. Water, the and a source of raw materials for construction and manufactur-
major constituent of all living entities, is the solvent and con- ing. Soil is an essential component of terrestrial ecosystems used
veyor of nutrients, which, together with the solid phase, become by nations as long-term capital to grow and develop. Because
the fertile substrate from which all planetary life springs. This this foundation is essential to the life forms within and on it, one
nurturing and life-supporting pedosphere zone is a biologically requires a fundamental understanding of this elastic, porous,
active, porous, and structured medium that effectively inte- three-phase system (solid, liquid, gas), and its components, pro-
grates and dissipates mass fluxes and energy. In its pristine state, cesses, and reactions in order to be able to effectively manage and
soil is a self-regulating, slowly evolving biogeochemical system exploit this vital resource. In the words of Roy Simonson “Soil
that weathers with time, simulating sponge-like behavior and resources are the earthen looms that shape the lives of the people.
regulating and buffering nutrient supply and water quality and The more completely they are understood, the better can be the
quantity for the growth of macro- and microflora and fauna. fabric of life woven on these earthen looms” (Wilding et al., 1984).
Furthermore, it determines the partitioning of water into sur- Every soil consists of one to several layers, called horizons, a
face and subterranean groundwater reservoirs. few to hundreds of centimeters thick that reflect the physical,
In addition to its primary role in promoting, supporting, chemical, and biological processes that have taken place dur-
and sustaining all forms of life, soil also acts as a living filter for ing its formation. Horizons are composed of natural aggregates
anthropogenic waste. Soil can recycle water through biochemi- called peds, which are made up of associations of mineral and
cally mediated processes that cleanse, purify, detoxify, and organic particles. Peds and particles are often separated from
counteract most toxins and pathogens in polluted waters that each other by pores that vary widely in size and shape. In addi-
would irreparably contaminate and degrade our environment. tion, individual peds and particles may be coated by materials
Despite being the repository of human and animal cadavers, such as clay, organic matter, sesquioxides, or precipitated salts.
including those from epidemics of pestilence and plague, all but Although the internal structure of peds is not readily visible to
a few vectors have been rendered harmless, and it is seldom, if the naked eye, their spatial arrangement involving particles and
ever, involved in the transmission of diseases. On the contrary, pores (soil architecture) greatly influences soil behavior because

xxiii
xxiv Introduction

the organization is frequently systematic and related to macro- bodies than about the soil underfoot” is as true today as it was
pore distribution. At the microscale, soil architecture governs then. There is need for much more investigation of our most pre-
soil water/solute movement and retention, soil structure/poros- cious resource to stave off the fate that befell our ancestors in
ity, soil strength/failure, mineral synthesis/weathering, move- the ancient empires of Babylon, Egypt, China, Europe, and the
ment of toxic and nontoxic wastes, soil/root environments, root Americas where soil degradation through nutrient loss, erosion,
growth/proliferation, nutrient transfers, soil erosion, and oxida- sodification, and salinization together with siltation of rivers
tion/reduction reactions. and storage facilities laid waste their land and water resources.
The ancients were constrained by their limited knowledge of
What Are the Soil Sciences? processes driving the system, but we will be judged by genera-
tions to come based on our superior understanding of the soil
Soil sciences are a spectrum of Earth sciences that address the system and the quality and stewardship of our land resources.
importance of soils as very slowly renewable natural resources. Modern parallels of soil and land degradation continue in
They involve the study of soil formation, classification, and both developing and industrialized countries. In addition to the
mapping; the physical, chemical, biological, and mineralogical problems facing the ancients that are still prevalent, chemical
properties of soil from microscopic to macroscopic scales of res- toxicities, irreversible land use conversion, environmental pollu-
olution; as well as the processes and behavior of soil systems and tion, and desertification are the modern plagues. Sustainability
their use and management. Soils are integrative links between of today’s culture is threatened by loss of biodiversity, popula-
the atmosphere, biosphere, lithosphere, and hydrosphere. Soil tion growth, and land degradation, leading to enhanced green-
sciences provide tools to integrate the components of Earth sci- house gas emissions culminating in global climate change. Land
ence systems, expanding knowledge of the causes and effects of degradation is a complex technical, socioeconomic, and politi-
spatial variability, and to take a more holistic approach to the cal issue without simple answers. Although soil scientists can
dynamic processes affecting ecosystems. provide technical solutions, without implementation as public
Soil sciences focus primarily on near-surface processes that policy, they are likely to be futile. Currently, public attention is
govern the quality and distribution of soil resources relative to focusing on soil, air, and water quality in efforts to maintain a
landform evolution (geomorphology), geochemical environ- clean environment. Soil sciences have a major role to play in this
ment (geochemistry), and organismal habitat (ecology/biology). arena.
Pedogenic processes are interactively conditioned by lithol-
ogy, climate, and relief through geologic time. Soils are welded What Is the Purpose of This Handbook?
together into landscapes like chains; processes that perturb and
impact higher topographic surfaces directly affect processes on Handbook of Soil Sciences is a revision of the first comprehen-
adjacent surfaces below. Pedologists and other soil scientists sive reference on the disciplines of soil science as practiced today.
study the energy flows and mass fluxes, which are the dynamic It contains definitive descriptions of each major area in the disci-
driving forces of pedogenesis through and over the three-dimen- plines, including fundamental principles, appropriate methods
sional soil system. They also quantify renewal and transfer vec- to measure each property, many examples of the variations in
tors for biomass production, rainfall, and dusts, which counter properties in different soils throughout the world, and guide-
constituent losses through drainage water, lateral interflow, and lines for the interpretation of the data for various applications
downslope migration or erosion products. (agricultural, engineering, environmental, biological, regula-
Soil sciences have their parentage in geology, chemistry, phys- tory, educational, hydrological, biogeochemical). This handbook
ics, and biology, but for the past 100 years have evolved as an assembles the current core of knowledge from all fields encom-
independent, interdisciplinary body of knowledge with strong passed within the soil sciences and provides a resource-rich
underpinnings to agriculture and, more recently, the environ- database that will give professional soil scientists, agronomists,
ment. Because of an unparalleled success that soil sciences have engineers, ecologists, biologists, naturalists, and students their
enjoyed in helping to bring ample food, fiber, feed, and fuel to point of first entry into a particular aspect of the soil sciences.
the world, the development of the basic soil sciences has evolved The contributions also serve those professionals seeking spe-
primarily as a by-product of research in agriculture, engineer- cific, factual reference information. The handbook provides a
ing, and the environment. There is growing evidence that the thorough understanding of soil science principles and practices
complexity of these problems requires a much broader approach based on a rigorous, complete, and cutting-edge treatment of the
to the science of the soil than can be stimulated by applied subject compiled by leading scientists in each field. It is designed
research alone. Soil sciences are taking their place alongside basic as a desk reference book.
research efforts in the biosciences, geosciences, and atmospheric This handbook has been extended to two books, Handbook
sciences to provide the reservoir of fundamental knowledge of Soil Sciences: Properties and Processes comprises five parts
needed to develop lasting solutions to the challenges of bal- dealing with soil physics, soil chemistry, soil mineralogy, soil
anced use and stewardship of the Earth. Despite the knowledge biology and biochemistry, and  pedology. Handbook  of Soil
accumulated over the past century, Leonardo da Vinci’s state- Sciences: Resource Management and Environmental Impacts
ment that “We know more about the movement of the celestial discusses soil physical, chemical, and biological interfacial
Introduction xxv

interactions; soil fertility and plant nutrition; interdisciplin- presented in the part on pedology as a framework in which to
ary aspects of soil science; and soil databases. discuss the soil orders in soil taxonomy and other classification
In the Handbook of Soil Sciences: Properties and Processes, the systems. The part continues with a discussion of land evalua-
part on soil physics opens with a description of the basic physi- tion followed by new chapters on hydropedology and subaque-
cal properties of soils followed by a treatment of their dynamic ous soils. Thereafter, digital soil mapping and its applications are
properties in relation to tillage and disturbance by machinery. presented, followed by a discussion of soil change in the anthro-
Soil water is discussed, including content/potential relation- pocene in which the bridge between pedology, land use, and soil
ships, its movement and transfer to the atmosphere both directly management is built.
and through the plant, and the co-transport of solutes in moving In the Handbook of Soil Sciences: Resource Management and
water. The nature of soil structure and its bearing on soil behav- Environmental Impacts, the new part on soil physical, chemi-
ior are explored followed by an examination of gas movement cal, and biological interfacial interactions opens with a discus-
under unsaturated conditions. The role of macropores as the sion of the methodology to study metal(oid)s and nutrients at
superhighway for bypass transport of water and solutes is con- critical zone interfaces followed by insights into the interactions
sidered. Thermal regime and heat transfer are discussed. Finally, between clay and organic materials in soils. Various aspects of
the heterogeneity of soils is described culminating in an evalua- the involvement of nanoparticles in chemical, biological, and
tion of spatial variability. hydrological processes are discussed, followed by the effects of
The part on soil chemistry begins with a discussion of the mineral and organic colloids on enzymatic activity in soils and
nature and dynamics of soil organic matter. The importance of its impact on biogeochemical processes. Thereafter, the effects of
the soil solution, for transport of nutrients and catalyst for reac- biophysical, biogeochemical, and biological processes on rhizo-
tions in soil, is then highlighted followed by an evaluation and sphere processes and reactions are discussed. Subsequent chap-
description of the kinetics of reactions in soils. The reactions ters deal with mineralogical, chemical, physical, and (micro)
taking place when oxygen becomes limiting are then explored biological interactions involved in the turnover and stabiliza-
followed by a detailed account of soil colloidal phenomena tion of organic matter and the transformations of metal(oid)s.
important in predicting the behavior of the finest soil fraction. The part concludes with a discussion of the physicochemical and
Ion exchange, sorption, and precipitation reactions are quanti- biological interfacial processes governing the fate and transport
tatively treated as a framework to evaluate the behavior of labile of nutrients and pollutants in soils.
constituents in soils. Catalytic reactions promoted by soil and its Bioavailability of macro- and micro-nutrients as well as their
constituents are examined followed by an account of the effects interactions are discussed in the part on soil fertility and plant
of acidity and alkalinity on soil reactions and behavior. nutrition prior to evaluating methods for estimating their poten-
Mineralogy of soils is covered in the next part starting with a tial availability to crops and methods of application as fertiliz-
discussion of the formation and occurrence of minerals in soils ers. The causes of soil acidity and strategies for its amelioration
followed by three parts in which structure, occurrence, identi- are also outlined. Finally, the efficiencies of nutrient and water
fication, and properties of phyllosilicates, oxide minerals, and use are discussed. Thereafter, various interdisciplinary aspects
poorly crystalline aluminosilicates are discussed. The part on of soil science such as salinity, sodicity, water repellency, wet-
soil biology and biochemistry begins with a discussion of viruses, land biogeochemistry, acid sulfate soils, soils and environmen-
bacteria, fungi, cyanobacteria and algae, followed by the topic of tal quality, soil erosion by wind and water, land application of
soil fauna comprising protozoa, nematodes, micro- and macro- wastes, and soil quality and conservation tillage are discussed.
arthropods, enchytriads, and vertebrates. The nature, function, Finally, the soil databases available to assess worldwide soil
and life cycles of each are described. Then the processes medi- resources are presented and discussed.
ated by these organisms, including nutrient transformations, are
discussed. A major portion of the discussion is devoted to nitro- Reference
gen transformations because of their importance in soils.
Following a discussion of the geomorphology of soil land- Wilding, L.P., N.E. Smeck, and G.F. Hall (eds.). 1984. Pedogenesis
scapes and the pedogenic processes and models involved in soil and soil taxonomy. II. The soil orders: Developments in soil
formation, descriptions of the systems used to classify soils are science 11B, p. v. Elsevier, Amsterdam, the Netherlands.
 I
Soil Physics
Markus Tuller
The University of Arizona

1 Physical Properties of Primary Particles  Joseph M. Skopp.................................................................................................1-1

Particle Density (ρp)  •  Particle Shape  •  Particle Size Distribution  •  Specific Surface Area  •  References
2 Soil Structure  Teamrat A. Ghezzehei........................................................................................................................................2-1
Introduction  •  Development and Dynamics of Soil Structure  •  Characterization of Soil Structure  • 
Concluding Remarks  •  References
3 Mechanics of Unsaturated Soils for Agricultural Applications  Rainer Horn and Stephan Peth.................................3-1
Introduction  •  Stress–Strain Relationships in Soils  •  Soil Strength–Stability Indicators and Their Measurement  • 
Effect of Soil Structure on Soil Strength and Deformation Processes  •  External Mechanical Forces and Stress Distribution
in Soils  •  Soil Deformation and its Effects on Physical and Physicochemical Properties  •  Modeling Soil Deformation and
Coupled Processes  •  Concluding Remarks  •  References
4 Soil Water Content and Water Potential Relationships  Dani Or, Jon M. Wraith, David A. Robinson,
and Scott B. Jones.......................................................................................................................................................................... 4-1
Introduction  •  Soil Water Content  •  Soil Water Energy  •  Soil Water Content—Energy Relationships  •  Resources  • 
Acknowledgments  •  References
5 Water Flow in Soils  David E. Radcliffe and Jirka Šimůnek...................................................................................................5-1
Introduction  •  Steady Flow in Saturated Soil  •  Steady Flow in Unsaturated Soil  •  Transient Water Flow  • 
Measurements of Hydraulic Properties  •  Numerical Methods  •  Infiltration  •  Redistribution  •  Evaporation  • 
Transpiration  •  Preferential Flow  •  Groundwater Recharge and Discharge  •  Summary  •  References
6 Water and Energy Balances in the Soil–Plant–Atmosphere Continuum  Steven R. Evett, John H. Prueger,
and Judy A. Tolk............................................................................................................................................................................ 6-1
Introduction  •  Energy Balance Equation  •  Water Balance Equation  •  Acknowledgments  •  References
7 Solute Transport  Feike J. Leij and Antonella Sciortino..........................................................................................................7-1
Introduction  •  Advection–Dispersion Equation  •  Solutions of the Advection–Dispersion Equation  •
Stream Tube Models  •  Nonaqueous Phase Liquids  •  References
8 Gas Transport in Soils  Dennis E. Rolston and Per Møldrup............................................................................................... 8-1
Introduction  •  Soil-Air Composition  •  Mechanisms of Gas Transport  •  Gas Transport Theory  •  Measuring Gas
Transport Parameters  •  Predictive Equations  •  Applications  •  References
9 Soil Thermal Regime  Robert Horton and Tyson Ochsner.....................................................................................................9-1
Introduction  •  Mechanisms of Heat Transfer in Soil  •  Surface Energy Balance  •  Soil Thermal Properties  •  Modeling
the Soil Thermal Regime  •  Measuring Soil Temperature  •  Measuring and Interpreting Soil Heat Fluxes  •  Managing the
Soil Thermal Regime  •  Soil Temperature and Global Climate Change  •  Concluding Remarks  •  References

10 Soil Spatial Variability  Ole Wendroth, Sylvia Koszinski, and Vicente Vasquez............................................................. 10-1
Sampling a Soil Process  •  Autocorrelation  •  Cross-Correlation  •  Semivariogram  •  Kriging  •  Cokriging  • 
Autoregressive State- Space Modeling  •  Spectral Analysis  •  Cospectral Analysis  •  Wavelet Analysis  •  Appendix  • 
Acknowledgments  •  References

I-1
I-2 Soil Physics

S
OIL PHYSICS is concerned with the application of for steady and transient water flow are provided. Moreover, soil
­physical principles to characterize the soil system and water movement is described in the context of the overall water
mass and energy transport processes within the critical balance and its key role in the hydrologic cycle.
zone, which extends from the bedrock to the top of the plant Transport processes are principally for water, energy, solutes,
canopy. The exploitation of soil physical principles is not only and gas. Generally, flow laws are related to an appropriate gradi-
feasible for natural systems, but also relevant for many indus- ent such as for soil water potential, temperature, or concentra-
trial and engineering applications such as oil recovery, filtration, tions of solutes. The individual descriptions are related to the
ceramics, powder technology, or nanoporous materials. Because appropriate measurable quantities to overall mass conversion.
soil physical processes are intimately intertwined with biologi- Chapter 6 contains a detailed description of the water and
cal and chemical processes simultaneously occurring within energy balances at the soil–plant–atmospheric interface,
the same soil volume, the soil physics part is also important for which represents a common convergence point for many of
other parts of this handbook. the world’s problems in food production, water resources,
The second edition of the soil physics part was notably and environmental pollution. Solute transport, the topic of
expanded, containing a new chapter about the soil thermal regime Chapter 7, is of fundamental importance for crop production
and many updates regarding recent theoretical and experimental (i.e., soil quality and fertility) and environmental pollution
advances. and sustainability.
Chapters 1 through 3 emphasize the soil solid phase. Included Separate chapters are devoted to soil gas transport and the
are descriptions and state-of-the-art measurement methods for soil thermal regime. While gas movement (Chapter 8) is histori-
physical properties of primary soil particles, and the arrange- cally linked to soil aeration relevant for plant growth, in-depth
ment and organization of primary particles into an overall knowledge about gas transport mechanisms is also important
structure of solids and pore space. At first, soil is considered as for contaminant remediation, the movement of volatile organic
static to facilitate definitions of particle density, shape, size, sur- chemicals from waste sites, the design of optimal plant growth
face area, bulk density, and porosity. Later, the mechanical prop- media for space exploration, and most importantly, the emission
erties of soils and dynamics induced by tillage operations and of greenhouse gases and associated public concerns with global
temporal variations due to natural and anthropogenic actions warming.
are thoroughly examined. The soil thermal regime and heat transport are described in
Soil water is the primary focus of Chapters 4 and 5, a major Chapter 9, which is new to the second edition of the soil physics
part of Chapters 6 and 7, and relevant for other chapters as well. part. Temperature governs numerous biological, chemical, and
Amount and energy state are the two most fundamental char- physical processes occurring in the soil. Plant germination and
acteristics of soil water that govern many hydrological, biologi- growth are closely related to soil temperature. Furthermore, soil
cal, and geochemical processes. Air content and gas exchange temperature affects hydraulic transport properties and impor-
with the atmosphere, soil temperature, movement of dissolved tant environmental processes such as gas exchange between soil
chemicals, or diffusion of nutrients to plant roots are intimately and atmosphere, the global carbon cycle, or transformation and
related to water content. In addition, changes in water content transport of contaminants.
and energy state affect many mechanical and engineering prop- Spatial variability, Chapter 10, is treated separately in recog-
erties of soils such as strength, compactibility, penetrability, or nition of the heterogeneity of all soil properties, in fact, of all
trafficability. Water content is appropriate to describe storage of measurable natural quantities. In soil science, the development
water, and knowledge about the energy state (i.e., water poten- of the quantitative aspects of variation is necessary for both the
tial) is needed to describe direction and magnitude of fluxes. description of the processes and for forecasting future events.
Standard and emerging methods for measurement of water This has been a rich area for coupling soil physical processes
content and potential as well as new numerical modeling tools with other areas of soil science and remote sensing.
 1
Physical Properties
of Primary Particles
1.1 Particle Density (ρp)................................................................................................................. 1-1
Definition  •  Typical Values–Mineral, Whole Soil  •  Measurement Methods—Water
Pycnometer, Air Pycnometer, Other
1.2 Particle Shape............................................................................................................................ 1-2
Definitions–Shape Factors, Fractals  •  Measurement Methods
1.3 Particle Size Distribution........................................................................................................ 1-3
Definitions  •  Typical Distributions  •  Dispersion and Fractionation  •  Sieving  • 
Sedimentation  •  Coulter Counter  •  Light Scattering  •  Other Methods  • 
Interpretation of Results
1.4 Specific Surface Area................................................................................................................ 1-7
Definitions  •  Typical Values—Separates, Whole Soil  •  Methods  • 
Joseph M. Skopp Geometric Models and Regression
University of Nebraska References.............................................................................................................................................. 1-9

This chapter discusses the following physical properties of pri- 1.1.2  T ypical Values–Mineral, Whole Soil
mary particles: particle density, particle shape, particle size
distribution (PSD), and surface area. The definitions and ideas Each individual soil mineral has a characteristic particle density.
behind these properties have built into it the concept or assump- Values for different minerals can be found in Klein and Hurlbut
tion of discrete primary particles as the primary soil constitu- (1985). Quartz, a predominant soil mineral, has a value of about
ent. If organic matter or amorphous materials and cementing 2.65 Mg m−3, which is why this value is frequently given as repre-
agents are abundant, then the importance of primary particles is senting all soils. In contrast, gypsum, biotite, and hematite have
reduced. In either case, the arrangement or packing of soil par- values of 2.32, 2.80–3.20, and 4.80–5.30 Mg m−3, respectively. The
ticles and these “glues” that control most physical properties of particle density of a soil is a weighted average over the distribution
the soil rather than a complete description of the primary par- of soil minerals present.
ticles will be presented in this chapter. A determination of particle density may be for individual
minerals, size fractions, or the soil as a whole. Organic matter
removal may take place in order to reduce variation. With stan-
1.1  Particle Density (ρp) dard procedures and removal of organic matter, a propagated
error of less than ±0.01 Mg m−3 is possible. (Propagated error is
1.1.1  Definition
the combination of all instrument errors when making a deter-
The particle density represents one of the fundamental soil phys- mination of a soil physical property.) Generally, determinate
ical properties. One can define particle density as the mass of errors (i.e., biases) play a greater role in the analysis of particle
soil particles divided by the volume occupied by the solids (i.e., density than indeterminate errors (i.e., random errors).
excluding voids and water). Typical values for mineral soils range Perhaps, the most interesting question in the determina-
from 2.5 to 2.8 Mg m−3 with some soils within the broader range tion of soil particle density is the role of organic matter (with a
of 1.0–3.0 Mg m−3. The standard value of 2.65 Mg m−3 applies typical density of 1.0 Mg m−3). Most standard methods remove
only to mineral soils dominated by quartz. Particle density pro- organic matter. Thus, the particle density reflects only the min-
vides few insights into soil physical processes. Consequently, one eral phase. This value is the best value for use in particle-size
frequently overlooks the errors associated with particle density. analysis. However, it may not be the best value for calculating
However, its value enters into a variety of calculations of more porosity. Including organic matter means that changes in soil
interesting soil properties (e.g., porosity and PSD). management may change this particle density.

1-1
1-2 Properties and Processes

1.1.3  Measurement Methods—Water

Pycnometer, Air Pycnometer, Other
Three methods of determining particle density will be examined. Regular shape Primary T
Other methods are discussed by Flint and Flint (2002). The most particle
common determination of a soil’s particle density uses a pyc-
nometer or some variation. A pycnometer is any device that can B
be made to retain a reproducible or measurable volume. The soil
sample is introduced into the pycnometer and the displaced vol-
ume of a fluid is determined. Water is typically the displaced L
fluid but air can also be used.
The water pycnometer method generally requires the removal
of organic matter prior to use. This reduces problems with trapped
air and decreases variability. The water pycnometer method Irregular shape
T
requires good temperature control (Blake and Hartge, 1986).
An alternative air pycnometer procedure uses a gas as the
displacing fluid and the ideal gas law to calculate the volume of
solids. The principles of an air pycnometer are straightforward B
but care must be taken to prevent temperature changes. The
air pycnometer does not require the removal of organic matter, L
which is particularly valuable when the total porosity (or total
void space) or air-filled porosity is required without knowing FIGURE 1.1  Ideal individual soil particle. (After Heywood, H. 1947.
soil bulk density or water content. Symposium on particle size analysis. Trans. Inst. Chem. Eng. 22:214.)
A less common method of determining particle density uses a
vibrating tube (Elder, 1979), which is filled with a solution or sus-
circumference of circle with same area
pension. The resonant frequency of the vibrating tube provides a Circularity = ,
very precise means of determining the density of the suspension. actual perimeter

actual perimeter
1.2  Particle Shape Rugosity =
circumference of circumscribing circle
.

1.2.1  Definitions–Shape Factors, Fractals

Particle shape influences specific surface as well as particle-size These last two terms work best for a 2D image or the projection
analysis and has a strong influence on the packing of particles of the particle outline onto a flat surface.
and soil strength, as well as transport properties. Unfortunately, A microscopic picture of soil describes either the solids or
particle shape is a difficult property to measure and few deter- the voids. A simple picture of the solids might be a sphere or
minations exist in the literature. Recent articles by Jones and cube while that of the voids might be a cylindrical tube or a slit
Friedman (2000), Santamarina and Cho (2004), and Cho et al. between two flat surfaces. These pictures or physical models of
(2006) show the range of soil properties that are influenced by the soil make it possible to deduce relations describing surface
particle shape. area, packing, water retention, or water movement.
A variety of terms exist for defining particle shape. Some of It is possible to apply these ideas to models that are not sim-
the definitions require reference to a figure of an ideal particle ple geometrical figures. Here, a “characteristic length” replaces
(Figure 1.1). Let L, B, and T represent the length, breadth, and the edge length of a cube and a dimensionless shape factor (Ck)
thickness, respectively, of a particle. Then, Heywood (1947) describes the deviation of the geometry from simple geometries
defines the following: (e.g., Table 1.1). These two factors are used to describe the area
and volume as

Flatness ratio = B / T,
A = C 2 L2 and V = C 3 L3 , (1.1)

Elongation ratio = L/B.
where
Other dimensionless terms are as follows: L is the characteristic length
C2 or C3 is the shape factor for area or volume, respectively
surface area of equivalent sphere
Sphericity = , For a cube, if L equals d (the length of an edge), find C2 = 6 and
actual surface area
C3 = 1. Examples of C2 and C3 for other shapes are in Table 1.1.
Physical Properties of Primary Particles 1-3

TABLE 1.1  Shape Factors for 3D Physical Models with L = d

Geometry Area C2 Volume C3
Sphere πd2 Π πd3/6 π/6

Disc or cylinder (πdh + πd2/2) (πh/d + π/2) πd2h/4 πh/4d

d

Cube 6d2 6 d3 1

Square rod 2d2 + 4dh 2 + (4h/d) d2h h/d

h

d
d

Two particles differing in size may or may not have the same This relation for spherical particles first appears in Einstein
shape. Typically, weathering or size reduction changes not only (1906). K = 2.5 is a constant for spheres but changes with the
the total dimension but also the shape factor. shape of the particle. Kahn (1959) applied this technique to
examine the shape of clay particles. Similar techniques (Egashira
and Matsumoto, 1981) provide estimates of a/b (the ratio of
1.2.2  Measurement Methods
major to minor axis) for montmorillonite (200–300), kaolinite
At least three methods exist to examine particle shape or shape (15–25), and mica (10–20).
factors. The first is direct observation under a microscope using The third method of particle-shape analysis uses the scatter-
an image analysis system (Davis and Dexter, 1972). Commercial ing characteristics of light passing through a dilute soil suspen-
image analysis systems exist that automatically provide output sion and relies on measurements of the angles of scattered light.
of shape factors or similar properties. Instruments commercially available for particle-size analysis
The second method is an indirect technique obtained from the can be used. This is an active area of research since particle shape
variation of viscosity with the concentration of suspended par- has an influence on the accuracy of particle-size analysis based
ticles. Increasing the solid concentration causes the suspension on light scattering (Naito et al., 1998).
viscosity to deviate from pure liquid viscosity. These deviations
are dependent on particle geometry as well as on concentration
of the suspension. The viscosity of the suspension (η) and the 1.3  Particle Size Distribution
viscosity of pure solvent (ηs) usually behave as follows: 1.3.1  Definitions
η / η s = 1 + Kf, (1.2) PSD is the most fundamental physical property of a soil and
defines soil texture. The particle sizes present and their relative
where abundance sharply influence most physical properties.
f is the volume fraction of suspended material Soil particle size (or effective diameter) provides the basis
K is an empirical constant, which is a shape parameter for a classification system. A range of diameters may be given a
1-4 Properties and Processes

special designation (e.g., 2.0–1.0 mm is “very coarse sand”). The A typical graphical expression of PSD uses the logarithm of
ratio between the upper and lower bound is approximately 2 and particle diameter (Figures 1.2 and 1.3). Soils frequently show a
particles within a given size range are called “soil separates.” The lognormal distribution of particle sizes, so that a graph of frac-
size boundaries vary with country or discipline. Comparisons tion versus the logarithm of particle diameters appears to be
of the names given to a size range are given elsewhere (Gee and normally distributed. The shape and position of the lines pro-
Bauder, 1986; Sheldrick and Wang, 1993). vides qualitative information about the soil texture.
The phrase “equivalent diameters” emphasizes the role of the Alternative methods of representing the fraction include
measurement technique in determining particle size. If identi- volume fraction and number fraction. Typically, conversion
cal particles are measured by different techniques, they may between distinct types of fractions may be necessary to compare
appear to have different diameters. It is conceivable that two distributions obtained with different methods. In these cases,
soils with identical PSDs (as determined by a single method) the assumption is made of spherical particles and a standard
will show differences in other physical properties due to dis- particle density. It is important to understand how the method
tinct particle shapes. being used represents the PSD.
Defining the diameter of an irregularly shaped particle is not
trivial. A single parameter, the diameter, characterizes a smooth
sphere. The symmetry of the sphere and its smoothness mean 1.3.3  Dispersion and Fractionation
that no other information is needed to describe it. Distorting the Particle size analysis (sometimes called mechanical analysis) con-
sphere (i.e., into a jelly bean shape) results in at least three pos- sists of isolating various particle-size increments and then measur-
sible diameters. Some particle-size analysis methods may orient ing the abundance of each size interval. Most methods accomplish
the particle into a preferred direction (e.g., settling of a particle this in two steps. First, the soil is dispersed or separated into indi-
in a liquid). Other methods (e.g., image analysis) may observe vidual primary particles. Second, the dispersed sample is fraction-
several possible orientations. ated, or the amounts of each size interval are measured.
There are three objectives of dispersion: (1) removal of
cementing agents, (2) rehydration of clays, and (3) physical sepa-
1.3.2  T ypical Distributions
ration of individual soil particles. It is sufficient to recognize that
Typical data for a variety of soils are presented in Table 1.2. organic matter and amorphous minerals are the primary bond-
Interpretation of particle-size analysis data requires either the ing agents. When either of these are present in large amounts
drawing of graphs or the calculation of summary coefficients, (e.g., histosols, andisols, or oxisols), then dispersion may be dif-
which are discussed in Section 1.3.7. ficult or meaningless. Generally, soil dispersion is carried out
Graphs of a PSD typically select the dependent variable as using a combination of chemical and mechanical means (Gee
either the cumulative fraction up to a size limit or incremental and Bauder, 1986; Loveland and Whalley, 1991; Sheldrick and
fraction of soil in a size interval. The incremental fraction (Fi) Wang, 1993; Gee and Or, 2002).
is usually the mass of particles within a size interval (X i−1 to X i) It is important to recognize that the fraction of soil that is
divided by the total mass of solids, with the index i specifying a single size cannot be determined. What is detected is the
the size interval. The cumulative fraction (Gi) is the sum of all fraction of soil within a particular particle-size interval or the
fractions for particle sizes less than the X i value. cumulative fraction of all particles less than a given size. The use

TABLE 1.2  PSD of Soil Samples

Sand Silt Clay
Fine
Very Coarse Coarse Medium Fine Very Fine Coarse Medium
Soil Series 2–1 mm 1–0.5 mm 0.5–0.25 mm 0.25–0.10 mm 0.1–0.05 mm 50–20 μm 20–10 μm 10–5 μm 5–2 μm 2–0 μm
Anthony 18.05 13.71 17.68 12.93 8.92 7.41 2.69 2.20 1.37 15.04
Ava 0.53 0.56 1.25 0.82 0.67 12.80 21.69 15.71 9.63 30.63
Chalmers 0.74 0.62 1.67 1.38 2.52 19.42 20.18 11.18 7.44 34.89
Davidson 0.71 2.38 6.52 6.02 3.39 3.32 4.83 4.08 7.43 61.32
Fanno 8.45 4.87 2.40 9.96 9.06 5.92 4.27 4.05 5.56 46.46
Kalkaska 0.19 1.79 47.99 36.26 5.19 1.34 1.01 1.33 0.18 4.67
Mohave 15.25 11.30 12.40 8.02 5.42 30.36 5.00 1.34 0.43 10.45
Molokai 1.29 2.64 4.57 6.64 7.91 5.78 8.30 6.08 4.88 52.00
Nicholson 0.67 0.31 0.44 0.42 1.18 12.90 13.47 15.27 5.41 49.89
Wagram 7.48 20.70 32.06 21.81 5.84 2.00 1.37 1.59 3.31 3.84
Source: Data from D.M. Hendricks (1997, personal communication).
Mass percent of total sample for the indicated size class.
Physical Properties of Primary Particles 1-5

40 1.3.4  Sieving
Clay Sand
35
The process of sieving is that of placing the particles on a pattern
of holes. Small particles may fall through while the sieve retains
30
the larger particles as the sieve is agitated. Either air or water may
be the fluid to support the particles as they sort on the sieve. Dry
Frequency, F (no units, %)

25
sieving has a lower practical limit of about 50 μm, while wet siev-
ing can separate smaller particle sizes. Changing the fluid can be
expected to change the observed frequencies. Sieve holes may
20
be square (using a wire cloth mesh) or round, although square
holes are most common. The use of sieves with square openings
15
will not result in measurements equivalent to those using sieves
with round holes (Tanner and Bourget, 1952).
10
The use of words such as effective or nominal diameters with
sieves is in recognition of the imperfect separation that may
5
occur. Placement of a soil sample on a sieve does not result in
instantaneous separation. Several factors influence the time to
0
achieve a fixed level of separation. These factors include sample
100 101 102 103
size, shaking intensity, particle shape, particle size, and hole
Particle diameter, d (microns) (midpoint of interval)
geometry. Since samples vary in their sieving characteristics, it
FIGURE 1.2  Frequency graph of PSD. is best to run a trial sample. Errors on a single set of sieves typi-
cally are less than 1%, while comparisons between sieves show
random errors of about 4%.
100
Many of the standard sieve sizes correspond to the class limits
for USDA soil separates. Surprisingly, no standard sieve is avail-
able for the 50 μm cutoff between the sand and silt separates.
Cumulative frequency (%)

75
Consequently, sieving cannot distinguish this class boundary
Clay Silt Sand using standard sieves.

50
1.3.5  Sedimentation
Soil type Below 50 μm, sieving is an inefficient and difficult procedure and
25
Sandy for soil samples, sedimentation in water is an alternative proce-
Loam
dure. A suspension of the dispersed sample (see Section 1.3.3)
is allowed to settle in water, a measurement can be made of the
0
density of particles suspended (mass of particles in a volume of
100 101 102 103 104
Particle diameter, d (microns)
liquid) at a specified depth within the sedimentation cylinder at
known times. Variations in the method occur as to the determi-
FIGURE 1.3  Cumulative frequency graph of PSD. nation of suspension density. In all cases, Stokes’s law (Streeter
and Wylie, 1975) is central to the derivation of an equation,
of sieves or sedimentation (e.g., pipette or SediGraph) typically which relates the time of settling to the size of particle sampled.
determines the mass fraction (mass of particles in a size interval Two classic means of determining the density of a suspen-
divided by total mass). Microscopic counting (e.g., image analy- sion exist: hydrometer and pipette methods. In the hydrom-
sis systems or Coulter counter) results in a number fraction eter method, the influence of suspension density on a floating
(number of particles in a size interval divided by total number object (the hydrometer) is observed. As density decreases (due
of particles). Photometric techniques (e.g., FlowCAM•) typically to settling out of soil particles), the hydrometer sinks. A cali-
determine the area fraction. Other methods result in volume or bration scale converts the depth of the float (i.e., hydrometer) to
line fractions depending on the sensing procedure. A second the suspension density (expressed as g L−1). The pipette method
complication of comparing PSDs from different methods is the directly removes a sample from the solution. The concentration
manner in which the particle diameter is determined. In some of solids is determined by drying a known volume of the pipet-
cases, this is done directly (e.g., image analysis), rely on settling ted sample. A proper accounting for dissolved salts requires a
times (e.g., SediGraph), or diameter inferred from volume or blank correction.
other properties (e.g., Coulter counter). Thus, while all the meth- The hydrometer method uses higher concentrations of soil
ods are capable of observing PSDs, not all the methods provide and may be less accurate than the pipette method. However, the
results that are equal or directly comparable. hydrometer method allows repeated sampling at many points
1-6 Properties and Processes

on the distribution (since no sample is withdrawn). Problems may rely on the angle of scattered light or on dynamic measure-
in the pipette method due to convection currents near the tip ments in the fluctuation of the scattered light to recover a PSD.
of the pipette, effect of sample removal, and greater potential for The first method relies on the Mie theory and assumes spheri-
operator error make the hydrometer method preferable in some cal particles. The second method interprets the fluctuations in
circumstances (Gee and Bauder, 1979). terms of a distribution of diffusion coefficients. These are inter-
Stokes’s law for the viscous drag on a sphere is combined with preted as representing an equivalent spherical particle having
buoyant and gravitational forces to obtain a settling equation. the same diffusion characteristics. An example of the use of light
The particle shape is also assumed to be a sphere in evaluating scattering for soils can be found in Cooper et al. (1984).
the other forces. Combining vertical forces and solving for v (the
particle velocity) gives rise to the settling equation:
1.3.8  Other Methods
v = 2r 2 g (ρp − ρw )a 9 η, (1.3) A variety of variations exist to fractionation by settling under the
influence of gravity in water. Settling can be speeded up through the
use of a centrifuge (Svedberg and Nichols, 1923). Settling can occur
where in air, called air elutriation (Jensen and Hansen, 1961). The settling
r is the “equivalent radius” equation for air elutriation is the same as previously developed for
g is the gravitational acceleration water except that the velocity is that of the air floating particles up
η is the viscosity and the viscosity is that of air. Complete avoidance of settling may
occur using microscopic methods to count and sort particles. Image
The particle velocity is the distance traveled divided by the time or analysis in conjunction with microscopic methods can determine
x/t. The settling equation allows a particle radius to be calculated particle shape or geometry parameters. Laser diffraction has also
at a particular x and t if the particle density and solution viscosity been used to obtain a PSD. More recently, acoustic methods have
are known. This equation is basic to all gravity sedimentation pro- been developed (Guerin and Seaman, 2004). The acoustic methods
cedures. Its use necessitates a number of assumptions not only in also have the ability to determine electrical charge properties of
the derivation but also in the procedures, whereby the experiment soil particles. A variety of additional methods are discussed in the
is executed and the equation applied (Baver et al., 1972). references by Davies (1984), Gee and Bauder (1986), Loveland and
Another alternative to determine the suspension density is by Whalley (1991), and Sheldrick and Wang (1993).
gamma-ray attenuation (Karsten and Kotze, 1984). This method
has the advantages of not disturbing the sedimentation column and
allowing repeated nondestructive sampling over a large number 1.3.9  Interpretation of Results
of settling times. Sedimentation by pipette or hydrometer yields a A graph can clearly present the elements of a PSD. However, it
mass frequency as a function of an effective settling diameter. is desirable to have a single parameter or a set of parameters to
express the properties of the distribution. This is the origin of
1.3.6  Coulter Counter soil texture class that summarizes the particle-size properties in
a single term. The phrase chosen depends on the relative abun-
Individual particles can be counted in suspension by measuring dance of sand, silt, and clay, irrespective of variations within
the change in electrical resistivity (or conductivity) as particles these size ranges (e.g., Figure 1.4). Typical textural triangles and
pass through a small opening. Each particle displaces a vol- the textural class names are given in Gee and Bauder (1986) and
ume of solution that is proportional to the signal. Thus, a single Loveland and Whalley (1991). Note that while the names of three
particle passing through the opening results in both a volume soil separates are similar to the names of textural classes, a tex-
measurement (for size) and an increase by one in the count of tural class name does not limit the sizes that may be present. In
the particles passing (Hurley, 1970). The commercial apparatus other words, a clay texture class contains sand, silt, and clay sep-
is called a Coulter counter and yields a number frequency as a arates while the clay separate contains only clay-sized particles.
function of a volume (or the equivalent radius of a sphere having The use of only the total amount of sand, silt, and clay to
the same volume). The range of diameters is typically between describe texture results in a bias that lies in the assumption
0.4 and 1600 μm (Multisizer 4 COULTER COUNTER•, brochure that all particles within the range of the sand (or silt or clay)
http://www.beckmancoulter.com/coultercounter/showDoc/doc. size are equivalent. For the clay fraction, this is a particularly
do?filename=&fileid=11567). misleading assumption and is partly responsible for the low
correlations frequently observed when clay content is used in
regression analysis. Two soils with the same percentage of clay
1.3.7  Light Scattering
may differ in the amounts of fine versus coarse clay. Additional
When light is passed through a suspension, several interactions differences in the shape and mineralogy of particles can also
can take place. Besides absorption, light can be scattered in a cause variations in soil behavior.
variety of directions. The behavior of the scattered light provides A more interesting approach determines the moments of the
an alternative means to obtain a PSD. Commercial apparatus size distribution (Folk, 1966). This gives a quantitative measure
Physical Properties of Primary Particles 1-7

100 Various combinations of these Dn characterize the distribution.

One example is the uniformity coefficient (Cu):
90
D60
80 Cu = . (1.6)
D10
70
The uniformity coefficient provides information as to how narrow
60 Clay the distribution is with 1 being the minimum when only a single
size is present. The second ratio is the coefficient of gradation (Cg):
% Clay

50
Si ay

Sa
(D30 )2
lty

n
cl

cla dy Cg = . (1.7)
40
Silty clay Clay
y
(D60 D10 )
30 loam loam Sandy
clay loam
Indirect descriptions of the PSD are possible through the use of an
20 Loam equation or model. These models contain parameters, which in turn
Silt loam characterize the distribution. The problem in using these models is
Sandy
10 loam
sa my first to determine the parameters; second, to determine the appro-
Silt
priateness of the model; and third, to interpret the parameters.
nd
a

Sand
Lo

0 Two modes of particular interest are the power function and

0 10 20 30 40 50 60 70 80 90 100
lognormal distribution. The use of a power function suggests an
% Sand
underlying fractal process. Where this applies, the exponent (δ)
FIGURE 1.4  Alternative texture triangle using clay (%) and sand relates to the fractal dimension (n):
(%) to determine texture class name. For example, a soil with 50% of
δ = 3 − n, (1.8)
clay and 30% of sand sized particles would be assigned a textural class
name of clay. (Reprinted from Elghamry, W., and M. Elashkar, 1962.
Simplified textural classification triangles. Soil Sci. Soc. Am. Proc. and n is between 0 and 3. Tyler and Wheatcraft (1992) applied
26:612–613. With permission of the Soil Science Society of America.) this technique to several materials and reported n values between
2 and 3. The lognormal model has also been useful (Shirazi and
of the mean (first ordinary moment), spread (second-order cen- Boersma, 1984). Campbell (1985) shows how to estimate the water-
tral moment or standard deviation), and asymmetry (third- holding properties of soil using lognormal model parameters.
order central moment or skewness) of a PSD. More importantly,
it increases the power of correlative studies relating texture and 1.4  Specific Surface Area
any other physical, chemical, or biological factors of interest. As
an example, the fourth moment of the size distribution has been 1.4.1  Definitions
related to soil compaction (Moolman, 1981). The surface area of the individual particles is an important
If the PSD is known to follow a lognormal distribution, then factor in nutrient or pesticide adsorption, water absorption,
the geometric mean diameter (dg) and the geometric standard soil strength, and soil transport properties. The surface area
deviation (σg) summarize the PSD. These can be estimated from of a soil has contributions from primary particles, amorphous
the mass fraction (f i) of soil that is sand, silt, or clay. Then, mineral coatings, and organic matter. These individual con-
tributions may overlap and cancel. Further, the surface area of
3

d g = e ∑1
fi ln(di )
, (1.4) some expanding minerals may change with the water content
and chemical composition of the soil solution.
The surface area is an extensive quantity (i.e., depends on how
σg = e
{∑ 3
f
1 i }
ln2 (di ) − (ln d g )2
, (1.5) much soil is present). A more satisfying alternative is the intro-
duction of an intensive quantity, the specific surface, which is
either the surface area per mass (Sm) or per volume (Sv). The spe-
where the di values are the average diameter of the size interval, cific surface per volume will change with soil compaction.
d1 = 0.001 mm, d2 = 0.026 mm, and d3 = 1.025 mm. See Shirazi
and Boersma (1984) for more details. The equations above can
1.4.2  T ypical Values—Separates, Whole Soil
be generalized if more than three soil separates have been mea-
sured and can be used even if the PSD does not follow a lognor- Typical values for specific minerals as well as values for whole
mal distribution. soils are presented in Table 1.3. Amorphous materials and soil
Other parameters exist in the engineering literature and else- organic matter (SOM) can greatly affect soil values. SOM has
where to describe a PSD. One approach defines the grain diameter been reported to have a specific surface as high as 1000 m2 g. The
(Dn) at which n% passes through a sieve. While D40 represents that whole soil values include the effects of PSD as well as SOM and
size for which 40% of the particles are smaller and 60% are larger. amorphous mineral levels for temperate zone soils.
1-8 Properties and Processes

TABLE 1.3  Ranges of Specific Surface of Clay Minerals,

Soil Components, and Whole Soils Compiled
from a Variety of Sources
Soils and Constituents Specific Surface (m2 g−1)
Kaolinite 15–20
Illite 80–100
Bentonite 115–260
Montmorillonite 280–500
Organic matter 560–800
Calcite 0.047
Crystalline iron oxides 116–184
Amorphous iron oxides 305–412
Allophane and imogolite 700–1500
Sands <10
Sandy loams and silt loams 5–20
Clay loams 15–40
Clays >25
Sources: Nelson, R.A., and S.B. Hendricks. 1943. Specific surface
of some caly minerals, soils, and soil colloids. Soil Sci. 56:285–296;
Bower, C.A. and F.B. Gschwend. 1952. Ethylene glycol retention by
soils as a measure of surface area and interlayer swelling. Soil Sci.
Soc. Am. Proc. 16:342–345; Orchiston, H.D. 1955. Adsorption of FIGURE 1.5  Surface coating with adsorbent molecules. Larger mol-
water vapor: III. Homoionic montmorillonites at 25°C. Soil Sci. ecules will not fit in smaller pores.
79:71–78; Borggaard, O.K. 1982. The influence of iron oxides on the
surface area of soil. J. Soil Sci. 33:443–449; Suarez, D.L., and J.D. where
Wood. 1984. Simultaneous determination of calcite surface area Vm is the volume of a monolayer
and content in soils. Soil Sci. Soc. Am. J. 48:1232–1235.
P0 is the gas pressure at saturation
C = exp[(E1 – E2)/RT] where R is the gas constant, T is the
1.4.3  Methods absolute temperature, E1 is the heat of adsorption of the
first monolayer, and E2 is the heat of subsequent layers or
Direct measurements usually rely on the adsorption of either a
the heat of liquefaction of the gas
gas (typically N2 or Ar under high vacuum) or a liquid (histori-
cally ethylene glycol; but more recently, ethylene glycol mono-
ethyl ether [EGME] or water) (Pennel, 2002). Either a multi- or While this equation is frequently linearized, nonlinear
monomolecular film is deposited or a gas adsorption isotherm regression should be used to estimate Vm from which the specific
is determined. A critical point in the use of all these proce- surface is calculated. The use of either a gas or liquid to deter-
dures is the means by which a multi- or monomolecular layer mine specific surface also raises questions about the size and
is obtained. Control of the adsorbed phase occurs through the nature (polar or nonpolar) of the adsorbing molecule (Figure
regulation of the gas phase. With gas adsorption, total pressure 1.5). The smaller molecule can be expected to measure a greater
is controlled while with liquid adsorption, the use of a desiccator surface area than a large one. Differences in surface area (when
helps to fix both the total pressure and partial pressure of the using distinct adsorbing molecules) are particularly noticeable
adsorbed component. In the EGME method (Carter et al., 1986), when soils contain expanding clay minerals.
a mixture of EGME and CaCl2 regulates the vapor pressure of Another direct method to determine specific surface exam-
EGME. In water absorption, a separate saturated LiNO3 solution ines photomicrographs of primary particles. The classical
regulates the relative humidity. The LiNO3 and EGME methods approach determines the probability of a needle (randomly
are convenient procedures for soils. However, both methods are placed on the photo) either falling within a pore or intersect-
sensitive to variations in temperature. Values for specific surface ing the pore edge (Scheidegger, 1960). Current image analysis
vary with the method used. instrumentation allows this evaluation as part of many soft-
The gas adsorption isotherm frequently takes the form of the ware packages. Unfortunately, most PSDs are not detailed
BET equation (Brunauer et al, 1938). Here, pressure (P) is varied enough in the smallest size range to accurately estimate spe-
and the volume of adsorbed gas (V) is observed, all at constant cific surface.
temperature. The two are related as follows:
1.4.4  Geometric Models and Regression
P 1 (C − 1)P Geometric models are used to show how particle size influences
(P0 − P) = + , (1.9)
V Vm C Vm CP0 specific surface and the general relation of particle geometry
Physical Properties of Primary Particles 1-9

103 References
102 Sm = (6 + d/h)/ρpd Baver, L.D., W.H. Gardner, and W.R. Gardner. 1972. Soil physics.
4th ed. John Wiley & Sons, New York.
Specific surface, Sm (m2 g–1)

101 Blake, G.R., and K.H. Hartge. 1986. Particles density. In A. Klute
d/h = 1
(ed.) Methods of soil analysis. Part 1. SSSA, Madison, WI.
d/h = 10
100 d/h = 0.1 Borggaard, O.K. 1982. The influence of iron oxides on the surface
area of soil. J. Soil Sci. 33:443–449.
10–1 Bower, C.A. and F.B. Gschwend. 1952. Ethylene glycol retention
by soils as a measure of surface area and interlayer swelling.
10–2 Soil Sci. Soc. Am. Proc. 16:342–345.
Brunauer, S., P.H. Emmett, and E. Teller. 1938. Adsorption of gases
10–3 2 µm clay limit in multimolecular layers. J. Am. Chem. Soc. 60:309–319.
Campbell, G.S. 1985. Soil physics with basic. Elsevier, Amsterdam,
10–4 the Netherlands.
10–6 10–5 10–4 10–3 10–2 10–1 100 101 Carter, D.L., M.M. Mortland, and W.D. Kemper. 1986. Specific
Particle diameter (cm) surface, p. 414–424. In A. Klute et al. (eds.) Methods of soil
analysis. Part 1. Physical and mineralogical methods. ASA,
FIGURE 1.6  Effect of particle diameter on specific surface for materi-
Madison, WI.
als of a single size.
Cho, G., J.D. Dodds, and J.C. Santamarina. 2006. Particle
shape effects on packing density, stiffness, and strength:
to specific surface. Start with the specific surface, Sm = A/ρpV, Natural and crushed sands. J. Geotech. Geoenviron. Eng.
where A is the surface area of solids and V is the volume of sol- 132:591–602.
ids. Then, A and V are expressed in terms of the shape factors C2 Cooper, L.R., R.L. Haverland, D.M. Hendricks, and W.G. Knisel.
and C3 and a characteristic dimension, L: 1984. Microtrac particle-size analyzer: An alternative
particle-size determination method for sediment and soils.
C2 Soil Sci. 138:138–146.
Sm = . (1.10)
ρp C 3 L Davies, R. 1984. Particle size measurement: Experimental techniques.

In M.E. Fayel and L. Otten (eds.) Handbook of powder science
This relation states that specific surface is the reciprocal of the and technology. Van Nostrand Reinhold Co., New York.
characteristic length of the particles. The shape factors also Davis, P.F., and A.R. Dexter. 1972. Two methods for quantitative
influence surface area. Using Table 1.3, for spheres, Sm = 6/ρpd description of soil particle shape. J. Soil Sci. 23:448–455.
while for a disc or flat plate, Sm = [4 + 2(d/h)]/ρpd. A large d/h Egashira, K., and J. Matsumoto. 1981. Evaluation of the axial ratio
ratio corresponds to a flat plate. A small d/h ratio corresponds of soil clays from gray lowland soils based on viscosity mea-
to a prism or needle-like shape. A ratio of d/h = 1 is identical surements. Soil Sci. Plant Nutr. 27:273–279.
to the result for spheres (Figure 1.6). The specific surface of fine Einstein, A. 1906. A new determination of molecular dimensions.
clays may be one or more orders of magnitude greater than for Ann. Phys. 19:289–306. Translated in: Investigations on the
coarse clays. theory of Brownian movement. Dover Press, New York.
Whole soils are best measured directly. In some cases, the Elder, J.P. 1979. Density measurements by the mechanical oscilla-
amount of clay and knowledge of the type of clay can provide tor, p. 12–25. In Methods in enzymology. Academic Press,
an approximate specific surface. Or and Wraith (1999) presented New York.
the following regression equations: Elghamry, W., and M. Elashkar, 1962. Simplified textural classifi-
cation triangles. Soil Sci. Soc. Am. Proc. 26:612–613.
Flint, A.L. and L.E. Flint. 2002. Particle density, p. 229–240. In J.H.
Sm = 5.65 × % clay − 18.9 for soils dominated
Dane and G.C. Topp (eds.) Methods of soil analysis. SSSA
by montmorillonite − kaolinite clays, (1.11) Book Series No. 5. ASA, Madison, WI.

Folk, R.L. 1966. A review of grain-size parameters. Sedimentology
6:73–93.
Sm = 1.87 × % clay + 6.0 for soils dominated Gee, G.W., and J.W. Bauder. 1979. Particle size analysis by hydrom-
eter: A simplified method for routine textural analysis and
by kaolinite − illite clays. (1.12)
a sensitivity test of measurement parameters. Soil Sci. Soc.
Am. Proc. 43:1004–1007.
These and all regression equations should be used with care. The Gee, G.W., and J.W. Bauder. 1986. Particle size analysis, p. 383–
method used to measure or calculate surface area must be con- 411. In A. Klute (ed.) Methods of soil analysis. Part 1. 2nd
sistent with the use that will be made for the value. ed. ASA, Madison, WI.
1-10 Properties and Processes

Gee, G.W., and D. Or. 2002. Particle-size analysis, p. 255–293. In Or, D., and J.M. Wraith. 1999. Temperature effects on soil bulk
J.H. Dane and G.C. Topp (eds.) Methods of soil analysis. dielectric permittivity measured by time domain reflec-
Part 4—Physical methods. SSSA Book Series No. 5. Soil tometry: A physical model. Water Resour. Res. 35:371–383.
Science. ASA, Madison, WI. Orchiston, H.D. 1955. Adsorption of water vapor: III. Homoionic
Guerin, M., and J.C. Seaman. 2004. Characterizing clay mineral montmorillonites at 25°C. Soil Sci. 79:71–78.
suspensions using acoustic and electroacoustic spectros- Pennel, K.D. 2002. Specific surface area, p. 308–313. In J.H. Dane
copy: A review. Clays Clay Miner. 52:145–157. and G.C. Topp (eds.) Methods of soil analysis. Part 4. SSSA
Heywood, H. 1947. Symposium on particle size analysis. Trans. Book Series No. 5. ASA, Madison, WI.
Inst. Chem. Eng. 22:214. Santamarina, J.C., and G.C. Cho. 2004. Soil behavior: The role of
Hurley, J. 1970. Sizing particles with a Coulter counter. Biophys. J. particle shape. In Advances in geotechnical engineering. 2:
10:7679. The Skempton Conference. March 2004. Thomas Telford
Jensen, E., and H.M. Hansen. 1961. An elutriator for particle-size Publishing, London, U.K.
fractionation in the sub-sieve range. Soil Sci. 92:94–99. Scheidegger, A.E. 1960. The physics of flow through porous
Jones, S.B., and S.P. Friedman. 2000. Particle shape effects on the media. Revised edition. University of Toronto Press,
effective permittivity of anisotropic or isotropic media con- Toronto, Canada.
sisting of aligned or randomly oriented ellipsoidal particles. Sheldrick, B.H., and C. Wang. 1993. Particle size distribution,
Water Resour. Res. 36:2821–2833. p. 123. In M.R. Carter (ed.) Soil sampling and methods of
Kahn, A. 1959. Studies on the size and shape of clay particles in analysis. Canadian Society of Soil Science, Lewis Publishers,
aqueous suspensions. Clays Clay Miner. 6:220–236. Boca Raton, FL.
Karsten, J.H.M., and W.A.G. Kotze. 1984. Soil particle size analy- Shirazi, M.A., and L. Boersma. 1984. A unifying quantitative
sis with the gamma attenuation technique. Commun. Soil analysis of soil texture. Soil Sci. Soc. Am. J. 48:142–147.
Sci. Plant Anal. 15:731–739. Streeter, V.L., and E.B. Wylie. 1975. Fluid mechanics, p. 752. 6th
Klein, C., and C.S. Hurlbut, Jr. 1985. Manual of mineralogy (after ed. McGraw-Hill Inc., New York.
James D. Dana). 20th ed. Wiley & Sons, New York. Suarez, D.L., and J.D. Wood. 1984. Simultaneous determination
Loveland, P.J., and W.R. Whalley. 1991. Soil analysis physical meth- of calcite surface area and content in soils. Soil Sci. Soc.
ods, p. 271–328. In K.A. Smith and C.E. Mullins (eds.) Soil Am. J. 48:1232–1235.
analysis: Physical methods. Marcel Dekker, Inc., New York. Svedberg, T., and J.B. Nichols. 1923. Determination of size and
Moolman, J.H. 1981. Soil textural properties influencing com- distribution of size of particles by centrifugal methods.
pactibility. Agrochemophysica 13:13–19. J. Am. Chem. Soc. 45:2910.
Naito, M., O. Hayakawa, K. Nakahira, H. Mori, and J. Tsubaki. Tanner, C.B., and S.J. Bourget. 1952. Particle-shape discrimina-
1998. Effect of particle shape on the particle size distri- tion of round and square holed sieves. Soil Sci. Soc. Am.
bution measured with commercial equipment. Powder Proc. 16:88.
Technol. 100:52–60. Tyler, S.W., and S.W. Wheatcraft. 1992. Fractal scaling of soil par-
Nelson, R.A., and S.B. Hendricks. 1943. Specific surface of some ticle-size distributions: Analysis and limitations. Soil Sci.
caly minerals, soils, and soil colloids. Soil Sci. 56:285–296. Soc. Am. J. 56:362–369.
 2
Soil Structure
2.1 Introduction.............................................................................................................................. 2-1
2.2 Development and Dynamics of Soil Structure.................................................................... 2-1
Soil Aggregation  •  Factors Affecting Soil Aggregation  •  Soil Fragmentation
2.3 Characterization of Soil Structure......................................................................................... 2-7
Qualitative Description  •  Morphological and Hydrologic Properties  • 
Stability of Soil Structure  •  Imaging Techniques
Teamrat A. Ghezzehei 2.4 Concluding Remarks.............................................................................................................. 2-13
University of California, Merced References............................................................................................................................................ 2-14

2.1  Introduction physical conditions of soil as related to its ease of tillage, fitness as
seedbed and its impedance to seedling emergence and root pen-
Soil structure refers to the organization and arrangement of etration.” It refers to the favorable physical state of agricultural
soil particles and the resultant complex maze of pores. It is a soil created by tillage, including balanced infiltrability and water
composite soil quality that exerts significant control over most retention, optimal aeration and exchange of gases, low resistance
physical, chemical, and biological processes that occur in both to root growth, resistance to erosion, and favorable conditions
natural and anthropogenically altered soils, including transport for microbial activity (Hadas, 1997). These conditions have in
and storage of liquids, gases, and heat; penetration and prolif- fact been the implicit goals of tillage over the ages. Interest in
eration of roots; microbial life; and decomposition and storage soil structure also arises from its importance to nutrient storage
of soil organic matter. It is an inherently complex soil property and cycling. A huge fraction of soil organic carbon is tied in soils
because the constituent particles are heterogeneous in size, as integral component of the structural units. Research in soil
shape, and chemical nature as well as because the mechanisms structure as reservoir of carbon and a large sink for atmospheric
that bond the particles are diverse. It is a hierarchical organiza- CO2 has been intensified in recent years because of the impor-
tion whereby fine primary particles bond together to form sec- tance of these processes to climate change issues (Six, 2004).
ondary particles and small secondary particles merge to form
bigger peds or aggregates. It is also a dynamic soil property, con-
tinuously changing in response to various internal and external 2.2  Development and Dynamics
drivers, including moisture and temperature fluctuations, bio- of Soil Structure
logical activity, and human intervention. As such it is a concept
that spans multiple spatial and temporal scales: the arrangement The concept of soil structure encompasses a broad spectrum
of colloidal clay particles in a floccule, the arrangement of clods of spatial arrangement of primary soil particles (Hillel, 1998;
on the surface of a tilled layer, an array of earthworm tunnels, Brady and Weill, 2008). At one extreme, we have single-grained
and the variability of soil strength from one point to another are structure characterized by random arrangement of sand and
all aspects of soil structure (Dexter, 1988). Due to these com- silt particles with little cohesion. Sand blown dunes and fresh
plexities, we still lack a truly objective description for it and a deposits of loess are examples of single-grained structure. At
universally accepted and quantifiable measure of soil structure the opposite extreme, we have large cohesive massive structure
does not exist yet (Hillel, 1998). of clay with no discernible internal features. Between these two
The importance of soil structure has been acknowledged for extremes, soil particles form aggregated structure made of quasi-
most of the recorded agricultural history. For much of this time, stable particles of various shapes and sizes. Older soil physics lit-
it was perceived as the soil tilth—the structural state of seedbed erature and U.S. National Soil Survey Handbook (USDA-NRCS,
resulting from tillage and affecting crop response (Hadas, 1997). 2007) classify the single-grained and massive soils as structure-
For accounts of early writings about soil tilth and plowing, see less. For this reason, the concept of soil structure is often used to
the review by Warkentin (2008) and the citations therein. The describe soil aggregates. Soil structure is inherently a dynamic
Soil Science Society of America (1996) defines soil tilth as “the feature that undergoes continuous change. There are two main

2-1
2-2 Properties and Processes

processes of soil structural change: (a) processes that lead to Hierarchical order Size Chronology
increased bonding or aggregation of noncohesive particles and Macroaggregates >250 μm
(b) processes that cause fragmentation of aggregates or massive
blocks of cohesive materials (such as polyhedral peds of soil-
containing clay). These processes can and do occur concurrently,
and it is not usually easy to separate aggregation from fragmen-
+ + +... Microaggregates 20–250 μm
tation. In the remainder of this section, we will discuss these two
processes in depth.

2.2.1  Soil Aggregation

+ + +... Domains + 2–20 μm
Prior to the 1930s, the concept of soil structure was synonymous silt particles
with soil texture. A great deal of effort went into correlating soil
physical properties with particle-size distributions. One attrac-
tive feature of soil texture is that it changes very little with time Clay particles <2 μm
and as a result it is a reproducible index. However, most primary
soil particles do not exist unattached. The vigorous mechanical
and chemical forces applied to break bonds prior to textural anal- FIGURE 2.1  Hierarchical conceptual model of soil aggregation.
ysis attest that the concept of “primary particles” does not have (Modified from Dexter, A.R. 1988. Advances in characterization of soil
much meaning in aggregated soils. At around 1930s, there was a structure. Soil Till. Res. 11:199–238; Six, J. 2004. A history of research
growing interest in agglomeration of soil particles mostly with on the link between (micro)aggregates, soil biota, and soil organic mat-
extensive research focused on flocculation of clay particles to the ter dynamics. Soil Till. Res. 79:7–31.)
extent that by mid-1940s soil aggregation became synonymous microaggregates and bonding of microaggregates results in
with flocculation. The following excerpt from a classic textbook macroaggregates. In general, each particle of a given hierarchical
Soil Physics by Baver (1940) describes the status of soil structure order is made of 102–104 particles of the next lower hierarchical
research at that time and what was about to happen afterward: order. It is not necessary to have all the orders in every soil. The
full spectrum of the hierarchical orders is likely to be present in
Soil aggregation is often confused with flocculation. soils that are rich in organic matter (Oades and Waters, 1991) for
Numerous studies have tried to describe soil aggregate reasons that will become apparent in Section 2.2.1.6. Particles of
formation and stability based on observations of floccula- lower hierarchical order are typically denser and stronger than
tion in dilute suspensions. These two are not synonymous. higher order particles (Dexter, 1988). This is due to the fact the
Flocculation is purely chemical process, and stability of the smaller order particles do not contain the larger (which are also
floccules is dependent on the presence of the flocculating weaker) pores that exist in higher order particles. An inverse cor-
agent. Stable-aggregate formation (granulation) requires relation between tensile strength and aggregate size in a given soil
that the primary particles be so firmly held together that was shown by Braunack et al. (1979) and Hadas (1987).
they do not disperse in water. This implies that aggrega- The dynamics of soil aggregation has two basic components:
tion requires some form of cementation of the flocculated (a) agglomerating processes that bring soil particles to close prox-
particles. In the words of Bradfield (1936) ‘Granulation is imity and (b) binding agents of organic and inorganic origins that
cementation plus!’ render the inter particle linkages semipermanent. Development
of the various hierarchical orders through the interplay between
For an extensive account of the historical development of the the agglomerating processes and binding agents is described later.
concept of soil structure, consult recent reviews by Warkentin
(2008) and Six (2004). 2.2.1.1  Clay Domains (<2 μm)
The current conceptual model of soil structure describes soil The basic building blocks of clays are aluminosilicate platelets
aggregation as a hierarchical arrangement of particles. First that have a thickness of a few nanometers and lateral dimensions
introduced by Tisdall and Oades (1982), the model has been of several hindered nanometers (Rouse et al., 2004). Electrostatic
refined continuously by several researchers, including Oades bonding of these clay platelets (flocculation) forms clay domains,
(1984), Hadas (1987), Dexter (1988), and Six (2004). The hier- the lowest unit in the hierarchical order of soil aggregation.
archies represent size and nature of particles of their respective When clay platelets are brought close to one another, both attrac-
constituents, nature of the bonds that form them, as well as tem- tive and repulsive forces can emerge. The repulsive forces arise
poral sequence of their creation. A schematic diagram depicting because the ions that are attached to clay surfaces have identi-
the hierarchical model is shown in Figure 2.1. The lowest order cal (positive) charges. The attractive forces have several origins.
in the hierarchy involves bonding of primary clay particles into Clay particles can be attracted to each other when the distance
clay domains. Bonding between clay domains and/or with fine between them becomes so short that they can share the positive
silt particles results in clusters. Aggregation of clusters creates ions. This form of attraction is highly dependent on the valency
Soil Structure 2-3

of the ions. Monovalent ions typically occupy large volumes 2.2.1.3  M icroaggregates (20–250 μm)
when hydrated, resulting in very large separation between clay Microaggregates are formed when clusters and silt particles are
particles. Therefore, clay particles in contact with solution of bound by persistent binding agents (i.e., humified organic mat-
monovalent ions exist in a dispersed state (opposite of flocculated ter and polyvalent metal cation complexes), oxides, and highly
state). In contrast, divalent cations have small hydrated volumes disordered aluminosilicates (Six, 2004). In the original intro-
and can be readily shared by adjacent clay particles resulting in a duction of the hierarchical conceptual model of soil structure
stable and compact flocculation. When clay particles are in con- (Figure 2.1), Tisdall and Oades (1982) implied that the transition
tact with acidic solution, the edges of the clay particles develop from lower to higher hierarchical orders is equivalent to chrono-
positive charges. In this condition, the edges of clay particles logical order (Six, 2004). Oades (1984) modified this notion and
are attracted to faces of other clay particles, which are typically suggested that microaggregates are formed within macroaggre-
negatively charged. The face–edge attractions are weaker and gates through the process of fragmentation (see Section 2.2.3;
more open than the face–face attractions mediated by divalent Dexter, 1988; Six, 2004).
ions. In general, flocculation is a complex physical–chemical
process that results in formation of stable clay domains through 2.2.1.4  Macroaggregates (>250 μm)
the binding of clay platelets by electrostatic attractions. The
tendency for clay particles to flocculate is expressed in terms of Macroaggregates are formed from microaggregates that are
critical coagulation concentration (CCC)—the minimum con- bound together by weak binding agents such as the hyphae of
centration of an electrolyte to initiate flocculation of dispersed roots and fungi as well as labile organic compounds derived
clay suspension (Hsu and Tseng, 1996; Saejiew et al., 2004; Hsu from exudates of soil microorganisms and roots (Six, 2004). As
et al., 2006; Liu et al., 2009). Advanced mathematical and experi- a result, the strength, porosity, and internal hydraulic conduc-
mental treatment of the formation and stability of clay domains tivity of macroaggregates are strongly influenced by soil man-
can be found in Smalley (2006). The CCC of soils depends on the agement practices. In addition, there is considerable variability
type of dominant clay minerals, organic matter content, pH, and of physical properties within individual macroaggregates. Park
cation exchange capacity (Frenkel et al., 1992; Heil and Sposito, and Smucker (2005a, 2005b) compared the porosity, hydraulic
1993a, 1993b; Heil and Sposito, 1995). conductivity, and erosive strength of whole macroaggregates in
the size range of 2–9.5 mm and concentric layers within indi-
2.2.1.2  Clusters (2–20 μm) vidual macroaggregates. The aggregates used in the study were
Clusters are formed through the bonding of clay domains derived from two soils subjected to three different management
and/or silt particles. This hierarchical order is so far the least practices, namely conventional tillage, no tillage, and native for-
understood and least studied. Clusters are predominantly est. Their findings show that porosity and hydraulic conductivity
formed when sand and silt particles are bonded together with of whole macroaggregates increase with increasing size, whereas
colloidal particles, including clay domains, iron and alumi- erosive strength decreases with increasing size. Within individ-
num oxides, and organic colloids (Baver, 1940). Soils that lack ual aggregates, the outer layers are more porous, more conduc-
colloidal constituents typically do not form aggregated soil tive, and less strong than the inner layers. In addition, they also
structure. Baver (1940) noted that there is a strong correlation showed that intensity of soil management decreases porosity,
between the concentration of 5 μm clay domains and aggre- hydraulic conductivity, and erosive resistance.
gates larger than 50 μm. Baver also noted that the correlation
between the concentration of 5 μm clay domains and aggregates 2.2.1.5  Clods (>25 mm)
larger than 100 μm is much weaker, suggesting that bonding by Clods are large lumps of soil that may or may not contain discern-
colloidal clay particles plays important role only at ∼50 μm or ible particles of lower hierarchical order. In agricultural soils,
below. When the mixtures contained organic matter, the cor- clods may be formed due to compaction by agricultural machin-
relations between colloidal clay and aggregation were weaker for ery. Depending on the state of the soil wetness during compaction
both >50 and >100 μm aggregate sizes, indicating that colloidal and the load of the machinery, the boundaries between macroag-
clays play smaller role in the presence of colloidal organic mat- gregates may be totally lost or remain as microcracks. The ulti-
ter. Colloidal organic matter such as mucilages exuded from soil mate goal of tillage in such soils is to reverse the creation of clods
microorganisms can bond clay clusters together and form very by liberating the aggregates “imprisoned” within clods (Dexter,
stable clusters (Turchenek and Oades, 1979). The bonds between 1988). Clods also represent large masses of soil created during
the granular particles are formed upon partially irreversible desiccation of clayey soils. In this case, the clods need not contain
desiccation of the colloidal particles that act as hardened glue. particles of lower hierarchical order (Dexter, 1988). These clods
Sideri (1936) has shown the irreversibility of the bonds between (or peds) and their formation process are of great importance,
desiccated clay and sand grains. In general, the strength of these particularly when dealing with subsoils. Subsoils typically do
bonds depends on the relative abundance of the colloidal par- not have aggregates but show a similarly complex structure. This
ticles in relation to silt particles, the size and chemical nature of structure is the major concern when it comes to subsoil compac-
the colloidal particles as well as wetting and drying history tion since damage to subsoil structure is, in contrast to topsoil
of the bonds. (aggregate) structure, considered almost irreversible.
2-4 Properties and Processes

2.2.1.6  Applications of the Hierarchical Model cracking during clay shrinkage. The sum of micropores and
of Soil Structure capillary pores can also be categorized as interaggregate and
The hierarchical soil aggregation is an elegant and compact con- intraaggregate pores (Hillel, 1998; Or et al., 2000). These cat-
ceptual model for describing the soil aggregation process across egorizations of soil pores are represented in flow and transport
multiple spatial and temporal scales. It has also been used cre- models using multiple overlapping continua. Dual-porosity
atively to elucidate some complex features of soil, including (a) and/or dual-permeability models, which separate the interag-
the nature of organic matter lost by soil disturbance and (b) mul- gregate and intraaggregate pores, are the most common forms
tiscale heterogeneity of soil pore space. These are described below. of such models (Durner, 1994; Nimmo, 1997).
According to the hierarchical model, microaggregates are
formed from clusters that are bound together by relatively stable 2.2.2  Factors Affecting Soil Aggregation
organic and inorganic colloidal particles. Whereas macroag-
gregates are formed when microaggregates are held together by The formation and stabilization of soil aggregates are influenced
weak organic bonds such as hyphae and labile organic matter. by a number of biotic and abiotic factors that operate in concert.
Therefore, mechanical soil disturbance (such as tillage) typi- Oftentimes, it is difficult to distinguish the role of any particular
cally degrades the weak links between microaggregates and factor from other factors.
results in loss of the relative abundance of macroaggregates at 2.2.2.1  Plants and Microorganisms
the expense of increasing the abundance of “liberated” microag-
gregates (Oades and Waters, 1991). This state is close to the ideal Soil microorganisms are largely supported by plants and their
soil tilth because (a) the fine pores within the microaggregates effect on soil aggregation cannot be viewed separately from the
act as reservoirs of water for the seeds, (b) the voids between effect of plant roots. The interaction between plants and soil
the microaggregates provide access to oxygen, and (c) the weak structure has been reviewed by Angers and Caron (1998), who
bonds between the aggregates exert minimal resistance to seed- recognized five classes of plants effects on soil structure.
ling establishment (Hadas, 1997). Because microaggregates are 2.2.2.1.1  Mechanical Effects of Root Penetration
formed within macroaggregates (Oades, 1984), the creation of
the ideal soil tilth is sustainable unless the labile organic matter When roots grow in soil, the volume occupied by the roots is
released during cultivation is continuously replenished. Elliot accommodated by loss of an equal volume of pore space from
(1986) used these concepts in describing the disproportion- the surrounding soil (Dexter, 1987b). Most of this displace-
ately high loss of labile organic matter during cultivation and ment occurs at the root tips, which osmoregulate their internal
his results were instrumental in establishing direct link between stresses to counter the mechanical strength of the soil that they
cultivation, loss of labile organic matter, and decreased aggrega- have to penetrate. The maximum stress that roots can exert
tion (Six, 2004). ranges from 1 (Dexter, 1987a) to 2 MPa (Goss, 1991). The result-
The hierarchical model of soil aggregation implies the exis- ing densification can be modeled as an expansion of a cylindri-
tence of hierarchical pore categories. Elliott and Coleman (1988) cal or spherical solid object within a homogenous continuum
proposed the following pore categories: (a) macropores, (b) of deformable material (Farrell and Greacen, 1966; Greacen
intermacroaggregate pores, (c) intramacroaggregate or inter- et al., 1968). These models, which were in good agreement with
microaggregate pores, and (d) intramicroaggregate pores. Such independent experimental observations, show that the density
categorization can be useful in explaining spatial segregation increases exponential from the undisturbed value at a distance
of soil microorganisms. These pore categories house (a) micro- away from the root to a maximum value on the root surface.
arthropods; (b) nematodes; (c) protozoa, small nematodes, and Based on these observations, Dexter (1987a) proposed an empir-
fungi; and (d) bacteria, respectively (Six, 2004). These concepts ical model that describes the soil porosity variation over short
are very powerful because they can also be used to introduce distances around plant roots:
spatial segregation of biochemical processes. For soil hydrologic
φ(r ) − φo ⎛ r − ro ⎞
processes, a slightly different pore categorization is employed = 1 − exp ⎜ −k , (2.1)
and this includes (a) micropores, (b) capillary pores, and (c) mac- φi − φ o ⎝ ro ⎟⎠

ropores (Hillel, 1998). Micropores are generally pores that are
less than 1 μm in diameter. Water in such pores is tightly held where
by adsorptive forces (Tuller et al., 1999) and its mobility is very ϕ is porosity
restricted (Tuller and Or, 2001). Capillary pores range in width r is radial distance measured outward from the center of a
from several micrometers to a few millimeters (Hillel, 1998) and cylindrical root
hold water that is subject to capillary laws and moves in accor- k is an empirical constant that ranges between 0.3 and 0.7
dance with Darcy and Buckingham–Darcy laws. The water held based on two soils and root radii (Dexter, 1987b)
in these pores represents the bulk of plant available and mobile
water. Macropores are several millimeters to a few centimeters The subscripts o and i denote values at the root surface and
in diameter and may be formed by burrowing organisms and/or far away from the root, respectively. Whereas these effects of
Soil Structure 2-5

localized compaction reduce overall infiltration when the roots and complex organic molecules that promote formation of stable
are living, the nearly vertical macropores left behind and sta- soil aggregates (Angers and Caron, 1998; Six, 2004).
bilized by decaying roots greatly enhance infiltration (Barley,
1954). Plants with large-diameter, long, and straight roots 2.2.2.1.5  Entanglement by Roots
(such as alfalfa) are known to promote macropore infiltration. Fine and coarse roots can increase stability of soil aggregates
The effect of roots on enhanced macropore flow increases with by physically entangling and enmeshing aggregates and par-
the number of years under plants such as alfalfa with minimal ticles of broad size range. Waldron et al. (1983) conducted
external disturbance (Meek et al., 1989, 1990). shear tests on cylindrical soil columns of 1.2 m diameter—
with fully developed root systems of alfalfa and yellow pine.
2.2.2.1.2  Moisture Dynamics Induced by Plants Their experiments showed that shear resistance of the rooted
Wetting and drying cycles promote soil aggregation as well as columns was significantly higher than identical columns that
fragmentation (see Section 2.2.2.4). Plant roots facilitate this were left bare. These large-scale effects are indeed exploited
effect by accentuating the wetting–drying cycles. Especially, in soil stabilization on sloppy areas using herbaceous plants
in soils that exhibit shrink–swell behavior, the pattern and and trees. Similar effects also operate at much smaller scale.
degree of cracking are strongly correlated with the distribu- Tisdall and Oades (1982) showed that millimeter-size aggre-
tion of the root system, spatial pattern of the plants (e.g., row gates are formed and stabilized by the direct entanglement
crops vs. random distribution), and the biomass productivity effects of fine roots and root hairs.
of the vegetation (see Angers and Caron, 1998 and citations These effects of plant roots operate in concert, and it is usually
therein). Plant roots also promote small-scale moisture het- very difficult to accurately distinguish the relative contribution
erogeneities, which are efficient in creating small-scale stress of each effect toward soil aggregation. However, there is ample
imbalances. These stress imbalances can be very instrumen- experimental evidence that demonstrates a positive correla-
tal in the creation of microcracks and failure planes within tion between vegetation and formation and stabilization of soil
macroaggregates and clods, thereby further promoting soil aggregates at multiple spatial and temporal scales (e.g., Angers
aggregation. Wetting and drying cycles induced by root hairs and Caron, 1998; Six, 2004; Gregory, 2006).
and fine roots were shown to cause orientated and compacted
clay particles in microenvironments that are 50–200 μm in size 2.2.2.2  Soil Fauna
(Dorioz et al., 1993). Soil fauna plays an important role in the dynamics of soil aggre-
gation by facilitating transport and breakdown of organic matter
2.2.2.1.3  Root Exudates
and forming burrows that enhance infiltration and fast moisture
Roots promote the creation of stable soil aggregation in their redistribution following rain or irrigation. The most influential
immediate vicinity (rhizosphere) by releasing polymers and soil faunas are perhaps earthworms. Earthworms are classified as
nutrient ions that (a) bind soil particles and microaggregates (a) epigeic species that live in the litter layers of forest soils with
together or (b) support microbial life that generates complex minimal effect on soil aggregation, (b) anecic species that form
and stable polymers and/or hyphae. Morel et al. (1991) has dem- and live in extensive burrows, and (c) endogenic species that feed
onstrated that adding sticky mucilages exuded by maize roots on soil enriched with organic matter (Bouché, 1977; cited by Six,
to soil particles promotes instantaneous aggregation. However, 2004). Networks of earthworm burrows, which are stabilized
these direct effects are typically transient not lasting much by the combined effects of compaction and mucous secretions
longer than 1 month. Consumption of the mucilages by soil (Edwards and Bohlen, 1996), form a system of fast-flow path-
microbes that release complex polysaccharides is considered one ways that enhance infiltration and aeration. Earthworms also
mechanism that prolongs the effect of root mucilages. In addi- play a significant role in the formation and stabilization of soil
tion, the carbon and nutrients released by roots of many plant aggregates by ingesting mixture of organic and inorganic soil
species support vesicular–arbuscular mycorrhiza (VAM), whose materials and excreting the stable mixtures as cast. Numerous
short hyphae are efficient in binding soil particles together and studies have shown that these casts are more stable than sur-
forming stable soil aggregates (Tisdall and Oades, 1979; Thomas rounding soil aggregates (e.g., Six, 2004 and references therein).
et al., 1986). The stability of earthworm casts depends on the degree of desic-
cation that they are subjected to, their age, and the nature of the
2.2.2.1.4  Carbon Inputs organic matter incorporated in them by earthworms (Shipitalo
In addition to the short-term direct effects of plant roots dis- and Protz, 1987, 1988; Shipitalo et al., 1988; Marinissen and
cussed earlier, plant roots and litter promote long-term soil Dexter, 1990). The amount of casting depends on feeding activ-
aggregation and stabilization through continuous supply of ity of the earthworms. Earthworms ingest larger volumes of
organic matter. It is estimated that around 20% of carbon assim- soil when the organic content of the soil (food) is lower result-
ilated by photosynthesis is deposited in the soil in the form of ing in more casting. In general, it is estimated that the topsoil of
exudates and dead roots (Gregory, 2006). Consumption of this temperate climates passes through the gut of earthworms every
organic matter by soil fauna and microbes releases recalcitrant 4 years (Gardner, 1991).
2-6 Properties and Processes

2.2.2.3  I norganic Binding Agents centimeters wide and deep is a common phenomenon (e.g.,
Inorganic binding agents comprise polyvalent cations (calcium Hillel, 1998; Brady and Weill, 2008). Similarly, in aggregated
and magnesium) as well as colloidal clays and oxides. Cal- soils, unbalanced shrinkage creates weak planes and micro-
cium  and magnesium operate at the lowest hierarchical order cracks that lead to the formation of microaggregates within
by promoting formation of stable clay domains. As such, their macroaggregates (Six, 2004). Swelling of aggregated soil (such
presence is very critical to the overall stability of soil structure as freshly tilled soil) results in joining of adjacent aggregates as
at all the higher hierarchical orders. Calcium, in the form of they begin to invade one another space. Dexter and coworkers
lime, is a common form of soil amendment applied to reclaim (unpublished data reported in Dexter, 1988) have shown that
dispersed sodic soils (Brady and Weill, 2008). In addition, cal- swelling significantly increases the tendency for spontaneous
cium and magnesium promote microaggregation by forming development of microaggregates in a thoroughly molded soil.
clay–polyvalent cation–organic matter complexes (e.g., Baver, In general, swelling and shrinkage can modify soil structure at
1940; Clough and Skjemstad, 2000). Oxides of iron and alumi- multiple scales to varying degrees and/or directions (formation
num can act as binding agents in three ways: (a) adsorption of vs. destruction). A somewhat related process is freezing- and
organic compounds on oxide surfaces, (b) electrostatic attrac- thawing-induced cracking of heavy clay soils. Farmers in cold
tion between positively charged oxides and negatively charged regions typically plow clay-rich soils very coarsely. Subsequent
clay surfaces, and (c) formation of bridges between primary and freezing and thawing of the big clods create several micro-
secondary particles coated with oxides (El-Swaify and Emerson, cracks and microaggregates (Scott, 2000).
1975; Oades et al., 1989; Six et al., 2000). The first two processes 2.2.2.4.2  Capillary Forces
act at the scale of microaggregates, whereas the latter process
is responsible for stabilization of macroaggregates in oxide-rich Soils subjected to wetting and drying cycles are known to
soils (Six, 2004). undergo structural changes by coalescence of adjacent aggre-
gates. This process is primarily driven by strong tensile forces
2.2.2.4  Wetting and Drying Cycles of capillary water (Keller, 1970; Silva, 1995; Or, 1996). Aggregate
coalescence is responsible for post-tillage hardening of agricul-
Most soils experience continuous wetting and drying cycles as tural soils (Cockroft and Olsson, 2000). Micromorphological
a consequence of a number of environmental and internal pro- studies show that coalescence of aggregates occurs by plastic
cesses, including precipitation, irrigation, drainage, evaporation, flattening and fusion of interaggregate contacts without any
and plant water uptake. These cycles induce soil aggregation need for additional cementing agent (Day and Holmgren, 1952;
and/or fragmentation through a number of processes, includ- Kwaad and Mucher, 1994). Plastic deformation occurs when the
ing swelling and shrinkage of clays, capillary stresses, as well as shear stress due to capillary forces exceeds the shear strength
transport, deposition, and hardening of organic and inorganic of the soil. Flattening of the contact faces was shown to greatly
binding agents. reduce the stresses, thereby restricting unlimited deformation.
In an analogous experiment, where external triaxial stress was
2.2.2.4.1  Clay Swelling and Shrinkage applied to mimic the effect of capillary forces, McMurdie and
In soils consisting of substantial amounts of expansive clay Day (1958) showed that soil aggregates behave in a manner
fractions, one of the prominent effects of changing soil water similar to plastic grains. Figure 2.2 depicts aggregates that were
content is the concurrent change of soil matrix volume. fused together by capillary forces during multiple wetting and
Nonuniform drying (hence, unbalanced shrinkage) creates drying cycles. Ghezzehei and Or (2000) used modeled aggregate
internal stresses that eventually lead to cracking. In struc- coalescence as a process driven by interplay between (a) energy
tureless heavy clay soils, formation of cracks that are several liberation from contraction of capillary menisci and (b) energy

5 mm
(a) (b) (c)

FIGURE 2.2  Coalescence of Millville silt loam soil aggregates (2–4 mm) under wetting–drying cycles. (a) Dry soil aggregates separated by mechani-
cal sieving, (b) cluster of aggregates formed by coalescence due to wetting–drying cycles, and (c) partly crushed cluster of aggregates. Note that coales-
cence took place mainly at the contact points, and most of the aggregates maintained part of their original boundaries. (From Ghezzehei, T.A., and
D. Or. 2000. Dynamics of soil aggregate coalescence governed by capillary and rheological processes. Water Resour. Res. 36:367–379. With permission.)
Soil Structure 2-7

dissipation by viscous deformation of aggregate contacts. The 2.2.3  Soil Fragmentation

model relies on the viscoelastic nature of wet soil aggregates
(Ghezzehei and Or, 2001). An important conclusion derived Soil fragmentation is the flip side of aggregation and it begins
from this model is the existence of a window of aggregate wet- with emergence of cracks within aggregates or massive struc-
ness where the capillary forces exceed the soil shear strength tureless soil volume. Cracks originate in soil when the strain
within which aggregate coalescence can occur. The window energy imposed by shrinking and swelling or tillage exceeds
narrows with each incremental increase in the interaggregate interparticle bonds (Hallett and Newson, 2001). Soil cracking
contact area and completely disappears after some critical weld- is generally classified into brittle and ductile cracking. Brittle
ing has occurred. Soil densification is traditionally viewed as cracking is applicable for dry soils. Brittle cracking can be
deterioration of soil qualities that favor plant growth (Cockroft viewed as a two-stage process. First, strain energy that exceeds
and Olsson, 2000). However, it is increasingly becoming appar- the interparticle bonds is needed to create failure planes. Once
ent that loss of large interaggregate pores is accompanied by the planes are created, the growth of crack obeys a linear elas-
increased connectivity between aggregates leading to enhanced tic law. In this case, the strain energy is stored in the reversible
unsaturated hydraulic conductivity (e.g., Carminati et al., 2007a, elastic crack.
2007b, 2008; Berli et al., 2008). For wet ductile soils, cracking is accompanied by substantial
plastic deformation, which dissipates a significant portion of the
2.2.2.4.3  Alteration of Organic and Inorganic Colloids strain energy. Unlike in brittle cracking, in ductile cracking the
Slow wetting can promote stabilization of microaggregates soil at the crack tip has the ability to flow and rearrange. This
by transporting dissolved organic carbon (produced dur- fluidity results in extra resistance to cracking, which is known
ing decomposition of organic matter and/or exuded by plant as “toughness” in material science (Hallett and Newson, 2001).
roots) to the interior of aggregates (Denef and Six, 2005). As a consequence, even if soil strength weakens upon wetting,
Drying facilitates localization of soil solutions in the fine crev- the increase in toughness results in resistance to cracking.
ices and wedges at interparticle contacts as pendular rings, Therefore, both very wet and very dry soils have strong resis-
where dissolved organic carbon and inorganic colloidal par- tance to cracking. Somewhere in the middle, there is a wetness
ticles are deposited and form semipermanent bonds (e.g., Reid condition where the combined effect of strength and toughness
and Goss, 1982). The surfaces of microaggregates coated with is low and cracking of soils is the easiest. When the energy for
dried organic matter are partially hydrophobic, which reduces cracking originates from shrinkage of clays, the energy also
their susceptibility to slaking (Caron et al., 1996; Czarnes depends on wetness.
et al., 2000a, 2000b). Park et al. (2007) compared the stabil-
ity of aggregates subjected to five wetting–drying cycles with
and without dissolved organic matter in the wetting solution. 2.3  Characterization of Soil Structure
They observed that addition of 0.25 mg g−1 glucose soil during We started this chapter by noting the lack of precise and con-
each wetting phase maintained the aggregate stability, while sistent definition of soil structure and the difficulties underly-
the aggregate stability deteriorated in the absence of additional ing this absence of precise definition are apparent from the
organic-matter supply. Planted soils that were kept at constant discussions in Section 2.2. The implications of this vagueness
water content were observed to have 10%–20% less aggregation are reflected in the methods employed for characterization of
than similar soils, which were allowed to periodically dry by soil structure. In the remainder of this section, we describe four
plant uptake (Reid and Goss, 1982; Materechera et al., 1992, major types of soil structure characterization that are commonly
1994). The foregoing observations indicate that wetting and employed in soil physics research. The first group of methods
drying cycles encourage aggregate stabilization by transport- involves qualitative description of soil structure routinely used
ing and altering organic matter. in soil survey. The second method is related to the morphologi-
2.2.2.5  External Stresses cal and hydrological soil properties that are influenced by soil
structure. The third approach reflects the persistence of a given
The primary objective of tillage of agricultural soils is to state of soil structure under disruptive forces. And finally, the
modify the structure so that the resulting morphological and fourth approach involves various imaging techniques.
hydrological properties favor optimal flow and storage of water
and oxygen as well as minimal resistance to germination and
root growth. Concurrently, tillage induces compaction and
2.3.1  Qualitative Description
permanent destruction of inherent structure below the plow
layer. A substantial portion of agricultural soil mechanics Soil profile description, as part of soil survey and mapping,
research has been devoted toward understanding and mini- involves qualitative characterization of structure in terms of
mizing the unintended consequences of tillage. Soil structural shape, size, and grade (distinctiveness). The terminology and
dynamics as a result of external stresses is described in detail designations used in Soil Survey Manual (Soil Survey Division
in Chapter 3. Staff, 1993) are summarized in the following.
2-8 Properties and Processes

TABLE 2.1  Size Classes of Soil Structural Units

Size Limits (mm)
Prismatic and
Granular Platy (Angular) (Rounded) Size Class Platy Columnar Blocky Granular
Blocky
Very fine <1 <10 <5 <1
Fine 1–2 10–20 5–10 1–2
Medium 2–5 20–50 10–20 2–5
Coarse 5–10 50–100 20–50 5–10
Very coarse >10 >100 >50 >10
Source: Soil Survey Division Staff. 1993. Soil survey manual. Soil
Conservation Service, USDA, Washington, DC.

Columnar Prismatic
Strong: It refers to structural units that are distinctly observable
FIGURE 2.3  Shapes of soil structure based on the classification in and that separate cleanly when the soil is disturbed.
Soil Survey Manual. (Adapted from Soil Survey Division Staff. 1993. Soil Qualitative description of soil structure in terms of shape,
survey manual. Soil Conservation Service, USDA, Washington, DC.) size, and grade is very valuable in understanding soil genesis as
well as in classification and mapping soils. However, there is no
2.3.1.1  Shape objective means of translating these qualitative descriptions to
The following terms are used to describe the field observable quantifiable characteristics of soil structure and associated mor-
shapes of individual structural units. Schematic illustrations of phological and hydrologic properties.
the various shapes (described below) are given in Figure 2.3.
Platy: Flat and horizontal structural units that commonly occur 2.3.2  Morphological and Hydrologic Properties
in clayey soils.
One of the main reasons we study soil structure is because it
Prismatic: Elongated structural units with flat vertical faces that influences a number of morphological and hydrologic proper-
are matched with the faces of adjoining structural units. The ties of soil that in turn determine storage and movement of vari-
vertices of the vertical faces are angular or subrounded and the ous fluids, chemical cycling, and transport, as well as growth
tops are typically flat. of plants and microbes. The most common morphological and
Columnar: These are similar to prismatic units, except that the hydrologic properties include porosity, bulk density, pore-size
tops are rounded and the vertical faces are also slightly rounded. distribution, water retention characteristic, and saturated/
Blocky: Equidimensional and polyhedral structural units with unsaturated hydraulic conductivity. Determination of these
flat or slightly rounded faces. The faces of these units are matched properties requires extraction of undisturbed soil cores or bet-
with the faces of adjoining units. ter yet use of an in situ method. The notion of “undisturbed soil
cores” and the great deal of care and effort invested in acquiring
Granular: These are similar to blocky units, except that the units
such samples are ultimately an indication of our recognition of
are more rounded and the faces are not matched with the faces
soil structure—the organization and arrangement of soil par-
of adjoining units.
ticles—as an important component of soil physical properties.
2.3.1.2  Size Numerous attempts to infer the hydrologic properties using
intrinsic soil properties (including particle-size distribution,
Five size classes are used to describe the size of soil structural
organic-matter content, and soil solution chemistry) have had
units: very fine, fine, medium, coarse, and very coarse (Table
only limited success because they do not account for the struc-
2.1). The size limits refer to the smallest dimension of plates,
tural component. The well-known method of Arya and Paris
prisms, and columns.
(1981) predicts water retention characteristic based on the knowl-
2.3.1.3  Grade edge of particle-size distribution, particle density, and bulk den-
sity. But this method works reasonably well only for soils that
Grade is used to describe the distinctness of individual struc-
are not aggregated. For aggregated soils, empirical equations
tural units and the proportion of units that hold together when
(also known as pedotransfer functions) are used to relate water
the soil is handled. Three grades are used:
retention characteristic and unsaturated hydraulic conductivity
Weak: It refers to barely observable structural units that disinte- functions to soil constituents and descriptions collected during
grate upon moderate handling. routine soil survey (Bouma and van Lanen, 1986; Schaap et al.,
Moderate: It refers to well-formed and readily recognizable 2001; McBratney et al., 2002). The method suffers from lack of
structural units. Most of the units retain their integrity upon physical basis for the prediction and its success greatly depends
moderate handling/disturbance. on the similarity of the database soils to the target soil.
Soil Structure 2-9

Soil bulk density (ρb) is defined as the oven-dry mass of a unit decreases by several orders of magnitude when a soil is drained.
volume of undisturbed soil. It is typically determined by measur- Therefore, determination of hydraulic conductivity of unsatu-
ing the volume and oven-dry mass of the same volume of soil. For rated soil is laborious and time consuming. Oftentimes, hydrau-
most applications, a core of soil sample is extracted from the desired lic conductivity of unsaturated soil is determined from water
depth of the target soil using a metal cylinder. Density of soil macro- retention curve using models that represent soil pores using
aggregates and clods can be determined by measuring the mass of mathematically tractable representations. Of these, the most
an individual clod and the volume it displaces when fully immersed common model is that of van Genuchten (1980), which relies on
in water (with a thin coat of wax to prevent water entry). a model of soil pores as bundle of capillary tubes (Mualem, 1976).
Porosity (φ) is a measure of the fraction of total soil volume Recent modifications of this indirect approach (Tuller and Or,
occupied by pores. It is determined by measuring the total vol- 2001) recognize the angularity of soil pores and adsorption of
ume of a given soil sample and the volume of its pores. If the thin films on clay surfaces and provide better predictive capabil-
average density of the solids is known (which is typically around ity albeit at higher computational complexity. For more detailed
ρp = 2650 kg m−3), then porosity can be readily determined from discussion on soil–water relations, see Part I Chapters 4 and 5.
the bulk density as φ = 1 – ρb/ρp. The above-described physical properties are dynamic in nature
Water retention characteristic curve describes the amount of undergoing continuous change at multiple scales in time as illus-
water that can be held in a soil by different degrees of capillary trated in Figure 2.4. The data of Silva (1995) shown in Figure 2.4a
forces. Its determination involves concurrent measurement of were derived from columns of Millville silt loam soil subjected to
water content and water potential (capillary pressure) at dif- wetting and drying cycles. Figure 2.4b depicts change in inter-
ferent degrees of wetness. While porosity and bulk density are aggregate porosity of Cotto clay soil under three tillage types
measures of the total volume of pores, water retention curve is (Rivadeneira, 1982). The interaggregate porosity, determined as
a measure of the pore-size distribution as well as wetting char- the ratio of the total porosity for the three tillage treatments to
acteristics of pore surfaces. Water retention curve of structured the porosity for zero tillage, is plotted as a function of time after
soils captures the hierarchical nature of soil aggregation (and the tillage. Change in total porosity is often accompanied by change
resulting pore space). Soils with well-defined macroaggregates in water retention curves. For the two illustrative examples
exhibit water retention curve with a discernible double-hump shown in Figure 2.4, the corresponding evolution of water reten-
feature. Such distinction is represented by considering the pore tion curve is shown in Figure 2.5. The striking feature of these
system as a sum of two overlapping pore systems: one for the data is that the comparable changes in porosity and water reten-
interaggregate pores and other for the intraggregate pores. tion curve occurred within a few hours for the Millville silt loam
Hydraulic conductivity describes the water flux through soil soil while it took several weeks for the Cotto clay. The dynam-
to conduct water under unit total water potential gradient. It ics of the Millville silt loam soil was driven by capillary forces
reflects not only pore-size distribution and wetting characteris- (Or et al., 2000) where as a complex interaction of various factors
tics of pore surfaces, but also connectivity between pores. Direct (including wetting and drying, plant roots, and microbial activ-
determination of hydraulic conductivity involves measure- ity) may have contributed for the dynamics of the Cotto clay soil.
ment of flux density across a volume of soil subjected to known Because of the complexity of factors that are involved in the
boundary water potentials. The value of hydraulic conductivity evolution of soil structure, the physical properties described

0.62 0.18
2–4 mm Till A
0.60 0.16
Relative interaggregate porosity

<8 mm Till B
0.58 Till C
Model fit (Or, 1996)
0.14
0.56
Total porosity

0.12
0.54
0.52 0.10
0.50
0.08
0.48
0.06
0.46
0.44 0.04
0 3,000 6,000 9,000 12,000 15,000 18,000 0 10 20 30 40 50 60
(a) Elapsed time (s) (b) Weeks after tillage

FIGURE 2.4  Rate of porosity loss, porosity measurements (a) versus elapsed time since initiation of wetting for two aggregate sizes (From Silva,
H.R. 1995. Wetting-induced changes in near surface soil physical properties affecting surface irrigation. Ph.D. Dissertation. Utah State University,
Logan, UT.) and relative interped porosity (b) for three different tillage practices versus weeks after tillage. (From Rivadeneira, J. 1982. Changes
in physical properties in the plow layer of Coto soil as a function of tillage methods, and correlations with tanier development (in Spanish with
English abstract). M.S. Thesis. University of Puerto Rico, Rio Piedras, Puerto Rico.)
2-10 Properties and Processes

102 102

101 101
Matric suction (m–1)

Matric suction (m–1)

100 100

10–1 Pre-wetting 10–1 No till

First cycle Till A
Second cycle Till B
10–2 Third cycle 10–2 Till C
Symbols: Exp. data Symbols: Exp. data
Lines: VG fit Lines: VG fit
10–3 10–3
0.1 0.2 0.3 0.4 0.5 0.6 0.3 0.4 0.5 0.6
(a) Water content (m3 m–3) (b) Water content (m3 m–3)

FIGURE 2.5  Comparison of evolution rates and shapes of soil water characteristic curves of two different soil types: (a) Millville silt loam soil
before and after three cycles of wetting and drying in a few-hour timescale. (From Silva, H.R. 1995. Wetting-induced changes in near surface soil
physical properties affecting surface irrigation. Ph.D. Dissertation. Utah State University, Logan, UT.) (b) Cotto clay soil under no till and three
different types of tillage practices after 11 weeks of treatment. (From Rivadeneira, J. 1982. Changes in physical properties in the plow layer of Coto
soil as a function of tillage methods, and correlations with tanier development (in Spanish with English abstract). M.S. Thesis. University of Puerto
Rico, Rio Piedras, Puerto Rico.) Note that the tilled treatments in (b) correspond to the prewetting loose state in (a).

above are often treated as semipermanent characteristics of 2.3.3  Stability of Soil Structure
soil. Recently, there have been modest successes in predicting
changes in soil structure and the associated physical properties. Aggregate stability refers to the ability of aggregates to persist
Ghezzehei and Or (2000) used energy-based analysis to develop under internal and external disruptive forces. The disruptive
a model that predicts the evolution of pore size during wetting force often impacts pores and/or aggregates of certain sizes only
and drying cycles. The model was subsequently used in a sto- resulting in destruction of one or more hierarchical orders while
chastic framework to predict evolution of pore-size distribution concurrently forming another hierarchical order. The destruction
and water retention curves (Or et al., 2000). Figure 2.6 depicts of a certain hierarchical order is accompanied by destruction of
evolution of the interaggregate pore space and the correspond- all higher orders. Therefore, when discussing the stability of soil
ing change in water retention after three cycles of wetting and structure, it is very important to be specific at what order the
drying. Here, only the interaggregate pore space is considered as destabilizing forces or processes operate (Dexter, 1988).
dynamic as it directly depends on structure. The intraaggregate The reaction of soil aggregates to disruptive forces depends
pore space is considered as constant as it depends mostly on the not only on the qualities of the soil itself but also on the nature
textural composition of the aggregates. of the disruptive forces. Therefore, the definition of aggregate

0.08 Textural PSD

10
Structural PSD
Matric suction R (m–1)

0.06
Frequency (m–1)

Textural PSD Textural SWC

Structural PSD Structural SWC
Composite PSD Composite SWC
0.04
1

0.02 1
2
3 3 2 1 1 23 3 2 1

0.00 0.1
0 20 40 60 80 0.0 0.1 0.2 0.3 0.4 0.5
(a) Pore radius (m) (b) Water content (m3 m–3)

FIGURE 2.6  Evolution of (a) soil pore-size distributions and (b) soil water characteristic curves resulting from two cycles of wetting and drying
(Figure 2.5a). Numbers represent the wetting–drying cycles (1 is initial; 2 is the end of first cycle; and 3 is the end of second cycle). Dashed lines
represent the evolving structural (interaggregate) pore system.
Soil Structure 2-11

stability and its characterization are linked with the disruptive Slow wetting can weaken aggregates by creating microcracks.
forces of interest. In general, we can identify two main types of Microcracks can be formed due to differential swelling of soil
stability: (a) the ability of the soil to retain its structure under aggregates, which in turn can be caused by nonuniform wetting
the action of water and (b) the ability of soil to retain its struc- of individual aggregates and/or internal heterogeneities. The
ture under the action of external mechanical stresses such as the microcracks do not always join and result in breakdown of the
impact of tillage implements and wheels (Dexter, 1988). aggregates. However, the creation of a network of microcracks
results in considerable reduction in strength (Dexter et al., 1984)
2.3.3.1  Water Stability making the aggregate susceptible to disruption by other forces.
Water impacts soil aggregate stability in a number of ways. The Microcracks induced by the stresses generated by differential
initial action of water when aggregates are wetted is slaking, swelling on wetting are oriented mainly perpendicular to the
which refers to the disruption of soil aggregates by the action wetting front (McKenzie and Dexter, 1985).
of entrapped air. During rapid wetting of dry aggregates, water On uncovered ground surface, the kinetic energy of raindrop
enters each individual aggregate through its entire outer surface. and flowing water can break down aggregates and transport the
This results in weakening of the outer layers of the aggregate, detached particles. Abrasion by particles suspended in flowing
while concurrently the pressure of the air entrapped inside the water provides additional scouring power that facilitates the dis-
aggregate rises. If and when the pressure of the entrapped air integration of wet aggregates (Hillel, 1998).
exceeds the strength of wetted outer layers of the aggregate, the Characterization of water stability of soil aggregates is con-
air escapes by breaking the aggregate into smaller fragments as ducted by simulating the processes that occur in nature. The
illustrated in Figure 2.7 (Emerson, 1954; Hillel, 1998). The vio- most widely employed characterization method simulates the
lence of aggregate breakdown by slaking depends on the com- action of flowing water (Kemper and Rosenau, 1986). In this
petition between air-pressure buildup and weakening of the soil method, a sample of soil aggregates is placed on top of a nest
strength upon wetting. For the entrapped air to gain pressure, it of sieves. The sieves are immersed in water and shaken in a
must be completely enclosed by saturated outer layers and must regular up-and-down motion at prescribed rate and vertical
have sufficiently large starting volume so that subsequent wetting distance. The aggregates retained in each of the sieves after a
can result in the required gas compression. Emerson (1954) iden- fixed period of shaking are collected and dried in oven. Kemper
tified a number of factors that determine such pressure buildup. and Rosenau (1986) suggest starting with 4 g of air-dry aggre-
The primary factor is the rate of wetting, which in turn depends gates with 1–2 mm diameter and subject them to wet sieving at
on the manner and source of wetting, the surface tension of the a rate of 35 cycles min−1 and vertical displacement of 1.3 cm for
wetting liquid, and wettability of the aggregates. For example, 3 min. Aggregates subjected to this treatment typically prewet-
aggregates with high-organic-matter content are less prone to ted slowly to avoid slaking. Wet sieving provides a distribu-
slaking because the slight hydrophobicity of organic residues tion of aggregate sizes. Van Bavel (1949) proposed the mean
prevents rapid and even wetting of their outer surfaces. Another weight diameter (MWD) as a single-valued index of aggregate
factor is the initial water content of the aggregates. Moist aggre- stability:
gates are typically less susceptible to slaking because they have
x max
smaller portion of their voids occupied by air as well as because
preexisting continuous water films lead to diffuse wetting front
as opposed to wet thin skin that forms upon wetting of very dry
MWD =
∫ xf (x)dx, (2.2)
0

aggregates. Aggregates do not slake during rapid wetting unless

the initial water potential is lower than −1 MPa (Grant and Dexter, where
1986). Slaking produces aggregates that are larger than 250 μm x is aggregate size
(Oades, 1986). If the air pressure is strong enough to break down xmax is the maximum aggregate size prior to wet sieving
the aggregates, slaking produces microcracks that are oriented f(x) is the empirical aggregate-size distribution
parallel to the wetting front (McKenzie and Dexter, 1985).
Before the availability of digital computers, the integration had
to be done manually using a graphing paper. To simplify the
time-consuming process, Youker and McGuinness (1956) pro-
posed the use of summation in place of the definite integral:
n

MWD = ∑x w , i i (2.3)
i =1

Dry aggregate Rapid wetting Slaking where

FIGURE 2.7  Slaking of an aggregate rapidly immersed in water. i = 1, 2, …, n is the index of sieves
(Modified from Hillel, D. 1998. Environmental soil physics. Academic x−i is the mean diameter of the ith size class
Press, San Diego, CA.) wi is the corresponding weight fraction
2-12 Properties and Processes

MWD computed by summation is typically larger than the value frictional attrition at their contacts that leads to overall densi-
computed by integration, especially if the number of the sieves is fication. If the stress is large enough to cause brittle failure of
as small as the typical nest of five sieves (Kemper and Rosenau, individual hard aggregates, some aggregates are fractured and
1986). This index of aggregate stability presupposes that the fragments released from the cracks fill larger voids. If the aggre-
aggregate sizes are normally distributed. However, aggregate- gates are soft, the aggregates deform at their contacts (points of
size distributions reported by Van Bavel (1949) were skewed and maximum stress) resulting in flattening of contacts (Day and
Gardner (1956) proposed the use of a log-normal distribution Holmgren, 1952; McMurdie and Day, 1958; Ghezzehei and Or,
based on additional data. Mazurak (1950) suggested the geomet- 2003a, 2003b). Similar flattening of contacts in response to inter-
ric mean diameter (GMD), which is better at representing a log- nal capillary forces was proposed by Ghezzehei and Or (2000).
normal distribution than MWD: The extent and rate of contact flattening (aggregate coalescence)
can be related to the rheology of the soil forming the aggregates.
n Ghezzehei and Or (2000, 2001) showed that wet soils have vis-
GMD =
∑ log(x )w .
i =1
n
i i
(2.4) coelastic behavior with the yield stress and apparent viscosity
values that decrease with increasing water content.

∑ w i =1
i

2.3.4  Imaging Techniques

The GMD is getting wider use only recently (e.g., Abid and
Lal, 2008) because of the extensive manual calculation it Imaging provides a direct and objective means of characterizing
involved prior to the age of digital computers (Kemper and soil structure. Unlike the above three approaches, it can provide
Rosenau, 1986). both qualitative and quantitative descriptions. The available
Stability of soil aggregates under the disruptive energy of imaging methods can be broadly classified into three groups:
raindrops is determined by subjecting individual aggregates to (a) thin-section micrography, (b) scanning electron microscopy
drops in a standardized manner (Hillel, 1998). The fraction of (SEM), and (c) x-ray computed tomography (CT).
the aggregate that remains intact after a prescribed duration or
the number of drops required to completely destroy the aggre- 2.3.4.1  Thin-Section Micrography
gate are used as indices of the stability of the aggregate. The key developments that led to micrographic methods in
soil research were thin-sectioning methods and petrographic
2.3.3.2  Mechanical Stability microscopy in early twentieth century. The publication of the
Mechanical stability refers to resistance of aggregates to external book Micropedology (Kubiena, 1938) introduced standardiza-
forces such as tillage implements and wind. We can recognize at tion of the methods and interpretation on micrographic studies
least three different types of external forces: tensile, compressive, of soil. The most important step of this method is the elaborate
and shear. Tensile forces applied to aggregates of a certain hier- and time-consuming process of preparing thin sections for
archical order tend to cause failure surfaces between the parti- microscopy. For comprehensive description of procedures, con-
cles and/or aggregates of the next lower hierarchical order while sult the Handbook for Soil Thin Section Description by Bullock
leaving those low-order aggregates intact (Dexter, 1988). This is et al. (1985). Briefly, the method involves impregnation of soil
generally because internal strength decreases with increasing pores with low-viscosity resins (such as unsaturated polyester,
hierarchical order (Braunack et al., 1979; Dexter, 1988). epoxy, and methyl methacrylate). To ensure complete satura-
Shearing of aggregated soil results in complex behavior that tion, this process is often carried out using dry sample under
depends on the water content and density of the aggregates. If vacuum. After the resin is allowed to harden, the sample is
the density of the structured soil is below a characteristic criti- affixed to microscope slide and sliced into thin sections, followed
cal value, the theory of critical state soil mechanics (Kurtay by polishing to remove traces of cutting. The final thickness of
and Reece, 1970; Hettiaratchi and Ocallaghan, 1980) suggests the thin section is typically 20–30 μm. Pigmented resins are
that the stress propagates through the volume of the soil result- used to enhance contrast. Thin-section preparation is inherently
ing in overall density reduction with disproportionate destruc- susceptible to several defects that can make subsequent image
tion of larger pores (Dexter, 1988). In contrast, if the structured interpretation difficult. These include scratches and striations,
soil is denser than the critical value, shearing is confined to entrapment of bubbles, contamination by translocated particles,
a narrow band near the source of the stress, rolling of round and/or cutting abrasives.
particles or alignment of platy clay particles can occur. In the Soil micrograph can be used to directly determine pore sizes
latter case, the gross changes in volume occur only in a small and pore-size distributions, pore geometry, as well as aggregate
proportion of the soil. sizes and shapes. Day and coworkers (Day and Holmgren, 1952;
Compression (uniaxial or multiaxial) typically results in den- McMurdie and Day, 1958; McMurdie, 1963) used soil microg-
sification that can extend throughout the volume of the soil. raphy to visualize deformation and welding of soil aggregates
Dexter (1988) recognizes three types of response to uniaxial and accompanying the evolution of interaggregate porosity.
compression of aggregated soils. Hard (typically dry) aggre- However, a single two-dimensional (2D) cross section does
gates respond to uniaxial compression by rearrangement and not provide a complete picture of the three-dimensional (3D)
Soil Structure 2-13

features of soil structure. Some common problems of 2D images A key step in interpretation and quantification of x-ray CT
include the following: (a) a given pore can appear to have differ- imagery is segmentation—the process of classifying the images
ent sizes depending on where the cutting plane passes through, into two or more types of regions (e.g., voids, solids, water, and
(b) a wavy tubular pore (such as earthworm cast) can intersect roots). The simplest approach is binarization of the gray-scale
the cutting plane multiple times and appear as a series of circu- image (e.g., into voids and solids) by setting a global thresh-
lar pores, and (c) adjacent particles (or aggregates) may appear old in the histogram of the gray scales. This method is prone
disconnected. to miscategorization due to overlapping gray values common to
the two populations (Taina et al., 2008). Alternative approaches
2.3.4.2  Scanning Electron Microscopy include locally adaptive thresholding, region-growing methods
Compared to optical microscopy, SEM provides far more supe- (that assume voxels belonging to an object are connected and
rior resolution albeit for much smaller field of view. Therefore, similar), probabilistic fuzzy clustering, and Bayesian methods
the application of SEM has been mostly used to study the (see Iassonov et al., 2009 and reference therein). Iassonov et al.
microstructure of clay domains and their associations with cat- (2009) used 14 segmentation algorithms that fall under global
ions and organic matter (Chen and Banin, 1975; Chenu, 1993; and locally adaptive approaches to derive soil porosity using
Skjemstad et al., 1996). Recently, a variation of SEM that utilizes common CT images. These algorithms yielded in vastly varying
flash freezing (Cry-SEM) has been successfully used to visual- results and only a few gave promising results suggesting the need
ize the microstructure of rhizosphere (Gregory, 2006; Refshauge of reliable, consistent, computationally efficient, and automated
et al., 2006; McCully et al., 2009). These methods are instrumen- algorithms applicable to a wide range of porous materials.
tal in further understanding the role of roots and mycorrhizae in
the development of soil structure (see Section 2.2.1). 2.4  Concluding Remarks
2.3.4.3  X-Ray Computed Tomography Soil structure is a term widely used in all branches of soil sci-
The application of 2D x-ray imaging in soil structure has been lim- ence. The concept of soil structure is well established and has
ited because of its inability to resolve the compounded effect in been continuously evolving. However, a precise definition of soil
the third dimension. For example, Farrell and Greacen (1966) and structure has not been adopted so far. Current definitions in
Greacen et al. (1968) used medical x-ray facility to study soil den- various fields of soil research are summarized here.
sity variations around a penetrometer inserted into a uniform soil. For an agronomist, it refers to the quality of soil that relates
These observations were later used to develop conceptual and quan- to crop growth and productivity and may refer to water-
titative model of soil–root interactions by Dexter (1987a, 1987b). holding capacity, ease of tillage, and suitability for root growth
In contrast, x-ray CT was adopted for soil research in early and microbial life. The agronomy-oriented literature on soil
1980s, soon after the technique was developed for medical appli- structure is replete with empirical correlations between vari-
cations. A thorough review of the application of x-ray CT in soil ous soil amendments (including lime, organic matter, and syn-
science and underlying principles is given by Taina et al. (2008). thetic polymers) and the resultant changes in soil properties
The method relies on the attenuation of x-ray as it passes that depend on structure (such as porosity, water retention, and
through a subject medium (such as soil). The degree of attenu- hydraulic conductivity).
ation is correlated with the bulk density as well as the actual For a conservationist, soil structure refers to resistance to
and/or effective atomic weights of the materials encountered water and wind erosion. Soil erodibility, a measure of the inher-
along the path. By integrating multiple projections of the same ent susceptibility of any given soil to erosion, is closely tied to the
cross-sectional plane, tomographic reconstruction produces an stability of soil aggregates. In fact, the concept of aggregate sta-
effective density map (gray-scale image) of the cross section. bility was originally introduced to characterize soil erodibility
Because these images are acquired noninvasively, it is possible (Yoder, 1936). Most aggregate stability characterization meth-
to obtain several images of adjacent thin layers. This method ods are designed to determine the ease with which particles can
has allowed visualization of undisturbed soil structure and the detach from soil aggregates by raindrop impact, flowing water,
associated pore network in full 3D. X-ray CT have been used to and/or wind. But it is still difficult, if not totally impossible, to
quantitatively characterize porosity, pore geometry (diameter, predict erodibility based on the knowledge of aggregate stabil-
perimeter, and area), tortuosity, and 3D hydraulic radius (e.g., ity because the methods of characterization cannot replicate all
Anderson et al., 1990; Perret et al., 1999; Gantzer and Anderson, aspects of the erosive forces (Bissonnais, 1996).
2002; Rachman et al., 2005). This method has also been suc- For biogeochemists and global-change researchers, soil
cessfully used in investigations of soil structural evolution due structure is viewed in association with nutrient storage and
to disruptive forces such as tillage and erosion (Rogasik et al., cycling (van Veen and Kuikman, 1990; Juma, 1993; Ladd et al.,
1999; Gantzer and Anderson, 2002; Lipiec and Hatano, 2003). 1996). Soil structure is not only a product of organic carbon,
Attempts to reduce the massive 3D x-ray CT description of soil but also a venue where carbon is stored and preserved from
structure to concise and mathematically tractable form have decomposition and released to atmosphere. Soil structure con-
been performed using mathematical morphology (e.g., Pierret trols storage and cycling of organic carbon through its influ-
et al., 2002) and mass fractals (Rachman et al., 2005). ence on the pore sizes that can be inhabited by soil organisms
2-14 Properties and Processes

as well as availability of water and oxygen. Large quantities of Bradfield, R. 1936. The value and limitations of calcium in soil
readily decomposable organic matter can be found in the vicin- structure. Am. Soil Surv. Assoc. Bull. 17:31–32.
ity of starving microbial populations but remains inaccessible Brady, N., and R. Weill. 2008. The nature and properties of soil.
to decomposers through chemical and physical protection (van 14th ed. Pearson Prentice Hall, Upper Saddle River, NJ.
Veen and Kuikman, 1990). Braunack, M., J. Hewitt, and A. Dexter. 1979. Brittle fracture of
A common theme that has been developed within these soil aggregates and the compaction of aggregate beds. J. Soil
diverse points of view is that the concept of soil structure spans Sci. 30:653–667.
multiple scales in time and space. The processes and factors Bullock, P., N. Fedoroff, A. Jongerius, G. Stoops, and T. Tursina.
involved in forming structure vary considerably with spatial and 1985. Handbook for soil thin section description. Waine
temporal scales. Similarly, the properties and functions influ- Research, Wolverhampton, U.K.
enced by soil structure vary depending on the scale of obser- Carminati, A., A. Kaestner, H. Fluhler, P. Lehmann, D. Or,
vation. The basis for this multiscale concept is the hierarchical E.  Lehmann, and M. Stampanoni. 2007a. Hydraulic con-
model of soil aggregation, which has been undergoing continu- tacts controlling water flow across porous grains. Phys. Rev.
ous refinement and elaboration since its inception by Tisdall E 76:026311.
and Oades (1982). However, the interrelationships between the Carminati, A., A. Kaestner, O. Ippisch, A. Koliji, P. Lehmann,
various factors involved in the creation and stabilization of soil R. Hassanein, P. Vontobel, E. Lehmann, L. Laloui, L. Vulliet,
structure on one hand and the numerous soil properties that and H. Fluhler. 2007b. Water flow between soil aggregates.
are directly determined by soil structure on the other hand are Trans. Porous Media 68:219–236.
very complex and rarely quantified. To make the concept of soil Carminati, A., A. Kaestner, P. Lehmann, and H. Fluhler. 2008.
structure a useful descriptive as well as predictive tool, there is a Unsaturated water flow across soil aggregate contacts. Adv.
need for quantification of the hierarchical conceptual model and Water Resour. 31:1221–1232.
the various factors that it entails. Caron, J., C.R. Espinolda, and D.A. Angers. 1996. Soil structural
stability during rapid wetting: Influence of land use on some
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 3
Mechanics of Unsaturated Soils
for Agricultural Applications
3.1 Introduction.............................................................................................................................. 3-1
3.2 Stress–Strain Relationships in Soils.......................................................................................3-3
Stress Theory  •  Strain Theory  •  Stress–Strain Processes
3.3 Soil Strength–Stability Indicators and Their Measurement..............................................3-8
Soil Consistency  •  Bulk and Proctor Density  •  Penetration Resistance  •  Precompression
Stress and Compressibility Indices  •  Shear Strength Parameters  •  Tensile Strength
of Aggregates and Bulk Soil  •  Other Methods to Determine Aggregate Stability
3.4 Effect of Soil Structure on Soil Strength and Deformation Processes...........................3-13
Mechanical Properties of Homogenized Soils  •  Mechanical Properties
of Aggregated Soils  •  Soil Deformation under Dynamic Stresses
3.5 External Mechanical Forces and Stress Distribution in Soils......................................... 3-16
Stress Application and Variations in the Contact Area  •  Stress Effects in the Soil  • 
Effect of Stress Application on Soil Strain
Rainer Horn 3.6 Soil Deformation and its Effects on Physical and Physicochemical Properties............ 3-21
Christian-Albrechts- 3.7 Modeling Soil Deformation and Coupled Processes........................................................3-22
Universität zu Kiel
Deformation and Failure  •  Coupling Soil Mechanical and Hydraulic Processes  • 
Example Application of the Finite Element Model
Stephan Peth
Christian-Albrechts- 3.8 Concluding Remarks..............................................................................................................3-24
Universität zu Kiel References............................................................................................................................................3-26

3.1  Introduction by Jayawardane and Stewart (1994), Soane and van Ouwerkerk
(1994), Horn (2000), and Horn et al. (2006) as well as by Birkas
Soils undergo intensive changes in their physical, chemical, et al. (2004). Oldeman (1992) showed that about 33 million ha of
and biological properties during natural soil development and arable land are already completely devastated by soil compaction
as a result of anthropogenic processes such as plowing, seal- in Europe alone while the total area of degraded land worldwide
ing, erosion by wind and water, amelioration, excavation, and exceeds about 2 billion ha. Physical (soil erosion and deforma-
reclamation of devastated land. In agriculture, soil compaction tion) and chemical processes are responsible for about 1.6 and 0.4
as well as soil erosion by wind and water are classified as the billion ha of degraded soils, respectively. Worldwide population
most harmful processes. Irrespective of land-use systems, soil growth will reduce the average area per person for food and fiber
deformation as the sum of soil compaction and shear processes production from 0.27 ha today to <0.14 ha within 40 years, and
leads to numerous environmental changes affecting soil qual- even if the advances in technological developments continue to
ity for crop production, soil biodiversity, filtering and buffering grow, more concern has to be made in order to prepare enough
functions of soils, soil-water household components, trace gas food for the population worldwide. Consequently, a more detailed
emissions, soil erosion and nutrient export, and related off-site analysis of soil and site properties is needed to manage soils in
effects (Figure 3.1). accordance with their potential properties. Numerous attempts
In forestry, normal plant and soil management, tree har- to predict the strength of the soils were made; however, all are
vesting, and clear-cutting also affect site-specific properties, based on static loading experiments, which assume that equilib-
including organic-matter loss and groundwater pollution and rium in settlement for stepwise increasing loads is achieved. This
gas emissions, which have the potential to cause global changes. approach neglects the dynamic nature of soil loading processes
Furthermore, soil amelioration especially by deep tillage prior during field traffic where loads are applied mostly short term and
to replanting often causes irreversible changes in properties where multiple loading events may cumulatively add to the total
and functions. These interrelationships have been described compression. Thus, the increase in irreversible deformation of

3-1
3-2 Properties and Processes

Damage due to increasing soil deformation

Heavy machinery
Effects on the environment compacts arable, Consequences for plant production
forest, and pasture Reduced growth,
soils higher uncertainty,
Dust emission increased less yield

After rain storm N2O gas

Increased fungi
emission
Rapid water table diseases, more
increase in rivers weeds
and lakes Erosion N - loss due to Reduced
stagnic water root growth
Surface water (less dense
runoff increase and deep)
Soil quality declines Soil biota suffers
due to
- Reduced pore
volume Effects on soil management
Reduced aeration Higher draft energy required
Water infiltration Higher fuel consumption
reduced
Soils remain longer Wet and cold soils result in
wet and cold smaller number of working days
Reduced groundwater More slaking problems More fertilizers needed
recharge Reduced water storage

FIGURE 3.1  Summary of the effects of stress application on soil properties and functions. (Translated and slightly modified from van der Ploeg, R.R.,
W. Ehlers, and R. Horn. 2006. Schwerlast auf dem Acker. Spektrum der Wissenschaft August, 80–88. ISSN: 0170-2971.)

arable soil by agricultural machinery can not only be related to to productivity losses of soils in farming regions, the loss in bio-
the increasing mass of machines (defined as static approach) but diversity and the effects on global changes by modifying physi-
also enhanced by the increase of wheeling frequency as a dynamic cochemical processes result in the emission of greenhouse gases
component. The relevance of wheeling frequency can be esti- and the mobilization of heavy metals in soils due to redox reac-
mated based on the calculations of Olfe (1995). Considering an tions, which in turn cause groundwater pollution threats.
average-sized wheat-production farm, the number of load repeti- If, on the other hand, the tilled soil dries out, transport by
tions in a time period of 5 years may add up to 50 events for 85% wind may occur, resulting in severe reductions in potential site
of the field and up to 100 events for permanent wheeling tracks. productivity. Furthermore, the preparation of a seedbed leads
An additional threat concerning soil degradation is caused by to abrupt changes in the transport of gas, water, ions, and heat
tillage erosion as the actual soil loss can exceed by far 20 Mg ha−1 between the tilled and deeper soil layers (Boone and Veen,
and per tillage operation. This effect is the more pronounced, the 1994; Ball et  al., 2000; Lipiec and Hatano, 2003). This is espe-
drier the soil, the weaker the aggregates, the higher the dynamic cially true concerning preferential flow through structured soils
energy input by agricultural machinery, and the greater the field (Hendrickx and Flury, 2001). When it comes to the quantifica-
size (Karlen, 2004; Reicosky et  al., 2005; da Silva et  al., 2006; tion of soil deformation with respect to the induced changes of
Van Oost et al., 2006). The kinetic energy applied during seed- physical functions, again the dynamic nature of soil loading
bed preparation under dry conditions alone already results in processes during field traffic must be considered, where loads
an increased mass transport by wind. Additionally, the unpro- are applied mostly short term and where multiple loading events
ductive water loss due to evaporation from an increased acces- may cumulatively add to the total compression, although the
sible pore and particle surface and the enhanced organic-matter statically determined precompression stresses are not exceeded
decomposition due to tillage both contribute to global change and should result in no further compression.
problems (Lal, 2005). Soil creep, mudflow after rainstorms, and Such anthropogenic changes make clear that the discussion
intensified surface-water runoff are due to reduced/prevented of soil process dynamics within the soil profile is most relevant.
vertical water infiltration in soils generating pronounced lateral Some of the interactions between soil structure, water status, and
fluxes of water, solids, and nutrients. The loss of shear strength, aeration of structured soils in relation to root growth and com-
defined by the angle of internal friction and cohesion, of near- pressibility of arable land have been described by Emerson et al.
saturated soils subject to buoyancy forces that cause such lateral (1978). In current discussions on sustainability, soil compaction
fluxes produces tremendous damage to the landscape and human is repeatedly mentioned as one of the main threats to agricul-
beings. Related economic impacts are estimated to exceed bil- ture, which should be avoided (Soane and van Ouwerkerk, 1994;
lions of euros worldwide (van den Akker et al., 1998). In addition Pagliai and Jones, 2002; Horn et al., 2006; Toth et al., 2008).
Mechanics of Unsaturated Soils for Agricultural Applications 3-3

The aim of this chapter is to analyze the relationships between where

stress, strain, and strength as well as the consequences of soil ua and uw are pore air and water pressures, respectively
deformation for physical and physicochemical properties. It also χ is a factor that is often assumed to be directly related to the
includes a description of well-established and new methods for degree of saturation (Sr)
measuring mechanical properties of soils and introduces possi-
bilities for modeling soil strength and stress–strain relationships At saturation (uw = 0 kPa), χ = 1, while at uw = −106 kPa, χ = 0.
from the micro- to the macroscale. For sandy, less compressible, and nonaggregated soils, χ can
be estimated as
3.2  Stress–Strain Relationships in Soils χ = 0.22 + 0.78Sr . (3.3)

3.2.1  Stress Theory For silty and clayey soils, the values of the parameters in
3.2.1.1  Definitions Equations 3.1 and 3.2 depend on soil aggregation, pore arrange-
ment and strength, and hydraulic properties. Thus, the material
Before discussing the methods of field and laboratory stress mea-
function of the components in structured soils is only valid as
surement as well as factors influencing compaction, one needs to
long as the internal soil strength is not exceeded by the exter-
differentiate between several terms used to define compressive
nally applied stresses. It changes if, for example, aggregates are
properties. These definitions have been taken from Fredlund
destroyed during soil deformation and the structural properties
and Rahardjo (1993), Hartge and Horn (1999), Parry (2004), and
reduce to those that depend merely on texture.
McCarthy (2007).
The extent of soil deformation can be described by stress–
3.2.1.2  Mechanical Stresses strain relationships and by their relative proportions. In the
absence of gravitational and other applied forces, effective
Stress is defined as force per area within a solid body. Stress
stresses in three-phase soil systems can be expressed as a ten-
can be induced by external or internal forces, which lead, if the
sor containing three normal stresses and six shearing compo-
body is nonrigid, to a change in the body’s volume and/or shape
nents; assuming symmetry of the stress tensor, the shear stresses
expressed as deformations or strains. The mechanical behav-
are reduced to three independent components. Therefore, three
ior of a soil can therefore be characterized by its stress–strain
normal stress (σx, σy, σz) and three shear stress (τxy, τxz, τyz) com-
relationships.
ponents must be determined to fully define the stress state at
Strength is typically referred to as the maximum amount of
every location in a solid body (Nichols et al., 1987; Horn et al.,
stress a solid material can withstand before it fails; thus, exceeding
1992). For an unsaturated soil, the stress state can be described
soil strength results in soil failure or yield. Strength depends on
completely by a symmetric matrix, which can be written as two
internal parameters such as particle-size distribution, type of clay
independent stress tensors (Fredlund and Rahardjo, 1993):
minerals, nature and amount of adsorbed cations, content and type
of organic matter, aggregation induced by swelling and shrinkage, ⎡σ x − ua τ yx τ zx ⎤
stabilization by roots and humic substances, bulk density, pore-size ⎢ ⎥
⎢ τ xy σ y − ua τ zy ⎥ (3.4)
distribution and pore continuity of the bulk soil and single aggre-
⎢ τ xz τ yz σ z − ua ⎥⎦
gates, water content, and/or matric potential (Horn, 1981). ⎣

3.2.1.2.1  Stress State and

The number of stress state variables required to define the stress ⎡(ua − uw ) 0 0 ⎤
state depends primarily upon the number of phases involved. ⎢ ⎥
⎢ 0 (ua − uw ) 0 ⎥. (3.5)
The effective stress σ′ can be defined as a stress variable for satu-
⎢ 0 0 (ua − uw )⎥⎦
rated conditions (Terzaghi, 1936) and is the difference between ⎣
the total stress (σ) and the neutral stress (uw), which is equal to
the pore water pressure: A graphical representation of the stress state variables and the
action of water menisci at intergranular contacts in an unsatu-
σʹ = σ − uw , (3.1) rated soil is provided in Figure 3.2.

For symmetric tensors, it is always possible to find a coor-
where dinate system in which the shear components become 0 and
σ′ is transmitted by the solid phase the tensor becomes diagonal. In this principal axis system and
uw is transmitted by the liquid phase, respectively assuming that the pore air pressure ua = atmospheric pressure,
the stress tensor in Equation 3.4 simplifies to
In unsaturated soil, stresses are transmitted by the solid, liquid, ⎡σ1 0 0⎤
and gaseous phases. Thus, Equation 3.1 becomes (Bishop, 1959) ⎢ ⎥
⎢0 σ2 0 ⎥ (3.6)
σʹ = (σ − ua ) + χ(ua − uw ), (3.2) ⎢0 0 σ3 ⎥⎦
⎣
3-4 Properties and Processes

(ua – uw) (σy – ua) Soil particle

aggregate
σ΄ Ts
Ts
τyz Water
τyx
meniscus
(uw) Ts
Ts σ΄

(ua – uw) Entrapped

soil air
τxz (ua)
(σx – ua)
( u a – u w) (b)
τzx τxy
σ΄ = Effective intergranular pressure
τzy Ts = Surface tension water
(σz – ua) ua = Air pressure
y uw = Pore water pressure
z
τ = Shear stress
(a) x σ = Normal stress

FIGURE 3.2  (a) Stress state variables for an unsaturated soil. (b) Schematic sketch of water menisci at interparticle/interaggregate contacts illus-
trating the effect of pore water pressure (uw) on intergranular tension stresses. (Supplemented after Fredlund, D.G., and H. Rahardjo. 1993. Soil
mechanics for unsaturated soils. John Wiley & Sons, New York.)

with principal stresses σ1, σ2, and σ3 acting on the solid. For a soil deformation. The hydraulic stress component (uw) can
single-valued characterization of the stress state, two invari- either be negative (concave water menisci) or positive (convex
ants of the stress matrix are often used—the mean normal stress water menisci). In case of convex menisci, it can result in weak-
(MNS) and the octahedral shear stress (OCTSS; Koolen, 1994): ening of the total soil system, especially when shear forces are
applied. In case of pure compression under saturated conditions,
1 however, effective and hence compressive stresses are reduced
MNS = (σ1 + σ2 + σ3 ), (3.7)
3 while the neutral stress (water pressure) bears part or even the
entire externally applied load. In most cases, air pressure (ua) in
1 Equation 3.2 is ignored, assuming that gas pressure in soil dur-
OCTSS = (σ1 − σ2 )2 + (σ2 − σ3 )2 + (σ3 − σ1 )2 . (3.8)
3 ing loading is in equilibrium with atmospheric conditions.
If, on the other hand, hydraulic stresses become negative
3.2.1.2.2  Stress Propagation (=suction), the contractive forces even increase the effective
Each applied force per contact area is transmitted into the soil in stress (Figure 3.2). In addition to capillary forces associated
three dimensions and can alter the physical, chemical, and bio- with water, salt effects (i.e., water potential = sum of matric and
logical properties of the soil (e.g., water infiltration, rootability) if osmotic potential) and hydrophobic substances can also increase
the internal mechanical strength is exceeded. Stress propagation soil strength by altering wetting angle, cohesion, internal fric-
theories are rather old and have been often modified and adapted tion, as well as elastic and viscous properties of the soil (Barré
to in situ situations. The fundamental theory of Boussinesq (1885) and Hallett, 2009; Markgraf and Horn, in press).
is only valid for completely elastic material, while Fröhlich (1934) Hydraulic stresses result in shrinkage in almost all soils. In
and Soehne (1958) included elastoplastic properties through the an initially homogenized state, soils undergo proportional and
introduction of concentration factor values (υk). More compre- thereafter residual shrinkage during the first drying phase.
hensive descriptions of these models are given by Koolen and Depending on the history of the formerly applied hydraulic
Kuipers (1983), Bailey et  al. (1986), Johnson and Bailey (1990), and mechanical stresses, the shrinkage curve pattern, how-
and Bailey et  al. (1992). Horn et  al. (1989) introduced precom- ever, shifts and it must be now differentiated between structural
pression stress (Pv)-dependent values for the concentration factor, shrinkage (=structural rigidity), virgin, and residual shrinkage
which are smaller in the recompression stress range, while they behavior (Groenevelt and Grant, 2001; Braudeau et  al., 2004;
increase in the virgin compression stress range. The latter can be Peng and Horn, 2005). Structural shrinkage defines the internal
explained by the plastic deformation behavior, which causes a soil strength caused by deformation related to capillary forces.
deeper stress transmission closer to the perpendicular line. Structural shrinkage is more pronounced, the more often and
intensive soil dries out. Horn (1994a), for example, described the
3.2.1.3  Hydraulic Stresses effect of the drying frequency and intensity on shrinkage behav-
The effective stress (Equation 3.1) defines the forces per given ior and pointed out that soil strength increases the more often
area, which can stabilize the soil particles against any kind of and longer contracting water menisci occur while only a few but
Mechanics of Unsaturated Soils for Agricultural Applications 3-5

very intense drying processes are mostly not capable of rear- Load–deformation–failure
ranging particles to form a rigid structure with smaller entropy – Undrained
(Horn and Dexter, 1989). – Elastoplastic
The power of capillary forces and their strengthening potential – Nonlinear and hysteretic
– Hydraulic stress dependent
for soil architectures can be demonstrated by a simple computa- – Initial strain
tion. Given the mass of the earth (∼6 × 1024 kg) and the area of,
Moisture Stress
for example, Germany (∼360,000 km2) of which 50% is arable soil
coupling coupling
(=180,000 km2) and assuming a thickness of the plowed topsoil Δε0 = f (h, σ) Δh = f (σ, ε0)
of 30 cm with a hypothetical specific surface area of 800 m2 g−1 – Shrink – Critical state
(for simplicity we assume the soil to consist of smectitic clay and – Swell – Effective stress
2%–4% of organic carbon), we would end up with a total surface
area of ca. 6.5 × 1019 m2. If we furthermore presume that water Transport processes
menisci at a potential of pF 4 would be effective over the total sur- (water, solutes, heat)
face (χ → 1, assuming a very high negative air-entry pressure), – Nonlinear and hysteretic
then the sum of menisci forces acting within the topmost 30 cm – Stress–strain dependent
of arable soils in Germany could carry the total mass of the earth. – Finite strain

3.2.1.4  Stress Coupling

FIGURE 3.4  Conceptual framework for modeling coupled soil
Based on the findings by Baumgartl (2003), who described mechanical and hydraulic processes. The stress-coupling routine models
the similarity of mechanical stress–strain curves and shrink- pore water pressure changes (Δh) as a function of stress (σ) or strain (ε0).
age curves resulting from hydraulic stresses (Figure 3.3), Peng The moisture-coupling routine models strain changes (Δε0) as a function
and Horn (2008) proved that the link between mechanical and of pore water pressure (h) and effective stress (σ′). (From Richards, B.G.,
hydraulic “pre”stresses results in nearly identical changes in and S. Peth. 2009. Modelling soil physical behaviour with particular
reference to soil science. Soil Till. Res. 102:216–224.)
shrinkage curves. Additionally, Baumgartl (2003) explained the
differences between mechanically induced collapse and matric According to Richards and Peth (2009), mechanical and
potential-dependent shrinkage patterns by the dimensionless hydraulic processes can be coupled by treating the initially inde-
χ factor, which, however, is difficult to determine experimen- pendent load-deformation and transport processes by an incre-
tally. Accounting for the interactions between mechanical and mental approach as shown in Figure 3.4. This coupling is most
hydraulic processes is very important to understand the defor- important in modeling the interaction between water flow and
mation behavior of unsaturated soils. Nevertheless, their deformation/failure as, for example, encountered in swelling
description is inherently complex involving effective stress the- soils, landslides on slopes during rainstorms, and consolidation
ory, loading rate dependency, and nonlinear hysteretic coupled of high water content soils. In a stress-coupling routine, changes
transport and stress–strain functions. in pore water pressure (h) are calculated as a function of changes
in stress (σ) or strain (ε), and in a moisture-coupling routine,
0.82 1.18 changes in stress or strain are calculated as a result of pore
0.80 1.16
water pressure changes related to both water transport and load
Load deformation. A detailed mathematical description of the finite
0.78
1.14 element model (FEM) used for mechanical and hydraulic stress
coupling and the underlying constitutive relations and material
Void ratio e (–)

Void ratio e (–)

0.76
1.12 parameters is given in Richards and Peth (2009).
0.74
1.10 3.2.1.5  Soil Strength Changes due to Stress-
0.72
Drying Dependent Effects on Hydraulic Properties
1.08
0.70
Hydraulic stress
Total stress application affects interparticle bonding as well as
0.68 1.06 pore-size distribution, pore geometry, and the degree of satura-
Mechanical stress
0.66 1.04
tion, which either weakens the soil during compression or makes
10 100 1,000 10,000 it even stronger. While the former is caused by soil settlement,
pF/σ1 (hPa) reducing pore volume and hence increasing the degree of satura-
tion, the latter is related to the stress-dependent water redistri-
FIGURE 3.3  Stress–strain relationships showing the similarity
bution in newly formed finer pores at the expense of bigger and
between compaction (right ordinate) and shrinkage curves (left ordi-
nate). (Modified from Baumgartl, T. 2003. Koppelung von mechanischen already air-filled ones causing more negative matric potential
und hydraulischen Bodenzustandsfunktionen zur Bestimmung und values, thus increasing effective stresses (Equation 3.2). Fazekas
Modellierung von Zugspannungen und Volumenän­derungen in porösen and Horn (2005) describe the effect of static loading on the tran-
Medien. Habilitation Thesis. Schriftenreihe Inst. Pflanzenernaehrung sition between stress-induced soil strengthening and weakening
und Bodenkunde, Germany, No. 62, 133 pp. ISSN: 0933-680X.) and found that this change occurs close to the precompression
3-6 Properties and Processes

stress value. The changes resulted initially in a strength increase reached due to a given static loading, the following so-called
and the pore water pressure became more negative, while at consolidated shear process again caused an additional compac-
higher stresses the pore water pressure even reached positive tion and an extra change in the pore water pressure values. The
values starting from −30 kPa initial matric potential. If exter- more rapid the shear process occurs and the smaller the hydrau-
nal forces are applied as repeated short-time loading (e.g., due lic conductivity even at increased hydraulic gradients, the more
to wheeling or trampling) or if shear deformation-induced positive become the pore water pressure values and the weaker
rearrangement of particles occurs, we also have to consider the total soil (Hartge and Horn, 1999).
the “water menisci pumping effect due to short-term suction
changes” because it enhances the weakening process due to a 3.2.2  Strain Theory
more pronounced and more complete swelling, finally resulting
in a complete soil homogenization (Horn, 1976, 2003; Pietola Mechanical processes in soil are generally stress dependent. All
et al., 2005; Krümmelbein et al., 2008). Janssen (2008) measured stresses exceeding the internal soil strength result in failure,
stress-induced changes in pore water pressure in paddy soil sam- which can be defined either by an irreversible plastic volume
ples. Increasing frequency of loading and unloading changed decrease (=soil compaction) or by a rearrangement of soil par-
water menisci forces from negative to positive pore water pres- ticles at a constant bulk soil volume (=shearing). Analogous to
sure values and caused complete soil softening. Similar effects stress, strain can be described by normal (εx, εy, εz) and shear
were also reported for short-term cyclic loading of homogenized strain (εxy, εxz, εyz) components, which are also described com-
soil, where even when the soil was unsaturated at an initial mat- pletely by a symmetric strain tensor:
ric potential of −6 kPa, positive pore water pressure was mea-
⎡ εx ε xy ε xz ⎤
sured during the short-term loading phases (Peth and Horn, ⎢ ⎥
2006b). Water-induced soil softening is also evident when shear ⎢ ε xy εy ε yz ⎥ . (3.9)
forces are applied to the soil surface, for example, by wheeling ⎢ ε xz ε yz ε z ⎥⎦
⎣
due to slip effects (Horn, 2000; Horn et  al., 2006). Horn et  al.
(1995) proved the effect of shear-induced changes in pore water In the corresponding principal axis system, the strain tensor
pressure in comparison with the previously applied static stress reduces to
(Figure 3.5). Even if the consolidated stress–strain state had been
⎡ε1 0 0⎤
⎢ ⎥
End of shearing ⎢0 ε2 0 ⎥. (3.10)
150 (normal and shear +10 0 ⎢0 0 ε3 ⎥⎦
Normal stress stress, removed) ⎣
applied +5
Shearing The volumetric strain (εvol) can be calculated as
Pore water pressure (kPa)

Height change (mm)

starts
100 0
Shear stress (kPa)

ε vol = ε1 + ε 2 + ε 3 = ε x + ε y + ε z . (3.11)

5
Note that the tensor trace is invariant under coordinate trans-
50 –10 formations. Furthermore, the strain components and their
proportions depend on internal and external parameters and
require the determination of all components in a 3D volume.

3.2.2.1  Volumetric Deformation

0 –20 10
0 10 20 Compression refers to a process that describes the increase in soil
Time (min) mass per unit volume (increase in bulk density) under an exter-
Pore water pressure Height Shear stress nally applied load or under changes in internal pore water pres-
sure. Considering the soil as a continuum, soil movement can be
FIGURE 3.5  Changes in shear stress, sample height, and pore water described as a translation field (d) whose local properties are usu-
pressure during shearing. The samples were predried to −6 kPa and pre- ally characterized by three components of its spatial derivative:
consolidated prior shearing. Upon shearing at the same applied stress,
the sample further consolidated (height change) and pore water pres-
sure increased reaching even positive values during shearing. After ⎡∂ ∂ ∂ ⎤
⎢ dx dy dz ⎥
normal and shear stress were removed, pore water pressure decreased
⎢ ∂x ∂x ∂x ⎥
to a final value more negative than the initial pore water pressure. →
∂ ∂ ∂ ⎥
(From Horn, R., T. Baumgartl, R. Kayser, and S. Baasch. 1995. Effect
∇ ⋅ d = ⎢ dx dy dz . (3.12)
⎢ ∂y ∂y ∂y ⎥
of aggregate strength on changes in strength and stress distribution in ⎢ ⎥
structured bulk soils, p. 31–52. In K.H. Hartge and R. Stewart (eds.) Soil ⎢∂ d ∂
dy
∂ ⎥
dz
⎢⎣ ∂z x ∂z ∂z ⎥⎦
structure: Its development and function. CRC Press, Boca Raton, FL.)
Mechanics of Unsaturated Soils for Agricultural Applications 3-7

Every change in stress state therefore results in soil deforma- where f defines the soil-specific material properties. In the case
tion. This divergence (volumetric strain) can be expressed as the of a linear elastic isotropic material, the tensor notation reads as
divergence of the deformation field: follows:

⎡ σx τ xy τ xz ⎤ ⎡ε x − εm ε xy ε xz ⎤
   ∂ ∂ ∂ ⎢ ⎥ E ⎢ ⎥
ε vol = div(d ) = ∇ ⋅ d = tr(∇ ⋅ d ) = dx + d y + dz , (3.13) ⎢ τ xy σy τ yz ⎥ = ε xy ε y − εm ε yz ⎥
∂x ∂y ∂z 1+ v ⎢
⎢ τ xz τ yz σz ⎦ ⎥ ⎢ ε z − ε m ⎥⎦
⎣ ⎣ ε xz ε yz

and results in volumetric compression or extension. The terms ⎡εm 0 0⎤

E ⎢ ⎥
of the right-hand side of Equation 3.13 show the correspond- + 0 εm 0⎥ (3.15)
3(1 − 2v) ⎢
ing strains in x, y, and z directions and how they are related to ⎢0
⎣ 0 ε m ⎥⎦
respective deformation components.
where
E = Δσ/Δε (Young’s modulus or modulus of elasticity)
3.2.2.2  Shear Deformation
ν is the Poisson’s ratio
Shearing a soil volume always leads to a pronounced volume
constant rearrangement of particles often resulting in signifi- The first tensor on the right-hand side of Equation 3.15 describes
cant changes in pore functions by decreasing pore connec- the volume constant shear deformation and the second tensor the
tivity or continuity and changes in interparticle strength due volumetric strain with the mean volume strain εm defined as
to a loss of cohesion (Figure 3.6). The stress/strain at which
the interparticle strength is lost and the soil begins to fail 1 1
ε m = (ε x + ε y + ε z ) = ε vol . (3.16)
is referred to as yield stress/strain. The resistance of a soil 3 3
toward shear deformation is described by shear moduli (G),
Further details on the notions of stress–strain relationships can
which will be explained in more detail in Section 3.3 (rheo-
be found in Fredlund and Rahardjo (1993) and Warrick (2002).
metrical parameters).
To describe nonlinear elastic–plastic soil behavior as a func-
tion of stress, soil–water suction, and stress history, Richards
(1978) introduced, based on the analysis of experimental data,
3.2.3  Stress–Strain Processes a constitutive model, where the mechanical material properties
Generally, mechanical processes in soils are described by the are defined as hyperbolic functions allowing to treat soil as non-
stress/strain equation: linear and irreversible hysteretic material. The stress-dependent
mechanical material properties are defined based on standard
soil mechanical material parameters (bulk modulus, shear mod-
  
⎡ σ x (x , t ) τ xy (x , t ) τ xz (x , t )⎤ ulus, and Mohr–Coulomb failure criteria), which can be readily
⎢    ⎥ derived from soil tests (e.g., consolidation test, shear test, triaxial
⎢ τ xy (x , t ) σ y (x , t )

τ yz (x , t )⎥
 ⎥
⎢ τ xz (x , t ) test; Section 3.3.4). Bulk modulus K and shear modulus G char-
⎣ τ yz (x , t ) σ z (x , t ) ⎦
acterize the stiffness and shear strength of the soil, respectively.
   The basic relationships for the two simple stress-dependent
⎡ ε x (x , t ) ε xy (x , t ) ε xz (x , t )⎤
⎢    ⎥ moduli are (Richards and Peth, 2009)
= f ⎢ ε xy (x , t ) ε y (x , t ) ε yz (x , t )⎥ , (3.14)
⎢ ε xz (x , t ) 
ε yz (x , t )

ε z (x , t ) ⎥⎦ K = k1σ nm + k2h m + k0 (3.17)
⎣
and
Shear displacement
⎛ ⎛ τ ⎞q⎞
G = ( g 1σ mp + g 2hr ) ⎜ 1 − ⎜ ⎟ ⎟ + g 0 , (3.18)
Loss of pore ⎝ ⎝ τf ⎠ ⎠

connectivity
where
σm is the previous maximum of the mean normal stress
((σ1 + σ2 + σ3)/3)
h is the soil water suction
τ is the shear stress
Shear displacement τf is the yield stress according to the employed yield criteria
(a) (b)

FIGURE 3.6  Schematic sketch of the effect of shear displacement on The shape of the material functions is further defined by empiri-
pore continuity (b) in comparison with an “unstressed” pore system (a). cal material constants k0–2, g0–2, n, m, p, r, and q, which are
3-8 Properties and Processes

derived directly from fitting soil test data or by back-analyzing 3.3.1.1  Liquid Limit
soil test results with an FEM approach (for further details see The liquid limit is determined with a Casagrande apparatus
Section 3.7.3 and Richards and Peth (2009)). (Casagrande, 1932) where a homogenized moist sample is placed
in a special bowl and a V-shaped trench is cut from the top to
3.3  Soil Strength–Stability Indicators the bottom (Kézdi, 1974). The bowl with the sample is bounced
and Their Measurement up and down by a special crank onto a hard rubber block at a
frequency of two strokes per second until the trench is closed at
Soil strength and elasticity are mechanical key determinants a length of <1 cm. The number of strokes when this condition is
for maintaining efficient functionality and ultimately quality met is counted and the gravimetric water content determined
of soils. Indicators describing and quantifying the mechani- on a subsample at the end of the test. The liquid limit is defined
cal resistance, deformation, and resilience of agricultural soils as the water content (Θg) where the test criteria are fulfilled at
are important for several reasons. One is to assess if external 25 strokes corresponding to a certain “standardized” amount of
mechanical loads applied to soils during field operations mod- energy applied to the soil. The test is repeated for at least four
ify solid–void architectures and volume relationships through water content values and the number of strokes plotted versus
particle relocations and how far this may detrimentally affect the water content on a semilogarithmic paper, finally producing
pore functions. Another is to evaluate the penetrability of soil a linear line. The liquid limit increases with clay and organic-
horizons and aggregates by roots and soil organisms while pros- matter contents, ionic strength, cation valency, and proportion
pecting soils for water, nutrients, and food. A third reason is to of 2:1 type clay minerals in the soil.
estimate the risk for soil mass movements and soil erosion pro-
cesses along slopes. 3.3.1.2  Plastic Limit
Soil scientists and civil engineers are likewise interested in The plastic limit is defined as the water content (Θg) when
measuring soil mechanical stability parameters, although with homogenized soil samples begin to crack and crumble when
sometimes contrasting goals. In fact, many of the mechanical rolled to a diameter <3 mm. It has practical implication in civil
parameters that are commonly used in agricultural soil science engineering and agriculture since it determines the lower criti-
originated in the field of civil engineering. On the other hand, cal water content at which soils become plastic and hence dif-
civil engineers have adapted methods from agricultural soil sci- ficult to till or excavate.
ence (e.g., Atterberg’s limits) and nowadays realize the impor-
tance of understanding soils as bioactive media where interacting 3.3.1.3  Plasticity Index
physical and biological processes in turn have a strong influence
The difference between the water contents (Θg) at the liquid limit
on soil strength. However, recognizing soils as deformable (elas-
(LL) and plastic limit (PL) is the so-called plasticity index (PI =
toplastic) multiphase systems with an internal structure, we
LL – PL), which is often used as an indicator for soil workability.
need to define boundary-dependent strength/stability limits in
With an increasing plasticity index, soils become more sensi-
order to estimate and ultimately predict deformation-induced
tive to plastic deformation. The higher the plasticity index the
changes in physical, chemical, and biological soil functions.
smaller is the water-content range at which soils can be tilled
Most commonly used and well-established parameters char-
efficiently and trafficked without considerable soil deformation.
acterizing the mechanical strength/stability of soils on multiple
The smaller is also the angle of internal friction over a wider
scales ranging from interparticle to pedon levels will be described
range of water contents. Many attempts have been made to cor-
in the following, including methods for their determination.
relate PI to soil strength (Kézdi, 1974; Hartge and Horn, 1992;
Where appropriate, we supplemented this section with new tech-
Kretschmer, 1997). In principle, this test only gives information
niques and methodologies in the field of soil mechanical research.
on minimum strength values correlated with soil water content.
It is furthermore limited to silty, loamy, and clayey soil samples
3.3.1  Soil Consistency while such correlation fails and is too insensitive for sandy mate-
The consistency of soils is a result of cohesive and adhesive rial. Thus, especially coarse-textured soils cannot be classified
forces acting between particles and between f luid-phase by these data.
molecules and the solid surface, respectively. Together, they
determine the interparticulate resistance to deformation, rup- 3.3.1.4  Rheometrical Parameters
ture, and flow. Soil wetness obviously has a strong influence on Advances in rheological research as an independent science have
the kind of reaction against external forces (e.g., hard, friable, brought sophisticated techniques for quantifying flow behavior
soft, plastic, sticky, and viscous). Atterberg (1911) has defined and deformation properties of viscoelastic substances (mainly
different classes of soil behavior based on soil wetness, which is fluids)—the most important parameters are shear modulus (G),
a simple yet useful method to judge soil consistency and hence plastic viscosity (ηp), and yield stress (τy).
workability. The so-called Atterberg’s limits quantify the soil’s Although first rotational viscometers (1888) and later rheom-
resistance to mechanical energy as a function of gravimetric eters (∼1951) have been developed, early modern microprocessor-
water content (Θg): based systems, which are available since the 1980s, added more
Mechanics of Unsaturated Soils for Agricultural Applications 3-9

options for rheological testing including creep, relaxation, and

oscillation tests. The methods are today well established and
widely used in polymer, chemical, and material sciences as well
as in the paper and food industries.
Despite its potential applicability, however, they are still not 4 mm
commonly employed in soil science research. One of the earli-
est contributions has been made though by Yasutomi and Sudo
(1967) who used a low-frequency forced oscillation viscometer
to study viscoelastic properties of soil. Later, Keren (1988) and
Hesterberg and Page (1993) used a viscometer to investigate
the influence of electrolyte composition and pH on rheologi- (a)
cal characteristics of clay mineral suspensions. Studies based
on mineral suspensions certainly aid the understanding of the
principle influence of surface chemistry on mechanical solid–
interface interactions but have the drawback of ignoring the
pertinent action of water as a lubricant during deformation
processes. More recently, Ghezzehei and Or (2001) have used
a rotational rheometer with a parallel-plate sensor system to
determine these rheometrical parameters on natural soils and
clay samples under more realistic field-moisture conditions.
Higher water contents and high stress amplitudes resulted in
lower viscosity of all investigated soils. Although this is not
surprising, the authors could demonstrate that rheometry is (b)
a suitable and sensitive technique that enables us to quantify
FIGURE 3.7  Rheometer with a parallel-plate measurement system.
rheological properties of soils based on physically well-defined
A remolded soil paste is placed between two furrowed plates by moving
boundary conditions. Also Markgraf et al. (2006) investigated down the upper rotational shaft. (a) The upper plate rotates (arrows indi-
rheological characteristics of natural soil samples (Avdat loess, cate the rotation in an oscillatory test) while the lower plate remains static.
smectitic vertisol, and kaolinitic oxisol) using a parallel-plate During oscillation, shear force (torque) and angular velocity are measured
rheometer. By conducting so-called amplitude sweep tests by sensors placed in the shaft of the upper plate. (b) Shows the sample after
(oscillatory test with continuously increasing deformation), they the test. A typical result of a rheometrical test is shown in Figure 3.8.
were able to reveal differences in structural stabilities between
the smectitic vertisol and the kaolinitic oxisol and the influence A typical rheological parameter calculated from an amplitude
of electrolyte concentrations on rheological parameters of Avdat sweep test is the shear modulus G = τ/γ, where τ is the shear stress
loess samples. and γ the shear strain. The shear modulus is distinguished into a
It would go beyond the scope of this chapter to describe the storage modulus G′ = τA/γA cos δ and a loss modulus G″ = τA/γA sin δ
principles of rheometry in great detail. We therefore will only representing the elastic and viscous part of deformation, respec-
outline the basic test and analysis procedures in the following. tively (Figure 3.8). The subscript A denotes the amplitude of the
Readers that are more interested in this technique will find use- deflection that corresponds to the shear stress and shear defor-
ful staring points in Ghezzehei and Or (2001), Markgraf et  al. mation pair. The phase shift angle δ describes the viscous reaction
(2006), and Mezger (2006). of the sample to the prescribed shear deformation or shear stress.
The sample (usually a remolded paste at defined water con- At δ = 0° (tan δ = 0), the sample deforms ideal elastic (system
tent) is placed between two parallel plates (diameter 2.5 cm) response is instantaneous, that is, stress is proportional to strain);
with an adjustable gap size commonly between 2 and 4 mm at δ = 90° (tan δ = ∞), the sample shows ideal viscous behavior
(Figure 3.7). To set up the test, the upper plate is slightly pressed (system response is shifted by 1/4th of a full oscillation). In other
against the sample to ensure contact and time is given for stress words, the higher the phase shift angle δ the higher is the vis-
dissipation. To avoid slip at the interface between the sample cous and the lower is the elastic part of deformation, respectively.
and the plates, both the upper and lower plates are furrowed. Hence, at small tan δ values, the storage modulus G′ exceeds the
In an amplitude sweep test, the upper plate rotates (oscillatory) loss modulus G″ and vice versa for tan δ values >1. The magni-
at a predefined frequency (e.g., 0.5 Hz) and variable amplitude tude of G′ or G″ in turn represents the resistance of the sample
beginning with very small shear deformations (corresponding against deformation irrespective of whether it is elastic or viscous.
to angular deflection) up to the maximum shear deformation However, at tan δ = 1, the yield point is reached indicating that
where the angular deflection is equal to the gap spacing between the sample reacts predominantly viscous. For shear deforma-
the plates (e.g., 4 mm deflection at a gap spacing of 4 mm). Shear tion exceeding the yield point, the sample becomes quickly more
strain γ is expressed as percentage ranging from 0% (no deflec- viscous (Figure 3.8). Tan δ is also referred to as loss factor since
tion) to 100% (maximum deflection). it indicates the fraction of mechanical energy introduced into
3-10 Properties and Processes

Linear viscoelastic
input results in maximum effect (=maximum density). To evalu-
range (LVE) ate the soil moisture condition where compaction of homoge-
Storage modulus G΄ and loss modulus G˝ (Pa)

nized soil samples is most efficient, Proctor tests are commonly

G˝
employed (Proctor, 1933). Here, a remolded soil at various water
contents (Θg) is filled into a container and compacted by drop-
ping a weight (∼2.5 kg) on the soil from a height of ∼30 cm and

Loss factor tan δ (–)

G΄ for a defined number of strokes (usually 25). A series of tests are
performed at different water contents and the resulting bulk
density measured after each test. Bulk densities and correspond-
ing water contents (Θg) are plotted on a graph, which represents
the so-called Proctor curve. The water content where the com-
Yield
paction reaches a maximum is called the optimum water content
point
(Θopt) and the maximum density is referred to as Proctor density
(ρp). The coarser the soil sample, the higher ρp and the smaller
Θopt. For example, sandy soils have higher ρp values than silty or
tan δ
clayey soils, while the latter require a higher water content (Θopt)
to reach the optimum bulk density. Further, the more hetero-
0.0001% 100%
Strain (%) geneous the grain-size distribution, the higher are ρp and Θopt.
Strongly aggregated soils behave like coarser soil materials, that
FIGURE 3.8  Schematic diagram showing a typical result of a rheo-
is, also here the proctor density is higher and the correspond-
metrical test. G′ = storage modulus (Pa) and G″ = loss modulus (Pa)
ing optimal water content lower than in less-aggregated soils.
correspond to the elastic and viscous deformation, respectively. Tan δ
indicates the viscoelasticity of the sample: for tan δ = 0, deformation is
If aggregates themselves are destroyed during the test, ρp gets
ideal elastic; for tan δ = ∞, deformation is ideal viscous; for tan δ = 1 smaller while Θopt increases compared with completely homog-
(yield point), deformation is equally viscous and elastic. Note that both enized material.
moduli (G′ and G″) and strain are plotted on log scale.
3.3.3  Penetration Resistance
the system that is lost in deformation. Note that possibilities Soil resistance to any kind of deformation is determined by
for variations in boundary conditions during rheometer tests various types of penetrometers. The most simple is a thin metal
(stress or strain controlled, different stress–strain paths, stress rod (<0.5 cm diameter) with a defined tip shape. Frequently,
relaxation, oscillation frequency) are numerous and choice of the tip angle is 30° to simulate root properties or earthworm
either methodology depends on the material under investiga- shapes. The penetrometer can be either pushed into the ground
tion. For soils, however, amplitude sweep tests have produced by the constant weight of a falling hammer or it can be driven
interpretable results and seem to be sensitive for a wide range by a motor at constant speed. The output readings can be either
of soil conditions (salt effects, water effects, and organic-matter penetration depth per hammer stroke or depth stress deple-
effects) and allow expressed as yield stress a quantification of tions, which have to be overcome by the penetrating body in
micromechanical soil strength (Markgraf et al., 2006; Markgraf more sophisticated models. Penetration resistance is corre-
and Horn, 2007). lated with root growth, earthworm activity, and tillage effects.
When penetration resistance exceeds 2 MPa, root growth is
often reduced by half, while values >3 MPa often prevent root
3.3.2  Bulk and Proctor Density
growth. Tillage may increase the critical stress value of a hard-
Bulk density is defined as mass per unit volume ignoring the pan to >3.5 MPa depending on the nature of the pore system
internal arrangement of solids and voids, which limits its use to and the type of soil structure. Because the penetrometer needle
interpret strength properties and functions of structured soils. is not as flexible as a root, which can choose planes of weak-
For example, two soils at the same bulk density, one aggregated ness for growth, penetrometer readings quantify resistances
and the other not, can have significantly different strengths. mainly in the vertical direction. In addition, the penetrometer
Employing bulk density for deriving site-specific soil proper- readings only integrate impeding effects and cannot identify
ties should therefore in general be done with care (Horn and its causes. Despite a voluminous literature on the effect of
Kutilek, 2009). increasing bulk density and water content on penetration resis-
Nevertheless, as far as remolded or freshly deposited soil tance, extrapolation to land management situations is limited.
material is concerned, bulk density may be a suitable indicator Penetrometer readings can be used to create maps of derived
for the degree of compaction of such soils. Especially, in civil properties (e.g., definition of sites with a given strength irre-
engineering, often the state of maximum compaction of a given spective of its origin). Such data can be interpreted using sta-
material is of interest and the water content where compactibil- tistical variograms, fractal analyses, or simply by stating that
ity of a soil material is at optimum, that is, where least energy values are spatially different.
Mechanics of Unsaturated Soils for Agricultural Applications 3-11

3.3.4  Precompression Stress a number of alternative approaches are found in the literature.
and Compressibility Indices For a review of different σp estimates refer to Grozic et al. (2003).

The compression of a soil means a change not only in total pore 3.3.4.3  Triaxial Test
volume but is generally accompanied by a change in pore-size Triaxial tests mimic in situ stress distributions and are most
distribution including related soil functions (e.g., permeability, realistic since horizontal and vertical stresses are defined and
storage of water, aeration, gas exchange, heat diffusivity). Hence, adjustable. However, they are also more difficult to conduct and
the determination of the soil’s resistance to compaction and more laborious than, for example, oedometer tests, where a high
the magnitude of volume changes in soils exposed to external number of samples can be measured, and, hence, spatial het-
mechanical stresses are of paramount importance for preserving erogeneity of natural soils is better reflected. Triaxial tests on
soil physical quality. A number of laboratory tests under pre- the other hand have the advantage that both volume and shape
cisely defined boundary conditions may be used to quantify soil changes are determined simultaneously on the same sample
strength and volume change behavior of soils (Table 3.1). and that failure occurs at the naturally weakest plane, which is
important for deriving material parameters used in modeling
3.3.4.1  Uniaxial Compression Test
approaches. In triaxial tests, undisturbed cylindrical soil sam-
Uniaxial compression tests are used to obtain approximate val- ples are loaded with an increasing vertical principal stress (σ1),
ues of shear strength and settlement behavior of fine-grained while the horizontal principal stresses (σ2 = σ3) are kept constant
soils at unconfined conditions. A vertical normal stress (σ1) is (equal to the cell pressure). Shear stresses occur in any plane
applied to the specimen (cylindrical or cubic sample), while the other than those of the principal stresses. Shear parameters
stresses on the planes mutually perpendicular to the σ1 direction (cohesion and angle of internal friction) can be determined from
(σ2 = σ3) are zero. The vertical stress is increased until the speci- the slope of Coulomb’s failure line embracing the Mohr circles
men fails, which determines the strength of the soil at the given at failure for various combinations of σ1 and σ2 = σ3 (e.g., Kézdi
water content. The results of the test can also be used to define (1974), Mitchell (1993), Wulfsohn et al. (1998)). Due to aggregate
the tensile strength of single soil aggregates (Section 3.3.6). deterioration and prevented drainage of excess soil water, the
Mohr–Coulomb failure line is bent toward smaller slope values at
3.3.4.2  Confined Compression Test higher mean normal stresses. However, the numbers of contact
Soil stress–strain relationships of undisturbed structured and points, strength per contact point, and pore geometry also affect
homogenized soils with respect to volume change behavior are triaxial test results.
quantified in confined compression tests (oedometer tests). In There are three types of triaxial tests: (1) In the consolidated
contrast to uniaxial compression tests, the stresses σ2 and σ3 drained (CD) test, the soil sample is equilibrated with the mean
are undefined (rigid wall of the soil cylinder) and the respec- normal stresses prior to an increase in the vertical stress (σ1);
tive strains are defined and equal to zero. Both time- and load- the pore water drains off when the decrease in volume exceeds
dependent changes in soil deformation are measured (recorded the air-filled pore space. Therefore, the applied stresses are
as settlement). The slopes of the virgin compression and the assumed to be transmitted as effective stresses via the solid
recompression line in a void ratio e versus log σ plot are referred phase. However, Baumgartl (1991) found an additional change
to as the compression index (Cc = −δe/δ log σ) and swelling in the pore water pressure during extended CD triaxial tests
index (Cs = −δe/δ log σ), respectively. The transition from the depending on soil hydraulic properties. Thus, shear speed and
region of overconsolidation (recompression) to normal consoli- low hydraulic conductivity, high tortuosity, and small hydraulic
dation (virgin compression) is defined by the precompression gradients further affect the drainage of excess soil water and the
stress, which separates the stress range where soil deformation effective stresses (Horn et al., 1995). (2) In the consolidated und-
is considered fully elastic (i.e., reversible) from the stress range rained (CU) test, pore water is prevented from draining off the
where soil deformation is elastoplastic (i.e., partly irreversible). soil as vertical stress increases. Thus, high hydraulic gradients
Precompression stress (σp) is most frequently determined based occur and the pore water reacts as a lubricant with a low surface
on the method by Casagrande (Casagrande, 1936); however, tension. Thus, in the CU test (considering total stresses), shear

TABLE 3.1  Methods of Determining Soil Strength

Method Dimension Derived Soil Condition
Uniaxial compression Pressure (Pa) Homogenized soil, structured bulk soil, and single
aggregates
Confined compression test Pressure (Pa) Precompression stress (Pa) Homogenized soil, structured bulk soil
Triaxial test Pressure (Pa) Cohesion (Pa), angle of internal Homogenized soil, structured bulk soil, and single
friction (°) aggregates
Direct shear test Pressure (Pa) Cohesion (Pa), angle of internal Homogenized soil, structured bulk soil, and single
friction (°) aggregates
3-12 Properties and Processes

parameters are much smaller and pore water pressure values are 0.75
much greater than those in the CD test. (3) The highest neutral
stresses and, therefore, the lowest shear stresses are measured in e[N] = –0.028 * log N + 0.702
the unconsolidated undrained (UU) test, where neither the effec-
tive stresses nor the neutral stresses are equilibrated with the 0.70

Void ratio e (–)

applied principal stresses at the beginning of the test. Thus, cohe-
sion and angle of internal friction in terms of total stresses are Cn
strongly dependent on the compression and drainage conditions Δe
during deformation. In terms of strength of agricultural soils 0.65 Δ log N
under traffic, texture, pore water pressure (in unsaturated condi-
tions referred to as soil matric potential), nature of aggregates,
and soil structure determine the preference for a particular test.
0.60
3.3.4.4  Cyclic Compression Test 0 1 2
The theoretical concept of precompression stress as an indicator Log number of cycles N (–)
for soil stability is based on the assumption that in the elastic
FIGURE 3.9  Compressibility as a function of repeated (“cyclic”) load-
range of deformation (recompression line), there is no perma- ing. The slope Cn (cyclic compressibility index) denotes the sen-sitivity
nent volume change. This is not strictly true since even at load of the soil toward cyclic compression at the same magnitude of external
magnitudes below σp, there is always a small but yet notice- load. (After Peth, S., and R. Horn. 2006b. The mechanical behavior of
able volume change. While volume changes for a low number structured and homogenized soil under repeated loading. J. Plant Nutr.
of loading events below the precompression stress mostly only Soil Sci./Z. Pflanzenernahr. Bodenkd. 169:401–410.)
insignificantly affect soil porosity, the situation may change for
a higher number of load repetitions. In fact, the formation of and direction of the shear plane, which is assumed to be affected
a plow layer and the development of a platy soil structure are only by normal and shear stresses, are fixed. Normal stress is
the result of numerous loading events rather than the product of applied to the specimen in the vertical and shear stress in the
once exceeding the precompression stress value (Peth and Horn, horizontal direction. To determine the Mohr–Coulomb failure
2006b). Volume change behavior for repeated loading condi- line, at least four to five samples need to be tested each with a
tions can be investigated by cyclic compression tests. Such tests different normal stress. The maximum shear resistance (τmax) is
allow estimating soil compaction due to short- and long-term determined from a shear stress–displacement curve and plotted
multiple machine passages or animal trampling in grazing areas against the corresponding normal stress (σn). Plotting all pairs
(Peth and Horn, 2006a; Krümmelbein et al., 2008). Samples are of τmax versus σn gives the Mohr–Coulomb failure line in which
measured in a standard oedometer device with a constant load the slope and intercept are the angle of internal friction (ϕ) and
applied for a number of load cycles (e.g., 100 cycles). Soil defor- cohesion (c), respectively. As in triaxial tests, cohesion and angle
mation expressed as change in void ratio follows a logarithmic of internal friction are influenced by shear speed and drainage
trend with number of load cycles (Figure 3.9). A simple model conditions for a given soil.
can be used to predict the compression of a soil subject to the
same load for multiple loading repetitions (Peth, 2004):
3.3.6  Tensile Strength of Aggregates
1
e(N ) = −Cn × log N + e . (3.19) and Bulk Soil
u

Tensile strength of soils is a measure of the direct strength of
Here, e and N are the void ratio and number of loading cycles, interparticle bonds, which depend on chemical bonding, clay
respectively. The axis intercept e1u denotes the void ratio in the type and content, water potential (menisci forces), and organic
unloaded condition after the first loading event. Only the follow- matter. Also the internal geometry of particle arrangements and
ing loading events are considered to belong to the cyclic loading preexisting shrinkage cracks determine shear failure and crack
process. The slope Cn in Equation 3.19 is referred to as cyclic com- propagation upon mechanical and hydraulic loads generating
pressibility and indicates the sensitivity of a soil toward cyclic tensile forces. Tensile strength is an important indicator for the
compression. The higher Cn the higher is the compression under structural stability from the aggregate scale to the bulk soil level
repeated loading. and a decisive factor for the preservation of physical quality of
soils subject to mechanical stresses. The most widely used tech-
nique to measure tensile strength of soil aggregates is the crush-
3.3.5  Shear Strength Parameters
ing test. Soil aggregates are placed between two parallel plates
The shear strength parameters, cohesion (c), and angle of inter- in their most stable position (flat side downward) and the upper
nal friction (ϕ), may be determined by triaxial tests as described plate is loaded either with a weight (e.g., water dripping slowly
above or in a direct shear test. During direct shear tests, the type into a bucket, Horn and Dexter, 1989, or by a load frame).
Mechanics of Unsaturated Soils for Agricultural Applications 3-13

The force when failure occurs is recorded and tensile strength is unit of surface area or to initiate a crack (Skidmore and Powers,
calculated according to Dexter and Kroesbergen (1985): 1982) and is called the apparent surface energy (Hadas, 1987).
Consequently, soil stability against shear or tensile stresses is
0.576 × F related to strength distribution in failure zones. In principle,
Y= , (3.20)
d2 soil structure will be stable if the applied stress is smaller than
the strength of the failure zone, that is, if the bond strength at
where the points of contact exceeds the shear or tensile stresses gener-
Y is the tensile strength ated by external loads. If the resisting forces are smaller than
F is the applied force the active forces, stresses are in disequilibrium and hence soil
d is the mean diameter of the aggregate given by deformation will occur to generate more contact points until
stress equilibrium is reached again. Reorientation of particles
(dx + d y + dz ) is accompanied by a change in soil structure and consequently
d= (3.21)
3 functions. In extreme stress situations (especially high shear
stresses) or when soil is subject to mechanical loads in unfavor-
with indices x, y, and z denoting the aggregate diameter of the able moisture conditions (near the liquid limit), soil structure
longest, intermediate, and shortest axes, respectively. may be almost completely returned to an immature state (homo-
Other indirect techniques have been proposed to investigate geneous soil). In contrast to shear stresses that lead to volume
crack growth and propagation in soils subject to tensile forces. One constant deformation, normal stresses result in volume change,
method is based on approaches adapted from fracture mechanics that is, compression, which is plastic as soon as the soil stabil-
where crack formation and propagation are measured by so-called ity is exceeded. In situ stress conditions during field operations
deep notch three-point bending tests (Hallett and Newson, 2001, (traffic, soil–tool interactions) are generally characterized by a
2005). Also direct tensile tests have been suggested to study crack combination of both shear and compressive stresses.
propagation and tensile strength of soils, for example, using bone-
shaped bulk soil samples that are torn apart by tension forces per-
pendicular to a predefined crack (Junge et al., 2000). 3.4.1  Mechanical Properties
of Homogenized Soils
3.3.7  Other Methods to Determine If only mechanical properties of homogenized soils are compared,
Aggregate Stability gravelly soils are less compressible than sandy or finer-textured
soils (Horn, 1988), and any deviation of the particles from the
Aggregate stability may also be determined by wet sieving. Here, spherical shape results in an increase in the shearing resistance
soil samples are prewetted to a given pore water pressure and then and soil strength (Gudehus, 1981; Hartge and Horn, 1999). Ellies
sieved through a set of sieves from 8 to 2 mm diameter. The dif- et al. (1995) found that the angle of internal friction for medium
ference between the aggregate-size distribution at the beginning and coarse sands at comparable bulk density and water content
and end of sieving under water for a given time is calculated as the but of different origins (quartz, basalt, volcanic ash, and shells)
mean weight diameter (MWD). This value is qualitatively related ranged from 25° to 50°. Soil strength also depends on the type
to aggregate strength and increases with increasing aggregate and content of clay minerals and exchangeable cations. At the
stability. The wettability of the solid interfaces has a pronounced same bulk density and pore water pressure, compressibility of
effect on the test results in wet sieving and direct comparison with homogenized soil increases with clay content and decreases with
strength parameters derived from mechanical stress applications soil organic-matter (SOM) content. Vice versa soils at the same
through polar loads is limited. Aggregate stability has also been clay content are more readily compressed at lower bulk density
measured by the application of ultrasonic dispersion techniques or higher moisture content. Cohesive forces between illite, smec-
where aggregate stability can be expressed by the input of ultra- tite, and vermiculite are greater than for kaolinite, which in turn
sound energy resulting in the breakup of aggregates into smaller has a larger angle of internal friction because of its size and par-
microaggregate units up to single particles (Raine and So, 1994). ticle shape. Additionally, the higher the valency of the adsorbed
A comparison of different methods to determine aggregate stabil- cations and the higher the ionic strength of the soil solution, the
ity is given by Baumgartl and Horn (1993). greater is the shearing resistance under otherwise similar condi-
tions (Yong and Warkentin, 1966; Mitchell, 1993).
3.4  Effect of Soil Structure on Soil Shearing resistance also increases depending on both the
Strength and Deformation Processes nature and content of SOM. In agricultural soils with the same
physical and chemical properties, the mechanical parameters
As mechanical stresses are applied, soil deformation occurs first (precompression stress, angle of internal friction, and cohesion)
at the weakest point(s) in the soil matrix and further increases are greater when the relative contents of carbohydrates, con-
in stress resulting in the formation of failure zones. The strength densed lignin subunits, bound fatty acids, and aliphatic poly-
of the failure zone is equal to the energy required to create a new mers are higher (Hempfling et al., 1990).
3-14 Properties and Processes

3.4.2  Mechanical Properties of Aggregated Soils Precompression stress (kPa)

0 50 100 0 50 100 0 50 100
Mechanical strength of structured soils depends on aggrega-
tion and history of hydraulic stresses (degree of maximum Ap Ap Ap
predrying), as well as the shape and internal arrangement of 2 2 2
particles, microaggregates, and voids. At comparable grain-size
distribution, bulk density, and pore water pressure, soil strength 4 4 Ah 4 Bga
Al
increases with aggregation (i.e., coherent < prismatic < blocky <

Depth (dm)
6 6 6
subangular blocky < crumbly). In the case of a platy structure,
AhC Cga
the strength depends on the direction of shear forces relative to 8 8
Bt 8
the preferred orientation of the particles. In the direction of the
Cca
elongated axes of aligned particles, shear strength is lower than 10 10
perpendicular to it. This means that not only mechanical stresses Bgt
are anisotropic but also strength properties that in turn are a 12 12 Cg
function of aggregation. However, both the magnitude of previ- C
ous hydraulic stresses (predrying intensity) and their dynamic Luvisol Mollisol Vertisol
changes determine soil strength. Therefore, mechanical proper-
ties also depend on the frequency of swell/shrink and wet/dry FIGURE 3.10  Precompression stress values for three soil profiles at
soil matric potential of Ψm = −6 kPa. (Modified from Horn, R. 1994b.
events and on the actual pore water pressure at the time of load-
Stress transmission and recompaction in tilled and segmently dis-
ing. Soils become stronger when redried and rewetted and when
turbed soils under trafficking, p. 53–87. In N.S. Jayawardane and
pore water pressure gradients over longer distances promote par- E.  Stewart (eds.) Subsoil management techniques. Lewis Publishers,
ticle movement and rearrangement until entropy is minimized Boca Raton, FL.)
(Semmel et al., 1990). The effect of pore water pressure on strength
itself is governed by the theory of effective stresses in unsatu- illuviation, which results in strength decrease in the Al horizon
rated soils (e.g., Bishop’s effective stress equation (Equation 3.2)). and an increase in the Bt horizon due to aggregation. On the
It has been extended from the early considerations of Terzaghi other hand, calcium precipitation in the Cca horizon of the mol-
(Terzaghi, 1936) for saturated soils; however, its application lisol also leads to a strength increase. In all three soils, the parent
remains difficult since the evaluation of the parameter χ in material (C horizon) was weakest although overburden pressure
Equation 3.2 is still complicated. It accounts for the tradeoff increases with soil depth suggesting the opposite should have
between pore water pressure (increases interparticle forces with been the case. This underlines the offset of soil strength parame­
curvature of menisci) and effective area of interparticle contact ters by pedogenic processes. On the other hand, anthropogenic
(when decreasing, the effect of pore water pressure is reduced). processes such as annual plowing and tractor traffic may create
The interrelationship of pore water pressure and effective area very strong plow pan layers with precompression stress values
of interparticle contact is structure dependent and hence also similar to the contact pressure of a tractor tire or even higher
χ is related to structure and not as sometimes assumed purely (up to 300%) due to lug effects. The transition from the region
a function of the degree of saturation. If the relative reduction of overconsolidation to the virgin compression line depends to a
in water-filled pores is smaller than the actual decrease in pore great extent on internal parameters and further on the hydraulic
water pressure (more negative matric potential), soil strength and mechanical stress history. In addition, strength decreases in
increases while if the decrease in the effective surface of water the Ap horizon due to plowing and seedbed preparation can be
menisci exceeds the decrease in matric potential (getting more observed until texture-dependent values are reached.
negative), the effective stress of such drier soils gets absolutely Pronounced strength decreases are also found in soil profiles
smaller. In principle, soil strength is promoted by two different that have been deep-loosened or deep-plowed (up to 60 cm) or
mechanisms: (1) the increase in strength results from an increase loosened and/or mixed with other soil material. In the case of
in the total number of contact points between single particles a partial deep loosening by a trenching slit plow (Reich et  al.,
(i.e., an increase in effective stress) and (2) the increase in shear 1985; Blackwell et al., 1989), traffic must be restricted by the use
resistance per contact point (Hartge and Horn, 1984). Therefore, of smaller machinery or controlled tracks perpendicular to the
even if soil bulk densities are similar, strength properties may homogenized soil volume.
be quite different. Also freezing and thawing affect soil strength, Soils with a well-developed vertical pore system are stronger
because aggregates become either denser or they are destroyed than those with randomized or horizontal pore arrangements
by ice lens formation during freezing. The exfoliation process since elongated pores are more stable with their symmetry axis
starts from the outer skin. Both effects are called soil curing, but oriented in the direction of the major principle stress (σ1) than
result in completely different strength values and physical prop- perpendicular to it. Therefore, vertical (bio) pores are less prone
erties of the bulk soil (Horn, 1985b; Kay, 1990). Pedogenic effects to compression than oblique or horizontally oriented pores and,
on natural mechanical strength of three soils are illustrated in thus, untilled or minimum tilled soils are stronger than conven-
Figure 3.10. Luvisols derived from loess are characterized by clay tionally tilled soils (Horn, 1986).
Mechanics of Unsaturated Soils for Agricultural Applications 3-15

Each soil deformation requires air-filled pore space and suffi- Angle of internal friction for a single aggregate (∼45°) is very high
ciently high hydraulic conductivity during compression to drain compared to bulk soil samples. However, aggregated bulk soil
off the excess pore water. The smaller the hydraulic conductiv- reveals higher friction angles than the homogenized soil at the
ity, the hydraulic potential gradient, and the pore continuity, the same bulk density. This shear strength gain is lost when stresses
more stable is the soil especially during short-term loading. In exceed the overall stability of the aggregated sample leading to
sandy soils, this effect is small and initial settlement equals the a reduction in the angle of internal friction to values similar for
total strain. With increasing clay content, however, the propor- homogenized soil. When the maximum value of stress exceeds
tion of initial to primary and secondary consolidation is reduced the maximum strength such that structure is homogenized, only
and time-dependent soil settlement becomes important. This texture-dependent properties remain.
results in an increase in precompression stresses for short-term
loading due to an increase in pore water pressure that dissipates 3.4.3  Soil Deformation under Dynamic Stresses
only slowly depending on the local hydraulic conductivity. Such
Standard mechanical stability indicators such as shear strength
drainage effects on the consolidation process are smaller in more
parameters (ϕ and c) and precompression stress (σp) are without
strongly aggregated soils and with coarser soil textures.
dispute suitable for characterizing the mechanical strength/­
The development of structure generally results in increas-
stability of soils and to assess if significant irreversible volumetric
ing soil strength since the formation of secondary large pores is
and shear deformation under given stress conditions are likely to
always accompanied by the development of denser aggregates.
occur. Horn et al. (2005), for example, have derived stability maps
Although the aggregate assemblages carry the same stresses over
on various scales down to farm level where sensitive and less sen-
fewer contact points, the aggregates themselves are more resis-
sitive areas are outlined, which could help farmers to avoid harm-
tant to shear stresses. Strength differences may also result from
ful subsoil compaction. We must, however, consider more in detail
changes in the angle of internal friction and cohesion as indicated
the repeated short-term loading because multiple loading events
in Figure 3.11 for a single aggregate, an undisturbed aggregate,
cumulatively add to the total compression, although concerning
and a homogenized bulk soil, respectively. More intense aggre-
precompression stresses no further compression maybe expected.
gation increases soil strength at comparable hydraulic stresses.
Zapf (1997), for example, argued that the increase in irreversible
50 deformation of arable soil by agricultural machinery is not only
related to the increasing mass of machines but also related to the
increase in wheeling frequency. Peth and Horn (2006b) estimated
40 that, based on the calculations of Olfe (1995), for an average-sized
Angle of internal friction φ [°]

wheat-production farm in a time period of 5 years, the number of

load repetitions may add up to 50 events for 85% of the field and
30 up to 100 events for permanent wheeling tracks.
Cyclic compression tests allow estimating soil deformation
due to repeated loading and hence assessing the effect of long-
20 term field traffic on subsoil compaction. Similar to other strength
parameters, cyclic compressibility (see coefficient Cn in Equation
3.19) for homogenous soils at the same bulk density is strongly
10 texture dependent (Figure 3.12). The finer the texture and espe-
cially the higher the clay content, the higher is the sensitivity
against cyclic compression (higher Cn values). Porosity changes
0 with increasing number of loading cycles are significant and
accumulate to up to ∼3.0 vol% after 100 cycles (for sandy loam,
Aggregate Figure 3.12). Assuming that mostly larger pores are affected
Bulk soil, aggregated, load range 0–50 kPa by compression, this would mean a reduction in air capacity
Bulk soil, aggregated, load range 50–150 kPa by additional 3.0 vol%, although the applied load (40 kPa) was
Bulk soil, homogenized, load range 0–50 kPa relatively low. Cyclic compressibility tests on undisturbed field
Bulk soil, homogenized, load range 50–150 kPa
samples reflect also the influence of structure and tillage man-
agement (Figure 3.13). Correlation between bulk density and Cn
was higher for conventionally tilled soils and only weak for the
FIGURE 3.11  Changes in shear strength at constant soil matric
potential Ψm = −6 kPa for various applied stress ranges for single aggre- conservation tillage system where Cn values were on an aver-
gates, bulk soil, and homogenized material. (Modified from Horn, R., age lower at similar bulk densities. The lack of a strong correla-
T.  Baumgartl, R. Kayser, and S. Baasch. 1995. Effect of aggregate tion between bulk density and Cn suggests a stabilizing effect of
strength on changes in strength and stress distribution in structured structure. Some of the aggregated soils show during cyclic load-
bulk soils, p. 31–52. In K.H. Hartge and R. Stewart (eds.) Soil structure: ing a stepwise compression curve with a few quasistable plateaus
Its development and function. CRC Press, Boca Raton, FL.) followed by stronger settlements until deformation is leveling off
3-16 Properties and Processes

4.0 0.61
Sand (Cn = 0.008 ± 0.00225)
3.5
Silty sand (Cn = 0.012 ± 0.00166)
3.0 0.60
Sandy loam (Cn = 0.034 ± 0.00546)
2.5

Void ratio e (–)

Aggregate
Δn (vol%)

0.60
2.0 breakup

1.5 0.59
1.0

0.5 0.59

0.0
1 10 100 0.58
Number of loading cycles 0 1 2
Log number of cycles (–)
FIGURE 3.12  Changes in porosity for different soil textures (homog-
enized samples) due to cyclic loading with a load of 40 kPa at the same FIGURE 3.14  Aggregate breakup during cyclic loading (“cyclic wear
initial bulk density (1.62 g cm−3). Samples have been equilibrated to a stan- of aggregates”). (After Peth, S., J. Rostek, A. Zink, A. Mordhorst, and
dard matric potential of −6 kPa prior to the tests. Note that the change R. Horn. 2010. Soil testing of dynamic deformation processes of arable
in porosity after the first loading–unloading event is omitted here (for soils. Soil Till. Res. 106:317–328.)
sand = 1.28, for silty sand = 1.22, and for sandy loam = 2.12 vol%). Error
bars indicate standard deviation (n = 14). Corresponding Cn values are
given in brackets (mean ± SD). (From Peth, S., and R. Horn. 2006b. The 3.5  External Mechanical Forces
mechanical behavior of structured and homogenized soil under repeated and Stress Distribution in Soils
loading. J. Plant Nutr. Soil Sci./Z. Pflanzenernahr. Bodenkd. 169:401–410.)
3.5.1  Stress Application and Variations
0.08 in the Contact Area
Any load applied at the surface is transmitted to the soil in three
dimensions by the solid, liquid, and gas phases. If air permeability
0.06 CT1: R2 = 0.90 is high enough to allow immediate deformation of the air-filled
pores, soil settlement is mainly affected by fluid flow. However,
fluid flow may be delayed because changes in water content or pore
Cn (–)

0.04 water pressure depend on the hydraulic conductivity, gradient, and

pore continuity. Thus, the intensity and form of pressure transmis-
CT2: R2 = 0.62
sion are again affected by soil strength. In the following discus-
0.02 CnT sion, stress distribution in both homogenized soils and aggregated
CT1 systems will be defined. Based on the theory of Boussinesq (1885)
CT2 CnT: R2 = 0.20 who solved the problem of a point load acting perpendicular on
an infinite half-space consisting of homogeneous, isotropic, and
0.00
1.00 1.20 1.40 1.60 1.80 linear elastic material, Fröhlich (1934) introduced a textural-
Bulk density (g cm–3) dependent concentration factor (vk) to give more “flexibility” to the
original Boussinesq solution for determining stress propagation
FIGURE 3.13  Correlation between initial soil bulk density and in soils. Under saturated conditions, vk ranges between 3 for very
cyclic compressibility coefficients (Cn) of a haplic luvisol (Marienstein/ strong material (which is defined as linear elastic and corresponds
Germany) with silt loam texture for different tillage systems: CT1 and
to the Boussinesq solution) and 9 for soft soil becoming higher
CT2 are two different conventionally tilled sites; CnT is conservation
with increasing clay content. In weak soils with high concentra-
tillage. (From Peth, S., and R. Horn. 2006b. The mechanical behavior of
structured and homogenized soil under repeated loading. J. Plant Nutr. tion factor, stresses are transmitted to greater depth but remain
Soil Sci./Z. Pflanzenernahr. Bodenkd. 169:401–410.) concentrated around the perpendicular line of the load center. On
the other hand, in strong soils with low values of the concentration
again (Figure 3.14). This behavior could be interpreted as stable factor, stresses are transmitted more horizontally and shallower.
aggregate units breaking under repeated loading just like steel At the same contact pressure, stresses are transmitted deeper
may break due to material wear. Although these results still when the contact area is larger. Furthermore, stress distribution
have preliminary character and certainly more systematic tests patterns in the soil are not only different for tire lugs and the inter-
are needed, they demonstrate the importance of considering vening area but are also affected by the stiffness of the carcass (Horn
dynamic stress paths in soil testing in order to derive realistic et  al., 1987). Thus, there are no well-defined equipotential stress
estimates of compaction under field loading conditions. lines in soils, but the concentration factor values must be related
Mechanics of Unsaturated Soils for Agricultural Applications 3-17

40 cm 42 cm 44 cm 46 cm 50 cm

20 cm 20 cm 20 cm 20 cm σz (kPa)
40 cm 40 cm 40 cm 40 cm 0
60 cm 60 cm 60 cm 60 cm –20
80 cm 80 cm 80 cm 80 cm
100 cm 100 cm 100 cm 100 cm –40
120 cm 120 cm 120 cm 120 cm –60
140 cm 140 cm 140 cm 140 cm –80
160 cm 160 cm 160 cm 160 cm
180 cm 180 cm 180 cm 180 cm –100
200 cm 200 cm 200 cm 200 cm –120
220 cm 220 cm 220 cm 220 cm
(a)
50 cm 50 cm

20 cm 20 cm

40 cm 40 cm
σz (kPa)
60 cm 60 cm
0

80 cm 80 cm –50

100 cm 100 cm –100

120 cm 120 cm –150

140 cm 140 cm –200

160 cm 160 cm –250

–300
180 cm 180 cm

200 cm 200 cm

220 cm σ0 = 100 kPa 220 cm σ0 = 200 kPa

(b)

FIGURE 3.15  (a) Stress distribution under a tire with the same ground contact pressure of 100 kPa but increasing contact area (tire size increases
from left to right) and (b) for the same tire size (100 cm diameter) but increasing ground contact pressure (σ0) due to higher wheel load, respec-
tively. Vertical stresses σz (kPa) have been modeled with an FEM approach assuming rotational symmetry of the contact area (i.e., circular tire-soil
contact shape). Note that only a part of the model domain is shown. The width of the model domain was 4.5 m to reduce boundary effects. The
horizontal white-dashed line indicates the usual plowing depth of 30 cm. Mechanical properties for the topsoil and the subsoil were assumed to be
the same. Following mechanical parameters were used for the simulation: cohesion c = 10 kPa, angle of internal friction ϕ = 20°, stress-dependent
bulk modulus K(σ) kPa = 800 × σ0.5 0.5
m + 50, stress-dependent shear modulus G(σ) kPa = (270 × σ m )(1 − (τ /τ f )
0.37
) + 50, where the yield stress τf (σn) =
c + σn tan ϕ. For further details on material functions and parameters, see Section 3.2.3 and Richards and Peth (2009).

to precompression stresses in relation to applied stress and con- understood that at a given surface load, the stress propagation
tact area for a given texture (DVWK, 1995). If additionally applied reaches the deeper the larger the contact area and that at a given
stresses do not exceed the internal soil strength defined by the pre- contact area stresses are transmitted deeper for higher ground
compression stress, the concentration factor is smaller as compared contact pressures (Peth and Horn, 2004; Figure 3.15a and b).
to the situation when the stresses result in a plastic deformation. When we consider the stress vector field during wheeling,
The latter is defined by higher values (Berli et al., 2003). the tangential redirection of stresses increases with stronger
The speed effect of wheeling, as well as the kind of stress wheel slip and less rigid tire or rubber belt (Figure 3.16a and b).
application (tire, rubber belt tire-inflation pressure), affects the Keller (2004), Arvidsson and Keller (2007), Cui et  al. (2007),
stress path at the soil surface and also causes enormous differ- and Keller et al. (2007a) proved the effect of various tire forms
ences in the stress propagation inside the soil volume. It is well and tire-inflation pressure on soil stress distribution and not
3-18 Properties and Processes

Soil surface
100
Wheeling direction

Vertical displacement (mm)

–5

–10

–15

–20

–25
–50 –45 –40 –35 –30 –25 –20 –15 –10 –5 0 5
(a) Horizontal displacement (mm)

Shear stress/
Wheeling direction Rubber belt tensile stress
0m (kPa)
Shear
stress –10.0
1m –5.0
Tensile 0.0
stress
5.0
2m 10.0
15.0
3m 20.0
25.0
30.0
4m
1m 2m 3m 4m 5m 6m 7m 8m 9m 10 m 11 m
(b)

FIGURE 3.16  (a) Vertical and horizontal movement of a displacement sensor installed in situ at 10 cm depth during wheeling with a
rubber belt tractor. (b) Modeled (FEM) distribution of shear/tensile stresses under a rubber belt tractor during wheeling. Note that mate-
rial properties used for the FEM are not the same as for the site where soil displacement has been measured in situ (a). Simulated stress
distribution has been conducted for a hypothetical case. Material properties and boundary conditions used in (b) were as follows: belt
length = 240 cm, tractor weight = 12.6 Mg, ground contact pressure σ0 = 67 kPa, horizontal stress transmitted via the belt = 32.5 kPa, cohe-
sion c = 10 kPa, angle of internal friction ϕ = 20°, stress-dependent bulk modulus K(σ) kPa = 800 × σ0.5 m + 50 , stress-dependent shear modulus
G(σ) kPa = (270 × σ0.5
m )(1 −(τ /τ f )
0.37
) + 50, where the yield stress τf (σn) = c + σn tan ϕ. For further details on material functions and parameters,
see Section 3.2.3 and Richards and Peth (2009).

only showed the heterogeneity of the stress distribution but load and wheel contact area. The benefits of new and smaller
also quantified the effect of changes in the tire forms and infla- more intelligent self-steering GPS-controlled agricultural
tion pressure on stress distribution. Burt et  al. (1989) already machines are still under debate, although it is a positive way to
described the enormous heterogeneity in the stress distribution minimize the still increasing and deeper stress transmission into
within the contact area that differed up to 300% and was higher soils taking place when using conventional (heavier) machines.
beneath the lugs and the lowest in between them close to the On the other hand, when soil scientists deal with traffic–soil
middle part of the area while due to carcass effects it reached interactions, they are mostly concerned about the effects of
extremely high values at the outer edge of the tire. stress application on soil properties and the future effects for
The question about the effect of traffic on stress distribution crop production, water infiltration, filtering and buffering, and
and its consequences on soil properties remains, even after more groundwater recharge. Recently, enhanced greenhouse gas emis-
than three decades of intensive discussion, still controversial, sions have been more often associated with the interaction of soil
which is most often caused by different scientific views or interests stress and soil deformation, which results in changes in aeration
in the subject. It is to be understood that the machine industry is and microbial activity. Legislation finally has to link both inter-
mostly interested in the development of more effective and more ests where stakeholders have to decide based on their admin-
powerful machines resulting in heavier traffic with higher wheel istrative perspectives and given  laws. The  debate  on  soil  use
Mechanics of Unsaturated Soils for Agricultural Applications 3-19

and soil protection has resulted in Germany in the German 3.5.2.2  Structure Effects on Stress Attenuation
Soil Protection Law (BBodSchG, 1998), while at European level The effect of aggregation on stress distribution and its conse-
such a law is still under discussion. However, the liability var- quences for ecological parameters are well understood. Under
ies to a great extent even in between different provinces within in situ conditions for soils with the same internal parameters,
Germany and the definition of main soil parameters (indicators) stress attenuation is greater the more aggregated soils are.
is not finalized (Horn and Fleige, 2009). Concentration factor values expressed as precompression stress
are smaller for better aggregated and drier soils (DVWK, 1995).
3.5.2  Stress Effects in the Soil Not only the pressure but also the size and shape of the contact
area affect stress distribution in unsaturated structured soils.
3.5.2.1  Internal Parameters Stress distribution calculations in a luvisol derived from
At a given bulk density and pore water pressure, applied stress loess under natural forest and its comparison with the identi-
at the soil surface will be transmitted deeper as silt and clay con- cal computation under arable management show the effect of
tents increase while stress attenuation will be greater in a smaller soil strength on stress attenuation (Figure 3.17a and b). Under
volume as the soil dries. For a given particle-size distribution, natural forest, especially the clay-enriched Bt horizon with a
water content, and bulk density, stress attenuation will increase prismatic–blocky structure (matric potential ∼ −30 kPa) attenu-
with increasing SOM content. Based on many stress distribution ated the applied stresses of the tractor and both combine har-
measurements in the field and in monoliths, a general correla- vesters while the topsoil (Ah- and the clay-depleted Al horizons),
tion scheme involving texture, precompression stress, and tire respectively, with a crumbly or coherent structure was deformed.
contact area to derive the concentration factor v k has been used Under arable conditions, approximately 1/4th of the pores
to approximately predict the stress distribution in soils (DVWK, within the top 100 cm were lost compared with the forest site,
1995); for more information see also Horn and Fleige (2003). which also resulted in higher precompression stress at all depths

Normal stress σn (kPa)

Horizon. 0 25 50 75 100 125 150 175
depth (cm)
Ap
25 Conventional tillage
App
40
Tractor 100
Al Combine harv.
60
L15 Mg
Bt
Combine harv.
25 Mg
100 Sugar beet harv.
Cv 147/49 cm
Sugar beet harv.
160/80 cm
Soil strength
(a)

Normal stress σn (kPa)

Horizon. 0 25 50 75 100 125 150 175
depth (cm)

Ah
25 Natural forest

Tractor 100
Al
60 Combine harv.
15 Mg
Bt
Combine harv.
25 Mg
100 Sugar beet harv.
Cv 147/49 cm
Sugar beet harv.
160/80 cm
Soil strength

(b)

FIGURE 3.17  Modeled stress distribution in a luvisol derived from loess under forest (b) and under conventional tillage (a). The concentration
factors were defined according to the degree of aggregation.
3-20 Properties and Processes

σ1/Pv in kPa (as a function of depth) can be also derived from Figure 3.18
0 100 200 300 400 500 600 (Zink, 2009). The luvisol derived from loess under long-term
0
conventional and conservation tillage management shows lim-
20
ited stress attenuation at given wheel loads with and without
Depth (cm)

40
reduced inflation pressure, which causes irreversible soil defor-
60
mation (stresses exceed the precompression stress).
80 Repeated short-term stress application results in an increase
Conservation tillage
100 in the matric potential and a higher water saturation within
(a)
the various horizons. Consequently, the repeated short-term
0 100 200 300 400 500 600 loading not only weakens the soil structure by deformation but
0
also pumps additional soil water from deeper depths (repeated
20
elastic rebound creates a suction mechanism), which further
Depth (cm)

40
enhances soil deformation. Semmel (1993) could prove that due
60 to repeated wheeling-induced soil softening, horizontal minor
80 stresses decreased while the major vertical stress increased dur-
Conventional tillage
100 ing 50 repeated wheeling events with a 3.7 Mg tractor. The soil
(b)
Soil stability pF 1.8 softening was also reflected by reduced soil strength and an
3.3 Mg; 50 kPa tire inflation pressure
increase in the concentration factor due to repeated wheeling.
3.3 Mg; 160 kPa tire inflation pressure
7.5 Mg; 250 kPa tire inflation pressure The same processes also occur in grassland ecosystems under
7.5 Mg; 350 kPa tire inflation pressure arid conditions during sheep trampling. Krümmelbein et  al.
(2008) could show that in grassland soils, which are intensely
FIGURE 3.18  Comparison of stress attenuation for different wheel loads trampled during winter, soil strength is reduced due to “knead-
and tire-inflation pressures in a luvisol derived from loess under conserva- ing,” which negatively affected hydraulic properties. Also, tree
tion (a) and conventional tillage (b). Dashed and solid lines with symbols harvesting in forest soils causes an intense increase in the pre-
indicate stresses derived from SST (stress rate transducer) measure­ments; compression stresses, formation of deeper ruts, reduced aeration,
solid line without symbol indicates horizon-specific precompression and a restricted plant growth as a result of dynamic soil loading
stresses. (From Zink, A. 2009. Bodenstabilität und Auswirkungen dyna-
(Vossbrink and Horn, 2004; Horn et al., 2007b). The controlled
mischer Lasteinträge auf physikalische Eigenschaften von Ackerböden
traffic lane concept could prevent large-scale soil deformation by
unter konservierender und konventioneller Bodenbearbeitung. Ph.D.
Thesis. Schriftenreihe Institut für Pflanzenernährung und Bodenkunde, restricting mechanical stresses to defined lanes, hence protect-
Germany, No. 84, 180 pp. ISSN: 0933-680X.) ing arable and forest land even during intensive future land use
(Alakukku et al., 2003; Chamen et al., 2003; Watts et al., 2005).
except for the Ap horizon and a more complete stress attenu- An interesting aspect of soil deformation caused by extremely
ation apart from the homogenized seedbed. However, the first heavy loads is shown in Figure 3.19. During a first time wheel-
introduction of the heavier sugar beet harvesters caused a ing event with a sugar beet harvester (35 Mg), a formerly formed
deeper and a more intense soil deformation while exceeding the rigid plow pan layer lying on top of a weaker subsoil may even
corresponding actual soil strength (Peth et al., 2006). The effect be destroyed by breaking the platy structure due to shear stress
of stress attenuation depending on soil structure and strength concentrations in the plow pan (Fazekas, 2005; Peth et al., 2006).

Loose topsoil

Compacted topsoil

Broken and curved plates Plow pan

Deeper compacted Compacted subsoil

subsoil

FIGURE 3.19  Schematic sketch of stress-induced changes in the plow pan layer as a consequence of the initial wheeling with a heavy sugar
beet harvester. (Modified from Fazekas, O. 2005. Bedeutung von Bodenstruktur und Wasserspannung als stabilisierende Kenngrößen gegen
intensive mechanische Belastungen in einer Parabraunerde aus Löss unter Pflug- und Mulchsaat. Ph.D. Thesis. Schriftenreihe des Institut für
Pflanzenernährung und Bodenkunde, Germany, No. 67, 170 pp. ISSN: 0933-680X.)
Mechanics of Unsaturated Soils for Agricultural Applications 3-21

Repeated wheeling of such a site may then result in deeper stress Wheel load (Mg)
penetration and consequently aggravates subsoil compaction. 3.3 6.5 7.5 3.3 6.5 7.5
–20
3.5.3  Effect of Stress Application on Soil Strain

Vertical soil movement of SST sensor (cm)

If external stress is smaller than internal soil strength, no defor- –20.5
mation results and vice versa. However, because the latter includes
soil compaction and shear processes, both the rut depth and the
–21
vertical movement of a given soil volume below the rut must be
known if we want to distinguish between both processes. The
extent to which soil deformation occurs during traffic and the –21.5
= Plastic deformation part
extent to which various tillage implements (­conventional/conser-
vation) deform a soil at a given pore water pressure are shown in = Position of sensor after wheel pass
–22
Figure 3.20. In the conventional tillage treatment in a loessial luvi- = Elastic deformation part (rebound)
sol, passage of a tractor (front/rear wheel) results in a pronounced
vertical (up to 8 cm) and horizontal forward and backward (up to
2 cm) displacement. Under conservation tillage, the same tractor –40
results in smaller soil deformations because of a higher internal
–40.5
Soil surface
100 Wheeling direction Tillage: Conservation Conventional
0
Conventional tillage FIGURE 3.21  Vertical-elastic (reversible) and plastic (irreversible)
Vertical displacement (mm)

soil displacement in a luvisol derived from loess for different wheel loads
–20 Front wheel
and management systems. Soil movement has been measured with a
DTS/SST (displacement transmitter/stress state transducer system).
–40 (From Zink, A. 2009. Bodenstabilität und Auswirkungen dynamischer
Rear wheel Lasteinträge auf physikalische Eigenschaften von Ackerböden unter
–60 konservierender und konventioneller Bodenbearbeitung. Ph.D. Thesis.
Schriftenreihe Institut für Pflanzenernährung und Bodenkunde,
–80 1 Pass Germany, No. 84, 180 pp. ISSN: 0933-680X.)
3 Pass
soil strength leading to a maximum vertical displacement of
–100 –80 –60 –40 –20 0 20 40 60 <4 cm after three traffic events and a much less pronounced hori-
(a) Horizontal displacement (mm) zontal displacement. With increasing aggregate development, soil
Soil surface strength increases and aggregate deterioration is less pronounced
100
Wheeling direction during displacement and alteration of the pore system due to the
0 infilling of interaggregate pores by smaller particles. Nevertheless,
Conservation tillage Front wheel
all stresses that are not attenuated to levels below soil strength
Vertical displacement (mm)

–20 result in volume alterations, even if the applied stresses vary for
Rear wheel
different soil types, land uses, tillage systems, and environmental
–40 conditions. The intense effect of wheel load on soil strain down to
40 cm depth in luvisols derived from loess under conventional and
–60 conservation management depicts the sensitivity of stress applica-
tion on changes in the pore system (Figure 3.21). With increasing
–80 wheel load at a given soil stress, the vertical height change is more
intense under conventional than under long-term conservation
tillage practice and affects also deeper soil depths irreversibly,
–100 –80 –60 –40 –20 0 20 40 60 which was also stated by Richards and Peth (2009).
(b) Horizontal displacement (mm)
Wheel load: 5 t
Water suction: –60 hPa 3.6  Soil Deformation and its Effects
FIGURE 3.20  Strain distribution in structured soils due to traffic. on Physical and Physicochemical
Particle movement is more pronounced in the conventionally tilled luvisol Properties
(a) while soil deformation is less intensive in the conservation tillage plot
(b). (From Wiermann, C., D. Werner, R. Horn, J. Rostek, and B. Werner. At mechanical failure, physical, chemical, and biological as well as
2000. Stress/strain processes in a structured unsaturated silty loam Luvisol physicochemical properties are affected. Stepniewski et al. (1994),
under different tillage treatments in Germany. Soil Till. Res. 53:117–128.) Pagliai and Jones (2002), Lipiec and Hatano (2003), Lipiec et al.
3-22 Properties and Processes

(2004), and Horn et  al. (2006) summed up the present knowl- 450
8 cm depth 12 cm depth
edge and underline the detrimental effects of soil deformation on 400
physical, chemical, and biological soil properties and functions. 350

Redox potential (mV)

Larink et al. (2001) and Langmaack et al. (2002) emphasize the 300
stress effect on biological activity and regeneration after stress 250
application and observed an intense change in species abun- 200
dances. Numerous papers defined in addition the effect of soil 150
deformation of penetration resistance, which is often primarily 100
linked with root growth, but these data can also be used to define 50
in situ “stresses at rest” as a measure of the actual compression
0
status of plots, fields, or even landscapes (Horn et al., 2007a). 0 12 0 35 0 47 0
Concerning changes in hydraulic properties under static load- Mechanical stress (kPa)
ing, which are of main importance for numerous processes, it
becomes obvious that both capacity properties like pore-size FIGURE 3.23  Changes in redox potential as a function of load in
two soils depths. (Data from Horn, R. 1985a. Auswirkung mecha-
distribution (water retention characteristic) and intensity rela-
nischer Belastungen auf die Redoxpotentiale von 3 Bodenmonolithen-
tions like the unsaturated hydraulic conductivity function show a
ein Laborversuch. J. Plant Nutr. Soil Sci./Z. Pflanzenernahr. Bodenkd.
severe change with applied stress (Figure 3.22; Horn et al., 1995). 148:47–53.)

Identical diagrams are also prepared for gas diffusion (Glinski

0.5
and Stepniewski, 1985), thermal properties, and also redox reac-
0.45 tions where a more intense stress dependency with remain-
ing smaller values is shown when the internal soil strength is
Water content (cm3 cm–3)

0.4
exceeded (Figure 3.23). A direct link between the mechanical
0.35 stress application and increased denitrification rates was pre-
sented by Flessa et al. (1998) and Liu et al. (2007).
0.3 However, not only these general changes, but also alterations
0.25 in vector properties of, for example, the hydraulic conductivity
(Doerner, 2005; Doerner and Horn 2009), reflect the strong effect
0.2 of stress–strain processes on soil functions. Wheeling-induced
0.15 formation of platy structures results in a pronounced horizontal
anisotropy of the hydraulic conductivity and intensifies lateral
0.1 water and solute movement, which enhances soil erosion and
0/∞ 2 4 6 pF
nutrient export. Particularly, shear-induced strain processes lead
to changes in transport functions also with consequences for gas
(a) Stress (kPa) 0 20 50 150 400
fluxes and compositions due to more pronounced flow path tor-
tuosities and reduced pore connectivity, which can be observed
–2
down to the aggregate scale (Ball et al., 1999; Peth et al., 2008).
Hydraulic conductivity log (cm s–1)

–3

–4
3.7  Modeling Soil Deformation
–5
and Coupled Processes
–6
In unsaturated structured soils, hydraulic, thermal, and/or
–7 gas transport processes must be mutually linked in order to
fully account for deformation-induced changes in soil func-
–8
tions. Especially, hydraulic and mechanical processes are tied
–9 up closely. This is evident for example in the action of hydrau-
lic stresses during shrinking and swelling and their conse-
–10 quences for soil strength or in the role of pore water pressures
0 20 40 60 80 100
Water suction (kPa) on consolidation and compression (effective stress theory).
Stress (kPa) 0 20 50 150 400
On the other hand, soil deformation and reorientation of par-
(b)
ticles and aggregates influence pore-size distribution and pore-
FIGURE 3.22  Change in water retention characteristic (a) and unsat- network geometries. Hence, hydraulic conductivity within the
urated hydraulic conductivity (b) as a function of applied mechanical matrix and structural pores is changed, which finally affects, in
stresses. turn, hydraulic stresses and subsequent deformation behavior.
Mechanics of Unsaturated Soils for Agricultural Applications 3-23

The  mathematical equations for water, gas, and heat trans- swelling soils. The model was later further improved by Gräsle
port in soils and the effects of tillage on changes in structure (1999) and tested by simulating standard mechanical laboratory
are available (Jury et  al., 1991). However, often physical soil tests. The modeling concepts Richards developed over decades
behavior is still investigated by treating either process in isola- are summarized in Richards and Peth (2009), including some
tion rather than accounting for their interdependency (Kirby, model applications for civil engineering and soil science prob-
1994; Kirby et  al., 1997; Keller et  al., 2007b). Richards (1992) lems. A detailed conceptual framework for modeling coupled
proposed a finite element model that was able to interactively soil mechanical and hydraulic processes in soils is represented
couple load deformation and flow processes in unsaturated and in Figure 3.24 (Gräsle et al., 1995). O’Sullivan and Simota (1995)

Instationary model for water flow

Volumetric water content Hydraulic potential

boundary conditions boundary conditions
Θb(x, t) Ψb(x, t)
Change in
volumetric water
content
∂Θ(x, t) Volumetric water content
∂t Θ(x, t)

Gradient of
Water flow hydraulic potential Hydraulic potential
J(x, t) Ψ(x, t) Ψ (x, t, Θ(x, t), e(x, t), ...)

Tensor of hydraulic conductivity

Ku(x, t, Ψ(x, t), e(x, t), ...)

Porosity
e(x, t)

Change in porosity
∂e(x, t) Structure
∂t

Strain tensor Stress tensor

ε(x, t) Bulk modulus σ(x, t)
Ke(x, t, σ(x, t), ε(x, t),Ψ(x, t), ...) Effective stress tensor
Shear modulus σe (x, t, Ψ(x, t))
G(x, t, σ(x, t), ε(x, t), Ψ(x, t), ...)
Shear strength
τf (x, t, σ(x, t), ε(x, t), Ψ(x, t), ...)
Displacement Stress
boundary conditions Tensile strength boundary conditions
db(x, t) σf (x, t, σ(x, t), ε(x, t), Ψ(x, t), ...) σb(x, t)

Quasistatic model for stress and strain

Hydraulic or mechanical processes only

Coupling due to changes in porosity or hydraulic potential
Coupling due to shearing and failure processes

FIGURE 3.24  Schematic representation of a coupled hydraulic elastoplastic model to define and quantify coupled processes in soils. (From
Gräsle, W. T. Baumgartl, R. Horn, and B.G. Richards. 1995. Interaction between soil mechanical properties of structured soils and hydraulic
process—Theoretical fundamentals of a model. Balkema 2, p. 719–724. In E.E. Alonso and P. Delage (eds.) Proc. First Int. Conf. Unsaturated Soils/
UNSAT’95, September 6–8, Paris, France. Balkema, Rotterdam, the Netherlands.)
3-24 Properties and Processes

and Defossez and Richard (2002) have reviewed some soil com- σ1 (kPa)
paction models and discussed problems when combining them 0 50 100 150 200 250 300 350 400 450
0
with environmental impact and crop production models.
–5
3.7.1  Deformation and Failure

Settlement (mm)
–10
This process describes the load/deformation/failure response Original height of the
of soil to a change in stress, strain, and/or displacement with –15 tested undisturbed
all other factors held constant. It includes (1) nonlinear elastic soil sample = 30 mm
behavior of the material as a function of stress and its history –20
and matric potential (Richards, 1978); (2) changes in initial
stress or strain as a result of swell/shrink behavior caused by –25 Measured
Modeled
changes in soil water suction, solute content, or temperature
(Richards, 1986); (3) stress/strain path dependency or hysteretic –30
behavior in load-deformation response (Richards, 1979); and FIGURE 3.25  Measured and simulated settlement of a consolidation
(4) shear and tensile failure with dilatance or compression and test (oedometer). The ordinate has been scaled to the original height of
with strain softening. the tested undisturbed soil sample (30 mm). (From Richards, B.G., and
S. Peth. 2009. Modelling soil physical behaviour with particular refer-
ence to soil science. Soil Till. Res. 102:216–224.)
3.7.2  Coupling Soil Mechanical
and Hydraulic Processes
strength with depth including the mechanical history of the
During any kind of soil deformation, changes in hydraulic prop-
soil (precompression stress). A comparison of measured stress
erties will occur, which is an important factor influencing the
(stress state transducer [SST]) data from a traffic experiment on
further deformation process as pointed out in the effective stress
a conservation tillage plot (shallow chiseling up to 8 cm, luvi-
equation of Terzaghi Equation 3.1. In addition, changes in soil
sol derived from glacial till) with stress distributions simulated
stress due to swelling or shrinkage will also cause changes in
by FEM using the mechanical parameters derived for three soil
soil water potential. This effect of stress on water potential is
horizons of the corresponding soil profile is shown in Figure
sometimes referred to as the stress potential or the stress com-
3.26. Simulations including and excluding the plow pan layer,
ponent of field measurements of soil water suction (Richards,
which was encountered in 20–40 cm soil depth, indicate that no
1986). Load-deformation analysis must therefore be coupled
good agreement between the measured and simulated stresses
with changes in soil water potential, including subsequent water
was obtained when the plow pan was not included in the FEM
flow (Figure 3.24). The displacements can also be used to calcu-
simulation. In contrast, if the corresponding mechanical data of
late the new geometry and material velocities for the analysis of
the plow pan were included in the simulation, then a reasonably
water flow in soils undergoing strain. Such analysis can be also
good agreement between the stress measurements and model
extended to 3D flow problems, which are of interest in the plow
prediction would be obtained (Figure 3.26). Similar examples
pan and in well-structured horizons below.
of the simulation of stress distributions under tires using this
FEM approach in conjunction with parameter estimations from
3.7.3  Example Application of the Finite mechanical laboratory testing are given in Peth et al. (2006) and
Element Model Richards and Peth (2009).

Modeling soil stiffness for various horizons with differing 3.8  Concluding Remarks
mechanical properties and the overall stress–strain relationships
of a complete soil profile requires the derivation of stress-depen- 1. Mechanical soil properties are useful indicators for the
dent moduli (bulk K and shear G modulus, see Section 3.2.3). development and physical quality of soil structure.
The mechanical material properties defined by K and G may be 2. The determination of soil strength requires the measure-
determined by back-analyzing consolidation and shear test data ment of volumetric stress and strain.
(Richards et al., 1997). In this approach, the soil test is simulated 3. Structure development in arable and forest soils always
with an FEM using an initial estimate of the material parameters, results in increased soil strength. With increased aggre-
which are subsequently modified until a good agreement between gation, strength increases and the characteristics of the
modeled and measured test data is achieved. An example where water retention curve become more pronounced.
a consolidation test has been simulated is shown in Figure 3.25. 4. In structured soils, hydraulic properties of inter- and intra-
Such stress-dependent mechanical soil properties may be used aggregate pores are different. Differences in hydraulic con-
to calculate stress distribution under loads within a soil profile ductivity, plant available water, and air capacity become
more accurately accounting for differences in soil stiffness and more pronounced as structure development  increases.
Mechanics of Unsaturated Soils for Agricultural Applications 3-25

4
Depth (dm)

8
SST-measurement
SST-measurement FEM without plow pan
FEM without plow pan FEM with plow pan (20–40 cm)

0 100 200 300 400 500 0 100 200 300 400 500
(a) Vertical stress (kPa) (b) Vertical stress (kPa)

FIGURE 3.26  Determined and modeled vertical stress versus depth in a luvisol derived from glacial till under conservation tillage (type Horsch).
The properties of a plow pan layer, which had been created until 1989 and which had a thickness of 20 cm (from 20 to 40 cm were not (a) and were (b)
included in the model). (Data from Kühner, S. 1997. Simultane Messung von Spannungen und Bodenbewegungen bei statischen und dynamischen
Belastungen zur Abschätzung der dadurch induzierten Bodenbeanspruchung. Ph.D. Thesis. Schriftenreihe des Institut für Pflanzenernährung und
Bodenkunde, Germany, 39, 190 pp. ISSN: 0933-680X.)

In  addition, root penetrability is reduced into aggregate 8. Structure development always involves reduced accessibil-
interiors but may be enhanced in cracks of the interag- ity to exchange sites for soil solutions, retarded exchange
gregate pore space. processes, and stronger chemical disequilibrium. Only
5. The increase in strength with decreasing pore water pres- at the lowest entropy (at an increased accessibility),
sure depends on the pattern of the water retention curve structured soils become macroscopically homogeneous.
for single aggregates and bulk soil. With reduced pore water potential (reduced flux rate),
6. With increasing degree of aggregation, pore water pres- the exchange process becomes more complete. At higher
sure at the same water content in the bulk soil becomes saturations, anaerobic soil volumes in aggregates become
more negative. Single aggregates are always stronger than more extensive for longer periods. Thus, soil physico-
the bulk soil or the homogenized material. This is related chemical properties vary intensely throughout the year.
to smaller increases in pore water pressure during load- 9. The coupled analysis of multifunctional and interactive pro-
ing and higher aggregate bulk densities. Shear strength cesses in unsaturated structured soils is an important topic
parameters (angle of internal friction and cohesion) are for future soil research but very complex. Long-term soil
always higher for single aggregates than for bulk soil. stability involves materials, which are unsaturated, nonlin-
However, as soon as applied stress exceeds the internal ear hysteretic, and the soil composition changes with time.
soil strength, single aggregate and aggregated bulk soils During tillage operations, many physical and mechanical
will become homogenized accompanied by a decline in properties are altered requiring a more precise definition of
strength. the actual conditions and their expected temporal changes.
7. Soil strength is strongly affected by spatial differences in 10. Measurements and modeling of coupled ion and water
pore water pressure. Hydraulic properties of single aggre- fluxes through unsaturated structured soils are most
gates and their arrangement in the bulk soil are therefore important for future work because aggregation affects
most important for predicting soil strength and stress ion diffusion, dispersion, and mass flow. Changes in
distributions in soils. Stress attenuation, stress distribu- pore systems and functions are also affected by mechani-
tion, and soil deformation due to loading under running cal stresses. Thus, model coupling is required and could
wheels or belts can vary to a great extent depending on in enhance the estimate of time-dependent effects on nutri-
situ soil conditions, machinery parameters, and frequency ent, heavy metal, or pesticide transport through struc-
of loading. Soil deformation should therefore be consid- tured soils also including the effect of drying or wetting or
ered as a dynamic rather than a static process. deformation (compaction) processes.
3-26 Properties and Processes

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Markgraf, W., R. Horn, and S. Peth. 2006. An approach to rhe- based microtomography. Soil Sci. Soc. Am. J. 72:897–907.
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Mezger, T. 2006. The rheology handbook. Vincentz, Hannover, Peth, S., J. Rostek, A. Zink, A. Mordhorst, and R. Horn. 2010. Soil
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171:936–944. tions in swelling soils. Aust. J. Soil Res. 24:457–467.
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 4
Soil Water Content and Water
Potential Relationships
4.1 Introduction..............................................................................................................................4-1
4.2 Soil Water Content...................................................................................................................4-1
Definitions  •  Measurement of Soil Water Content  •  Applications of Soil Water
Dani Or
Content Information
Eidgenössische Technische
Hochschule Zürich 4.3 Soil Water Energy................................................................................................................... 4-11
Total Soil Water Potential and Its Components  •  Interfacial Forces and Capillarity  •
Jon M. Wraith The Capillary Model  •  Measurement of Soil Water Potential Components
University of New Hampshire 4.4 Soil Water Content—Energy Relationships........................................................................4-20
Soil Water Characteristic  •  Measurement of SWC Relationships  •  Fitting Parametric SWC
David A. Robinson Expressions to Measured Data  •  Hysteresis in the Soil–Water Characteristic Relation
Centre for Ecology & Hydrology
4.5 Resources.................................................................................................................................4-23
Scott B. Jones Acknowledgments..............................................................................................................................4-24
Utah State University References............................................................................................................................................4-24

4.1  Introduction The purpose of this chapter is to introduce the basic concepts
related to the amount and energy state of water in soil. These
Water in soil occupies pore spaces that arise from the physical concepts are prerequisite to quantify and manage soil water
arrangement of the particulate solid phase, competitively and storage, to obtain predictions concerning rates and directions
often concurrently with the soil gas phase (Chapters 1, 2, and 8). of water flow and solute transport, to utilize soils as building or
While hidden from casual view, substantial volumes of water are foundation materials, and for many other purposes. The term
commonly stored in soils. For example, one hectare of medium- soil water is used here to represent the soil liquid phase, which
textured soil 1 m deep and having field capacity water content is typically a water solution containing dissolved salts, organic
of 20% by volume may store sufficient water to fill 4000 200 L substances, and gases.
barrels. This reservoir serves as a resource pool for plant growth The water status in soils is defined by (1) the amount of
and a substantial buffer in areas having scattered or sporadic water in the soil or soil water content (θ), and (2) the force by
precipitation. Other soil organisms, many of which are benefi- which water is held in the soil matrix, soil energy content or
cial, especially to biogeochemical cycling, also rely heavily on soil water potential (ψ). These soil water attributes are related
the water-holding characteristics of soils for their existence. On to each other through a function known as the soil water char-
the other hand, soil water is a highly dynamic entity, exhibit- acteristic (SWC).
ing substantial variation in both time and space (Western et al.,
2002). This is particularly true near the soil surface and in the
presence of active plant roots. Changes in soil water content and 4.2  Soil Water Content
its energy status affect many soil mechanical properties includ-
ing strength, compactibility, and penetrability, and may cause Many agronomic, hydrologic, and geotechnical practices require
changes in the bulk density of swelling soils. The liquid-phase knowledge of the amount of water contained in a particular soil
characteristics affect the soil gaseous phase and the rates of volume (Robinson et al., 2008b; Vereecken et al., 2008). Some of
exchange between these phases, as well as other important soil the most common methods used to characterize and determine
properties such as the hydraulic conductivity that governs the soil water content, on a mass or volume basis, in the laboratory
rate of water and soluble chemical flow. or in situ will be described.

4-1
4-2 Properties and Processes

4.2.1  Definitions 4.2.1.4  Soil Water Storage

4.2.1.1  Soil Water Content on Mass It is often convenient to express the quantity of soil water in a
Basis (Gravimetric) specific soil depth increment in terms of soil water storage or
equivalent depth of soil water (units of length). Equivalent depth
Mass or gravimetric soil water content is expressed relative to
of soil water, De (m), is calculated as De = θv × D, where D is the
the mass of oven dry soil according to
soil depth increment (m) having volumetric water content θv.
This quantity is useful to relate aboveground water dimensions
water mass ( wet soil mass ) − ( dry soil mass ) of rainfall, irrigation, or evaporation (L) to belowground dimen-
θm = = , (4.1)
dry soil mass dry soil mass sions (θv, m3 water m−3 soil). For example, one may wish to quan-
tify changes in soil water content arising from addition of water
by rainfall or loss of water by evaporation (Chapter 6). A useful
and has units of kg kg−1 or other consistent mass units. rule of thumb is that 1 L of water delivered to 1 m2 of soil is equiv-
alent to a 1 mm depth increment of water. For suitable accuracy,
it is often necessary to sum the equivalent depth relationship
4.2.1.2  Soil Water Content on Volume Basis
over discrete soil depth layers having distinct water contents:
It is often desirable to express water content on a volume basis.
The volumetric water content (θv) is defined as the volume of n

water per bulk volume of soil: De = ∑θ D ,

vi i (4.5)
i =1

volume of water (mass of water/density of water ) where i denotes depth increments.

θv = = .
bulk volume of soil sample volume

(4.2) 4.2.2  Measurement of Soil Water Content
4.2.2.1  Thermogravimetry
It also represents the depth ratio of soil water (i.e., the depth of
water per unit depth of soil). The conversion between gravimet- This is a direct and destructive method whereby a soil sample
ric and volumetric water contents requires knowledge of the soil is obtained by augering or coring into the soil; its volume need
dry bulk density (ρb), which is the ratio of oven dry soil mass not be known. The sample is weighed at its initial wetness and
to its original volume, and the density of water. The conversion then dried to remove interparticle absorbed water, and some,
formula is given by the following: but not always all structural water trapped within clay lattices
known as crystallization water. The conventional protocol is
to oven dry the samples at 105°C until the soil mass becomes
ρb stable; this usually requires 24–48 h or more, depending on the
θ v = θm , (4.3)
ρw sample size, wetness, and soil characteristics (texture, aggrega-
tion, etc.). The difference between the wet and dry weights is the
where ρw is the density of water (1000 kg m−3 at 20°C). mass of water held in the original soil sample (Section 4.2.1.2).
Alternatively, a soil sample of known original volume may be Despite the somewhat arbitrary specification of a standard oven
processed as in the gravimetric method, and θv determined from temperature (105°C) and the variable drying period (depending
Equation 4.2. on specific conditions), the gravimetric method is considered
the standard against which many indirect techniques are cali-
brated. The method is not without bias and/or error, however,
4.2.1.3  Water Content on Relative Saturation Basis and Gardner (1986) discussed some sources of these including
the potential for water loss between sampling time and initial
An additional means of characterizing the soil water content is
weighing, precision of the three weights involved (wet, dry, and
in terms of the degree of saturation:
tare), and the unknown amount of soil texture-dependent resid-
ual water associated with the clay fraction.
(volumeof water-filled pore space) θ v The primary advantages of gravimetry are the direct and
Θ= = , (4.4)
total volumeof soil pore spacee θ vs relatively inexpensive processing of samples. The shortcom-

ings of this method are its destruction of the sample location,
labor- and time-intensive nature, the time delay required for
where θvs is volumetric soil water content under completely drying (although this may be shortened by use of a microwave
water-saturated conditions. This index ranges from zero in com- rather than conventional oven, the methodology has not yet
pletely dry soil to unity in a saturated soil. The degree of satu- been standardized), and the fact that the method is destructive
ration is also commonly termed effective saturation or relative thereby prohibiting repetitive measurements within the same
water content. soil volume.
Soil Water Content and Water Potential Relationships 4-3

4.2.2.2  Neutron Scattering Neutron probe calibration Amsterdam silt loam

0.35
This is a nondestructive but indirect method commonly used
0.3 VWC = 0.329(CR) – 0.056
for repetitive field measurement of volumetric water content
R2 = 0.982

VWC (m3 m–3)

(Greacen et al., 1981). It is based on the propensity of H nuclei 0.25
to slow (thermalize) high-energy fast neutrons. A typical neu- 0.2
tron moisture meter consists of (1) a probe containing a radioac- 0.15
tive source that emits high-energy (2–4 MeV) fast (1600 km s−1) 0.1
neutrons, as well as a detector of slow neutrons; (2) a scaler to 0.05
electronically monitor the flux of slow neutrons; and optionally
0
(3) a data logger to facilitate storage and retrieval of data (Figure 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
4.1a). The radioactive source commonly contains a mixture of Count ratio (CR)
241Am and Be at 10–50 mCi. The 241Am emits β particles that

strike the Be and cause emission of fast neutrons. FIGURE 4.2  A neutron moisture meter calibration relationship.
When the probe is lowered into an access tube, fast neutrons
are emitted radially into the soil where they collide with various therefore proportional to the amount of H nuclei in the sur-
atomic nuclei. Collisions with most nuclei are virtually elastic, rounding soil. The primary source of H in soil is water; other
causing only minor loss of kinetic energy by the fast neutrons. sources of H in a given soil are assumed to be constant and are
Collisions with H nuclei, which have similar mass of neutrons, accounted for during calibration. Although several non-H sub-
cause a significant loss of kinetic energy and slow down the fast stances including C, Cd, Bo, Cl, and Li, which may be present in
neutrons (consider a marble [neutron] colliding with a simi- trace amounts in some soils, may also thermalize fast neutrons,
larly sized ball bearing [H nucleus] vs. a stationary bowling ball these may generally also be effectively compensated through
[larger atomic nucleus]). When, as a result of repeated colli- soil-specific calibration.
sions, the speed of fast neutrons diminishes to those at ambi- Calibration of the neutron probe is therefore required to
ent temperature (about 2.7 km s−1), with corresponding energies account for background H sources and other local effects (soil
of about 0.03 eV, they are called thermalized or slow neutrons. bulk density, trace neutron attenuators), and is conveniently
Thermalized neutrons rapidly form a cloud of nearly constant achieved by paired measurements of soil water content and neu-
density near the probe, where the flux of the slow neutrons is tron probe counts. The calibration curve (Figure 4.2) is usually
measured by the detector. The average loss of the neutrons’ linear and relates θv to slow neutron counts or count ratio (CR):
kinetic energy, thus the relative number of slow neutrons, is
θv = a + b(CR), (4.6)

Neutron
probe
where CR is the ratio of slow neutron counts at a specific loca-
tion in the soil to a standard count obtained with the probe in its
Access tube
cap
shield. For many soils, the calibration relation is approximately
the same. Use of the count ratio rather than raw slow neutron
counts compensates for the slow decay of the radioactive source
Sphere of
Access over time.
influence
tube
The sphere of influence about the radiation source varies
Data logging between about 15 cm (wet soil) and approximately 70 cm (very
display
Dry dry soil), depending on how far fast neutrons must travel in
rD order to collide with a requisite number of H nuclei. An approxi-
mate equation for the radius of influence (r, in cm) as a function
Probe
(source and of soil wetness is (IAEA, 1970):
detector)

rw Frequency r = 15(θv )−1/3 . (4.7)

Wet
domain
reflectometer
Thus, the neutron-scattering method is unsuitable for measure-
(a) (b) ment near the soil surface because a portion of the neutrons may
escape the soil. Advantages of this method include the ability
FIGURE 4.1  An illustration of (a) a neutron probe device for measur-
ing soil water content; symbols rD and rW represent different radii of to repeatedly measure θv at the same locations, averaging of the
measurement in dry and wet soils and (b) an electromagnet-based sen- measured water content over a substantial soil volume, moderate
sor using frequency domain reflectometry (Diviner 2000, Sentek Sensor equipment cost (generally about $4000–$6000), and the ability
Technologies, Stepney, Australia, with permission) to determine soil to measure soil water content at multiple depths and locations
water content in an access tube. using the same equipment. Limitations or disadvantages include
4-4 Properties and Processes

the radiation hazard and attendant licensing requirements, rela- been used to establish the relationship between εeff and θv. The
tively poor (and uncertain) spatial resolution, unsuitability for first approach is empirical, whereby mathematical expressions
near-surface measurements, and the soil-specific calibration are simply fitted to observed data without using any particu-
requirement. lar physical model. For example, Topp et al. (1980) found good
agreement using a third-order polynomial between apparent
4.2.2.3  Electric and Dielectric Methods dielectric constant (κa) and θv for a range of soils:
Measurement methods based on changes in soil electrical prop-
−2 −2 −4 2 −6 3
erties, due to changes in soil water content, have been used for θ v = −5.3 × 10 + 2.92 × 10 κ a − 5.5 × 10 κ a + 4.3 × 10 κ a ,
decades (Smith-Rose, 1934; Babb, 1951), mostly in the area of (4.8)
agriculture and exploration geophysics. Background informa-
tion concerning such applications may be found in a number of where κ is used to differentiate a measured value from the
sources, including Olhoeft (1985), who addressed low-frequency intrinsic material value εeff. This relationship provides adequate
electrical properties of porous media, Selig and Mansukhani description for many mineral soils and for the water content
(1975), who discussed early attempts to use resistance and range θ < 0.5 (which covers the entire range of interest in most
capacitance techniques for soil water content measurements, mineral soils), with an estimation error of about 0.013 for θv.
and Hoekstra and Delaney (1974) concerning soil dielectric However, Equation 4.8 fails to adequately describe the κa−θv
properties at very high frequencies. Presently, the most common relationship for water contents exceeding 0.5, and for organic
electrical approaches for soil water content measurement may rich soils, mainly because the Topp et al. calibration was based
be grouped according to (1) time domain dielectric methods on experimental results for mineral soils and concentrated in
(Topp et al., 1980; Robinson et al., 2003), (2) capacitance meth- the range of θv < 0.5.
ods (Dean et al., 1987; Paltineanu and Starr, 1997), (3) fixed fre- The second approach uses dielectric mixing models and
quency methods (Blonquist et al., 2005a), (4) resistance methods the volume fraction of each of the soil phases to derive a pre-
(Spaans and Baker, 1992; Leib et al., 2003), (5) geophysical elec- dictive relationship between εeff and θv. In many soils κa =
trical methods (Robinson et al., 2008a), and (6) remote-sensing εeff, but as bulk soil electrical conductivity (ECa) increases
methods (Moran et al., 2004). so κa may diverge from εeff on an instrument-dependent basis
Determination of dielectric properties is the physical prin- (Kelleners et al., 2005). Such physically based approaches
ciple that underlies many of these methods to determine water vary in their degree of complexity and have been presented
content. In the megahertz region of the electromagnetic spec- by a number of authors (Dobson et al., 1985; Friedman, 1998;
trum, the dielectric values for solid, water, and air are relatively Cosenza et al., 2003).
frequency independent (Figure 4.3). As the dielectric value of Of the physically based models, Robinson et al. (2005) pre-
water is ∼80 and that of solid and air is ∼5 and 1, respectively, the sented a layer model for coarse-textured soils. The result was a
proportion of water in a porous material has a dominant effect formula for determining water content based on εeff, the measured
on the effective dielectric value (εeff ). Two basic approaches have porosity φ, and the saturated (εsat) and dry (εdry) dielectric values.

120.0
Real dielectric value water
L-Band
Imaginary dielectric value water
100.0 GPR Saturated quartz sand
TDR/TDT Air dry smectitic clay soil
80.0
Unsaturated smectitic clay soil
Permittivity

E20 HP TP
60.0 ES Saturated smectitic clay soil
EC-5
40.0 E20 ECH2O-20
HP Hydraprobe
TP Thetaprobe
20.0
ES Enviroscan
EC5 ECH2O-EC5
0.0 GPR Ground penetrating radar
1.E+06 1.E+07 1.E+08 1.E+09 1.E+10 1.E+11 TDR Time domain reflectometry
Frequency (Hz) TDT Time domain transmission
L-Band active remote sensing

FIGURE 4.3  A frequency domain diagram showing the permittivity/dielectric spectrum of water, the real part (ε′) indicating energy “storage,”
and the imaginary part (ε″) indicating energy “loss.” Data are presented for sand and for clay with varying degrees of saturation. The change in clay
permittivity response with frequency is called dielectric dispersion. The boxes with symbols indicate the approximate frequency and bandwidth
for the corresponding sensing methods.
Soil Water Content and Water Potential Relationships 4-5

Assuming a value of 2.8 for εdry, the model only requires that the and the one applied by Dobson et al. (1985) and Dirksen and
porosity and εsat be known to determine the water content. Dasberg (1993), which adds a “bound” water phase, written as

⎛ ε eff − ε dry ⎞
θ = ϕ⎜ ⎟ . (4.9) (3(ε s − ε eff ) + 2θ bw (ε bw − ε fw ) + 2ϕs (ε a − ε s )
⎜⎝ ε sat − ε dry ⎟⎠ + ε eff θ bw (ε s /ε fw − ε s /ε bw ) − ε eff ϕs (ε s /ε a − 1))
θ= , θ > θ bw ,
(ε eff (ε s /ε fw − ε s /ε a ) + 2(ε a − ε fw ))
A more sophisticated version of the model was presented in (4.11)
Robinson et al. (2005), where additional mixing models were
used to calculate εsat and εdry, resulting in a physically based
model with no fitting parameters that accurately described the where
εeff − θv relationship in media with different solid-phase dielec- φs is the solid volume fraction
tric values. The advantages of the mixing model approach are subscripts of ε define the solid phase, s, gas phase, g, free
that it is based on physics and is therefore instrument or sen- water phase, fw, and bound water phase, bw (∼4.2)
sor independent and it provides the flexibility to include vari-
able mineral phase dielectric values, temperature and frequency The volumetric bound water content, θbw, assumes a monomo-
effects, and geometry and porosity effects. This is illustrated for lecular layer of tightly bound water of a thickness δ = 3 × 10−10 m
a range of porosity in Figure 4.4. spread over the soil-specific surface area, S (cm2 g−1), for a bulk
Clay minerals, especially the 2:1 smectites and vermiculites, density, ρb (g cm−3) (i.e., θbw = δ × ρb × S).
can give a frequency dependent dielectric response (Figure 4.3). Due to the broad applicability of these models for under-
As a result, they can give εeff − θv responses that diverge from standing measurements made using time domain reflectome-
standard empirical models such as Equation 4.8, generally giving try (TDR), insertion probes, ground penetrating radar (GPR),
lower εeff values for a respective value of θv. De Loor (1968) pre- and remote sensing, significant effort has been made in try-
sented a model to describe the effective dielectric value (εeff ) of the ing to improve our understanding of the dielectric proper-
soil, which assumes a consistency of isotropically mixed plate-like ties of porous media. Recent attempts to better understand
particles, suitable for describing clays. The model can take two the dielectric behavior of soils and porous media include,
forms, a simplified version including solid, water, and air phases: particle-size distribution (Robinson and Friedman, 2001),
particle geometry (Friedman and Robinson, 2002; Chen
and Or, 2006), soil temperature (Or and Wraith, 1999), fre-
3(ε s − ε eff ) + 2ϕs (ε a − ε s ) − ε eff ϕs (ε s /ε a − 1) quency dependence (Chen and Or, 2006), and dielectric phase
θ= , (4.10)
ε eff (ε s /ε fw − ε s /ε a ) + 2(ε a − ε fw ) configuration in aggregated media (Miyamoto et al., 2003;
Blonquist et al., 2006). For a long time, bound water was pro-
posed as the physical reason for the lower dielectric responses
40
of clay soils (Jones and Or, 2003), but more recent literature
Sandy soil
suggests that particle shape, orientation (Jones and Friedman,
35 Modeled
Model prediction = 0.4 2000), and phase configuration (Blonquist et al., 2006) must
30 Model prediction = 0.5 also be considered.
Model prediction = 0.6
Effective permittivity

25
4.2.2.4  T ime Domain Reflectometry and Time
20 Domain Transmissometry
Progress in devices for accurate measurement of reflected
15
electromagnetic signals traveling along transmission lines led
10 to the introduction of several measurement methods for soil
dielectric properties using transmission lines embedded in
5 the soil, such as TDR (Topp and Ferré, 2002; Robinson et al.,
2003). TDR measures the apparent dielectric constant of the
0 soil (κa) surrounding a TDR probe, at microwave frequencies
0 0.1 0.2 0.3 0.4 0.5 0.6 from megahertz to gigahertz (Figure 4.3). The propagation
Volumetric water content velocity (v) of an electromagnetic wave along a transmission
FIGURE 4.4  The dielectric water content relationship modeled using line (TDR probe) of length L embedded in the soil is deter-
the approach described in Robinson et al. (2005). The different lines mined from the time response of the system to a pulse gen-
indicate the change in calibration due to the change in porosity. erated by the TDR cable tester (Figure 4.5). The propagation
4-6 Properties and Processes

Time domain reflectometry unit

Signal propagates down the coaxial cable and is reflected from

Timing the end of the probe electrodes back to the sampling unit

Sampling
Pulser
unit Coaxial cable

Step voltage pulse Probe head

generated in the
pulser TDR probe electrodes
Amplitude

in the soil
Oscilloscope
display
Time

FIGURE 4.5  Schematic diagram of a TDR instrument attached via a coaxial cable to a three-rod TDR probe.

velocity (v = 2L/t) is a function of the apparent dielectric 4.2.2.5  Capacitance Probes

response of the soil according to The electrical capacitance of two electrodes inserted in the soil is
dependent upon the soil dielectric constant. The basic relation-
2 2
⎛ c ⎞ ⎛ ct ⎞ ship between the soil dielectric constant and the electrical capac-
κa = ⎜ ⎟ = ⎜ ⎟ , (4.12)
⎝ v ⎠ ⎝ 2L ⎠ itance between two parallel plates of area A and spacing d is

Aε* ε 0
where C= , (4.13)
c is the velocity of electromagnetic waves in vacuum (3 × 108 d
m s−1)
t is the travel time for the pulse to traverse the length of the where
embedded TDR probe in both directions (down and back) ε* is the relative complex dielectric constant of the soil, which
contains both real (ε′) and imaginary (ε″) components
A comprehensive body of literature now exists on TDR, and (Figure 4.3), with ε* = ε′ − iε″, i = √−1
especially the electrode sampling volume (Ferre et al., 1998). ε0 the dielectric constant of free space = 8.854 × 108 F m−1
The main advantages of TDR over other methods for repeti-
tive soil water content measurement are (1) superior accuracy to Note that the relative dielectric constant (ε*) is the ratio of
within 1% or 2% of θv, (2) minimal calibration requirements (in the complex dielectric constant to that of free space = ε*/ε0.
many cases soil-specific calibration is not needed), (3) no radia- Capacitance devices for field water content measurement are
tion hazards associated with neutron probe or gamma attenu- often based on annular electrode design rather than parallel
ation techniques, (4) excellent spatial and temporal resolution, plates (Kutilek and Nielsen, 1994; Fares and Polyakov, 2006)
and (5) simple to obtain continuous soil water measurements to facilitate depth measurements down boreholes (Dean et al.,
through automation and multiplexing (Baker and Allamaras, 1987; Figure 4.1b).
(1990)). Limitations of the TDR method include relatively high Commercial capacitance soil water gauges often use a reso-
equipment expense, limited applicability under highly saline nant LC circuit relating changes in resonant frequency of the
conditions due to signal attenuation, and the soil-specific cali- circuit to changes in the soil capacitance (Kelleners et al., 2004).
bration required for soils with high clay or organic matter con- Some gauges use a more direct capacitance bridge method to
tents. Severe attenuation of TDR waveforms in the presence of determine the unknown soil capacitance. Among the common
high salinity and/or some clays having high surface area and capacitance-based measurement systems capable of soil water
surface charge may interfere with, or even preclude, water con- content profiling are the Sentry 200-AP (Troxler, NC) evalu-
tent measurements. ated by Evett and Steiner (1995), which uses access tubes and a
Time domain transmission (TDT) sensors have more recently permanently installed modular bank of sensors (EnviroSCAN,
emerged (Blonquist et al., 2005b) as low cost, stand-alone sen- Sentek, Australia) evaluated by Paltineanu and Starr (1997).
sors that have comparable measurement characteristics to TDR. Advantages of capacitance methods include their lack of
These sensors are analogous to TDR, but rather than measur- radiation hazard and lower expense than transmission line
ing the reflected signal, they measure the travel time around an approaches such as TDR. However, research indicates greater
electrode loop buried in the soil. Utilizing SDI-12 digital tech- sensitivity to bulk soil ECa and salinity (Kelleners et al., 2005).
nology, they represent a new generation of multifunctional soil They also share the neutron probe’s variable and uncertain mea-
moisture sensors, also capable of determining bulk soil ECa and surement volume, and annular air gaps around sensors that
soil temperature. utilize access tubes can cause substantial measurement errors.
Soil Water Content and Water Potential Relationships 4-7

Hence, buried probe designs seem to perform more reliably at measurement of electrical resistance within the sensor’s porous
present than those inserted into soil access tubes. Finally, capac- matrix. The commonly used term gypsum block arises from
itance methods share similar issues of relating the measured early models that were in fact made of gypsum (Bouyoucos and
dielectric constant to soil water content as do other dielectric- Mick, 1940), and from the practice of saturating the matrix of
based approaches. many sensors made from alternative materials with gypsum to
buffer local soil ionic effects. The sensor is embedded in the soil
4.2.2.6  Fixed Frequency Insertion Probes and allowed to equilibrate energetically with the soil solution.
Several new sensors and measurement methods are based on The matric potential of water in the sensor is estimated from the
combinations of capacitive, reflective, and frequency-shift prin- measured electrical resistance through previously determined
ciples, all of which are governed by the soil dielectric proper- calibration of the sensor itself (electrical resistance vs. matric
ties. This trend appears highly promising for the development potential). Under equilibrium conditions, the sensor matric
of accurate and cost-effective sensors for soil water content mea- potential is equal to the soil water matric potential; however,
surement. Examples of such stand-alone sensors (Figure  4.6) the sensor water content may be different than that of the soil.
are the ThetaProbe (Gaskin and Miller, 1996) operating at Hence, these measurements are often used to infer soil water
about 100 MHz (Delta-T Devices Ltd, Cambridge, U.K.); the matric potential from which the soil water content may be esti-
50 MHz Hydra Probe (Campbell, 1990; Seyfried and Murdock, mated based on a known relationship between these quantities
2004; Stevens, Beaverton, OR); the 5 MHz ECH2O EC-20 probe (Gardner, 1986). With appropriate calibration for a particular
(McMichael and Lascano, 2003; Decagon Devices, Pullman, soil (sensor electrical resistance vs. soil water content), the sen-
WA), and newer sensors such as the Delta-T SM200 and WET sor can also be used to infer soil water content directly (Kutilek
sensors (Delta-T Devices Ltd, Cambridge, U.K.) both of which and Nielsen, 1994). The main advantages of electrical resistance
operate around 20 MHz and an array of Decagon Devices sen- sensors are their low cost and simple measurement require-
sors including the EC-5, 10-HS, EC-TM, and 5TE, which all ments. Measurements may be obtained using a simple resistance
operate at 70 MHz frequency (Decagon Devices, Pullman, WA). meter or more conveniently acquired automatically using a data
logger. On the other hand, the usual requirement for specific
4.2.2.7  Electrical Resistivity Methods calibration of each individual sensor and for each soil to obtain
Changes in the electrical resistivity of soils with changes in water acceptable accuracy, and lack of sensitivity under wet condi-
content (and with soluble ionic constituents) have been used to tions, render this measurement method appropriate mostly as a
develop simple and inexpensive sensors to infer soil water status. qualitative indicator of soil water status (Spaans and Baker, 1992;
These sensors usually consist of concentric or parallel electrodes Leib et al., 2003).
embedded in a porous matrix and connected to lead wires for
4.2.2.8  Geophysical Methods
The need for water content measurement at intermediate scales,
1 6
such as the field to small watershed scale (Western et al., 2002),
is driving an interest in using geophysical methods to bridge
the gap between point measurements, using sensors such as
2 7
TDR, and spatial measurements, using remote-sensing methods
(Robinson et al., 2008b). Methods such as GPR, electrical resis-
3 8 tivity imaging (ERI), and electromagnetic induction (EMI) have
all been used to determine the spatial patterns of water content.
Unlike many point sensors, where the operation and interpreta-
4 9 tion have become routine, geophysical methods still require a
firm degree of user skill in both operation and interpretation.
However, they offer the advantages of providing more spatially
5 10 dense data and are non- or minimally invasive. Nevertheless,
both ERI and EMI measure bulk soil ECa, with all the associ-
ated problems accompanied by a determination of water content
FIGURE 4.6  Array of different electromagnet-based sensors, which from approximate direct-current (DC) electrical measurements.
use dielectric measurement techniques to determine soil water con- In addition, GPR uses unguided waves that can make soil water
tent. Sensors include (1) TDR probe, (2) Acclima TDT, (3) Campbell
content interpretation more difficult. As a result, the data from
Scientific 650 sensor, (4) Delta T ML2x sensor (Theta probe), (5)
geophysical imaging are often termed “soft data” and used as an
Stevens Water Hydra Probe sensor, (6) Decagon Devices 5TE sensor,
(7) Decagon Devices EC-5 sensor, (8) Decagon Devices 10HS sensor, aid to help interpret more spatially sparse point measurements.
(9) Delta T Devices WET sensor, and (10) Delta T Devices SM200 sen- GPR measures electromagnetic wave propagation time
sor. Measurement techniques include travel-time analysis (1, 2, and 3), through the ground (Huisman et al., 2003a), utilizing the
capacitance measurements (4, 6, 7, 8, 9, and 10), and impedance mea- transmission and reflection of high frequency (1 MHz–1 GHz)
surements (5). electromagnetic waves within the soil. It offers the advantage
4-8 Properties and Processes

of obtaining rapid on-the-go measurement, with penetration measurements also tend to be cost effective and allow measure-
depths dependent on operation frequency and bulk soil ECa. ments in isolated terrain. Dielectric remote-sensing methods
Low frequencies usually equate to greater depths of penetration, can be divided into “passive” and “active” methods.
while soil ECa values >1 dS m−1 (smectitic and saline soils) may Passive methods rely on the sun illuminating the ground
attenuate the signal to such an extent that no valuable informa- surface and measure the naturally emitted radiation from the
tion is obtained (Weihermuller et al., 2007). A variety of methods ground and do not work when it is cloudy. The radiation is
have been adopted to determine water content from GPR data measured using an instrument called a radiometer (Njoku and
and are reviewed in Huisman et al. (2003a) and Annan (2005a, Entekhabi, 1996), and of growing interest are the systems that
2005b). Methods for determining water content include estima- can be building or vehicle mounted. The soil emits radiation that
tion of ground wave velocity (Hubbard et al., 2002; Huisman increases with temperature and is termed the soil emissivity. In
et al., 2003b); common offset profiling (Lunt et al., 2005); com- the microwave region, the dielectric value of the soil, as well as
mon midpoint measurements (Greaves et al., 1996); and surface the surface geometry or roughness, affects how closely the sur-
reflectivity (Redman et al., 2002; Serbin and Or, 2004). face resembles a perfect emitter or blackbody. As a result of the
Both ERI (Samouelian et al., 2005) and EMI (Sheets and dependence of emissivity on dielectric properties, water content
Hendrickx, 1995) determine water content by exploiting changes has a strong impact on measurements (Schmugge et al., 1974;
in soil ECa brought about by changes in water content. However, Hallikainen et al., 1985). The amount of surface soil contribution
soil ECa is temperature, texture, and solute dependent, which to the emission varies with wavelength or frequency, becom-
can make interpretation difficult. Skilled users try to minimize ing thinner as frequency increases. Measuring at a frequency
certain factors, such as temperature effects by measuring at of 1.4 GHz, the emitted radiation is considered sensitive to the
the same time during the day on repeated days, and by avoid- upper 3–5 cm (Laymon et al., 2001).
ing measurements at the hottest times. Determination of water Active sensing methods usually have a source to illuminate
content in soils with few, or no, retained cations, such as many the soil surface and measure the response. Measurements using
highly weathered tropical or coarse-textured soils, often remains active methods are also depth dependent, according to mea-
beyond the limits of these techniques. surement frequency, with L-band (1–2 GHz) being considered
The ERI method uses a low-frequency alternating-current to optimal for soil moisture determination (Entekhabi et al., 2004).
determine the electrical resistivity. Electrodes are evenly spaced Like passive for similar frequencies, the L-band active methods
in soil, often 0.25 to more than 5 m apart along a transect, and are considered to represent a response from the upper 5 cm of
the resistivity is measured between different pairs of electrodes soil. One of the major advantages for the active method is that it
(Samouelian et al., 2005). By increasing the spacing between does not rely on the soil surface being illuminated by the sun and
the measurement electrodes, greater depths of exploration can can operate in almost all weathers. This has led to greater inves-
be achieved. By measuring multiple electrodes simultaneously, tigation of ground-based methods using horn antennas (Lambot
a 2D transect can be rapidly obtained. Successful application et al., 2004, 2006; Serbin and Or, 2004).
has been demonstrated using ERI for water content determi- Common to both measurement methods is the use of the data
nation along transects by Michot et al. (2003) and Amidu and to determine soil moisture, and increasingly data assimilation
Dunbar (2007). methods are being developed to determine dynamic soil mois-
EMI instruments are configured with a receiver at one end ture behavior (Ni-Meister, 2008). Data assimilation allows the
and a transmitter loop at the other. The transmitter is energized merging of observations with a system-dynamic model so that
and creates magnetic field loops that penetrate into the ground. an improved estimate of the soil moisture state can be achieved.
These magnetic loops produce electrical field loops that in turn The direct data insertion approach (Jackson et al., 1981) takes
create a secondary magnetic field. At low induction numbers, remotely sensed soil moisture data and inserts them into the
the combined primary and secondary magnetic fields measured dynamic model when available. However, it does assume that
in the receiver are proportional to the bulk soil ECa (McNeill, remotely sensed observations give the “true” moisture con-
1980). As a result, EMI is noninvasive and can be linked to a tent. More recent developments include the use of the extended
GPS and field computer for the collection of spatial field data. Kalman filter, which is a sequential data assimilation tool,
The use of EMI to determine water content was initially reported providing an optimal estimate for current and future states of
by Kachanoski et al. (1988). Due to the instrument sensitivity a linear system. Hydrological processes are often nonlinear and
to water and clay contents, Abdu et al. (2008) have proposed so efforts have been made to linearize hydrological processes so
using the instrument to estimate soil moisture storage in small that soil moisture data can be used (Walker and Houser, 2001).
watersheds.
4.2.2.10  Heat Pulse Probes
4.2.2.9  Remote-Sensing Methods Determination of water content using soil thermal properties
Remote-sensing methods may be vehicle, aircraft, or satellite is becoming increasingly popular. Water content can be deter-
based. They offer the ability to measure a large spatial area that mined from the volumetric heat capacity (Csoil) or from the soil
is often more appealing to hydrologists in view of the scales at thermal conductivity (λsoil). The soil volumetric heat capacity
which they work (Moran et al., 2004). Airborne or spaceborne can be determined from the sum of the heat capacities of soil
Soil Water Content and Water Potential Relationships 4-9

solid, liquid, and gaseous phases (De Vries, 1963). Campbell The modulus of the magnetization vector aligned with the exter-
(1985) introduced a simplified model for mineral soils Csoil, nal field is proportional to the number of 1H nuclei in the sam-
which disregards the heat capacity of air: ple. Assuming that water content is proportional to the number
of 1H nuclei, the proportion of water can be determined. Hinedi
C soil = C s (1 − ϕ) + C w θ, (4.14) et al. (1993) demonstrated this linear relationship for granular
media in the laboratory and subsequently the technique has
where been increasingly applied to soils by a number of researchers
C is the heat capacity with subscripts w and s for water and (Bird et al., 2005). Field NMR instruments have been developed
solid phases respectively for industrial applications and are described in Wolter and Krus
φ is the porosity (2005). The one-sided access (OSA)-NMR system (Perlo et al.,
2005) is noninvasive and can be placed flat on a surface, mea-
Given the measurement of Csoil using a sensor, θ can be deter- suring water content to a depth of 5–30 mm. Recent advances
mined given the values of Cs and Cw from calorimetric methods have also been made by the oil industry with the development of
(Kluitenberg, 2002). Water content determined from thermal borehole NMR (Kleinberg and Jackson, 2001). The advantage of
conductivity, like ECa and dielectric properties, is dependent these methods is the ability to obtain additional information on
on the pore-scale geometry of the granular material (De Vries, the structure of the porous media (Song et al., 2000).
1963; Campbell, 1985), and is thus soil specific. A critical constraint to advancing field-based process hydrol-
Campbell et al. (1991) proposed the dual-probe heat pulse ogy is the lack of spatially dense data to monitor changes in water
(DPHP) method as a way of determining soil thermal proper- content in time and space. Wireless sensor networks are develop-
ties. The method can measure the C, λ, or thermal diffusivity, α, ing as a new technology that allows sensors to be distributed in
from which θ can be determined. A short heat pulse is applied space, and wirelessly beam back measurements over radio links
from a heater in one of the sensor needles and the temperature to a computer, so that real-time monitoring in time and space
response is measured in a second needle separated by a short can be obtained (Akyildiz et al., 2002; Martinez et al., 2004). Soil
distance. The method has now been tested extensively in the lab- moisture monitoring networks are emerging. Cardell-Oliver
oratory (Bristow et al., 1993; Bristow, 1998; Basinger et al., 2003) et  al. (2005) presented a novel reactive soil moisture network
and in field soils (Tarara and Ham, 1997; Heitman et al., 2003). that captures data with greater frequency in response to rainfall
events. Some of the challenges faced in design and implementa-
4.2.2.11  Emerging and Other Technologies tion are considered in Robinson et al. (2008b).
Laboratory investigations have resulted in a number of tech- Other methods for soil water measurement include gamma ray
niques emerging that are based on sound and light transmis- attenuation techniques using dual-probe apparatus for bulk density
sion. Brutsaert and Luthin (1964) and Mack and Brach (1966) and water content, x-ray computed tomography, and field techniques
were the first to report the sensitivity of acoustic wave propaga- such as distributed fiber optic determination and the geophysical
tion to soil water content. Recent developments include work by use of gravity. Additional information on these and other methods
Adamo et al. (2004) and Blum et al. (2004) with acoustic tomog- may be found in Dane and Topp (2002), Baker (1990), Campbell and
raphy to study unsaturated flow. Recently, Lu (2007) proposed Mulla (1990), Carter (1993), and Robinson et al. (2008a).
that the acoustic properties are more closely related to the matric
potential of the soil than to the water content and thus provide a
4.2.3  Applications of Soil Water
means to determine matric potential over a wide range. The use
Content Information
of light, in particular, measurements of changes in the refractive
index, has proved a valuable laboratory technique for measuring 4.2.3.1  The Water Balance
2D water flow in Hele-Shaw cells. Tidwell and Glass (1994) dem- A primary use of soil water content information is for evaluation
onstrated that using a light source behind a cell and measuring of the hydrologic water balance described by
the transmission the spatial distribution of water content in the
cell can be determined.
P + I = ET + D + R − ΔW, (4.15)
Nuclear magnetic resonance (NMR) was first demonstrated
in 1946 (Purcell, 1952; Bloch, 1953). Gummerson et al. (1979)
were quick to adapt this to imaging unsaturated water flow in where
porous media. Bottomley et al. (1986) later used the technology P is precipitation
to image the water content in root systems. The imaging method I is irrigation
utilizes the fact that the hydrogen nucleus (1H) possesses the ET is evapotranspiration (evaporative water loss from the soil
strongest nuclear magnetic moment. These nuclei are randomly and from plants)
aligned in the absence of a strong magnetic field. On the applica- D is drainage or deep percolation
tion of an external magnetic field, the magnetic moments align R is surface runoff
with the field, antiparallel or parallel. An excess of antiparal- ΔW is change in water storage within the profile (soil water
lel alignment provides a detectable macroscopic magnetization. depletion)
4-10 Properties and Processes

ΔWi = ΔZ*i Δθi presence of impeding layers or a water table, which affect the rate
θ
and extent of water redistribution.
Another often misunderstood soil water content-related index
is the permanent wilting point, which is defined as the water
content at which plants can no longer extract soil water at a rate
sufficient to meet physiological demands imposed by loss of
water to the atmosphere, and thus irreversibly wilt and die. This
water content (θvWP) is primarily dependent on the soil’s ability
Soil depth (Z)

to transmit water, but also to some degree on the plant’s ability

to withstand or mitigate drought. Though commonly taken as
θv at −1.5 MPa (−15 bars) matric potential, there is substantial
Initial θ variation among plant species in their abilities and mechanisms
Final θ
to resist soil drought, with some plants, such as dryland shrubs
and trees, surviving to potentials of approximately −8 MPa, well
below the standard wilting point index. The permanent wilting
ΔW= Σ ΔWi
i point should not be confused with the phenomenon of transient
wilting, which is commonly observed during the afternoon
when evaporative demand is greatest. In this case, plants are able
FIGURE 4.7  Schematic of soil water depletion calculations for a soil
to rehydrate to some extent at night.
profile divided into four depth increments. Total change in water stor-
age is the sum of depletion in each layer. A primary practical use of field capacity and wilting point con-
cepts is the determination of a plant-available soil water range
W is defined as the equivalent depth of water (De) stored in (PASW; Figure 4.8). Soil water storage available for plant use is
the soil profile under consideration and ΔW = (Winitial − Wfinal) generally calculated as being between field capacity and wilting
(Figure 4.7). These parameters are all associated with a given point (θvFC−θvWP), as water contents higher than θvFC, while usu-
specific time interval. The convention used here is that inputs ally plant-available, are generally not sustained for long periods
to the soil profile are taken as positive and outputs negative. of time except under specific circumstances. Plant-available soil
The concept is based on conservation of mass (water) and is water storage is an important factor in the determination of
similar to the familiar exercise of balancing inputs and out- irrigation amounts for a cropped field or other soil–plant sys-
goings from a checking account, for example. Under typical tem. For practical purposes, irrigation amounts in excess of field
conditions, ΔW is fairly significant over the short term (weeks capacity are lost to deep percolation, and thus, should be avoided
to months), but generally evens out to about zero over one to in the interests of water resource efficiency as well as potential
several years. Measurement of water content for water bal- leaching of soluble chemicals (Chapter 7).
ance studies requires the determination of profile soil mois- A useful rule of thumb is to estimate θFC as θs/2, and θWP
ture. An international study (IAEA, 2008) found that the as θFC/2; in other words, a soil exhibiting this property would
neutron probe remains the most accurate and precise method
for the determination of profile soil water content in a range
of soil types. Of the sensors tested, they found that conven- 60
tional TDR and the neutron probe method were the only
indirect methods to have acceptable accuracy for field water 50 ation
balance studies. Satur
Volumetric water content

40 city
4.2.3.2  Field Capacity, Wilting Point, apa
Field c
r
and Plant-Available Soil Water e wate
nabl
30 Drai
Observations of water content changes in the soil profile fol-
ater
lowing wetting by irrigation or rainfall show that the rate of a ble w
20 avail
change decreases in time. In some cases, water content attains Plant poin
t
tw ilting
a nearly constant value within 1–2 days after wetting, following Plan
10
soil water redistribution in response to internal drainage. Field
capacity is defined as the water content at which internal drain-
0
age becomes essentially negligible. The attainment of a near con-
d

am

lt
nd

am
m

ay

ay
an

Si
oa
oa

stant water content at field capacity (θvFC) is not always assured.

Cl
cl
Sa

Lo

lo
ys

l
yl

lty
lt

ay
am

nd

Si

Si

It is dependent on (1) the depth of wetting and the antecedent

cl
Sa
Lo

lty

(initial) water content of the soil profile (for a soil that is moist at
Si

the onset of wetting and for deep wetting, the rate of redistribu- FIGURE 4.8  Schematic of estimated PASW content for a range of soil
tion is slower and the apparent value of θvFC is higher) and (2) the textural classes.
Soil Water Content and Water Potential Relationships 4-11

have lost 50% of its saturated water content at field capacity, Ecohydrology has emerged as a distinct subdiscipline within
and another 50% of the remaining water by the wilting point. hydrology and focuses in part on soil moisture (Rodriguez-Iturbe
Richards (1954) was probably the first to make this observation. and Porporato, 2005). However, ecologists have been studying
Banin and Amiel (1970) and Dahiya et al. (1988) have also dem- soil moisture and soil temperature for many years with regard
onstrated that the assumed ratio is a good approximation, based to their role in determining plant community spatial organiza-
on measured correlations on many soils. tion and net primary productivity (Pastor and Post, 1986). Soil
moisture provides the reservoir of water for plant growth and
4.2.3.3  Sources of Additional Information determining the available pool of water and its functionality is
on Soil Water Content Indices seen as increasingly critical in explaining and predicting vegeta-
The information on these indices is fragmentary due to their tion response in drier climates (Ryel et al., 2008).
dependency on other conditions in the soil profile (field capac-
ity) and the plant in question (wilting point). The work of Slater 4.3  Soil Water Energy
and Williams (1965) provides a reasonable framework for esti-
mating field capacity, and more recent information may be As previously stated, water status in soils is characterized by both
found on the Internet. A study by Waters (1980) is a good source the amount of water present and by its energy state. Soil water
of information regarding the wilting point. Dahiya et al. (1988) is subjected to forces of variable origin and intensity, thereby
presented strong correlations among the saturation percentage, acquiring different quantities and forms of energy. The two pri-
field capacity, wilting point, and available water based on data mary forms of energy of interest here are kinetic and potential.
for 438 soils, with correlation coefficients in excess of 0.92. Banin Kinetic energy is acquired by virtue of motion and is propor-
and Amiel (1970) provided similar information concerning rela- tional to velocity squared. However, because the movement of
tionships among clay content, surface area, and water content at water in soils is relatively slow (usually <0.1 m h−1), its kinetic
several index points. Petersen et al. (1996) also related soil sur- energy is negligible. The potential energy, which is defined by
face area and other properties to their water-holding capacity. the position of soil water within a soil body and by internal con-
ditions, is largely responsible for determining soil water status
4.2.3.4  The Role of Soil Moisture in Hydrology, under isothermal conditions.
Biogeochemistry, and Ecology Like all other matter, soil water tends to move from where the
Soil moisture plays a critical role across a range of scales within potential energy is high to where it is low, in its pursuit of a state
hydrology. Entekhabi et al. (1996) demonstrated the mutual known as equilibrium with its surroundings. The magnitude of
interaction between soil moisture states and atmospheric pro- the driving force behind such spontaneous motion is a differ-
cesses. Soil moisture becomes an important source of atmo- ence in potential energy across a distance between two points of
spheric water at continental scales, a fraction of which falls as interest. At a macroscopic scale, one can define potential energy
precipitation back on the land surface downwind from the site relative to a reference state. The standard state for soil water is
of the original evapotranspiration. Soil moisture also plays an defined as pure and free water (no solutes and no external forces
important role in determining the albedo of soils (Idso et al., other than gravity) at a reference pressure, temperature, and
1974), this has become increasingly important in the global elevation, and is arbitrarily given the value of zero (Bolt, 1976).
energy balance, as land-use change has occurred and more
soils are cultivated and urbanization expands. At the watershed
4.3.1  Total Soil Water Potential
scale, the antecedent moisture conditions play a critical role in
and Its Components
determining if rainfall will infiltrate or runoff, especially where
saturation excess runoff processes dominate (Dunne and Black, Soil water is subject to several force fields whose combined
1970). As a result, significant effort has been placed on trying to effects result in a deviation in potential energy relative to the
determine water content across small watersheds (Grayson et al., reference state called the total soil water potential (ψT) and is
1997; Western and Grayson, 1998; Western et al., 1999). defined as follows:
Biogeochemical cycling describes the transformation of ele-
ments from one form to another. Soil moisture has been recog- The amount of work that an infinitesimal unit quantity
nized from early in the history of soil science as a controlling of water at equilibrium is capable of doing when it moves
factor over rates of weathering and soil formation (Jenny, 1941). (isothermally and reversibly) to a pool of water at similar
In addition to controlling some weathering processes, such as standard (reference) state (similar pressure, elevation, tem-
hydrolysis and hydration, which are important for the release of perature, and chemical composition).
nutrients, for example, phosphorus, perhaps more importantly
moisture controls microbial activity in soils (Skopp et al., 1990). It should be emphasized, however, that there are alternative
The microbial activity is the powerhouse behind many soil pro- definitions of soil water potential using concepts of chemi-
cesses, for instance, nitrification and the evolution of CO2 from cal potential or specific free energy of the chemical species
microbial respiration (Stanford and Epstein, 1974; Schjonning in water (which is different than the soil solution, termed soil
et al., 2003; Turcu et al., 2005). water here). Some of the arguments concerning the proper
4-12 Properties and Processes

definitions and their scales of application are presented by Corey more readily than salts. The effects of ψs are otherwise negligible
and Klute (1985), Iwata et al. (1988), and Nitao and Bear (1996). when only liquid water flow is considered and no diffusion bar-
Recognizing that these fundamental concepts are subject to rier exists. The two most important diffusion barriers in the soil
ongoing debate, only simple and widely accepted definitions of are (1) soil–plant root interfaces (cell membranes are selectively
these quantities, which are applicable at macroscopic scales and permeable) and (2) soil water–air interfaces; thus, when water
which yield an appropriate framework for practical applications, evaporates, salts are left behind. In dilute solutions, the solute
will be presented. potential (also called the osmotic pressure) is proportional to the
The primary forces acting on soil water held within a rigid concentration and temperature according to
soil under isothermal conditions can be conveniently grouped
as (Day et al., 1967) (1) matric forces resulting from interactions ψ s = −RTC s , (4.17)

of the solid phase with the liquid and gaseous phases, (2) osmotic
forces owing to differences in chemical composition of the soil
where
solution, and (3) body forces induced by gravitational and other
ψs is in kPa
inertial force fields (centrifugal).
R is the universal gas constant (8.314 × 10−3 kPa m3 mol−1 K−1)
The thermodynamic approach whereby potential energy
T is the absolute temperature (K)
rather than forces are used is particularly useful for equilibrium
Cs is solute concentration (mol m−3)
and flow considerations. Equilibrium would require the vector
sum of these different forces acting on a body of water in differ-
A useful approximation, which may be used to estimate ψs in
ent directions to be zero; this is an extremely difficult criterion
kPa from the ECa of the soil solution at saturation (EC s) in
to deal with in soils. On the other hand, potential energy defined
dS m−1, is
as the negative integral of the force over the path taken by an
infinitesimal amount of water, when it moves from a reference
ψ s = −36EC s . (4.18)
location to the point under consideration, is a scalar quantity.
Consequently, the total potential can be expressed as the alge-
braic sum of the component potentials corresponding to the dif- ψp is pressure potential defined as the hydrostatic pressure
ferent fields acting on soil water: exerted by unsupported water (i.e., saturating the soil) overly-
ing a point of interest. Using units of energy per unit weight
ψT = ψm + ψs + ψ p + ψz . (4.16) provides a simple and practical definition of ψp as the vertical
distance from the point of interest to the overlying free water
surface (unconfined water table elevation). The convention used
ψm is the matric potential resulting from the combined effects here is that ψp is always positive below a water table or zero if
of capillarity and adsorptive forces within the soil matrix. the point of interest is at or above the water table. In this sense,
Dominating mechanisms for these effects include (1) adhesion nonzero magnitudes of ψp and ψm are mutually exclusive; either
of water molecules to solid surfaces due to short-range London– ψp is positive and ψm is zero (saturated conditions) or ψm is nega-
van der Waals forces and extension of these effects by cohesion tive and ψp is zero (unsaturated conditions), or ψp = ψm = 0 at
through H bonds formed in the liquid, (2) capillarity caused the free water table elevation. Another definition that is used in
by liquid–gas (LG) and liquid–solid–gas interfaces interacting some quarters is to combine ψm and ψp as used here into a single
within the irregular geometry of soil pores, and (3) ion hydra- component that adopts negative magnitude under unsaturated
tion and binding of water in diffuse double layers. There is some conditions and positive magnitude under saturated conditions.
disagreement regarding the definition of this component of the ψz is gravitational potential, which is determined solely by the
total potential. Some consider all contributions other than grav- elevation of a point relative to some arbitrary reference point and
ity and solute interactions (at a reference atmospheric pressure). is equal to the work needed to raise a body against the earth’s
Others use a tensiometer (Section 4.3.4) to measure and provide gravitational pull from a reference level to its present position.
a practical definition of the matric potential in a soil volume of When expressed as energy per unit weight, the gravitational
interest (Hanks, 1992). The value of ψm ranges from zero when potential is simply the vertical distance from a reference level
the soil is saturated to negative numbers when the soil is dry to the point of interest. The numerical value of ψz itself is thus
(note that ψm = 0 mm is >ψm = −1000 mm). Because it is often not important (it is defined with respect to an arbitrary refer-
more convenient or intuitive to work with positive than negative ence level); what is important is the difference or gradient in ψz
quantities, the term matric suction or tension is commonly used. between any two points of interest. This value will not change
Each of these represents the absolute value of ψm. with different reference point locations.
ψs is the solute or osmotic potential determined by the pres- Soil water is at equilibrium when the net force on an infini-
ence of solutes in soil water, which lower its potential energy and tesimal body of water equals zero everywhere, or when the total
its vapor pressure. The effects of ψs are important in the presence potential is constant in the system. Though the last statement is
of (1) appreciable amounts of solutes and (2) a selectively per- a logical consequence of the definitions above, it is not strictly
meable membrane or a diffusion barrier, which transmits water true as pointed out by Corey and Klute (1985). They argue that
Soil Water Content and Water Potential Relationships 4-13

constant total potential is a necessary but not a sufficient condi- only under partial saturation when all the three phases (liquid,
tion, and for thermodynamic equilibrium to prevail, three con- gas, and solid) are present, some of the properties of water in
ditions must be met simultaneously: (1) thermal equilibrium or relation to porous media, which give rise to this phenomenon,
uniform temperature, (2) mechanical equilibrium meaning no must be discussed.
net convection producing force, and (3) chemical equilibrium
meaning no net diffusional transport or chemical reaction. In 4.3.2.1  Surface Tension
most practical applications, however, the macroscopic definition At the interface between water and solids or other fluids such
of the total potential and equilibrium conditions based on it is as air, water molecules are exposed to different forces than are
completely adequate (Kutilek and Nielsen, 1994). molecules within the bulk water. For example, water molecules
The difference in chemical and mechanical potentials between inside the liquid are attracted by equal cohesive forces to form
soil water and pure water at the same temperature is known as H  bonds on all sides, whereas molecules at the air–water inter-
the soil water potential (ψw): face feel a net attraction into the liquid because the density of
water molecules on the air side of the interface is much lower
ψ w = ψm + ψs + ψ p . (4.19) and all H bonds are toward the liquid. The result is a membrane-
like water surface having a tendency to contract; thus energy is
stored in the form of surface tension (as in a stretched spring).
Note that the gravitational component (ψz) is absent in this defi- Different liquids vary in their LG surface tension (σLG) expressed
nition. Soil water potential is thus the result of inherent properties as energy per unit area = force per unit length. For example,
of soil water itself, and of its physical and chemical interactions water at 20°C: 72.7 mN m−1 = mJ m−2; ethyl alcohol: 22 mN m−1
with its surroundings, whereas the total potential includes the (=dyn cm−1 = erg cm−2); and mercury: 430 mN m−1.
effects of gravity (an external and ubiquitous force field).
Total soil water potential and its components may be expressed 4.3.2.2  Contact Angle
in several ways depending on the definition of a unit quantity of If liquid is placed in contact with a solid in the presence of a gas
water. Potential may be expressed as (1) energy per unit of mass, (three-phase system), the angle measured from the solid–liquid
(2) energy per unit of volume, or (3) energy per unit of weight. (SL) interface to the LG interface is the contact angle (γ). For a
A summary of the resulting dimensions, common symbols, and drop resting on a solid surface at equilibrium, the vector sum
units are presented in Table 4.1. of the forces acting to spread the drop (outward) is equal to the
Only μ has actual units of potential; ψ has units of pressure, opposing forces. This relationship is summarized by Young’s
and the units of h are in head of water (length). However, the equation (Adamson, 1990):
above terminology (potential energy vs. units of potential) is
widely used in a generic sense in the soil and plant sciences. The
σLG cos γ + σSL − σGS = 0, (4.21)
various expressions of soil water energy status are equivalent,
with
where σ is the respective interfacial surface tension. The equilib-
μ = ψ/ρw = gh, (4.20) rium contact angle is therefore

⎡ σ − σSL ⎤
where γ = cos −1 ⎢ GS ⎥. (4.22)
ρw is density of water (1000 kg m−3 at 20°C) ⎣ σLG ⎦
g is gravitational acceleration (9.81 m s−2)
When liquid is more attracted to the solid (adhesion) than to
other liquid molecules (cohesion), the angle is small and the
4.3.2  Interfacial Forces and Capillarity
solid is said to be wettable by the liquid. Conversely, when the
The matric potential is often the largest component of the total cohesive exceeds the adhesive force, the liquid repels the solid
potential in partially saturated soils. To better understand the and γ is large (Figure 4.9). The contact angle of water on clean
origins of this important potential, which attains nonzero values glass is very small and is commonly taken as 0°. The contact

TABLE 4.1  Units, Dimensions, and Common Symbols for Potential

Energy of Soil Water
Units Symbol Name Dimensions SI Units cgs Units
Energy/mass μ Chemical potential L2 t−2 J kg−1 erg g−1
Energy/volume Ψ Soil water M (L t2)−1 N m−2 (Pa) erg cm−1
potential, suction,
or tension
Energy/weight h Pressure head L m cm
4-14 Properties and Processes

Gas
γ

Liquid

(a)

Gas R1 R2
R1
Liquid
γ

(b)

FIGURE 4.9  Liquid–solid–gas contact angles for (a) a small angle

where the liquid wets the solid and (b) a large angle in which the liquid
is repelled by the solid surface.

angle of soil water on soil minerals is also commonly assumed

FIGURE 4.10  Radii of curvature for pendular ring of water between
∼0°. The different contact angles of water and other liquids with
two spherical solids.
soil solids, soil air, and with each other, are important contribu-
tors to the behavior of multiphase organic liquid/water/soil/air
mixtures. 4.3.3  The Capillary Model
4.3.2.3  Curved Surfaces and Capillarity 4.3.3.1  Capillary Rise
Surface tension is associated with the phenomenon of capillar- When a small cylindrical glass tube (capillary) is dipped in
ity. When the LG interface is curved rather than planar (flat), the free water, a meniscus is formed as a result of the contact angle
resultant surface tension force normal to the LG interface creates between the water and the walls of the tube and from consider-
a pressure difference across the interface. The pressure is greater ation of minimum surface energy. The smaller the tube the larger
at the concave side of the interface by an amount that is dependent the degree of curvature, resulting in a larger pressure difference
on the radius of curvature and the surface tension of the fluid. For across the air–water (gas–liquid) interface. The pressure at the
a hemispherical LG interface having radius of curvature R, the water side (PW) will be lower than atmospheric pressure (P0). This
pressure difference is given by the Young–Laplace equation: pressure difference will cause water to rise into the capillary tube
until the upward force across the water–air interface is balanced
ΔP = 2σ /R, (4.23)
by the weight of water in the tube (Figure 4.11). Because the radius
of meniscus curvature R = r/cos γ, where r is the tube radius, the
where
height that water will rise in a capillary tube of radius r with
ΔP = Pliq − Pgas when the interface curves into the gas (water
γ contact angle is
droplet in air)
ΔP = Pgas − Pliq when the interface curves into the liquid (air
bubble in water, water in a small glass tube) 2σ cos γ
h= . (4.25)
ρw gr

In many instances, a bubble may not be spherical or an element
of liquid may be confined by irregular solid surfaces resulting in Combining all the constants in Equation 4.25 (using typi-
two (or more) different radii of curvature such as water in pen- cal values at room temperature) yields a simple and useful
dular rings between two spherical solid particles (Figure 4.10). approximation:
The Young–Laplace equation for this case is given by:

⎛ 1 1 ⎞ 14.84
ΔP = σ ⎜ + ⎟ . (4.24) h(m) = . (4.26)
⎝ R1 R 2 ⎠ r(μm)

Note that (1) this equation reduces to Equation 4.23 for R1 = R 2 When expressed as potential energy per unit weight, ψm = −h
and (2) the sign of R i is negative for convex interfaces (R 2 < 0) and thus may be related to equivalent pore radius through
and positive for concave interfaces (R1 > 0). Equation 4.25.
Soil Water Content and Water Potential Relationships 4-15

Soil sample

P0

h2 R

Pw
γ
h1

R2 < R 1
h2 > h1

Irregular Equivalent
soil pore cylindrical
capillary
FIGURE 4.11  Capillary rise in cylindrical glass tubes.
FIGURE 4.12  Concept of equivalent cylindrical capillary to represent
soil pore spaces.
4.3.3.2  Conceptual Models for Water
in Soil Pore Space
moves from the tensiometer along a potential energy gradient to
The complex geometry of soil pore space creates numerous com- the soil through the saturated porous cup, thereby creating suc-
binations of interfaces, capillaries, and wedges around which tion sensed by the gauge. Water flow into the soil continues until
films of water are formed, resulting in a variety of air–water and equilibrium is reached and the suction inside the tensiometer
solid–water contact angles. Water is thus drawn into and/or held equals the soil matric potential. When the soil is wetted, flow
by these interstices in proportion to the resulting capillary forces. may occur in the reverse direction, that is, soil water enters the
In addition, water is adsorbed onto solid surfaces with consider- tensiometer until a new equilibrium is attained. The tensiometer
able force at close distances. Due to practical limitations of the equation is
present measurement methods, no distinction is made between
the various mechanisms affecting water in porous matrices (i.e.,
ψ m = ψ gauge + (z gauge − z cup ). (4.27)
capillarity and surface adsorption). Common conceptual mod-
els for water retention in porous media and matric potential rely
on a simplified picture of soil pore space as a bundle of capil- The vertical distance from the gauge plane (zgauge) to the cup
laries. The primary conceptual steps made in such models are (zcup) must be added to the matric potential measured by the
illustrated in Figure 4.12. The representation of soil pores as gauge (expressed as a negative quantity) to obtain the matric
equivalent cylindrical capillaries greatly simplifies modeling potential at the depth of the cup, when potentials are expressed
and parameterization of soil pore space. The roles of water films per unit of weight. This accounts for the positive head at the
at very low saturation levels and the unique contribution of sur- depth of the ceramic cup exerted by the overlying tensiometer
face adsorption to the matric potential are beyond the scope of water column.
this chapter. Interested readers are referred to reviews by Nitao Electronic sensors called pressure transducers often replace
and Bear (1996) and Parker (1986). the mechanical vacuum gauges. The transducers convert
mechanical pressure into an electric signal, which can be more
4.3.4  Measurement of Soil Water easily and precisely measured. In practice, pressure transduc-
Potential Components ers can provide more accurate readings than other gauges, and
in combination with data logging equipment are able to supply
4.3.4.1  Tensiometer for Measuring Soil continuous measurements of soil matric potential. Portable ten-
Matric Potential siometers that may be extended into boreholes for use at depths
A tensiometer consists of a porous cup, usually made of ceramic to several hundred meters have also been developed (Hubbell
having very fine pores, connected to a vacuum gauge through a and Sisson, 1996). Achieving and maintaining adequate hydrau-
water-filled tube (Figure 4.13). The porous cup is placed in inti- lic contact between the porous cup and the soil at these depths
mate contact with the bulk soil at the depth of measurement. was identified as an important issue, but these sensors may be
When the matric potential of the soil is lower (more negative) highly useful in some mining, engineering, deep recharge, and
than the equivalent pressure inside the tensiometer cup, water hazardous waste applications.
4-16 Properties and Processes

Cable to
datalogger Pressure
transducer
Vacuum Digital
Head with readout
gauge pressure
transducer
–0.235 bar

Saturated Bar
porous
ceramic
Soil water
(outside)
Needle inserted
Water-filled into septum
tube stopper

Water
(inside)

Porous ceramic cup

FIGURE 4.13  Pressure transducer and vacuum gauge tensiometers showing porous ceramic cup.

The standard tensiometer range is limited to suction values energy is expressed per unit of weight). The piezometer is a
(absolute value of the matric potential) <100 kPa (1 bar or 10 m hollow tube placed in the soil to depths below the water table.
head of water) at sea level, and this value decreases proportion- It extends to the soil surface and is open to the atmosphere.
ally with elevation. Thus, other means are needed to measure or The bottom of the piezometer is perforated to allow for soil
infer soil matric potential under drier conditions. water under positive hydrostatic pressure to enter the tube.
Peck and Rabbidge (1969) described an osmotic tensiometer Water enters the tube and rises to a height equal to that of the
that relied on a confined aqueous solution behind a semiper- free water table. The water level within the piezometer may be
meable membrane, rather than using free water as the refer- determined using a variety of manual or automated measure-
ence state. A membrane highly impermeable to the confined ment techniques.
solution allowed their device to cover the entire range of 0 to
−1.5 MPa, unless soil solutes were excluded from the instru- 4.3.4.3  Water Vapor Pressure for Measuring
ment by a vapor gap. Following the design of these osmotic ten- Water Potential
siometers, polymer tensiometers have been developed, which Under equilibrium conditions, the soil water potential is equal
utilize synthetic polymers (i.e., polyethylene glycol, polyacryl- to the potential of water vapor in the surrounding soil air.
amide, and polyvinylpyrrolidone) in place of solutes to fill a A  psychrometer measures the relative humidity (RH) of the
small reservoir connected to the pressure transducer (Bakker water vapor, which is related to the water potential of the vapor
et al., 2007). Keys to successful operation include reduction of (ψw) through the Kelvin equation:
thermal sensitivity, the prevention of polymer degradation or
leakage from the reservoir using a secondary membrane, and
RH = e/eo = exp[(Mw ψ w )/(ρw RT)], (4.28)
maintenance of soil–ceramic contact for hydraulic continuity
at low potentials.
where
4.3.4.2  Piezometer for Measuring Hydrostatic e is water vapor pressure
Pressure Potential eo is saturated vapor pressure at the same temperature
In a saturated soil such as below a water table, soil water is Mw is the molecular weight of water (0.018 kg mol−1)
under positive hydrostatic pressure. The pressure potential R is the ideal gas constant (8.31 J K−1 mol−1 or 0.008314 kPa
(ψp) equals the vertical distance from a point in the soil to m3 mol−1 K−1)
the surface of the free water table (recall that one expresses T is absolute temperature (K)
potential in terms of distance, length, or head when potential ρw is the density of water (1000 kg m−3 at 20°C)
Soil Water Content and Water Potential Relationships 4-17

Rearranging and taking a log transformation of Equation wet-bulb temperature, dew point temperature, vapor pressure,
4.28 yields RH, humidity ratio, specific enthalpy, and specific volume
(inverse air density). Measurements commonly carried out
RTρw in soil access dry- and wet-bulb temperature using thermo-
ψw = ln(e/eo ). (4.29)
Mw couple psychrometry or dew point temperature using chilled

mirror techniques, where matric potential is often related to
the soil vapor pressure. In the following, we briefly describe
Equation 4.29 can be further simplified for the range of e/eo near 1
the psychrometric chart and the interrelations among differ-
often encountered in soils (the entire range of plant-available
ent thermophysical properties and then review the associated
water is between e/eo = 1 and 0.98):
measurement techniques.
The psychrometric chart depicted in Figure 4.14 requires
RTρw ⎛ e ⎞ ⎛ e ⎞
ψw = ⎜ − 1⎟ ≈ 462 T ⎜ − 1⎟ , (4.30) a pair of known or measured values in order to determine the
M w ⎝ eo ⎠ ⎝ eo ⎠ unknown properties for a given condition. Typically dry-bulb

(air) temperature is measured along with wet-bulb temperature.
for ψw in kPa. Note that because most salts are nonvolatile, the For example, assuming a thermocouple psychrometer measured
psychrometric measurement of ψw is the sum of the osmotic and a dry-bulb temperature of 25°C and a wet-bulb temperature
matric potentials (ψw = ψm + ψs). The soil–air interface acts as a of 23°C, the resulting RH according to this chart is 85%. This
diffusion barrier in allowing only water molecules to pass from value is computed from the ratio of the vapor pressure to the
liquid to vapor state. saturation vapor pressure at 25°C, which are 20.2 and 24.8 mm
Understanding measurements of soil water potential using a Hg, respectively. The corresponding dew point temperature is
determination of the soil air-phase humidity can be enhanced observed to be 22.1°C.
by a psychrometric chart because one can observe relation-
ships among the different measurement techniques. A psy- 4.3.4.4  Psychrometry for Measuring
chrometric chart depicts the physical properties of moist air Soil Water Potential
computed for a fixed pressure or elevation. Thermophysical A psychrometer measures the difference between dry-bulb
properties depicted in the chart may include dry-bulb and and wet-bulb temperatures to determine the RH. The dry

34
Psychrometric chart
1500 m above sea level (85 kPa) 30 30 32
30
28
26
25 25 24 eo
Twb 22
Tdp 20 e
%
20 90 18
20
16
Vapor pressure (mm Hg)

%
70 14
15 15
We 12
t bu
% lb t
Dewpoint (°C)

10 50 em
per 10
atu
re ( 8
5 °C)
30% 5 6
0 0 4
10% RH –10 2
Tdp Tdb
–40 0
0 5 10 15 20 25 30 35 40 45 50
Dry bulb temperature (°C)

FIGURE 4.14  Psychrometric chart showing relationships between dry-bulb (Tdb), wet-bulb (Twb), and dew point (Tdp) temperatures in addition to
water vapor pressure (e) and saturation vapor pressure (eo) for an elevation of 1500 m (85 kPa). In this example, a psychrometer measures dry-bulb
(Tdb) and wet-bulb (Twb) temperatures of 25°C and 23°C, respectively, indicating a RH of 85%. From the chart, a corresponding dew point tempera-
ture (Tdp) is 22.1°C and the vapor pressure of 20.2 mm Hg and a saturation vapor pressure of 24.8 mm Hg (note: RH = e/eo).
4-18 Properties and Processes

bulb is the temperature of the ambient air (nonevaporating is measured and used to infer the RH (or relative vapor pres-
surface), and the wet bulb is the temperature of an evaporat- sure) using the psychrometer equation:
ing surface (generally lower than the dry-bulb temperature).
The RH determines the rate of evaporation from the wet- e ⎡s + γ ⎤
bulb junction, and thus the extent of temperature depression =1− ⎢ ⎥ ΔT, (4.31)
eo ⎣ eo ⎦
below ambient.
A thermocouple psychrometer consists of a fine-wire
chromel–constantan or other bimetallic thermocouple. A ther- where
mocouple is a double junction of two dissimilar metals. When s is the slope of the saturation water vapor pressure curve
the two junctions are subjected to different temperatures, they (s = deo/dT)
generate a voltage difference (Seebeck effect). Conversely, when γ is the psychrometric constant (about 0.067 kPa K−1 at 20°C)
an electrical current is applied through the junctions, it cre- ΔT is the temperature difference (K)
ates a temperature difference between the junctions by heating
one while cooling the other, depending on the current’s direc- The slope (s) and eo are functions of temperature only and can
tion. For typical soil use, one junction of the thermocouple be approximated by closed-form expressions (Brutsaert, 1982).
psychrometer is suspended in a thin-walled porous ceramic A typical temperature depression measurable by a good psy-
or stainless screen cup buried in the soil (Figure 4.15a), while chrometer is on the order of 0.000085 C kPa−1. This means that
another is embedded in an insulated plug to measure the ambi- any errors in measuring wet-bulb depression can introduce large
ent temperature at the same location. In psychrometric mode, errors into psychrometric determinations. Thermal equilibrium
the suspended thermocouple is cooled below the dew point is, therefore, a prerequisite to obtaining reliable readings, as any
by means of an electrical current (Peltier cooling) until pure temperature difference between wet and dry sensors resulting
water condenses on the junction. The cooling current then from thermal gradients will be (erroneously) incorporated into
stops, and as water evaporates, it draws heat from the junction the RH calculation.
(heat of vaporization), depressing it below the temperature of Summarizing, psychrometric measurements of soil water
the surrounding air until it attains a wet-bulb temperature. The potential are based on equilibrium between liquid soil water
warmer and drier the surrounding air, the higher the evapora- and water vapor in the ambient soil atmosphere. The drier the
tion rate and the greater the wet-bulb depression. The difference soil, the fewer water molecules escape into the ambient atmo-
in temperatures between the dry- and wet-bulb thermocouples sphere resulting in lower RH (lower vapor pressure). When the

Measurement chamber overturned

Sample holder

Measurement chamber
WP4-T

Dry bulb
junction Peltier cooler

Chilling mirror

Wet bulb Detector

junction
Circulation fan
5 mm

Thermopile

Ceramic
shield or Infrared temp.
3 mm
screen
(a) Thermocouple psychrometer (b) Dewpoint potentiometer

FIGURE 4.15  A field psychrometer (a) with porous ceramic shield. (Wescor, Inc. Logan, UT. With permission.) Dew point potentiometer
(b) (Decagon Devices, Inc.) showing the internal components providing soil sample temperature measurement (dry bulb in Figure 4.14) and the
chilled mirror measurement for dew point temperature determination. The system provides soil water potential calculations from measurements
in the range of −0.1 down to −300 MPa.
Soil Water Content and Water Potential Relationships 4-19

osmotic potential is negligible, the soil water potential measured measured by a thermocouple fixed at a known distance from the
by a psychrometer is nearly equal to the soil matric potential. heating source (Phene et al., 1971; Bristow et al., 1993). Sensors
In principle, soil psychrometers may be buried in the soil and are individually or uniformly calibrated in terms of heat dissipa-
left for long periods, although corrosion is a problem in some tion versus sensor wetness (i.e., matric potential). A typical use-
environments. ful matric potential range for such sensors is −10 to −1000 kPa.
A similar line-source sensor with a fine-wire heating ele-
4.3.4.5  Dew Point Potentiometer for Measuring ment axially centered in a cylindrical ceramic matrix having
Soil Water Potential a radius of 1.5 cm and length of 4.2 cm is depicted in Figure
In a cooling process, the temperature at which water vapor con- 4.16. A thermocouple is located adjacent to the heating element
denses into water is known as the dew point temperature (Tdp) at mid-length. Both the heating wire and the thermocouple are
and occurs near 100% RH. This temperature is illustrated in contained in the shaft portion of a hollow needle. Because the
Figure 4.15b, where Tdp is 22.1°C corresponding with the dry- thermocouple is located adjacent to the heating element, as
and wet-bulb temperature intersection point in the previous the soil dries and water moves out of the ceramic, the magnitude
example. Note that the dew point temperature is also found of temperature change during a given period under constant
by drawing a horizontal line to the left intersecting the 100% heating current and duration will increase due to the reduced
humidity curve and dropping vertically to the corresponding thermal conductivity of the porous matrix. The magnitude of
air (dry bulb) temperature. In Figure 4.15b, a detailed measure- the measured temperature increase and/or decrease is often lin-
ment system from a Decagon WP4-T illustrates the electronics early related to the natural logarithm of matric potential. The
and hardware, which measure the soil water potential using the accuracy and operational limits of these sensors were evaluated
chilled mirror dew point technique. by Reece (1996), who also presented an improved calibration
method for between-sensor variability, based on normalizing
4.3.4.6  Reference Porous Matrix Properties sensor readings by oven dry sensor thermal conductivity. A pri-
for Measuring Matric Potential mary advantage of these sensors is their wide range of applica-
The interdependence of soil matric potential and water content bility from about −0.1 to −12.0 MPa.
facilitates indirect methods for inferring the energy of soil water Electrical resistance sensors have been used in soils for matric
from water content-dependent physical property measurements potential determination since the work of Bouyoucos and Mick
where a well-characterized and repeatable porous matrix can (1940) and continue to be developed to this day. Ongoing efforts
be produced. Measurement approaches have included thermal, seek to overcome limitations associated with temperature and
electrical, dielectric measurements within porous media includ- salinity dependence on the resistance measurement (see Section
ing plaster of Paris, ceramics, fiberglass, porous plastics, and 4.2.2.7). The measurement method is popular because sensors
natural soils (Wraith and Or, 2001). The measurable physical are inexpensive to produce. Measuring the dielectric of a refer-
property (heat capacity, thermal conductivity, electrical resis- ence porous medium can be used to infer soil matric potential.
tivity, dielectric constant) of a porous matrix is affected by its Early studies used TDR probes embedded in plaster of Paris or
water content and hence related to its matric potential. With ceramic with a well-characterized θ−ψ relationship in the range
the reference matrix sensor buried in the soil, changes in soil of −30 to −1000 kPa (Noborio et al., 1999). Commercially avail-
matric potential result in a gradient between the soil and the able dielectric-based sensors provide a narrower measurement
reference matrix that induces a water flux between the two mate- range of −10 to −500 kPa but are less expensive to produce. Some
rials until a new equilibrium potential is established. Reference limitations of this method include possible effects from salinity
matrix sensor physical properties being measured are influenced
by these water content changes. In this manner, the measured Line-source heat dissipation sensor
sensor response yields quasi-direct information on the soil mat-
ric potential and indirect information on soil wetness where a
water retention relationship is known. A common challenge of
these sensors is quality mass production of the reference porous
medium whose θ−ψ relationship exhibits low variance and Porous
whose hydraulic properties are compatible with the soil being matrix
measured. Accuracy, repeatability, and spatial resolution of spe-
Heating
cific sensors or methods are important considerations to their
element
potential applications and in the analysis of soil matric potential
measurements.
Heat dissipation sensors contain line- or point-source heat-
ing elements embedded in a rigid porous matrix with fixed
Thermocouple
pore space. The measurement is based on applying a heat pulse
by passing a constant current through the heating element FIGURE 4.16  Schematic of CSI 229 heat dissipation sensor. (From
for a specified time and analyzing the temperature response Campbell Scientific, Inc., Logan, UT.)
4-20 Properties and Processes

on the dielectric measurement, especially at measurement fre- some cases, (3) the difficulty in obtaining undisturbed samples
quencies below 100 MHz, and an altered θ−κ relationship occur- for laboratory determinations, and (4) a slow rate of equilibrium
ring in frozen soils. under low matric potential (i.e., dry soils).
In situ methods are considered the most representative for
determining SWCs, particularly when a wide range of ψm–θv
4.4  Soil Water Content—Energy values are obtained. An effective method to obtain simultane-
Relationships ous measurements of ψm and θv utilizes TDR probes installed
in the soil at close proximity to transducer tensiometers and/ or
4.4.1  Soil Water Characteristic
other matric sensors, with the changing values of each attri-
An SWC curve describes the functional relationship between soil bute monitored through time as the soil wetness varies. Large
water content (θm or θv) and matric potential under equilibrium changes in ψm and θv can be induced under highly evapora-
conditions. The SWC is an important soil property related to tive conditions near the soil surface or in the presence of active
the distribution of pore space (sizes, interconnectedness), which plant roots.
is strongly affected by texture and structure, as well as related
factors including organic matter content. The SWC is a primary 4.4.2.1  Laboratory Estimation Using Pressure
hydraulic property required for modeling water flow, for irriga- Plate and Pressure Flow Cell
tion management, and for many additional applications related The pressure plate apparatus consists of a pressure chamber
to managing or predicting water behavior in the porous system. enclosing a water-saturated porous plate, which allows water
An SWC is a highly nonlinear function and is relatively difficult but prevents air flow through its pores (Figure 4.18). The
to obtain accurately. Because the matric potential extends over porous plate is open to atmospheric pressure at the bottom,
several orders of magnitude for the range of water contents com- while the top surface is at the applied pressure of the cham-
monly encountered in practical applications, the matric poten- ber. Sieved soil samples (usually <2 mm) are placed in retain-
tial is often plotted on a logarithmic scale. Several SWC curves ing rubber rings in contact with the porous plate and left to
for soils of different textures demonstrating the effects on poros- saturate in water. After saturation is attained, the porous plate
ity (saturated water content) and on the slope of the relationships with the saturated soil samples is placed in the chamber and
resulting from variable pore-size distributions are depicted in a known gas (commonly N2 or air) pressure is applied to force
Figure 4.17. water out of the soil and through the plate. Flow continues
until equilibrium between the force exerted by the air pres-
sure and the force by which soil water is being held by the soil
4.4.2  Measurement of SWC Relationships
(ψm) is reached.
Several methods are available to obtain the measurements Soil water retention in the low suction range of 0–10 m (=1 bar =
needed for SWC estimation. The basic requirement is for pairs of 0.1 MPa) is strongly influenced by soil structure and its natural
ψm–θ measurements over the wetness range of interest. Among pore-size distribution. Hence, undisturbed intact soil samples
the primary experimental problems in determining an SWC are (cores) are preferred over repacked samples for the wet end of
(1) the limited functional range of the tensiometer, which is often the SWC. The pressure flow cell (Tempe cell) can hold intact soil
used for in situ measurements, (2) inaccurate θ measurements in samples encased in metal rings. The operation of the cell follows
that of the pressure plate, except the pressure range is usually
10,000
lower (0–10 m). The porous ceramic plates for both the pressure
plate and the flow cell must be completely saturated, a process
1,000 which may take a few days to achieve. Following equilibrium
Clay
between soil matric potential and the applied air pressure, the
soil samples are removed from the apparatus, weighed, and oven
Matric head (m–1)

100
Silt loam
dried for gravimetric determination of water content. An esti-
mate of the soil sample bulk density must be provided to convert
θm to θv in the case of disturbed samples. Because of differences
10 Sand in pore sizes and geometry, the water content of repacked soils at
a given matric potential should not be used to accurately infer θ
1 of intact soils at the same ψm.
Several pressure steps may be applied to the same samples
when using flow cells. The cells may be disconnected from the
0.1 air pressure source and weighed to determine the change in
0.0 0.1 0.2 0.3 0.4 0.5
water content from the previous step, then reconnected to the air
Volume water content (m3 m–3)
pressure and a new (greater) pressure step applied. Water out-
FIGURE 4.17  Example of soil water retention relationships for three flow from the cells may also be monitored and related by volume
soil textures. or mass to the change in sample water content.
Soil Water Content and Water Potential Relationships 4-21

Containment
rings

Gas pressure
Pressure
manifold

Saturated Soil sample

porous plate
Chamber
pressure
Soil sample Pc
Brass cylinder

Pa
Saturated Atmospheric Pressure plate
(a) porous plate (b) pressure apparatus (5 bar)

FIGURE 4.18  (a) Pressure flow cell (Tempe cell) and (b) pressure plate apparatus used to desaturate soil samples to desired matric potential.

4.4.2.2  Field Measurement Methods—Sensor Pairing 103

Despite the paramount importance of SWC determination in
Psychrometer
situ, suitable measurement techniques are severely lacking at
present. The most common approach is to use paired sensors 102
Matric potential (m–1)

such as neutron moisture meter access tubes or TDR waveguides

Pressure plate
and tensiometers to determine water content and matric poten-
tial simultaneously and in the same soil volume. Single probes 101
that combine TDR with tensiometry have also been proposed Tempe cell Tensiometer
(Baumgartner et al., 1994). The limitations of most sensor pair-
ing techniques stem from (1) differences in the soil volumes 100
sampled by each sensor (e.g., large volume averaging by a neu- Hanging water column
tron moisture meter vs. a small volume sensed by a heat dissipa-
tion sensor or a psychrometer), (2) the time required for matric 10–1
θr θs
potential sensors to reach equilibrium, and (3) limited ranges Soil water content
and deteriorating accuracy of different sensor pairs. This often
FIGURE 4.19  Typical ranges of application for some common matric
results in limited overlap in SWC information measured using
potential measurement or inference methods.
different techniques and problems with measurement errors
within the range of overlap. at the limits (wet and dry ends) while closely fitting the nonlin-
A summary of common methods available for matric potential ear shape of θ(ψm) data.
measurement or inference and their range of application is pre- An effective and commonly used parametric model for relat-
sented in Figure 4.19. Note that most of the available techniques ing water content to the matric potential was proposed by van
have a limited range of overlap (or do not overlap at all), and Genuchten (1980) and is denoted as VG:
most are laboratory methods not suitable for field applications.
m
θ − θr ⎡ 1 ⎤
Θ= =⎢ n⎥
, (4.32)
4.4.3  Fitting Parametric SWC Expressions
θs − θr ⎣ 1 + (α | ψ m |) ⎦
to Measured Data
Measuring an SWC is laborious and time consuming. Measured where
θ−ψ pairs are often fragmentary, and usually constitute rela- θr and θs are the residual and saturated water contents,
tively few measurements over the wetness range of interest. For respectively
modeling and analysis purposes and for characterization and α, n, and m are parameters directly dependent on the shape
comparison between different soils and scenarios, it is therefore of the θ(ψ) curve
beneficial to represent the SWC in a continuous and parametric
form (Fredlund and Xing, 1994). A parametric expression of an A considerable simplification is gained by assuming that m =
SWC model should (1) contain as few parameters as necessary to 1  − 1/n. Thus, the parameters required for estimation of the
simplify its estimation and (2) describe the behavior of the SWC model are θr, θs, α, and n. θs is usually known and is easy to
4-22 Properties and Processes

103 Matric potentials are expressed as positive quantities in both VG

Brooks and Corey and BC parametric expressions.
van Genuchten
Estimation of VG or BC parameters from experimental data
Measurements
102 requires (1) sufficient data points (at least 5–8 θ(ψm) pairs) and
Matric potential (m–1)

(2) a program for performing nonlinear regression. Recent

versions of many computer spreadsheets provide relatively
101
simple and effective mechanisms for performing nonlinear
regression. Details of the computational steps required for fit-
ting an SWC to experimental data using commercially avail-
able spreadsheet software are given in Wraith and Or (1998).
100
In addition, computer programs for estimation of specific
parametric models are also available such as the RETC code
LCV silt loam soil (van Genuchten et al., 1991).
10–1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 Fitted parametric models of VG and BC to silt loam θ(ψ)
Volumetric soil water content (m3 m–3) data measured by Or et al. (1991) are presented in Figure 4.20.
The resulting best fit parameters for the VG model are α =
FIGURE 4.20  VG and BC parametric models fitted to measured 0.417 m−1; n = 1.75; θs = 0.513 m3 m−3; and θr = 0.05 m3 m−3 (with
water retention data.
r2 = 0.99). For the BC model, the best fit parameters are λ = 0.54;
ψb = 1.48 m; θs = 0.513 m3 m−3; and θr = 0.03 m3 m−3 (with r2 =
obtain experimentally with good accuracy, leaving only three
0.98). Note that the most striking difference between the VG and
unknown parameters (θr, α, and n) to be estimated from the
the BC models is in the discontinuity at ψ = ψb for BC.
experimental data in many cases. Note that θr may be taken as
The water retention character of multiporosity porous media
θ−1.5 MPa, θair dry, or a similar value, though it is often advantageous
can be described by superimposing multiple SWC curves
to use it as a fitting parameter.
(Durner, 1994) on measured data such as those illustrated in
Another well-known parametric model was proposed by
Figure 4.21 using the following expression.
Brooks and Corey (1964) and is denoted as BC:

λ
θ − θr ⎡ ψb ⎤
Θ= = ψm > ψ b k mi
θs − θr ⎢⎣ ψm ⎥⎦ ⎡ 1 ⎤
Θ =1 ψm ≤ ψb,
(4.33) Θ= ∑ wi ⎢ ni ⎥
⎣ 1 + (α i | ψ m |) ⎦
, (4.34)
i =1

where
ψb is a parameter related to the soil matric potential at air where
entry (subscript b represents bubbling pressure) i is an index
λ is related to the soil pore-size distribution k is the number of SWC curves to be fitted with weighting, w i

15
h (m) =
R (μm)
1e+5 1e–4

1e+4 1e–3
dθ
= psd
1e+3 dψ 1e–2
Internal 1–2 mm
Matric potential (m–1)

pores aggregates
1e+2 1e–1
Pore radius (μm)

1e+1 1e+0
Internal External
1e+0 pores pores 1e+1

1e–1 1e+2
External
pores
1e–2 1e+3

1e–3 1e+4
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6
Volumetric water content (m3 m–3) Pore size density (m–1)

FIGURE 4.21  SWC of dual-porosity aggregates (1–2 mm) mapped to a corresponding pore-size distribution using Equation 4.25.
Soil Water Content and Water Potential Relationships 4-23

In this stable ceramic aggregate, the large disparity between

internal and external pore domains results in a four-order-
of-magnitude difference in the mean pore diameters mapped
1000 1000
using Equation 4.26. The pore-size density (psd) obtained from
the slope of the SWC (dθ/dψ) is informative for surface area
estimation and understanding transport phenomena. Sources

Matric potential (m–1)

of additional experimental and parametric SWC informa-
tion include (1) the Unsaturated Soil Hydraulic Database 100 100
(UNSODA) (Leij et al., 1996), which is a computer database

Dr
y
compiled by the US Salinity Laboratory, which contains an

in
gc
exhaustive collection of retention (SWC) and unsaturated W

ur
et

e v
hydraulic conductivity information for soils of different tex- tin
10 gc 10
tures from around the world. While the authors/compilers have ur
ve
attempted to provide some indices of data quality or reliability,
the users are advised (as always) to use their own experience
and discretion in adapting others’ data to their own applica-
tions; and (2) the regression studies by McCuen et al. (1981) 0 0
and Rawls and Brakensiek (1989) provide a wealth of infor- 0.0 0.2 0.4 0.6
mation on the BC parameter values for many soils including Soil water content
estimation of the hydraulic parameters based on other, often
FIGURE 4.22  Concept of hysteresis in soil–water characteristic
more easily available, soil properties. These estimates may be relationships.
sufficiently accurate for some applications and could be used to
obtain first-order approximations.

R
4.4.4  Hysteresis in the Soil–Water
r
Characteristic Relation
Drying
Water content and the potential energy of soil water are not
Wetting

uniquely related because the amount of water present at a given Gas

matric potential is dependent on the pore-size distribution and 1
Liquid
the properties of air–water–solid interfaces. A θ(ψ) relation- So
lid
ship may be obtained by (1) taking an initially saturated sample 2
and applying suction or pressure to desaturate it (desorption)
or by (2) gradually wetting an initially dry soil (sorption). These
two pathways produce curves that in most cases are not identi- (a) (b)
cal; the water content in the drying curve is higher for a given FIGURE 4.23  “Ink bottle” effect (a) and the contact angle effect (b).
matric potential than that in the wetting branch (Figure 4.22).
This is called hysteresis, defined as the phenomenon exhibited
by a system in which the reaction of the system to changes is 4.5  Resources
dependent upon its past reactions to change.
The hysteresis in SWC can be related to several phenom- A number of resources are available for readers interested in
ena: (1) the ink bottle effect resulting from nonuniformity additional insight or information concerning soil water content
in shape and sizes of interconnected pores as illustrated in and energy. The following suggestions are by no means inclu-
Figure 4.23a; drainage is governed by the smaller pore radius sive but should serve augmenting and extending the discussions
r, whereas wetting is dependent on the larger radius R; (2) presented here, as well as providing a source of additional refer-
different liquid–solid contact angles for advancing and reced- ences. We advise readers to consult the references we have cited
ing water menisci (Figure 4.23b); (3) entrapped air in a newly in relevant sections of the chapter, as well as various texts, mono-
wetted soil (e.g., pore doublet) (Dullien, 1992); and (4) swell- graphs, and review chapters. Soil physics and related textbooks,
ing and shrinking of the soil under wetting and drying, which which address soil water content and water energy include those
may alter the porosity and pore-size distribution. Based on of Childs (1969), Hanks (1992), Hillel (1998), Kirkham and
early observations of the phenomenon by Haines (1930) as Powers (1972), Kutilek and Nielsen (1994), Marshall et al. (1996),
well as present day theories (Mualem, 1984; Kool and Parker, Hillel (1998), and Jury and Horton (2004). Several chapters in
1987), the role of individual factors remains unclear and is the monograph edited by Dane and Topp (2002), as well as that
subject to ongoing research. edited by Carter (1993), contain valuable information. A number
4-24 Properties and Processes

of excellent review papers or chapters are also available, includ- Bakker, G., M.J. van der Ploeg, G.H. de Rooij, C.W. Hoogendam,
ing Baker (1990), Campbell and Mulla (1990), and Parker (1986). H.P.A. Gooren, C. Huiskes, L.K. Koopal, and H. Kruidhof.
Some Internet sites contain valuable information related to soil 2007. New polymer tensiometers: Measuring matric pres-
water content and energy. These include various individual or pro- sures down to the wilting point. Vadose Zone J. 6:196–202.
fessional organization pages, discussion groups (e.g., the soil mois- Banin A., and A. Amiel. 1970. A correlative study of the chemical
ture group SOWACS), and others. However, Internet addresses tend and physical properties of a group of natural soils of Israel.
to change rather frequently, and new sources may be added. This Geoderma 3:185–198.
means it is generally more efficient to conduct keyword searches Basinger, J.M., G.J. Kluitenberg, J.M. Ham, J.M. Frank, P.L.
using one or more of the available search engines than to rely on Barnes, and M.B. Kirkham. 2003. Laboratory evaluation of
potentially outdated web addresses. Extensive geospatial digital the dual-probe heat-pulse method for measuring soil water
soil databases are being established such as the USDA Web Soil content. Vadose Zone J. 2:389–399.
Survey and websites detailing worldwide resources can be found Baumgartner, N., G.W. Parkin, and D.E. Elrick. 1994. Soil water
online (e.g., compendium of online soil survey), In addition, there content and potential measured by hollow time domain
are numerous numerical modeling tools available online, which reflectometry probe. Soil Sci. Soc. Am. J. 58:315–318.
are useful for simulating soil water dynamics (e.g., Hydrus 1-D). Bird, N.R.A., A.R. Preston, E.W. Randall, W.R. Whalley, and
A.P. Whitmore. 2005. Measurement of the size distribution of
Acknowledgments water-filled pores at different matric potentials by stray field
nuclear magnetic resonance. Eur. J. Soil Sci. 56:135–143.
Partial funding for this work was provided by the Utah Bloch, F. 1953. The principle of nuclear induction. Science
Agricultural Experimental Station (UAES) and the Montana 118:425–430.
Agricultural Experimental Station (MAES). Blonquist, J.M., Jr., S.B. Jones, I. Lebron, and D.A. Robinson.
2006. Microstructural and phase configurational effects
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 5
Water Flow in Soils
5.1 Introduction.............................................................................................................................. 5-1
5.2 Steady Flow in Saturated Soil..................................................................................................5-2
Darcy Equation  •  Saturated Flow Parameters  •  Flow Perpendicular to Layers  • 
Flow Parallel to Layers  •  Flow to a Drain
5.3 Steady Flow in Unsaturated Soil.............................................................................................5-4
Buckingham–Darcy Equation  •  Unsaturated Hydraulic Conductivity  • 
Macroscopic Capillary Length  •  Analytical Solutions for Steady Flow
5.4 Transient Water Flow...............................................................................................................5-8
Governing Equations
5.5 Measurements of Hydraulic Properties.............................................................................. 5-11
Laboratory Methods  •  Field Methods  •  Inverse Solutions and Parameter
Optimization  •  Pedotransfer Functions
5.6 Numerical Methods...............................................................................................................5-13
5.7 Infiltration................................................................................................................................ 5-14
Infiltration into a Uniform Soil  •  Soil Crusts and Subsurface Layers  • 
Infiltration Equations  •  Borehole Infiltration  •  Subsurface Irrigation
5.8 Redistribution......................................................................................................................... 5-21
5.9 Evaporation.............................................................................................................................. 5-21
5.10 Transpiration...........................................................................................................................5-22
Soil–Plant–Atmosphere Continuum  •  Root Water Uptake
5.11 Preferential Flow.....................................................................................................................5-24
David E. Radcliffe Macropores  •  Fingering and Funnel Flow
University of Georgia
5.12 Groundwater Recharge and Discharge...............................................................................5-27
Jirka Šimůnek 5.13 Summary..................................................................................................................................5-30
University of California, Riverside References............................................................................................................................................5-30

5.1  Introduction the single process of evapotranspiration. Only water that is not
returned to the atmosphere by evapotranspiration may percolate
Water movement in soils is a key process that affects water quan- to the deeper soil zone and eventually reach the groundwater. If
tity and quality in the environment. Since the transport of solutes the water table is close enough to the soil surface, the process of
is closely linked with the soil water flux, any quantitative analy- capillary rise may move water from the water table through the
sis of solute transport must first evaluate water fluxes into and capillary fringe toward the root zone and the soil surface.
through soil. Water typically enters the soil surface in the form of Water movement in soils occurs under both saturated and
precipitation or irrigation or by means of industrial and munici- unsaturated conditions. Saturated conditions occur below the
pal spills (Figure 5.1). Some of the rainfall or irrigation water may water table where pressure head (h) is positive and water move-
be intercepted by the plant canopy. If the rainfall or irrigation ment is predominately horizontal, with lesser components of flow
intensity is larger than the infiltration capacity of the soil, water in the vertical direction. While unsaturated conditions and neg-
will be removed by surface runoff or will accumulate at the soil ative pressure heads generally predominate above the water table
surface until it evaporates back to the atmosphere or infiltrates (in the vadose zone), localized zones of saturation can exist espe-
into the soil. Part of the water that infiltrates is returned back cially following precipitation or irrigation or above an imperme-
to the atmosphere by evaporation. Water that infiltrates into the able zone. As a general rule, water movement in the vadose zone
soil profile may also be taken up by plant roots and eventually is vertical but can also have large lateral components.
returned to the atmosphere by plant transpiration. The pro- Governing equations for water flow can be developed for either
cesses of evaporation and transpiration are often combined into steady or transient conditions, but analytical solutions usually

5-1
5-2 Properties and Processes

where
Jw is the volumetric flow rate of water per unit cross-sectional
Transpiration
area (L T−1)
Interception Ks is the saturated hydraulic conductivity (L T−1)
Irrigation H is the total head (L)
Rainfall
Evaporation z is the spatial coordinate (L)
Runoff
Jw may be positive or negative depending on flow direction (the
usual convention is positive for flow up or to the right). Darcy’s
Root zone

law can be extended to 2D and 3D flow.

e
rag

Root water
Unsaturated zone

Darcy’s equation takes the same form as several other impor-

Sto

uptake
tant laws in science, among them, Fick’s law for molecular dif-
fusion, Ohm’s law for electric current flow, and Fourier’s law for
heat conduction. It shows that for water to move there must be
Deep drainage a difference in water potential (see Chapter 4 for definition), but
Capillary rise the rate of water flow will depend on the hydraulic gradient and
Water table the hydraulic conductivity of the soil.
Saturated

Groundwater recharge
zone

5.2.2  Saturated Flow Parameters

For saturated flow, the most important soil parameter is satu-
FIGURE 5.1  Water flow processes in soil. (From Šimůnek, J., M. Šejna, rated hydraulic conductivity, which is a function of the fluid and
H. Saito, M. Sakai, and M.Th. van Genuchten. 2008. The HYDRUS-1D soil properties:
software package for simulating the movement of water,  heat, and
multiple solutes in variably saturated media, Version 4.0, HYDRUS
kρl g
Ks = , (5.2)
Software Series 3. Department of Environmental Sciences, University η

of California Riverside, Riverside, CA.)
where
k is the intrinsic permeability of the soil (L2)
exist only for steady conditions. Although true steady flow may
ρl is the density of the fluid (M L−3)
occur only rarely, transient flow usually approaches steady flow
g is the gravitational acceleration (L T−2)
at long times, and the steady flow equations help to show what
η is the coefficient of dynamic viscosity of the fluid (M L−1 T−1)
factors may be important under transient conditions. Numerical
methods can be used to solve transient flow problems.
It is apparent from this equation that temperature has an effect
In the following sections, we start with steady water flow and
on Ks since it will affect ρl and η. It is generally true that while a
describe the governing equations and show several examples using
given soil will have a constant k as long as the soil structure is not
analytical solutions. Then we follow with transient water flow.
affected by the liquid, it will have a different Ks for different fluids.
The governing equations and initial and boundary conditions are
Soils with low porosity, few large pores, and poor intercon-
described along with a brief introduction to numerical methods.
nectivity between pores have low Ks. Rawls et al. (1982) compiled
Then, we describe in detail the important transient flow processes:
values of Ks from 1323 soils collected over 32 states of the United
infiltration, evaporation, redistribution, transpiration, preferential
States. Average Ks for 11 of the 12 United States Department of
flow, and groundwater recharge. The HYDRUS numerical models
Agriculture (USDA) soil textural classes (the silt class is miss-
(HYDRUS (2D/3D), Šimůnek et al., 2006; HYDRUS-1D, Šimůnek
ing) from Rawls et al. (1982) are shown in Table 5.1. Brooks and
et al., 2008) are used to illustrate these processes. More detail on the
Corey (1964) water retention curve parameters (see Chapter 4
model simulations can be found in Radcliffe and Šimůnek (2010).
for information on water retention functions) are also shown.
Saturated hydraulic conductivities were highest in coarse-tex-
5.2  Steady Flow in Saturated Soil tured soils (sand, loamy sand, etc.) and declined in fine-textured
soils (clay, silty clay, etc.), due to larger pores in coarse-textured
5.2.1  Darcy Equation soils. This can be corroborated by examining air-entry pressure
The equation that describes steady water flow through soil was heads ha (absolute value of the pressure head at which the largest
developed by H. Darcy (Darcy, 1856; Hubbert, 1956). For 1D capillary pore empties), which are higher in fine-textured soils,
flow, it can be written as indicating that the largest capillary pore is relatively small.
Saturated hydraulic conductivity varies widely among soils
within a textural class, especially in the more fine-textured
∂H classes in Table 5.1. In Figure 5.2, Ks for 324 soil samples from
J w = −K s , (5.1)
∂z the UNsaturated SOil hydraulic properties Database (UNSODA)
Water Flow in Soils 5-3

TABLE 5.1  Brooks and Corey (1964) Soil Hydraulic Parameters (Ks, θr, θs, ha, and λ)
for 11 Textural Classes
Textural Class Ks (cm day−1) θr (cm3 cm−3) θs (cm3 cm−3) ha (cm) λ (−) λc (cm)
Sand 504.0 0.020 0.417 −7.26 0.592 9.88
Loamy sand 146.6 0.035 0.401 −8.69 0.474 12.28
Sandy loam 62.16 0.041 0.412 −14.7 0.322 22.18
Loam 31.68 0.027 0.434 −11.1 0.220 17.79
Silt loam 16.32 0.015 0.486 −20.7 0.211 33.38
Sandy clay loam 10.32 0.068 0.330 −28.1 0.250 44.16
Clay loam 5.52 0.075 0.390 −25.9 0.194 42.27
Silty clay loam 3.60 0.040 0.432 −32.6 0.151 55.03
Sandy clay 2.88 0.109 0.321 −29.2 0.168 48.61
Silty clay 2.16 0.056 0.423 −34.2 0.127 58.96
Clay 1.44 0.090 0.385 −37.3 0.131 64.07
Source: Rawls, W.J., D.L. Brakensiek, and K.E. Saxton. 1982. Estimation of soil water properties.
Trans. ASAE 25:1316–1320, 1328.
Macroscopic capillary length (λc) calculated using Equations 5.11 and 5.16.

5.2.3  Flow Perpendicular to Layers

Saturated hydraulic conductivity (cm day–1)

100,000

10,000 Most soils other than entisols and inceptisols have well-devel-
oped horizons or layers, which have different hydrologic charac-
1,000 teristics including Ks. Above the water table, water usually flows
100
vertically so that flow is perpendicular to these layers. Below the
water table, flow can occur parallel to the layers.
10 Steady flow through a layered soil can be described by mak-
ing an analogy with electric current flow through resistors in
1
series (Jury and Horton, 2004). For a soil column with N lay-
0.1 ers of thickness L1, …, LN and saturated hydraulic conductivity
K1,  …,  K N (column on the left side of Figure 5.3), the effective
0.01
0.001 0.01 0.1 1 saturated hydraulic conductivity Keff (L T−1) is:
Clay fraction (g g–1)
N

FIGURE 5.2  Saturated hydraulic conductivity as a function of clay

K eff =
∑ L . j =1
j
(5.3)
fraction for 324 soils from the UNSODA database. (From Nemes, A., N

M.G. Schaap, F.J. Leij, and J.H.M. Wösten. 2001. Description of the unsatu-

∑ L /K
j =1
j j

rated soil hydraulic database UNSODA version 2.0. J. Hydrol. 251:151–162.)

The effective hydraulic conductivity is not a simple arithmetic aver-
database (Nemes et al., 2001) are plotted as a function of clay age of conductivities of individual layers or their limiting value,
content. Saturated hydraulic conductivity tends to decline as but a weighted average that considers the layer thicknesses as well
clay content increases, but there is considerable scatter at higher as their conductivities. Thus, the thickness of layers is important.
clay contents. The clayey soils with high Ks are probably soils
with strong structure. Hence, soil structure as well as soil tex- K1
ture affects water flow in all but very sandy soils.
K2
Saturated hydraulic conductivity is highly variable in space,
not only in the vertical direction as horizons change but also
K...
in the horizontal direction within the same horizon (Nielsen
Keff
et al., 1973; Russo and Bresler, 1980; Russo and Bouton, 1992).
Saturated hydraulic conductivity also varies in time at much
shorter scales than that of pedogenesis. This is especially true KN
near the soil surface where land use, biology, and weather
have more of an effect. Some authors have suggested that soil
properties should be divided into static and dynamic proper-
ties (Grossman and Reinsch, 2002; Tugel et al., 2005). Hence, FIGURE 5.3  A soil column with N layers of thickness L1, …, LN and
the effect of texture and mineralogy on Ks might be considered saturated hydraulic conductivities K1, …, KN on the left. An equivalent
static, whereas other effects might be considered dynamic. uniform column on the right with a saturated hydraulic conductivity Keff.
5-4 Properties and Processes

Because the flux across all layers is the same under steady-flow R
conditions, Darcy’s law can be used to show that when water
flows down through a high-conductivity to a low-­conductivity
layer (e.g., a sand horizon over a clay horizon), a pressure head
occurs at the interface that is greater than would be present
in a uniform soil. This elevated pressure slows flow through
the upper layer and speeds flow through the lower layer until
flow through both layers is the same. In the reverse situation,
zmax
(e.g., a clay over a sand), the interface pressure head is less than z x
in a uniform soil, which speeds flow through the upper layer and z0
slows flow through the lower layer. In a saturated, layered soil
under steady flow, the pressure head distribution is linear with Barrier
depth within each layer but with a different rate of change. 2s
For flow from low- to high-conductivity layers where a large
difference in conductivity is present, negative pressure heads can FIGURE 5.4  Geometry considered for defining the Dupuit–
occur at the interface that exceed the air-entry pressure head of Forchheimer drainage equation (5.6). Water height in the ditch or
soil in the lower layer. This causes unsaturated conditions in the drain is z 0. (From Warrick, A.W. 2003. Soil water dynamics. Oxford
lower layer that greatly reduce flow through the profile. This University Press, Oxford, U.K.)
often occurs when a surface seal or crust is present. Another way where z is the height of the water table (L). Under these condi-
to equalize flow through a layered soil with a low-conductivity tions, it can be shown that the maximum height of the water
layer over a high-conductivity layer is for water to flow through table zmax (L) between the drains or ditches is
only part of the less restrictive layer. This is a form of preferential
flow called fingering. Both surface seals and fingering are dis-
cussed later in this chapter. Rs 2
z max = + z 02 . (5.6)
Ks

5.2.4  Flow Parallel to Layers
From this equation, it can be seen that the water table will not
For flow parallel to layers (which usually occurs below the water rise as high between the drains and ditches when Ks is large.
table), the resistances of particular layers can be considered in Also, the greater the rainfall or irrigation rate, the higher the
parallel (more water flows through high- than low-conductivity water table will rise. The larger the spacing between drains,
layers). If the soil layers are of equal thickness, then Keff is the the higher the water table will rise. Equation 5.6 can be used to
arithmetic average of the hydraulic conductivities. For layers of determine the distance for separating drains in order to main-
different thicknesses, Keff is a weighted average where the layer tain the water table within a given range from the soil surface.
thicknesses are the weights: This equation is also useful later in the chapter when we consider
groundwater recharge and hillslopes.
N

K eff =
∑ j =1
LjK j
. (5.4) 5.3  Steady Flow in Unsaturated Soil
N

∑ j =1
Lj
The unsaturated zone lies between the water table and the soil
surface (Figure 5.1). In this region, the water content of the soil is
5.2.5  Flow to a Drain less than saturation (θ < θs), many pores are air filled, and pres-
sure heads are negative.
Flow to a drain provides another example of steady saturated Rising above the water table is the capillary fringe, a zone where
flow (Dupuit, 1863; Forchheimer, 1930). An equation can be water is under tension but very near saturation. The capillary
developed for the maximum height of the water table between fringe is important for water flow because only a slight change
two drains or ditches under steady-flow conditions (Warrick, in water content or pressure head can cause a sharp change in
2003; Figure 5.4). For a steady rainfall or irrigation rate R (L T−1) the water table position (Sklash et al., 1986). Also, lateral flow
and a drain separation distance 2s (L) with the water level in the increases in this zone (Liu and Dane, 1996; Abit et al., 2008).
ditch or drain maintained at a height z0 (L), the assumption is The thickness of the capillary fringe depends on the water
that water in the saturated zone will flow only in the horizontal retention curve and can be approximated by the air-entry pres-
direction and the gradient will be the change in height of the sure head (ha). From Table 5.1, it is apparent that sands have
water table: thinner capillary fringes than unstructured clays. Capillary
fringes are also found around other zones of saturation in the
dz unsaturated zone, such as injection boreholes, surface seepage
J x = −K s , (5.5)
dx basins, and losing streams.
Water Flow in Soils 5-5

5.3.1  Buckingham–Darcy Equation associated with Burdine’s pore-size distribution model, leading
to the hydraulic conductivity function:
In the unsaturated zone, larger pores drain more readily than
smaller pores, as can be noted using the capillary rise equation
K (Se ) = K s Se1+ l + 2 / λ , (5.11)
(see Chapter 4). Therefore, the hydraulic conductivity is much
smaller under unsaturated than saturated conditions due to
water moving through smaller pores or as films along the walls where
of larger pores. At very low water contents, continuous fluid λ [-] is the pore-size distribution index from the Brooks and
paths may not exist and water may move in the vapor phase. The Corey (1964) water retention function (see Table 5.1)
unsaturated hydraulic conductivity is therefore represented as a l is a pore-connectivity parameter (assumed to be 2.0)
function of pressure head K(h) or as a function of water content S e is effective saturation [-]:
K(θ). Buckingham (1907) modified Darcy’s equation for unsatu-
rated flow as follows: θ − θr
Se = , (5.12)
θs − θr
∂H ∂(h + z ) ⎛ ∂h ∂z ⎞
J w = − K (h) = − K (h) = − K (h) ⎜ +
∂z ∂z ⎝ ∂z ∂z ⎟⎠ where
θs is the saturated volumetric water content (L3 L−3)
⎛ ∂h ⎞ θr is the residual volumetric water content (L3 L−3)
= − K (h) ⎜ +1 , (5.7)
⎝ ∂z ⎟⎠

The van Genuchten (1980) water retention function is similarly
where the total head or hydraulic head is the sum of the pressure coupled most often with the model of Mualem to give
head and gravitational head, H = h + z.
K (Se ) = K s Sel [1 − (1 − Se1/m )m ]2 (5.13)

5.3.2  Unsaturated Hydraulic Conductivity

where m [-] and n [-] are empirical shape parameters from
As is the case with the water retention functions, equations have the van Genuchten (1980) water retention function and it is
been developed to describe the hydraulic conductivity function. assumed that
One of the simplest equations is the Gardner (1958) equation:
1
αh
m =1− , n > 1. (5.14)
K (h) = K s e , (5.8) n

where α (L−1) is a positive constant dependent on the soil. Since h The pore-connectivity parameter l in Equation 5.13 was esti-
is negative, the exponential term causes K(h) to drop rapidly as mated by Mualem (1976) to be 0.5 as an approximate average
h becomes more negative. A coarse-textured soil (sand), which for many soils. However, Schaap and Leij (2000) recommended
has a rapidly decreasing hydraulic conductivity function com- using l = −1 as an appropriate value for most soil textures.
pared to a fine-textured soil (clay), would be expected to have a Finally, Durner (1994) associated a dual-porosity retention
larger value of α. model with Mualem’s pore-size distribution model to give
Other simple equations include the Campbell (1974) equation:
K (Se )
m
⎛ θ⎞ (w1Se1 + w2Se2 )l {w1α1[1 − (1 − Se11/ m1 )m1 ] + w2α 2[1 − (1 − Se12/ m2 )m2 ]}2
K (θ) = K s ⎜ ⎟ , (5.9) = Ks ,
⎝ θs ⎠ (w1α1 + w2α 2 )2

(5.15)
where m is a fitting parameter [-], and the Haverkamp equation
(Haverkamp et al., 1977) where
wi [-] are the weighting factors for the overlapping regions of
Ks the water retention functions
K (h) = , (5.10)
1 + (h/a)N αi [-] and mi [-] are fitting parameters for the separate func-
tions S ei (i = 1, 2)
where a (L−1) and N [-] are fitting parameters.
Many hydraulic conductivity functions have been derived Values of K(h) vary by orders of magnitude with pressure
using the pore-size distribution models of Burdine (1953) or head, are sensitive to texture, clay mineralogy, and structure,
Mualem (1976), in combination with various water retention and are highly variable in space and (in some cases) time.
functions (water retention functions are discussed in Chapter 4). Figure 5.5 presents examples of hydraulic conductivity func-
The Brooks and Corey (1964) retention equation is commonly tions for the sand, loam, and clay textural classes, using the
5-6 Properties and Processes

5.3.3  Macroscopic Capillary Length

Sand
Hydraulic conductivity (cm day–1)

100
Loam A useful way to quantify the unsaturated hydraulic conductiv-
10 Clay ity function in a single parameter is in terms of the macroscopic
1 capillary length λc (L) defined as
0.1
h0
0.01
λc =
∫hi
K (h) dh
, (5.16)
0.001
K (h0 ) − K (hi )
0.0001
0.00001 where
0.000001
h0 (L) is a pressure head at or near zero
1 10 100 1000 hi (L) is a more negative pressure head such that h0 > hi (White
Pressure head (cm) and Sully, 1987)

There are a number of ways to interpret λc. One way is a

100
K(h)-weighted average pressure head over the range from h0 to
Hydraulic conductivity (cm day–1)

10 hi (except that it is a positive number). If λc is small, this indi-

1
cates that the effective pressure head for unsaturated flow is near
zero. In other words, K(h) is negligible except for pressure heads
0.1 near zero (and water contents near saturation). This would be
0.01 the case for a sand where K(h) rises sharply at the wet end of the
0.001 curve. An unstructured clay might have a larger λc, because the
effective pressure head for unsaturated flow is more negative and
0.0001
K(h) does not approach zero as fast at the dry end of the curve.
0.00001 Typical values for λc in four broad groups of soils are shown in
0.000001 Table 5.2. The effect of structure in fine-textured soils is appar-
0 0.1 0.2 0.3 0.4 0.5 ent in that an unstructured clay has a λc of 25 cm, whereas a
Volumetric water content (–) structured clay has a λc of 2.8 cm. Values for λc are also shown in
Table 5.1 for each of the textural classes. These values were cal-
FIGURE 5.5  Examples of unsaturated hydraulic conductivity curves
as a function of pressure head (top) and volumetric water content (bot- culated using Equation 5.16 with h0 = 0 cm, hi = −15,000 cm, and
tom) for the sand, loam, and clay soil textural classes based on the the Brooks and Corey (1964) equation for K(S e) (Equation 5.11).
Brooks and Corey (1964) equation (Equation 5.11) and parameters in In both tables, leaving aside the effect of structure, λc increases
Table 5.1. as the clay content increases.
If the Gardner equation (Equation 5.8) is used to describe
Brooks and Corey (1964) unsaturated hydraulic conductivity K(h) in Equation 5.16, it can be shown that
equation (Equation 5.11) and the parameters given in Table 5.1. 1
The hydraulic conductivity curves are presented as functions λc = . (5.17)
α
of both the pressure head (top) and water content (bottom). It
is apparent that Equation 5.11 results in a linear relationship
between ln K(h) and ln h. Notice that the hydraulic conductivity TABLE 5.2  Soil Texture/Structure Categories for Estimation
at saturation is significantly larger for the sand than for the loam of Macroscopic Capillary Length (λc)
or clay. This difference is often several orders of magnitude. Also
Soil Texture/Structure Category λc (cm)
notice that the hydraulic conductivity decreases several orders
of magnitude as the soil becomes unsaturated. This decrease, Coarse and gravelly sands; may also include some highly 2.8
structured soils with large cracks and/or macropores
when expressed as a function of the pressure head (Figure 5.5,
Most structured soils from clays through loams; also includes 8.3
top), is much more significant for the sand than for the loam, unstructured medium and fine sands
and even more so than for the clay. The decrease for the sand is Soils that are both fine textured (clayey) and unstructured 25
so dramatic that eventually the hydraulic conductivity becomes Compacted, structureless, clayey materials such as landfill caps 100
smaller than for the loam or clay. These properties of the hydrau- and liners, lacustrine or marine sediments, etc.
lic conductivity function are sometimes used in the design of
Source: Adapted from Elrick, D.E., and W.D. Reynolds. 1992. Infiltration
capillary barriers in landfill covers to divert water from flowing from constant-head well permeameters and infiltrometers, p. 1–24. In G.C. Topp,
through the underlying waste or in thin sand or gravel layers at W.D. Reynolds, and R.E. Green (eds.) Advances in measurement of soil physical
the soil surface to prevent or limit evaporation. properties: Bringing theory into practice. SSSA, Madison, WI.
Water Flow in Soils 5-7

Thus, a small value of λc indicates a rapid exponential decrease 0

of the K(h) function. Macroscopic capillary length appears in a
–10
number of equations later in this chapter, where it represents the
effect of soil texture (and the shape of the unsaturated hydraulic –20
conductivity curve) on unsaturated water flow. –30

–40

Depth (cm)
5.3.4  Analytical Solutions for Steady Flow
–50
It is useful to consider several cases of steady unsaturated flow.
Although true steady flow may occur only rarely under unsatu- –60
rated conditions, transient flow (discussed later in this chapter) –70
usually approaches steady flow over long time periods, and the
steady flow equations help to show what factors may be impor- –80
i = 0.5 cm day–1
tant under transient conditions. –90 i = 1.5 cm day–1
As noted before, steady 1D flow in a uniform soil can be
–100
described by the Buckingham–Darcy equation (Equation 5.7).
–40 –30 –20 –10 0
If the water content is uniform with depth, then ∂h/∂z = 0, Pressure head (cm)
only gravity causes flow and the flux is equal to the hydraulic
conductivity: FIGURE 5.6  Distribution of h as a function of z for a steady low infil-
tration rate (0.5 cm day−1) and a steady high infiltration rate (1.5 cm
J w = − K (h). (5.18) day−1) based on Equation 5.20.

The distribution of h versus z predicted by Equation 5.20 for
In this case, h is the same at all depths. This is called gravity flow
a Chino clay with Ks = 1.95 cm day−1, a = −23.8 cm, and N = 2
or unit-gradient flow.
(Gardner and Fireman, 1958) is shown for a low (i = 0.5 cm day−1)
Analytical solutions to the Buckingham–Darcy differential
and a high (i = 1.5 cm day−1) infiltration rate in Figure 5.6. The
equation (Equation 5.7) have been developed for a number of
distribution of h is curvilinear, contrary to a uniform or a layered
steady-flow conditions. The usual procedure is to rewrite the
saturated soil, especially with the lower infiltration rate, which
equation in an integral form (Jury and Horton, 2004):
causes a lower h at the surface. At the water table, the pressure
head is zero, of course. Near the surface, especially at the high
h2
dh infiltration rate, the curve is nearly vertical indicating that grav-
∫ 1 + (J
h1
w/K (h))
= z1 − z 2 . (5.19)
ity flow is the dominant form of flow (Equation 5.18).
Another example of steady downward flow is 3D water flow from
a point source such as a ring placed at the soil surface (Figure 5.7).
If the equation for K(h) is such that the integral on the left side A steady infiltration rate will be approached after a period of time.
can be evaluated (has an analytical solution), then the differen- Wooding (1968) developed an equation for these circumstances:
tial equation can be solved.
An example is steady infiltration (Jw = −i) in a uniform soil
⎛ 4λ ⎞
from the surface to a water table at depth L (Jury and Horton, i s = K (h0 ) ⎜ 1 + c ⎟ , (5.21)
⎝ πr ⎠
2004). This might occur in a soil remediation effort designed
to flush contaminants from the unsaturated zone down into
the capture zone of a well. In this case, h1 = 0 at the water table, Water level
where z1 = −L. The other limit is an arbitrary depth below the Ring
surface (h2 = h and z2 = z) so that integration will result in an Soil surface
r
equation for the distribution of h with depth under steady flow
conditions. The K(h) function is described using the Haverkamp
equation (Equation 5.10). To get an integral that can be evalu-
ated, it is assumed that N = 2 in the Haverkamp equation. It can
be shown (Jury and Horton, 2004) that the solution is

Ks ⎡ (1 − (i /K s ))(i /K s ) ⎤
h=a − 1 tanh ⎢ − ( L + z )⎥ , (5.20) is
i ⎢⎣ a ⎥⎦

FIGURE 5.7  Steady 3D infiltration of water from a ring of radius r at
where tanh(x) is the hyperbolic tangent function. the soil surface.
5-8 Properties and Processes

where TABLE 5.3  Dimensionless Coefficients for the Polynomial

is is the steady infiltration rate (L T−1) (Equation 5.24) Describing the Geometric Factor G,
r is the radius of the ring (L) Valid for H/r < 10
K(h0) is the hydraulic conductivity (L T−1) corresponding to Soil Texture/Structure A1 A2 A3 A4
the pressure head of the water supply at the soil surface
Sand 0.079 0.516 −0.048 0.002
(z = 0) Structured loams and clays 0.083 0.514 −0.053 0.002
Unstructured clays 0.094 0.489 −0.053 0.002
It is apparent by comparing Equations 5.21 and 5.18 that
the second term in Equation 5.21 accounts for the increased Source: Bosch, D.D., and L.T. West. 1998. Hydraulic conductiv-
ity variability for two sandy soils. Soil Sci. Soc. Am. J. 62:90–98.
infiltration rate from a ring due to lateral flow into dry soil
(Figure 5.7). It is no surprise that this term includes λc since
this represents the effect of capillarity, which will vary with the equation can be expressed in a form comparable to the
soil texture and the shape of the K(h) function. If water is Wooding equation (Equation 5.21):
ponded at the surface, h 0 > 0 and K(h 0) should be what cor-
responds to K s in the field. Experiments have shown that the ⎛ H λc H2 ⎞
field-saturated hydraulic conductivity (K fs) is less than the is = K s ⎜ 1 + + . (5.23)
⎝ Gπr
2
Gπr 2 ⎟⎠
saturated hydraulic conductivity that would be measured on
a carefully saturated, intact core in the lab (K s). This has been
attributed to the effect of entrapped air under field condi- The similarity between Equation 5.23 and the Wooding equa-
tions that reduces the cross-sectional area available for water tion (Equation 5.21) is apparent. In sequence, the terms inside
flow and the water potential gradient. Bouwer (1969) recom- the brackets in Equation 5.23 account for the effect of gravity,
mended using a value for K fs equal to one-half of K s for pre- the shape of the unsaturated hydraulic conductivity function
dicting the steady-state infiltration rate. (note the λc term), and hydrostatic pressure in the borehole.
The Buckingham–Darcy differential equation can also be Bosch and West (1998) fitted a polynomial equation to the
solved for steady flow from a borehole (Figure 5.8): data of Elrick and Reynolds (1992) to determine the value of G:

2 3
⎛ H λc H 2 ⎞ 1 ⎡ H ⎛H⎞ ⎛H⎞ ⎤
Qs = K s ⎜ πr 2 + + , (5.22) G= ⎢ A1 + A2 + A3 ⎜ ⎟ + A4 ⎜ ⎟ ⎥ . (5.24)
⎝ G G ⎟⎠ 2π ⎢ r ⎝ r⎠ ⎝ r⎠ ⎥
⎣ ⎦

where The values of the coefficients A1, …, A4 [-] in this polynomial

Qs is the steady volumetric flow rate (L3 T−1) depend on texture and structure (Table 5.3). Equation 5.22 is
H is the height of water ponded in the borehole (L) used to measure Ks using a borehole permeameter, described
r is the radius of the hole (L) later in this chapter.
G is a dimensionless geometric factor that depends primarily
on the ratio of H/r (Elrick and Reynolds, 1992) 5.4  Transient Water Flow
If the steady infiltration flux is is defined as the volumetric flow In this and the following sections, we address transient water
rate divided by the cross-sectional area of the borehole Qs/πr2, movement. Analytical solutions of the differential equations
that govern soil water flow for nonsteady, unsaturated flow
conditions are very few. Simplifications of the unsaturated
Soil surface
flow equations have been developed to describe infiltration
because of the importance of this transient flow process.
r Alternatively, numerical models are commonly used to solve
most transient flow problems in the unsaturated zone.
H
5.4.1  Governing Equations
Here, we discuss the Richards equation and the initial condi-
tions and boundary conditions that apply to transient water flow.

5.4.1.1  The Richards Equation

is
A conservation equation for nonsteady vertical water flow can be
developed by considering a representative elementary volume.
FIGURE 5.8  Steady 3D infiltration of water from a borehole. The water flux into this volume during a small time interval
Water Flow in Soils 5-9

Δt must be equal to the water flux out of the volume, plus the The Richards equation (in any form) is a nonlinear partial
change in water stored within the volume, and any sources or differential equation. It is similar to the heat-flow equation that
sinks. The resulting conservation equation is includes convection and conduction but differs in one very
important way. The coefficient K(h) that multiplies the gradient
term is a function of the dependent variable h. This makes it a
∂θ ∂J
= − w − S(h), (5.25) nonlinear partial differential equation. Because of its strongly
∂t ∂z nonlinear makeup, only a relatively few simplified analyti-
cal solutions can be derived. Most practical applications of the
where Richards equation require a numerical solution (see Section 5.6).
θ is the volumetric water content (L3 L−3) Alternatively, the equation is simplified in some manner as hap-
t is time (T) pens with infiltration equations (see Section 5.7.3).
z is the spatial coordinate (L) (positive upward)
5.4.1.2  Initial Conditions
Jw is the water flux (L T−1)
S(h) is a pressure head dependent sink (L3 L−3 T−1) (a negative The solution to the Richards equation will depend on the initial
S is a source), usually accounting for root water uptake and boundary conditions specified. Initial conditions charac-
(transpiration) terizing the initial state of the system can be specified either in
terms of the water content
Equation 5.25 is often referred to as the mass conservation
equation or the continuity equation. The conservation equation θ(z , t ) = θi (z , 0) (5.29)

must be combined with one or several equations describing Jw
to produce the governing equation for variably saturated water or the pressure head
flow. Formulations of governing equations for the different
types of flow (uniform and preferential flow) are all based on h(z , t ) = hi (z , 0), (5.30)
this continuity equation. If the Buckingham–Darcy equation
(Equation 5.7) is substituted for Jw, the result is
where θi (L3 L−3) and hi (L) are initial values of water content and
pressure head, respectively. For numerical models, it is generally
∂θ(h) ∂ ⎛ ∂h ⎞ ∂K (h)
= K (h) ⎟ + − S(h). (5.26) best to specify initial conditions in terms of the pressure head,
∂t ∂z ⎜⎝ ∂z ⎠ ∂z since this variable is the driving force for water flow. Specifying

initial conditions in terms of the water content often leads to
This partial differential equation, first developed by Richards unrealistically large pressure-head gradients, and consequently
(1931), is the equation governing flow in the unsaturated zone. water fluxes, across textural boundaries.
The first term on the right-hand side accounts for the effect of
5.4.1.3  Boundary Conditions
capillarity on water movement and the second term on the right-
hand side accounts for the effect of gravity. It can be expanded to Two types of conditions can be specified on boundaries of the
two and three dimensions. transport domain: system-dependent and system-independent
Equation 5.26 is the mixed form of the Richards equation in boundary conditions. System-independent boundary conditions
that there are two dependent variables: θ and h. Various other are boundary conditions for which the specified boundary value
formulations of the Richards equation are possible. For example, (i.e., pressure head, water content, water flux, or gradient) does
when the time derivative of the water content is expanded using not depend on the status of the soil system. System-dependent
the chain rule as follows: boundary conditions are boundary conditions for which the
actual boundary condition depends on the status of the system
and is calculated by the model itself.
∂θh dθ ∂h ∂h
= = Cw (h) (5.27) Several system-independent boundary conditions may be
∂t dh ∂t ∂t
applied to the transport domain boundaries. When the pres-
sure head at the boundary is known, one can use the Dirichlet or
one obtains the pressure-head form type-1 boundary condition:

∂h ∂ ⎛ ∂h ⎞ ∂K (h) h(z , t ) = h0 (z , t ), (5.31)

Cw (h) = K (h) ⎟ + − S(h), (5.28)
∂t ∂z ⎜⎝ ∂z ⎠ ∂z

where h 0 is a prescribed pressure head (L). This boundary
where Cw(h) is the soil water (or hydraulic) capacity function condition is often referred to as a pressure-head boundary con-
(L−1) that characterizes the slope of the retention curve. The only dition. This boundary condition must be used when simulating
independent variable is h: ponded infiltration; for describing the hydrostatic pressure at
5-10 Properties and Processes

the boundary between the soil and standing or flowing water evaporation rate can be significantly reduced to an actual evapo-
in a furrow, lake, or river; to specify the water level in a well; or ration rate that is again controlled by the soil.
to define the position of the groundwater table. The water flux System-dependent atmospheric boundary conditions can be
across a Dirichlet boundary is not known a priori but must be implemented mathematically using an approach of Neuman et al.
calculated from the mathematical solution (either analytical or (1974), which limits the absolute value of the flux such that the fol-
numerical) of the governing flow problem. lowing two conditions are satisfied:
When the water flux across the boundary is known, one can
use the Neumann or type-2 boundary condition: ⎛ ∂h ⎞
K (h) ⎜ + 1⎟ ≤ E (5.34)
⎝ ∂z ⎠
⎛ ∂h ⎞
−K (h) ⎜ + 1⎟ = J 0 (z , t ), (5.32)
⎝ ∂z ⎠
and
hA ʺ h ʺ hS , (5.35)
where J0 is a prescribed water flux (L T−1). This boundary
condition is often referred to as a flux boundary condition.
where
A Neumann boundary condition must be used only along
E is the maximum potential rate of infiltration or evaporation
boundaries where the flux is known, provided the flux does
under the current atmospheric conditions (L T−1)
not depend on the soil system. Hence, this boundary condi-
h is the pressure head at the soil surface (L)
tion cannot be used to model precipitation or irrigation since
hA and hS are, respectively, the minimum and maximum pres-
the precipitation or irrigation rate may exceed the infiltration
sure heads allowed under the prevailing soil conditions (L)
capacity of the soil, in which case ponding will occur and the
actual boundary flux will decrease.
The value for hA is determined from the equilibrium conditions
A particular form of the type-2 boundary condition is the
between soil, water, and atmospheric water vapor, whereas hS is
gradient boundary condition:
usually set equal to zero (which would initiate instantaneous
∂h surface runoff) or results from the accumulation of excess water
+ 1 = g 0 (z , t ), (5.33)
∂z in the surface ponding layer, in which case its value must be cal-
culated from the difference between the infiltration and precipi-
where g0 is a prescribed total gradient (L L−1). Equation 5.33 is tation (or irrigation) rates. When one of the limits of Equation
commonly used to specify a unit vertical hydraulic gradient sim- 5.35 is reached, a prescribed head boundary condition will be
ulating free drainage from the bottom of a soil profile when the used to calculate the actual surface flux. Methods for calculating
water table is situated far below the domain of interest. The con- E and hA on the basis of atmospheric data have been discussed
dition is consistent with unit-gradient conditions (see Equation by Feddes et al. (1974).
5.18) often observed in field studies of water flow, especially dur- Another example of a system-dependent boundary condition
ing redistribution (Sisson, 1987; McCord, 1991). is a seepage face through which water leaves the saturated part
In many applications, neither the flux across nor the pressure of the flow domain. The boundary condition in this case can be
head or gradient at a boundary is known a priori but follows from formulated mathematically as follows:
interactions between the soil and its surroundings (e.g., the atmo-
sphere or deeper subsurface). The boundary representing the J 0 (z , t ) = 0 for h(z , t ) < 0,
soil–air interface, which is exposed to atmospheric conditions, (5.36)
h0 (z , t ) = 0 for h(z , t ) ≥ 0.
is one example of the system-dependent boundary. The poten-
tial water flux across this interface is controlled exclusively by This boundary condition states that there is no flux across the
external conditions (precipitation or evaporation). However, the boundary as long as the boundary is unsaturated and that
actual flux depends also on the (transient) moisture conditions the pressure head changes to zero once saturation is reached.
in the soil. Soil surface boundary conditions may change from The flux across the boundary is then calculated from the flow
prescribed flux to prescribed head conditions (and vice versa). field by solving the governing flow equations. This boundary
This occurs, for example, when the precipitation rate exceeds the condition can be used at the bottom of certain types of lysim-
infiltration capacity of the soil, resulting in either surface runoff eters or along tile drains.
or accumulation of excess water on top of the soil, depending A special system-dependent boundary condition is sometimes
upon the soil conditions. The infiltration rate in that case is not implemented in 1D numerical models (e.g., van Dam et al., 1997;
controlled anymore by the precipitation rate but instead by the Šimůnek et al., 2006) to account for flow to horizontal subsurface
infiltration capacity of the soil. A system-­dependent boundary tile drains. An equivalent drainage flux from the bottom of the
condition also occurs when the potential evaporation rate, as cal- simulated soil profile is then calculated using an appropriate ana-
culated from meteorological conditions (the evaporative demand lytical solution for the tile drainage system (e.g., Hooghoudt, 1940;
of the atmosphere), exceeds the capability of the soil to deliver Ernst, 1962; van Hoorn, 1997). The drainage equations involved
enough water toward the soil surface. In this case, the potential generally hold for steady-state flow into the drain and depend
Water Flow in Soils 5-11

upon the geometry of the system (e.g., depth of tile drain, depth similar to the constant-head method for Ks by adding water at the
to impermeable layer, location of water table midway between two top of the core at a rate that does not cause ponding (Booltink and
drains, and possibly information about soil layering). Bouma, 2002a). The total potential within the core is measured
at two heights using miniature tensiometers and the steady flux
5.5  Measurements of Hydraulic is recorded. The Buckingham–Darcy equation (Equation 5.7) is
solved for K(h), where h in this case is the average pressure head
Properties within the core. Steady evaporation from the top of a core can also
Accurate measurement of hydraulic parameters by both labora- be used to measure K(h) by placing tensiometers at several heights,
tory and field methods is essential for the prediction of water recording the steady evaporation rate, and calculating the gradi-
movement in soils. However, uncertainties in parameter esti- ent between each pair of tensiometers (Arya, 2002).
mates arise because of spatial variation, measurement accu- Steady unsaturated flow can be imposed on a long soil core by
racy, and scale effects. Many of these methods use steady flow supplying water continuously at a rate less than Ks. This can be
conditions but recent advances have been made in using tran- done by applying a crust made of a mixture of gypsum and sand,
sient conditions. The important laboratory and field methods or cement and sand, to the soil surface (Booltink and Bouma,
commonly employed in estimating hydraulic properties using 2002b). The steady water flux is measured with a constant posi-
steady-flow conditions are discussed below with additional pro- tive head above the crust. Because of the low Ks of the crust, flow
cedures available in Dane and Topp (2002). Transient flow meth- in the core is unsaturated (see Section 5.2.3). A tensiometer in
ods using inverse solutions and parameter optimization are also the core records h, and if a unit gradient is assumed, then the
discussed. Lastly, pedotransfer functions (PTFs) as an alterna- measured flux is K(h). Successive flux measurements with differ-
tive to direct measurement of hydraulic properties are described. ent crusts, each with a different conductivity, provide measure-
ments of K(h) over the range of pressures achieved. Bouma and
5.5.1  Laboratory Methods Denning (1972) used this method in the field, as well.
In all laboratory methods of measuring Ks and K(h), the effect
The constant-head and falling-head methods are common for of the chemistry of the added water on clay dispersion must be
measuring Ks. In the former method, a constant head of water considered. The goal is to prevent dispersion so that pore-size
is maintained at the top and bottom of a soil core and the steady distribution and connectivity do not change during the mea-
water flux Jw is recorded (Reynolds and Elrick, 2002a). The gradi- surement, which can be achieved by using a dilute solution with
ent is known, given the heads at the top and bottom of the core a divalent cation (Chiang et al., 1987).
and the length of the core, so Darcy’s equation (Equation 5.1)
can be used to determine Ks.
In the falling-head method, a standpipe is attached to the top 5.5.2  Field Methods
of a soil core and the head at the top is allowed to drop over time Common field methods for measuring Ks are use of the ring infil-
(Reynolds and Elrick, 2002c). Under these conditions, it can be trometer and borehole permeameter. Ring infiltrometers can be
shown that used to pond water on the soil surface and measure the soil infil-
L ⎛ b0 + L ⎞ tration rate (Reynolds et al. 2002). It is usually assumed that the
Ks = ln , (5.37) Wooding equation (Equation 5.21) describes the 3D steady infil-
t1 ⎜⎝ b1 + L ⎟⎠
tration rate. Typical values of λc (Table 5.1 or 5.2) can be used to
where convert steady flow rates to Ks using this equation. Concentric
b0 is the height of water ponded (L) at the top of the core at double rings have been used to force 1D flow in the interior ring.
time zero In this case, the steady infiltration rate is an estimate of Ks in a
b1 is the height of water ponded (L) at a later time t1 (T) uniform soil. However, Bouwer (1986) found that, for the typical
dimensions used in a double ring, flow was not 1D.
The falling-head method is useful in soils with very low Ks, where it is Borehole permeameters are used to measure saturated
difficult to collect sufficient drainage from a core to measure Jw accu- hydraulic conductivity below the soil surface in the unsaturated
rately within an interval of several hours. The initial reading b0 can zone (Reynolds and Elrick, 2002b). They consist of a Mariotte
be recorded and the core left overnight before recording b1 without siphon (McCarthy, 1934) that maintains water at a constant level
concern about the effect of evaporation on the collected drainage. in a borehole and they allow measurement of the flow rate into
Values of Ks measured on cores in the laboratory will depend the soil. The steady flow rate into the borehole Qs is measured
on what measures are used to remove entrapped air from the and then Equation 5.22 applies, but there are two unknowns in
soil before making the measurement. Flushing the core with this equation: Ks and λc. One approach is to measure Qs at two
CO2, wetting the core slowly from the bottom, and measuring Ks values of H in the same borehole and solve simultaneous equa-
under conditions of an upward flux are commonly used. tions for Ks and λc. Since changing the level of H in the borehole
A number of methods have been developed for measuring necessarily changes the region of soil that is being sampled, soil
unsaturated hydraulic conductivity on cores in the laboratory. heterogeneity in the form of layering or macropores can result
Unsaturated hydraulic conductivity can be measured in a manner in unrealistic and invalid (i.e., negative) Ks and λc. As many as
5-12 Properties and Processes

30%–80% of measurements of Ks and λc in structured soils may such as pressure heads or water contents at different depths and
be invalid (both negative) according to Elrick and Reynolds times. Predicted and measured fluxes or cumulative fluxes across
(1992). Alternatively, a single measurement of Qs may be used boundaries can also be used as variables. In the first term, mq is
and λc estimated using Table 5.1 or 5.2. Studies suggest that this the number of different sets of measurements, nqj is the number
method yields values of Ks that are usually accurate to within a of measurements in a particular measurement set, q *( j z , t i ) repre-
factor of 2 (Reynolds et al., 1992). sents specific measurements at time ti for the jth measurement set
Tension infiltrometers (also called disc permeameters) are a pop- at depths z (a vector of locations), q *j (z , t i , b) are the correspond-
ular method for determining unsaturated hydraulic conductivity ing model predictions for the vector of optimized parameters (e.g.,
and other hydraulic parameters in field soils. They consist of a cir- θr, θs, α, n, Ks, etc.) and vj and wij are weights associated with a par-
cular porous plate or membrane, which is placed on the soil surface ticular measurement set or point, respectively. The second term
or an excavated surface. Water is supplied to the plate under tension on the right-hand side of Equation 5.38 represents differences
using a Mariotte bottle arrangement and the rate of water entry into between independently measured and predicted soil hydrau-
the soil can be measured on a graduated cylinder or with a pres- lic properties (e.g., θ(h) or K(h) data), while the terms mp,  npj,
sure transducer (Clothier and Scotter, 2002). In some cases, a ring j θi ), pj(θi, b), v j , and wij have similar meanings as for the first
p*(
is attached to the tension infiltrometer to allow ponded infiltration term but now apply to hydraulic properties. The last term on the
measurements at the same location (Perroux and White, 1988). Two right-hand side of Equation 5.38 represents a penalty function for
approaches are common, one in which the infiltration rate is mea- deviations between prior knowledge of the soil hydraulic param-
sured after it attains a steady rate and the other in which the early eters b*j and their final estimates bj, with nb being the number of
nonsteady infiltration rate is measured (Warrick, 1992). parameters with prior knowledge and vˆj representing preassigned
weights. Minimization of the objective function is accomplished
5.5.3  Inverse Solutions and Parameter in HYDRUS using the Levenberg–Marquardt nonlinear minimi-
Optimization zation (Marquardt, 1963).
Transient flow parameter optimization methods are
Modeling transient water flow requires an accurate estimation of described by Hopmans et al. (2002). With these methods,
a number of hydraulic parameters including the soil water reten- both the soil retention and unsaturated hydraulic conductiv-
tion curve, saturated hydraulic conductivity, and the unsaturated ity functions can be estimated from a single transient experi-
hydraulic conductivity function. As an alternative to direct mea- ment. Inverse methods can be used in laboratory experiments
surement of these parameters, they can be estimated indirectly and in field experiments. A common laboratory experiment is
using inverse modeling. This differs from the direct methods the multistep outflow method. In this method, a pressure cell
where steady-flow conditions are required due to the analytical similar to what is used for the determination of a water reten-
solutions that are used. Whereas steady-state methods invert tion curve is employed. The air pressure on the cell is increased
Darcy’s equation, transient methods invert the Richards equa- once (the one-step method) or a number of times to successively
tion. Inverse methods for these conditions have become possi- higher pressures (the multistep method) much like what is done
ble because advances in computer science have made obtaining when measuring a water retention curve. However, instead of
numerical solutions much quicker, so solutions can be run waiting until the cell reaches equilibrium at a given pressure
repeatedly to find the optimum parameter values. to measure the water content, pressure head in the cell and
Inverse modeling is a form of model calibration, which is fre- water flow out of the cell are measured continuously during
quently used in hydrology (Gupta et al., 2003). It requires a set the experiment. The observed and predicted pressure heads in
of observed data such as measured water contents or pressure a multistep method experiment analyzed using HYDRUS-1D
heads. In model calibration, the objective is usually to obtain are shown in Figure 5.9. Four pressure changes were used and
better model predictions. Parameter optimization differs in that the experiment ran for nearly 200 h. After eight iterations,
the objective is to determine the best estimate of the parameters HYDRUS-1D reduced the objective function sufficiently for the
as an alternative to directly measuring them. final parameters to be considered optimized. Other transient
The HYDRUS models have an inverse modeling capability. The flow experiments that can be used for parameter optimization
objective function Φ that is minimized in HYDRUS-1D is defined as include evaporation, use of a tension infiltrometer, and field
mq nqj drainage (Hopmans et al., 2002).
Φ(b, q, p) = ∑ ∑w vj i ,q [q *(
j z , t i ) − q j (z , t i , b)]
2

j =1 i =1
5.5.4  Pedotransfer Functions
mp n pj nb
Considering that direct measurements of the unsaturated soil
+ ∑v ∑w
j =1
j
i =1
i ,q [ p *j (θi ) − p j (θi , b)]2 + ∑ vˆ (b* −b ) .
j =1
j j j
2
hydraulic properties are relatively difficult and time consuming,
 (5.38) many have attempted to predict soil hydraulic properties from
more easily measurable surrogate properties, such as soil texture.
The first term on the right-hand side of Equation 5.38 repre- Relationships between the soil hydraulic and other properties are
sents the deviations between measured and predicted variables commonly called PTFs. The functions are usually obtained using
Water Flow in Soils 5-13

fractions (Model 2), then adding a measured bulk density (Model 3),
and water contents at 33 (Model 4) and 1500 kPa (Model 5).
Although very convenient to use, PTFs can produce relatively
large errors in the predicted soil hydraulic properties. Schaap
et al. (1998) and Schaap and Leij (1998) reported that the root
mean square errors (RMSE) for water content and log(Ks) pre-
dictions were 0.108 and 0.741, respectively, using the simplest
Rosetta model (Model 1). They still obtained relatively large
RMSE values of 0.063 and 0.610 for water contents and log(Ks),
respectively, with Model 5 that requires the most detailed infor-
mation. Other studies found that the accuracy for predicting
water content using various PTFs is relatively good (RMSE of
0.02–0.11 cm3 cm−3) compared to predicting log(Ks) (RMSE no
better than 0.5) (Jaynes and Tyler, 1984; Ahuja et al., 1989; Tietje
and Hennings, 1996; Donatelli et al., 2004).

5.6  Numerical Methods

Numerical methods can be used to solve the Richards equation
FIGURE 5.9  Observed pressure head (circles) and predicted pres-
under conditions where analytical solutions do not exist. These
sure head (curve) in a multistep outflow experiment analyzed using methods were first applied to soil water movement in the early
HYDRUS-1D. 1960s (Ashcroft et al., 1962; Hanks and Bowers, 1962). The two
most common methods are finite differences and finite elements
various mathematical and statistical approaches, such as regression (Huyakorn and Pinder, 1983; Smith, 1985). For 1D flow, the first
(Rawls and Brakensiek, 1985; Vereecken et al., 1989, 1990; Rawls step is to discretize the soil profile into a number of depth inter-
et al., 1991) or neural network analysis (Schaap et al., 1998; Schaap vals Δz. The point at which intervals join is called a node. Time
and Leij, 2000). PTFs can be used to predict either the soil hydraulic is also discretized by intervals Δt. The depth and time intervals
properties directly, such as the water content at specified pressure can vary. A set of algebraic equations is developed that include
heads or the saturated hydraulic conductivity, or parameters in the the pressure head or water content at each node at a given time
analytical models used for the soil hydraulic properties (Rawls and level. This leads to a system of simultaneous equations that can
Brakensiek, 1985; Vereecken et al., 1989, 1990). Recent reviews of be solved to find the pressure head or water content using matrix
PTFs are given by Leij et al. (2002) and Pachepsky et al. (2006). algebra at each time level. The method can be applied to 2D and
The HYDRUS models implement the Rosetta Lite module of 3D problems in which case, spatial discretization leads to a grid.
Schaap et al. (2001) to predict soil hydraulic parameters using five Commonly used numerical models that solve the Richards
different levels of input data. The simplest model (Model 1) uses equation to simulate water flow in variably saturated soils are
the average of fitted hydraulic parameters within a textural class shown in Table 5.4. In the following sections, HYDRUS-1D and
in the USDA textural triangle. The four other models use progres- HYDRUS (2D/3D) are used to illustrate important transient flow
sively more detailed input data, starting with the sand, silt, and clay processes.

TABLE 5.4  Widely Used Numerical Models for Simulating Variably Saturated Water Flow in Soils
Model Name Internet Address Reference
COUP http://www.lwr.kth.se/vara%20datorprogram/CoupModel Jansson and Karlberg (2001)
DAISY http://code.google.com/p/daisy-model/ Hansen et al. (1990)
HYDRUS-1D http://pc-progress.com/en/Default.aspx?hydrus-1d Šimůnek et al. (2008)
HYDRUS-2D http://pc-progress.com/en/Default.aspx?hydrus-2d Šimůnek et al. (1999)
HYDRUS (2D/3D) http://pc-progress.com/en/Default.aspx?hydrus-3d Šimůnek et al. (2006)
MACRO http://www.mv.slu.se/BGF/Macrohtm/macro.htm Jarvis (1994)
RZWQM http://www.ars.usda.gov/Main/docs.htm?docid=17740 Ahuja and Hebson (1992)
SHAW http://www.ars.usda.gov/Services/docs.htm?docid=16931 Flerchinger et al. (1996)
SWAP http://www.swap.alterra.nl/ van Dam et al. (1997)
SWIM http://www.clw.csiro.au/products/swim/ Verburg et al. (1996)
TOUGH2 http://www-esd.lbl.gov/TOUGH2/ Pruess (1991)
UNSAT-H http://hydrology.pnl.gov/resources/unsath/unsath.asp Fayer (2000)
VS2DI http://wwwbrr.cr.usgs.gov/projects/GW_Unsat/vs2di1.2/ Healy (1990)
5-14 Properties and Processes

5.7  Infiltration
Infiltration is a key process because it determines how much
water from rainfall, irrigation, or a contaminant spill enters the
soil and how much becomes runoff. It is also important in ero-
sion since there can be no erosion without runoff to transport
and scour sediment. In this section, we describe infiltration into
a uniform soil, the effect of soil crusts and subsurface layers,
infiltration equations, infiltration from a borehole, and subsur-
face irrigation.

5.7.1  Infiltration into a Uniform Soil

In this example, HYDRUS-1D is used to simulate infiltration
into a uniform soil with the hydraulic properties of the Ap
horizon of a Cecil sandy loam soil in Georgia (Table 5.5). The
water retention parameters were obtained by fitting the van
Genuchten (1980) equation to the data from Bruce et al. (1983)
using the RETention Curve (RETC) optimization software (van
Genuchten et al., 1991). See Radcliffe and Šimůnek (2010) for FIGURE 5.10  Pressure heads as a function of depth for various times
more details. during infiltration into a uniform loamy sand; T0 = 0.0 h, T1 = 0.1 h, T2 =
Infiltration once ponding starts at the surface is simulated. 1.0 h, and T3 = 2.0 h.
Therefore, the surface boundary condition for infiltration after
ponding occurs (with no surface storage) is a pressure head at the of higher pressure heads moves down through the soil over time.
soil surface equal to zero (Dirichlet or type-1 boundary condition): For a given soil, the abruptness of the wetting front will depend
on the shape of the θ(h) and K(h) functions. Both of these depend
h(0, t ) = 0. (5.39)
on pore-size distribution. For coarse-textured soils with a narrow
pore-size distribution, the wetting front will be more abrupt; in
It is assumed that there is no flux (Neumann or type-2 boundary
a fine-textured soil, the wetting front will be more diffuse.
condition) at the bottom boundary (z = −250 cm):
In this case, the wetting front is very sharp as one might expect
in a loamy sand. The wetting front is a combination of new water
J w (−250, t ) = 0. (5.40) added by the rain and old water displaced to lower depths.

The numerical solution can also be used to estimate the
For initial conditions, the soil profile has a pressure head of infiltration rate i(t) as a function of time. The infiltration rate
−100 cm at all depths: is the water flux at the soil surface, so it is described by the
Buckingham–Darcy equation for the flux at the surface:
h(z , 0) = −100. (5.41)
⎡ ∂h ⎤
i(t ) = − J w (t ) z = 0 = ⎢ K (h) + K (h)⎥ , (5.42)
The numerical solution is used to plot profile distributions of ⎣ ∂z ⎦ z =0

pressure head for different times after water began to pond at the
surface of a soil during an infiltration event. These are shown in where the vertical bar and subscript indicates that the flux is
Figure 5.10 for various times. During infiltration, a wetting front evaluated at the soil surface.

TABLE 5.5  Soil Properties and van Genuchten (1980) Water Retention and Hydraulic Conductivity
Parameters for the Cecil Loamy Sand, plot 4, of Bruce et al. (1983)
Horizon Texture Depth (cm) θr (cm3 cm−3) θs (cm3 cm−3) α (cm−1) n Ks (cm h−1)
Ap Loamy sand 0–21 0.032 0.399 0.0495 1.46 19.19
BA Clay loam 21–26 0.137 0.346 0.1396 1.25 7.69
Bt1 Clay 26–102 0.000 0.433 0.0382 1.08 10.73
Bt2 Clay 102–131 0.000 0.424 0.0058 1.09 0.206
BC Clay loam 131–160 0.000 0.423 0.0042 1.14 0.035
C Sandy clay loam 160–250+ 0.000 0.449 0.0078 1.22 0.467
Water Flow in Soils 5-15

40 To get a more realistic simulation, one can specify slightly dif-

35
ferent initial and boundary conditions. For the surface bound-
ary condition, a system-dependent boundary condition (see
Infiltration rate (cm h–1)

30 Equations 5.34 and 5.35) is used that starts with a flux equal to
25 a rainfall rate of 25 cm h−1. When the soil near the surface wets
up sufficiently that the pressure head at the first node reaches 0
20
(hS in Equation 5.35), the boundary condition changes to a
15 ­constant-pressure-head boundary condition equal to 0 (ponding
10 with no surface storage). For the bottom boundary condition, a
constant-pressure-head boundary condition of zero is used to
5 represent a water table at a depth of 250 cm. For the initial condi-
0 tions, a pressure-head distribution starting with −250 cm at the
0.0 0.5 1.0 1.5 2.0 soil surface and increasing linearly to the pressure head of 0 cm
Time (h) at the bottom of the model space is specified. This represents a
FIGURE 5.11  Infiltration rate as a function of time in a uniform soil profile where the pressure heads are in equilibrium with a
loamy sand. water table at a depth of 250 cm.
The simulated distribution of pressure heads as a function
of depth for various times are shown in Figure 5.12. The ini-
The infiltration rate is shown in Figure 5.11. It decreases with tial equilibrium distribution of pressure heads is apparent. The
time and approaches an asymptotic minimum infiltration rate. movement of a wetting front down the profile is also apparent
Experimental observations confirm that i(t) follows the pattern with the front reaching a depth of about 200 cm at the end of
in this figure. This is for a uniform soil with no layers or crust- the simulation. Compare this figure with the earlier example
ing at the surface and relatively wet antecedent water contents. of infiltration into the same soil with an initial distribution of
Equation 5.42 can be used to understand this pattern. When pressure heads equal to a constant −100 cm (Figure 5.10). The
infiltration first starts, the wetting front is steep and very close results are similar except for the initial distribution of pres-
to the surface (Figure 5.10). As a result, ∂h/∂z at the surface is sure heads.
large and the first term in Equation 5.42 produces a large value The simulated infiltration rate as a function of time is shown
for i(t). Under these conditions, the gradient in pressure head in Figure 5.13. Infiltration is a constant flux equal to 25 cm h−1
(due mainly to capillarity) is responsible for the rapid move- until about 0.2 h and then decreases to a steady rate of 19.19
ment of water into a moist soil. The second term in Equation cm h−1, which is Ks for the soil. The effect of the system-depen-
5.42 represents the effect of gravity and may have little effect on dent boundary condition at the surface is apparent when this
water movement during the initial stages of infiltration. Later in
the infiltration event, the wetting front has moved deeper into
the soil (Figure 5.10). As a result, ∂h/∂z at the surface is much
smaller (maybe even zero) and the first term in Equation 5.42
(and capillarity) has little effect. When the first term approaches
zero, i(t) ≈ Ks and only gravity causes flow. Under these circum-
stances, a minimum infiltration rate is reached and it is approxi-
mately the saturated hydraulic conductivity of the Cecil Ap
horizon, 19.19 cm h−1 (Table 5.5), as demonstrated in Figure 5.11.
Because the initial high infiltration rate in a dry soil is due
to the pressure head gradient term, if the soil is wetter before
the rainfall event, the initial infiltration rate will be lower.
However, the final infiltration rate in both a wet and a dry soil
will be the same, approximately K s.
Cumulative infiltration I(t) (L) is the integral of the infiltra-
tion rate:

∫
I (t ) = i(t ) dt .
0
(5.43)

FIGURE 5.12  Resulting pressure head distributions in the infiltra-

It is the area under the rate curve in Figure 5.11. Once the infiltration tion example with an equilibrium initial distribution of pressure heads:
rate becomes constant, cumulative infiltration increases linearly. T0 = 0.0 h, T1 = 0.1 h, T2 = 1.0 h, and T3 = 2.0 h.
5-16 Properties and Processes

30

25
Infiltration rate (cm h–1)

20

15

10

0
0.0 0.5 1.0 1.5 2.0
Time (h)

FIGURE 5.13  Infiltration rate as a function of time in the infiltration

example with a system-dependent boundary condition.

figure is compared to the earlier infiltration example (Figure

5.11). With the rainfall rate of 25 cm h−1, once the infiltration rate
for the soil drops below this rate, water starts to run off (assum-
FIGURE 5.14  Pressure heads as a function of depth for various times
ing that surface storage is negligible). In the earlier example, we during infiltration into a layered soil: T0 = 0.0 h, T1 = 0.1 h, T2 = 1.0 h,
assumed that water was ponded at the surface from the begin- and T3 = 4.0 h.
ning of the infiltration event. It would take a very high-intensity
rainfall event to cause ponding early in the event (more than When the wetting front reaches this horizon, water flow is slowed
40 cm h−1, see Figure 5.11). The system-dependent boundary con- causing pressure to build above the Bt2 horizon. This produces
dition used in this example is more realistic. a larger gradient in pressure head across the lower horizons and
compensates to a degree for the low conductivities. At a depth of
5.7.2  Soil Crusts and Subsurface Layers approximately 160 cm, pressure heads have become more negative
than the initial conditions. This is due to the increase in Ks that
Another factor that can cause the infiltration rate to decrease is occurs in the C horizon (Table 5.5).
the formation over time of a surface seal or crust at the soil sur- As noted earlier in Section 5.2.3, under steady saturated flow,
face. A surface seal is a very thin layer (1–5 mm) at or just below pressure heads are distributed linearly with depth within a hori-
the soil surface that forms due to the breakdown of soil aggre- zon. In Figure 5.14, the distribution is linear above the wetting
gates and chemical dispersion of clay particles under raindrop front, indicating that θ is constant (saturated) in this region. At
impact. The clay particles fill the soil pores and create a layer the wetting front, the lines curve, indicating that θ is changing
with a saturated hydraulic conductivity several orders of magni- over time in this region (unsaturated).
tude less than the undisturbed soil (Miller and Radcliffe, 1992). The effect of soil layers on the infiltration rate in the layered
This low-conductivity layer can prevent saturation of the soil soil is shown in Figure 5.15. The infiltration rate for a uniform
just beneath the seal due to the suction that occurs at the inter-
face (see Section 5.2.3), further reducing the infiltration rate. 40
Subsurface clay layers near the surface can also reduce infiltra- Uniform soil
35 Layered soil
tion rates. An unstructured clay layer will usually have a lower Ks
Infiltration rate (cm h–1)

than an overlying sand layer and reduce Keff (Equation 5.3) and i(t) 30
once the wetting front enters the clay layer. Again, HYDRUS-1D 25
can be used to plot distributions of pressure heads and water
20
contents in a soil profile that consists of the various horizons of a
Cecil sandy loam soil in Georgia (Bruce et al., 1983; Table 5.5). The 15
boundary and initial conditions are the same as in the first infil- 10
tration example for a uniform soil (Equations 5.39 through 5.41).
The pressure heads at various times are shown in Figure 5.14. The 5
curves are remarkably different from Figure 5.10 for a uniform 0
soil, due primarily to the presence of positive pressures that have 0.0 0.5 1.0 1.5 2.0
peak values at a depth of 100 cm after 1 h. This depth corresponds Time (h)
to the top of the Bt2 horizon. This horizon and the horizons below FIGURE 5.15  Infiltration rate as a function of time in a uniform soil
it have sharply lower Ks than the horizons above (Table 5.5). and a layered soil.
Water Flow in Soils 5-17

soil with the same properties of the first horizon in the lay- The distribution of water contents after 24 h is shown in Figure
ered soil (the curve in Figure 5.11) is included for compari- 5.17. The wetting front has become distorted because water can-
son purposes. Initially, the infiltration rates are the same, but not enter the dry sand layer. The reason for this is that pressure
once the wetting front reaches the second (BA) horizon after heads at the leading edge of the wetting front are negative and
about 0.2 h, the infiltration rate in the layered soil decreases. water cannot enter the smallest air-filled pores in the sand layer
This is due to a pressure head gradient at the soil surface that until pressure heads increase to the point where capillarity will
opposes infiltration (Figure 5.14) caused by the lower K s in draw water into these pores (the water entry pressure head for
the BA horizon. A more severe drop in the infiltration rate the sand). This stalls the wetting front until pressure heads rise
occurs after about 0.4 h when the wetting front reaches the to the critical level for entry. Since the pore-size distribution is
Bt2 horizon. After entering this horizon, the infiltration rate narrower in the sand, it is not long after water first enters the
in the layered soil approaches a constant value. Thus, layers sand that the pressure is high enough at the wetting front to fill
have an effect on the infiltration rate at the surface through the largest capillary pores in the sand. Once the sand is satu-
their effect on movement of the wetting front. rated, it no longer impedes flow because Ks is high in the sand
A dry coarse-textured layer under a fine-textured layer will compared to the clay layer above. Baver et al. (1972) referred to
also impede deeper movement of the wetting front and reduce the action of a buried dry sand layer in temporarily impeding
the infiltration rate but through a different mechanism. To illus- water flow and infiltration as a check valve. This principle is used
trate this problem, a 2D water flow model, HYDRUS (2D/3D), is in the design of golf greens, which have a sand surface layer over
used for a soil profile consisting of a clay loam layer to a depth of a coarse gravel layer at about 50 cm. The gravel layer prevents
20 cm, underlain by a sand layer that extends to a depth of 50 cm. drainage from the root zone under frequent light irrigations, but
The van Genuchten (1980) hydraulic parameters are taken from if there is a heavy rain, the gravel layer will fill and drain the root
the textural class averages of Carsel and Parrish (1988) (clay loam: zone, so that the green does not become waterlogged.
θr = 0.095, θs = 0.41, α = 0.019 cm−1, n = 1.31, Ks = 0.26 cm h−1,
and l = 0.5; sand: θr = 0.045, θs = 0.43, α = 0.145 cm−1, n = 2.68,
5.7.3  Infiltration Equations
Ks = 29.7 cm h−1, and l = 0.5). The model region is 100 cm in width
and a point source of water (as might occur with drip or fur- Because of the importance of the infiltration process, simpli-
row irrigation) is placed at a distance of 50 cm from the left side fied solutions to the Richards equation have been developed to
(h0 = 0). The initial pressure heads are −500 cm everywhere. predict infiltration. Most of the infiltration equations have been
The distribution of water contents 10 h after the point developed for conditions when rainfall does not limit infiltra-
source of water is started is shown in Figure 5.16. The location tion. In this case, the infiltration rate is less than the rainfall or
of the sand layer is apparent in that it has a lower water con- irrigation rate and runoff occurs. Soil hydraulic properties con-
tent (θ = 0.05 cm 3 cm−3) under the initial pressure head than trol the infiltration rate so it is profile controlled (Hillel, 2004),
the clay loam layer (θ = 0.25 cm 3 cm−3). At this early time, the also called ponded infiltration, although the depth of ponding
wetting front has not reached the sand layer and the wetting may be negligible if surface storage is small. Two examples are
front is semicircular in shape. shown that represent very different approaches: the Green and

0.045 0.078 0.112 0.145 0.178 0.211 0.244 0.277 0.311 0.344 0.377 0.410

Water content - th[-], Min = 0 .045, Max = 0.410

FIGURE 5.16  Distribution of water contents after 10 h in a soil profile consisting of a clay loam layer from 0 to 20 cm and a sand layer from 20
to 50 cm.
5-18 Properties and Processes

0.045 0.078 0.112 0.145 0.178 0.211 0.244 0.277 0.311 0.344 0.377 0.410

Water content - th[-], Min = 0.045, Max = 0.410

FIGURE 5.17  Distribution of water contents after 24 h in a soil profile consisting of a clay loam layer from 0 to 20 cm and a sand layer from 20
to 50 cm.

Ampt (1911) equations and the curve number (CN) method. Equation 5.44 are then I(t) and hf. White and Sully (1987) showed
Many infiltration equations have been developed including that the wetting front pressure head can be approximated using
those by Kostiakov (1932), Horton (1940), Philip (1957), and the macroscopic capillary length λc (Tables 5.1 and 5.2):
Parlange et al. (1985).
λc
5.7.3.1  Green–Ampt Equations hf = − , (5.46)
2b
Green and Ampt (1911) developed a simplified mechanistic
equation for infiltration by assuming that the wetting front in a where b is a dimensionless factor that has a theoretical range of
soil was a square wave or sharp front. Although this is approxi- 1/2 to π/4 but can be assumed to be equal to 0.55 in most cases
mately true only in coarse-textured soils, there is no error in pre- (Warrick and Broadbridge, 1992). Hence, the only unknown in
dicting the infiltration rate as long the amount of water behind Equation 5.44 is I(t), but the equation cannot be solved directly
the predicted square front is equal to the amount of new water for this variable because it appears both inside and outside the
behind the true wetting front. natural log function. Therefore, it must be solved iteratively.
The Green–Ampt equation for cumulative infiltration in a Alternatively, Equation 5.44 can be solved for t and the times
uniform soil, including the effect of gravity, is: corresponding to a range of values for cumulative infiltra-
tion can be calculated. In contrast to White and Sully (1987),
⎛ I (t ) ⎞ Haverkamp et al. (1985) found that it was best to consider hf a
I (t ) = K (h0 )t + ΔhΔθ ln ⎜ 1 + , (5.44)
⎝ ΔhΔθ ⎟⎠ fitting parameter.

Once the cumulative infiltration curve as a function of time
is known, the infiltration rate can be calculated as the instanta-
where
neous slope of this curve:
Δθ = θ0 − θi , (5.45)
Δh = h0 − hf , dI (t )
i(t ) = . (5.47)
dt

where
θi is the initial water content 5.7.3.2  CN Approach
θ0 is the water content at the surface The CN method is an empirically determined rainfall–runoff
relationship that provides an indirect estimate of the total depth
The pressure head h0 corresponds to the water content θ0. The of water that infiltrates during a storm (McCuen, 1982; NRCS,
pressure head hf is the pressure head at the wetting front. Under 2004). It does not give the infiltration rate i(t) but simply the
ponded conditions, θ0 and K(h0) can be approximated by θs and cumulative runoff R at the end of the storm. The method is based
Ks, respectively, and h0 can be assumed to be zero (for negligi- on numerous measurements of runoff for many soil types and
ble ponding) or the depth of ponded water. The unknowns in considers soil texture, soil drainage class, antecedent moisture
Water Flow in Soils 5-19

conditions, and vegetative cover. The total runoff (R in cm) during Equation 5.42). In infiltration-excess runoff, there is a large gradi-
an event is as follows: ent favoring infiltration, but the soil conductivity is not sufficiently
high to prevent runoff. In saturation-excess runoff, the conductiv-
(P − 0.2S)2 ity may be very high, but the gradient is low or even favors exfil-
R= , P > I a , R = 0, P ≤ I a , (5.48)
P + 0 . 8S tration (a seep). A final distinction is that the infiltration-excess
approach is essentially a 1D (vertical) view of the infiltration pro-
where cess. The saturation-excess approach is a 3D view.
P is the total precipitation in cm
S is the water storage capacity of the soil in cm
Ia is the initial abstraction in cm 5.7.4  Borehole Infiltration
Infiltration from a borehole is a 3D flow problem (see Figure 5.8).
The water storage capacity is calculated using the CN: It can be modeled in two dimensions, however, using cylindrical
coordinates available in HYDRUS (2D/3D).
2540 Infiltration is simulated from an unlined borehole with a con-
S= − 25.4. (5.49)
CN stant head of water into a loamy sand. The van Genuchten (1980)
hydraulic properties are taken from the Rosetta Lite database in
CNs are tabulated in Chapter 9 of The National Engineering HYDRUS: θr = 0.049, θs = 0.39, α = 0.0347 cm−1, n = 1.75, and Ks =
Handbook (NRCS, 2004) and vary with land use, ranging from near 4.38 cm h−1. Since infiltration from a borehole will be symmetrical
0 for a dry, fully vegetated, highly permeable surface to near 100 around the vertical centerline of the borehole (in the absence of any
for an impervious surface. The CN method assumes that an initial slope or heterogeneities in the soil surrounding the borehole), a 2D
amount of rain must occur before runoff starts and this is called the slice through the soil from the centerline of the ­borehole on the left
initial abstraction Ia, which is assumed to be equal to 0.2S. Runoff is radiating out into the soil to the right is simulated. The horizontal
zero until precipitation exceeds Ia (see Equation 5.48). dimension of the model space is 100 cm and the vertical dimension
The CN also varies with the soil hydrologic group, which ranges is also 100 cm with the soil surface at the top (Figure 5.18). A bore-
from Group A (soils with low runoff potential when thoroughly wet) hole with a radius of 5 cm penetrates to a depth of 30 cm below the
to Group D (soils with high runoff potential when thoroughly soil surface. The boundary condition at the bottom of the model
wet). Hydrologic groups are described in Chapter 7 of the National space (at a depth of 100 cm below the soil surface) is a free-drain-
Engineering Handbook (NRCS, 2004) and they are also given for age boundary condition simulating a deep water table (see Section
all U.S. soil series in the National Soil Information System (NASIS; 5.4.1.3). To simulate water ponded in the borehole to a height 10 cm
NRCS, 2009). This information is also available through the Web above the bottom of the borehole, a constant-head boundary con-
Soil Survey at http://websoilsurvey.nrcs.usda.gov/app. The CN can dition is used. Along the boundary representing the bottom of the
be adjusted for antecedent runoff conditions I through III, rep- borehole and up the side wall to a height of 10 cm, the boundary
resenting dry, normal and wet conditions but some studies have condition is a constant pressure head of 10 cm in equilibrium with
found that this does not improve the predictions (see Chapters 9 the lowest nodal point on this boundary. This ensures that the pres-
and 10, NRCS, 2004). With the CN approach, there is an emphasis sure at the bottom of the borehole is 10 cm and pressure decreases
on management and cover. This is a recognition of the importance linearly up the side wall to a value of 0 at 10 cm above the borehole
of crusting (and impervious surface percentage) on infiltration. bottom. All other points along the model-space boundary are a no-
The use of soil hydrologic groups is also a recognition of the flux boundary condition. The distribution of pressure heads after
importance of the soil profile (e.g., subsurface impeding horizons), 3 h of simulation are shown in Figure 5.18. Capillarity has drawn
not just the hydraulic properties of the surface layer. the wetting front into the soil in all directions including upward
A distinction can be made between infiltration-excess runoff and toward the soil surface. The influence of gravity is most apparent in
saturation-excess runoff (Beven, 2001). Infiltration-excess runoff the saturated region immediately surrounding the ponded portion
occurs when downward movement of water into the soil is less than of the borehole where a teardrop shape to the contour is apparent.
the rainfall rate. This is also called Hortonian flow after Horton The infiltration rate from the borehole as a function of time is
(1933). This type of process is described by the Green–Ampt (1911) shown in Figure 5.19. The volumetric infiltration rate (Q in cm3
equations. Saturation-excess runoff occurs when water moves lat- h−1) has been converted to the infiltration flux (i in cm h−1) by divid-
erally within the soil during a storm and causes lower hillslope ing by the bottom area of the borehole (πr2). The infiltration rate
positions to be saturated, thereby decreasing the infiltration rate to declines to a near-steady value within one-half hour, much like
less than the infiltration capacity. This is also called the variable- 1D infiltration into a uniform soil with water ponded at the sur-
source-area concept (Hewlett and Troendle, 1975) because the area face (see Figure 5.11). Unlike 1D infiltration, however, the steady
where runoff occurs expands with the size of the storm as the soil value in the borehole infiltration example is much greater than
landscape becomes wetter. The CN approach can be considered a the soil Ks (4.38 cm h−1). This is because flow is occurring in three
saturation-excess approach (Steenhuis et al., 1995). Another way dimensions (Darcy’s law for 1D flow does not apply) and because
to look at the difference between these processes is to consider the gradient is much more than a unit gradient. This is why the
the gradients and conductivities (components of Darcy’s law, see borehole equation (Equation 5.22) must be used to calculate Ks.
5-20 Properties and Processes

L = 30

L = 100

L = 100

–120.000 –90.000 –80.000 –70.000 –60.000 –50.000 –40.000 –30.000 –20.000 –10.000 0.000 10.000

Pressure head - h[cm], Min = –105.900, Max = 10.000

FIGURE 5.18  Distribution of pressure heads after 3 h in the borehole infiltration example.

600

L=4
500
Infiltration rate (cm h–1)

400

300

200

100 L = 60

0
0.0 0.5 1.0 1.5 2.0
Time (h)

FIGURE 5.19  Infiltration rate as a function of time in the borehole

infiltration example.

5.7.5  Subsurface Irrigation

L = 50
Irrigation using a buried irrigation line results in flow of water
that can be modeled as 2D infiltration. Skaggs et al. (2004)
compared measured water contents in a Hanford sandy loam 0.050 0.076 0.103 0.129 0.155 0.182 0.208 0.235 0.261 0.287 0.314 0.340
soil with those simulated using HYDRUS-2D. Soil properties
were estimated using the Rosetta database for van Genuchten
(1980) parameters (θr = 0.021, θs = 0.34, α = 0.023 cm−1, n = Water content - th[-], Min = 0.050, Max = 0.340
1.4, Ks = 1.6 cm h−1, and l = −0.92). The irrigation line was bur- FIGURE 5.20  Distribution of water contents around a subsurface
ied at a depth of 5 cm. The model space consisted of a 2D soil irrigation line after 10 h. (From Skaggs, T.H., T.J. Trout, J. Šimůnek, and
block, 50 cm wide and 60 cm deep with the soil surface at the P.J. Shouse. 2004. Comparison of HYDRUS-2D simulations of drip irriga-
top  (Figure 5.20). It  was assumed that water flow would be tion with experimental observations. J. Irrigat. Drain. Eng. 130:304–310.)
Water Flow in Soils 5-21

symmetrical about the vertical centerline of the irrigation pipe which the wetting front moved (about 200 cm) during the rain-
so only half the area around the pipe was simulated. All of the fall event and is the last time in the earlier infiltration example
boundaries were considered to be zero-flux except for a 2-cm (Figure 5.12). It is clear that pressure heads continued to change
diameter semicircle on the left boundary, which represented beyond 2 h with pressure heads decreasing at more shallow
the irrigation line. The boundary condition on this semicircle depths. The curves are moving in the direction of the equilib-
was specified as a flux of 6.37 cm h−1 (the irrigation rate in cm3 h−1 rium distribution (the initial conditions in Figure 5.21), but even
for a given segment of irrigation line divided by one-half the after a week of redistribution they are far from a true equilib-
surface area of the irrigation line segment). Water contents are rium distribution. This is because as pressure heads decrease at
shown after 10 h of simulated irrigation in Figure 5.20. The wet- shallow depths, unsaturated hydraulic conductivity decreases
ting front has moved out in a nearly cylindrical manner due and water movement is slower. The average pressure head in the
to capillarity but some distortion of the wettest contour due profile after about a week is close to −100 cm, which is the pres-
to gravity is apparent. The HYDRUS simulations agreed quite sure head often used to estimate field capacity in coarse-textured
well with the measured distributions of water contents (Skaggs soils (Romano and Santini, 2002).
et al., 2004).
5.9  Evaporation
5.8  Redistribution Evaporation is the reverse process of infiltration: a flux out of
Once a rainfall event is over, water movement does not cease. For the soil at the surface. HYDRUS-1D is used to illustrate this
example, the final distribution of pressure heads in Figure 5.12 process with the same loamy sand employed for the borehole
will continue to change after 2 h even if there is no further pre- example (θr  = 0.049, θs = 0.39, α = 0.0347 cm−1, n = 1.75, and
cipitation. This process is known as redistribution or drainage Ks = 4.38 cm h−1, l = 0.5). The surface boundary condition is a sys-
(Jury and Horton, 2004). In theory, with a water table at a depth tem-dependent boundary condition for evaporation: an evapo-
of 250 cm, pressure heads will return to the initial distribution rative flux of 1 cm day−1 (0.042 cm h−1) until the surface dries to a
of an equilibrium profile with pressure heads increasing linearly pressure head of −15,000 cm (E = 0.042 cm h−1, hA = −15,000 cm,
from −250 cm at the surface to 0 cm at the water table (Figure see Equations 5.34 and 5.35). At that time, the boundary con-
5.12). In reality, it takes so long for redistribution to occur that dition switches to a constant pressure head of −15,000 cm. The
an equilibrium profile rarely occurs unless the water table is resulting water content profiles for different times after evapora-
at a very shallow depth. To see this, the previous infiltration tion started are shown in Figure 5.22.
simulation shown in Figure 5.12 is extended to 1 week (168 h) The numerical solution shows that water contents decrease
with no precipitation (or evapotranspiration) beyond 2 h using with depth as time progresses due to the loss of water through
HYDRUS-1D. evaporation at the surface. Instead of a wetting front seen in
The resulting pressure head distribution is shown in Figure
5.21. The pressure head at time T1 = 2 h shows the depth to

FIGURE 5.22  Water contents as a function of depth for various times

FIGURE 5.21  Simulated pressure head distributions in the redistri- during evaporation from a uniform loamy sand: T0 = 0 h, T1 = 3 h,
bution example: T0 = 0 h, T1 = 2 h, T2 = 84 h, T3 = 126 h, and T4 = 168 h. T2 = 6 h, T3 = 12 h, T4 = 24 h, and T5 = 48 h.
5-22 Properties and Processes

0.05 For photosynthesis to occur, however, CO2 must enter the plant

leaves and reach chloroplasts. As a result, plants must maintain
0.04 open stomata, which allow CO2 to enter the interior of leaves
Evaporation rate (cm h–1)

(Figure 5.1). Plant cells must be moist to function so the open

stomata result in a continuous loss of water from the interior of
0.03
the leaf through the stomata due to evaporation. This water must
be replenished by plant uptake of water through the root system
0.02 or the plant leaf cells will desiccate and the plant will wilt.
Water moves through the plant to the atmosphere along a
0.01 continuous path. This is called the soil–plant–atmosphere con-
tinuum (Philip, 1966). Water moves from the soil across the
0.00 plant root to the xylem vessels. It then moves up the xylem ves-
0 5 10 15 20 25 30 35 40 45 sels to the plant leaves. In the leaves, water exits the xylem vessels
Time (h) and moves through leaf cells to the stomatal cavities where it
evaporates. A steady gradient of decreasing water potential pulls
FIGURE 5.23  Evaporation rate as a function of time in a uniform
loamy sand. water from the soil through the plant to the atmosphere. Water
is drawn first from the surface horizons where roots are more
the infiltration example, in this case, a drying front progresses numerous. As this water is depleted, a plant draws water from
deeper into the soil. The evaporation rate for the same soil is deeper in the soil, but this requires more of an energy gradient
shown in Figure 5.23. Evaporation is high initially and constant. due to the effect of gravity. Also root densities (length of root per
During this period, evaporation from the soil is able to keep up volume of soil) decrease with depth.
with the potential evaporation rate of 0.042 cm h−1. The reason There is a limiting leaf-water potential, below which stoma-
for the high initial evaporation rate is the steep gradient in water tal guard cells begin to lose turgor and close. As soon as this
potential between the wet soil and the dry air above the soil happens, the actual evapotranspiration rate drops below the
and the high hydraulic conductivity of the wet soil surface layer potential rate: ET < ET0. Stomata can be partially closed, which
(Figure 5.22). During this period, the decrease in the hydrau- reduces transpiration but does not completely stop it. If stomata
lic conductivity of the surface layer is fully compensated by the close completely then ET = 0.
increase in the hydraulic gradient. This period is referred to as
stage one evaporation (Hillel, 2004). After about 10 h, the evapo- 5.10.2  Root Water Uptake
ration rate starts to drop. At this point, the soil surface has dried
completely (reached the minimum pressure head of −15,000 cm) Root water uptake can be considered a sink term in the Richards
and the actual evaporation rate becomes less than the poten- equation (Equation 5.26). Various terms have been developed
tial rate. The evaporation rate decreases with time because the including those by Molz (1981), Jarvis (1989), and Vrugt et al.
hydraulic gradient at the surface gradually decreases. This period (2001). Feddes et al. (1978) modeled root water uptake as a func-
of decreasing evaporation rate is referred to as stage two evapo- tion of soil water pressure head h:
ration. Eventually, the evaporation rate approaches a constant
residual rate where most of the flux at the surface is in the vapor S(h) = α(h)Sp , (5.50)

phase. This final period is referred to as stage three evaporation.
The heat and radiant energy balance at the soil surface deter- where
mines the potential evaporation rate ET0. This varies from day- S(h) is the root water uptake or volume of water removed
to-day and even minute-to-minute as wind speed, radiation, and from a unit volume of soil per unit time (T−1)
relative humidity change. The actual evapotranspiration rate ET Sp is the potential water uptake rate (T−1)
is usually less than ET0. Part of the evapotranspiration demand is α(h) is a dimensionless stress response function of the
satisfied by soil evaporation. As can be seen in Figure 5.23, evapo- pressure head (0 ≤ α ≤ 1)
ration can be high when the soil is wet (e.g., shortly after a rainfall
event) but rapidly drops to a very low rate. Thus, evaporation alone The stress response function is shown in Figure 5.24a. Water
usually will not meet the potential evapotranspiration demand ET0. uptake is assumed to be 0 close to saturation due to a lack of
oxygen in the root zone (pressure head greater than h1). For a
pressure head less than h4 (the wilting-point pressure head),
5.10  Transpiration water uptake is also assumed to be zero. Water uptake is optimal
between pressure heads of h2 and h3. The pressure head h3 may
5.10.1  Soil–Plant–Atmosphere Continuum
be adjusted depending on the transpiration rate so that it is more
Where nondormant plants are present, most of the evapora- negative when transpiration rates are low (optimal root water
tive demand is satisfied by transpiration. Photosynthesis uses uptake occurs over a wider range in pressure head at lower
only about 1% of the water transpired by plants (Hillel, 2004). transpiration rates).
Water Flow in Soils 5-23

1.2
Water stress response

1.0
0.8
function, α

0.6
0.4
0.2
0.0
h4 h3 h2 h1 0
(a) Soil water pressure head, h

1.2
Water stress response

1.0
0.8
function, α

0.6
0.4 h = h50
0.2
0.0
2.5 2.0 1.5 1.0 0.5 0.0
(b) Reduced pressure head, h/h50 FIGURE 5.25  Precipitation (a negative surface flux) as a function of
time in the transpiration example.
FIGURE 5.24  Plant-water stress response function α(h) as used by
(a) Feddes et al. (1978) and (b) van Genuchten (1987).
(as negative fluxes) for 1995 in Athens, Georgia. There is a dry
Van Genuchten (1987) suggested an S-shaped root water stress period in early spring and there are large rainfall events in the
response function (Figure 5.24b). The parameter h50 represents early fall.
the pressure head at which root water uptake is reduced by 50% Potential and actual evapotranspiration (root water uptake
during conditions of negligible osmotic stress. Note that in con- in this case) are shown in Figure 5.26. It is clear that potential
trast to the response function of Feddes et al. (1978), this response evapotranspiration is low during the winter months and reaches
function does not consider the reduction near saturation due to peak values of nearly 1 cm day−1 in summer. Actual evapotrans-
low oxygen levels. Van Genuchten (1987) also expanded the root piration is identical to potential evapotranspiration until about
water stress response function to include osmotic effects. day 80 when the first dry spell starts. At this point, actual tran-
HYDRUS-1D can be used to simulate evapotranspiration. spiration drops below the potential rate due to plant-water stress
The same loamy sand as in the previous examples (θr = 0.049, and remains below the potential rate for much of the summer.
θs = 0.39, α = 0.0347 cm−1, n = 1.75, and Ks = 105.12 cm day−1) is In the fall, when potential evapotranspiration rates decrease and
used to simulate plant transpiration. The simulation is run for the soil profile water contents start to increase, actual and poten-
1 year using precipitation and potential evapotranspiration from tial evapotranspiration rates again coincide.
Athens, Georgia, for 1995, when total precipitation was 141 cm The pressure head at a depth of 5 cm is shown in Figure 5.27.
(slightly greater than the long-term average of 127 cm). The sim- When the first dry period occurs in the early spring, the pres-
ulation is for a grass lawn that is not dormant in winter. sure head at this depth drops quickly to the minimum value
A system-dependent atmospheric boundary condition with of −15,000 cm (wilting point) due to root uptake. The pressure
surface runoff is used for the upper boundary condition to sim- head at a depth of 50 cm (Figure 5.28) also drops to the wilting
ulate infiltration and evaporation. The free-drainage boundary point but the drop occurs later. With the rainfall that starts
condition is used to simulate a deep water table for the lower shortly after 100 days, pressure head near the surface recovers,
boundary condition (see Section 5.4.1.3). The Feddes et al. (1978) but the pressure head at 50 cm remains at wilting point because
water uptake reduction model (Equation 5.50) is used with this rainfall does not penetrate to deeper depths in the soil pro-
threshold pressure heads appropriate for grass: h1 = −10 cm, file. At about 120 days, there has been sufficient rainfall that
h2 = −25 cm, h3 = −300 cm for high transpiration rates and pressure heads at both depths return to near zero. However, the
−1000 cm for low transpiration rates, and h4 = −15,000 cm (see pressure head at the deeper depth soon returns to wilting point
Figure 5.24a). A full canopy is assumed and consequently there because water from small rainfall events that keep the shal-
is no evaporation. A root distribution that decreases linearly low depths relatively wet do not penetrate to deeper depths.
from the soil surface to a depth of 100 cm is specified. A higher rainfall period from about 140 to 180 days results in
The potential surface flux as a function of time is shown in pressure heads near zero at both depths. After about 180 days,
Figure 5.25. Since there is no evaporation, the only potential the pressure head at the deeper depth returns to wilting point
surface flux is precipitation, so this is a plot of daily rainfall and stays there until the large rainfall event on about day 230.
5-24 Properties and Processes

FIGURE 5.26  Potential root water uptake (left) and actual root water uptake (right) of water as a function of time in the transpiration example.

FIGURE 5.27  Pressure head as a function of time at a depth of 5 cm in FIGURE 5.28  Pressure head as a function of time at a depth of 50 cm
the transpiration example. in the transpiration example.

In contrast, the pressure head near the surface responds to

the small rainfall events during this interval. Late in the sea- 5.11  Preferential Flow
son, a large rainfall event on about day 280 and lower poten-
tial evapotranspiration rates result in pressure heads at both Increasing evidence exists that variably saturated flow in many
depths returning to near zero. field soils is not consistent with the uniform flow pattern typi-
Overall, these results show that even in a slightly wetter than cally predicted with the Richards equations (Quisenberry and
normal year in a region of the United States with relatively high Phillips, 1976; Luxmoore, 1981; Flury et al., 1994; Hendrickx and
rainfall, this lawn experienced considerable water stress during Flury, 2001). This is due to the presence of macropores, fractures,
the summer. This is due in large part to the low plant-available or other structural voids or biological channels through which
water in such a coarse-textured soil. water and solutes may move preferentially while bypassing a large
Water Flow in Soils 5-25

part of the matrix pore space. Preferential flow and transport Another way to simulate the effect of macropores on water flow
processes are probably the most frustrating processes hampering is through the use of scaling. This is a procedure designed to sim-
accurate predictions of contaminant transport in soils and frac- plify the description of the spatial variability in the soil hydrau-
tured rocks. Contrary to uniform flow, preferential flow results lic properties. Here, we describe scaling as implemented in the
in irregular wetting of the soil profile as a direct consequence HYDRUS models. It is assumed that variability in the hydraulic
of water moving faster in certain parts of the soil profile than in properties of a given soil profile can be approximated by means
others. Hendrickx and Flury (2001) defined preferential flow as of a set of linear scaling transformations, which relate the soil
constituting all phenomena where water and solutes move along hydraulic characteristics θ(h) and K(h) at a point in the soil to ref-
certain pathways while bypassing a fraction of the porous matrix. erence characteristics θ*(h*) and K*(h*). The technique is based on
Water and solutes for these reasons can propagate quickly to far the similar media concept introduced by Miller and Miller (1956)
greater depths than would be predicted with the Richards equa- for porous media, which differ only in the scale of their internal
tion describing uniform flow. geometry. The concept was extended by Simmons et al. (1979) to
The most important causes of preferential flow are the pres- materials that differ in morphological properties, but that exhibit
ence of macropores and other structural features, development of scale-similar soil hydraulic functions. Three independent scaling
flow instabilities (i.e., fingering) caused by profile heterogeneities factors are employed in HYDRUS. These three scaling parameters
or water repellency (Hendrickx et al., 1993), and funneling of flow may be used to define a linear model of the actual spatial variabil-
due to the presence of sloping soil layers that redirect downward ity in the soil hydraulic properties as follows (Vogel et al., 1991):
water flow. While the latter two processes (i.e., flow instability
and funneling) are usually caused by textural differences and K (h) = α K K *(h*),
other factors at scales significantly larger than the pore scale,
θ(h) = θr + α θ[θ *(h*) − θ*]
r , (5.51)
macropore flow and transport are usually generated at the pore
or slightly larger scales, including scales where soil structure first h = α hh * ,
manifests itself (i.e., the pedon scale; Šimůnek et al., 2003).
in which, for the most general case, αK, αθ, and αh are mutu-
ally independent scaling factors for the hydraulic conductivity,
5.11.1  Macropores water content, and the pressure head, respectively. Less general
Uniform flow in granular soils and preferential flow in struc- scaling methods arise by invoking certain relationships between
tured media (both macroporous soils and fractured rocks) can αK, αθ, and αh. In HYDRUS, scaling factors for each node can
be described using a variety of multipermeability models. While be generated stochastically by specifying the mean and standard
single-permeability models assume that a single-pore system deviation of the factors. Spatial correlation of the scaling factors
exists that is fully accessible to water, dual-permeability models can also be included.
assume that the porous medium consists of two interacting pore As an example of scaling, HYDRUS (2D/3D) is used to simulate
regions, one associated with the interaggregate, macropore, or infiltration under conditions of incipient ponding of water at the
fracture system, and one comprising the micropores (or intra- surface into a 2D block of soil 300 cm in width and 100 cm deep.
aggregate pores) inside soil aggregates or the rock-soil matrix. The soil is a loam with hydraulic properties taken from the Rosetta
The simplest formulation for water flow is a single-permeability Lite database (θr = 0.061, θs = 0.399, α = 0.011 cm−1, n = 1.474, and
(equivalent porous medium) model applicable to uniform flow in Ks = 0.50 cm h−1). A standard deviation of 1.0 is specified for log αK
soils. Other models apply in some form or another to preferential with a correlation length 10 times larger in the vertical direction
flow or transport. Dual-permeability models are those in which than the horizontal direction. The spatial distribution of Ks for a
water can move in both the inter- and intraaggregate pore regions given realization is shown in Figure 5.29. In this case, the stochas-
(or matrix and fracture domains). These models in various forms tic assignment of scaling factors has produced two zones of high
are now also becoming increasingly popular (Pruess and Wang, Ks and the larger correlation length in the vertical direction has
1987; Gerke and van Genuchten, 1993). They differ mainly in how stretched these zones along the z-axis. The distribution of water
they implement water flow in and between the two pore regions. contents in this soil profile 0.3 h after infiltration began is shown
Common approaches to calculating water flow in macropores or in Figure 5.30. Preferential flow in the two zones causes the wet-
interaggregate pores use Poiseuille’s equation (Ahuja and Hebson, ting front to advance further in these areas.
1992), the Green and Ampt or Philip infiltration models (Chen
and Wagenet, 1992), the kinematic wave equation (Germann,
5.11.2  Fingering and Funnel Flow
1985), or the Richards equation (Gerke and van Genuchten, 1993).
Multipermeability models are based on the same concept as Fingering and funnel flow occur in layered soil profiles where a
dual-permeability models but include additional interacting pore fine-textured layer overlies a coarse-textured layer. Fingering can
regions. These models can be readily simplified to the dual-perme- occur when there is no slope to the coarse-textured layer. In an
ability approaches. Recent reviews of preferential flow processes experiment to examine fingering, Baker and Hillel (1990) used
and available mathematical models are provided by Hendrickx a plexiglass chamber 75 cm wide, 52 cm high, and 1.3 cm thick.
and Flury (2001), Šimůnek et al. (2003), and Jarvis (2007). The  top layer was fine sand with particle sizes between 45 and
5-26 Properties and Processes

0.068 11.001 21.935 32.868 43.801 54.735 65.668 76.601 87.534 98.468 109.401 120.334

Min = 0.068, Max = 120.334

FIGURE 5.29  Spatial distribution of Ks (cm h−1) generated by HYDRUS (2D/3D) using scaling to simulate preferential flow in a loam soil block
that is 300 cm in width and 100 cm in depth.

0.324 0.331 0.338 0.345 0.351 0.358 0.365 0.372 0.379 0.385 0.392 0.399

Water content - th[-], Min = 0.324, Max = 0.399

FIGURE 5.30  The effect of preferential flow on water contents 0.3 h after infiltration began simulated by HYDRUS (2D/3D) in a loam soil block
that is 300 cm in width and 100 cm in depth.

106 μm. The sublayer consisted of a coarse-textured sand with a d

particle-size range that varied from experiment to experiment.
When the wetting front reached the coarse layer, water could 0.25
0.5
not enter because the wetting front pressure head was less than 2
3
the water entry value for the coarse sublayer (as shown in the 4
5 5 5
HYDRUS simulation in Figure 5.17). The wetting front would 6
7
pause at the interface and over time the wetting front pressure
head would increase. When the wetting front pressure head
increased to the value required to enter the smallest pore in
the coarse sublayer, water started to infiltrate. Eventually, the 7
7
wetting front pressure head increased to a value where the flux
through the coarse sublayer was equal to or greater than the 8 8
8
flux through the top layer. Baker and Hillel (1990) called this
the effective water entry value he. If the flux was greater through
FIGURE 5.31  Tracings (alternating solid and dashed lines) of wetting
the coarse-textured sublayer than through the fine-textured top
front position with time during infiltration in the experiment by Baker
layer, then the only way for flow in the two layers to be equal and Hillel (1990). The numbers in the figure show the time (minutes) of
was for water to flow through a fraction of the sublayer in dis- the wetting fronts. The sublayer in this case consisted of a coarse sand
creet fingers (Figure 5.31). The effective water entry value cor- with particle sizes between 500 and 710 μm. (From Baker, R.S., and
responded with the inflection point on the water release curve. D. Hillel. 1990. Laboratory tests of a theory of fingering during infiltra-
This represented the dominant pore size. The fraction of wetted tion into layered soils. Soil Sci. Soc. Am. J. 54:20–30.)
Water Flow in Soils 5-27

Oscillating dripper Above the coarse layer, pressure head increased at the interface
180 cm
in the downslope direction because more and more water was
being diverted. If the infiltration rate was high enough, pressure
head reached the water entry value and infiltration occurred
Dye drippers at 20 cm intervals before the end of the embedded layer was reached. At the tip of
the embedded layer was a toe area where water never infiltrated
Fine soil
the coarse layer. This was because the pressure was relieved by
flow around the toe. Thus, funneling above sloping coarse lay-
Coarse soil 15 cm 110 cm
ers results in water (and solutes) penetrating only a portion of
Tensiometers (spaced at 19 cm intervals)
a soil profile and is therefore a type of preferential flow (Kung,
1990a, 1990b).

φ1 1 cm 5.12  Groundwater Recharge

and Discharge
FIGURE 5.32  Schematic of the experimental setup of a plexiglass cham-
ber 180 cm wide, 110 cm tall, and 1 cm thick, filled with fine soil and a discon- The processes of groundwater recharge, groundwater discharge,
tinuous 15 cm thick coarse layer used by Walter et al. (2000). (From Walter, the position of the water table, and streamflow are all interre-
M.T., J.-S. Kim, T.S. Steenhuis, J.-Y. Parlange, A. Heilig, R.D. Braddock, lated in a humid environment (Fetter, 1988). This can be seen
J.S. Selker, and J. Boll. 2000. Funneled flow mechanisms in a sloping layered by simulating the wetting of an initially dry hillslope using
soil: Laboratory investigations. Water Resour. Res. 36:841–849.)
HYDRUS (2D/3D). In this case, the 2D model space is much
soil in the coarse sublayer at steady state was equal to the ratio of larger than any of the earlier simulations. The hillslope is 100 m
the flux through the top layer and K(he) in the sublayer. long in the horizontal direction and extends from a ridgetop on
When the coarse sublayer has a slope, funneling occurs. In the left to a stream channel on the right (Figure 5.34). At the
another experiment, Walter et al. (2000) packed fine sand into ridgetop, the soil surface is 50 m above the bottom of the model
a plexiglass chamber 1 cm in thickness with a discontinuous, space. At the stream channel, the soil surface is 20 m above the
embedded, layer of coarse sand (Figure 5.32). They investigated bottom of the model space. The stream channel is 5 m deep (indi-
the effect of slope and infiltration rate. Different color dyes were cated by the nickpoint in Figure 5.34). The soil surface is given
applied to intervals at the infiltration surface once steady flow a convex shape. The boundary condition at the soil surface is a
was achieved to show stream lines. constant flux of 2 cm day−1. The boundary condition on the left is
During infiltration when the wetting front reached the coarse a no-flux condition appropriate for a ridgetop, where no lateral
layer, it could not enter this layer because the wetting front pres- flow (only recharge) is expected. The bottom boundary condi-
sure heads were less than the water entry value, just as shown in tion is also a no-flux condition indicating impermeable rock.
the HYDRUS (2D/3D) simulation (Figure 5.17). Since there was The boundary condition beneath the stream channel where no
a slope to the layer, water funneled laterally to the end of the lateral flow (only discharge) is expected is a no-flux boundary
layer before penetrating deeper into the chamber (Figure 5.33). condition. The boundary condition at the stream channel is a
seepage condition, a type of system-dependent condition dis-
cussed previously in Section 5.4.1.3. The initial pressure heads
are −100 m everywhere in the hillslope. The hydraulic proper-
ties of the hillslope are that of a loam soil textural class in the
Carsel and Parrish (1988) database (θr = 0.078, θs = 0.43, α =
0.036 cm−1, n = 1.56, and Ks = 24.96 cm day−1). The simulation is
run for 1000 days.
To do this simulation accurately, so that the short-term
response of the hillslope to a rainfall event would produce timely
streamflow, would require many more nodes than we have used
here (we used 3921). Fiori and Russo (2007) found that a 3D
numerical model that included preferential flow was required
to simulate the short-term response. Our example used a low-
constant flux at the soil surface instead of daily rainfall. We did
FIGURE 5.33  Photograph of an experimental run with an angle of 7.1° not include evaporation or root water uptake driven by daily
and an infiltration rate of 120 mm day−1 by Walter et al. (2000). (From Walter, potential evapotranspiration. However, our simulation will be
M.T., J.-S. Kim, T.S. Steenhuis, J.-Y. Parlange, A. Heilig, R.D. Braddock, adequate to show the long-term response to wetting.
J.S. Selker, and J. Boll. 2000. Funneled flow mechanisms in a sloping layered The distribution of hillslope pressure heads over time are
soil: Laboratory investigations. Water Resour. Res. 36:841–849.) shown in Figures 5.34 through 5.36. After 100 days, a wetting
5-28 Properties and Processes

L = 50

L = 100

–160.000 –140.000 –120.000 –100.000 –80.000 –60.000 –40.000 –20.000 0.000 1.000 2.000 100.000

Pressure head - h[m], Min = –101.404, Max = 33.749

FIGURE 5.34  Pressure heads after 100 days in the hillslope example.

L = 50

L = 100

–160.000 –140.000 –120.000 –100.000 –80.000 –60.000 –40.000 –20.000 0.000 1.000 2.000 100.000

Pressure head - h[m], Min = – 101.404, Max = 33.749

FIGURE 5.35  Pressure heads after 570 days in the hillslope example.

front of unsaturated pressure heads has moved uniformly hillslope to wet up is the lower left corner because this region
downward in the hillslope to a depth of about 5 m (Figure 5.34). is farthest from the soil surface and the extending wetting zone
After 570 days, the wetting front has reached the bottom of the coming in from the right. On the right boundary, the water
model space on the right (where the distance from the soil sur- table has reached the bottom of the channel so water will start
face is the shortest) and a zone of saturated soil has expanded exiting the hillslope through the seep into the stream channel.
from the right corner to cover nearly the entire lower region Further rise in the water table next to the stream channel is
of the hillslope (Figure 5.35). The top of the 0–1 cm pressure limited due to the loss of water to the stream. After 800 days,
head contour represents the water table. The last portion of the the water table beneath the ridgetop has risen to a height of
Water Flow in Soils 5-29

L = 50

L = 100

–160.000 –140.000 –120.000 –100.000 –80.000 –60.000 –40.000 –20.000 0.000 1.000 2.000 100.000

Pressure head - h[m], Min = –101.404, Max = 33.749

FIGURE 5.36  Pressure heads after 800 days in the hillslope example.

about 35 m above the bottom of the model space (Figure 5.36). until about day 500 when the water table intersects the stream
On the right, the water table comes very close to the soil surface channel. The seepage flux increases until about 800 days when it
at about 5 m upslope from the stream channel. The water table attains a steady value of 2 m2 day−1, which is the steady infiltra-
at the stream channel has risen to the point that it is about 3 m tion rate through the soil surface (input equals output). At that
above the bottom of the channel indicating that the height of point, the slope of the water table is such that a sufficient gradi-
water in the stream should be 3 m. There was no further change ent has been generated, given the hydraulic conductivity of the
in the water table from the positions seen for day 800 through soil that the hillslope can transmit the incoming water at the
the remainder of the simulation (up to 1000 days), indicating rate at which it enters the hillslope. Hence, the water table can
that the system has reached a steady state of dynamic equilib- never be completely flat or there would be no gradient and no
rium. The shape of the water table is a subdued replica of the flow through the hillslope (unless there is no input). The steep-
hillslope topography. ness of the water table will depend on the input and the hydrau-
In Figure 5.37, the flow through the seepage boundary is lic conductivity and length of the hillslope.
shown as a function of time. There is no seepage to the channel The effect of hydraulic conductivity on the slope of the water
table can be seen by rerunning the simulation with a saturated
hydraulic conductivity that is 10 times the value for the loam in
the example so far (249.6 instead of 24.96 cm day−1). The distri-
bution of pressure heads after 1000 days is shown in Figure 5.38.
The water table is nearly flat because only a very small gradient is
required to produce the equilibrium flow through the hillslope,
given the high Ks in this example. In this case, the shape of the
water table is not as reflective of the hillslope topography.
Overall, these results are similar to what was shown ear-
lier in Figure 5.4 in regard to flow to drains. In that simplified
analysis of steady flow, it was found that the water table had
an elliptical shape and the maximum height of the water table
was a function of the infiltration rate at the soil surface, the
saturated hydraulic conductivity of the soil, and the distance
between the drains (which would correspond to the hillslope
length in these examples).
These simulations imply that during wet periods (such as
winter months in the eastern United States), the water table
FIGURE 5.37  Seepage flow in the hillslope example. will rise to an average height characteristic of the climate and
5-30 Properties and Processes

L = 50

L = 100

–160.000 –140.000 –120.000 –100.000 –80.000 –60.000 –40.000 –20.000 0.000 1.000 2.000 100.000

Pressure head - h[m], Min = –101.415, Max = 18.296

FIGURE 5.38  Pressure heads after 1000 days in the hillslope example using a saturated hydraulic conductivity 10 times the value for a loam soil.

hillslope hydraulic properties. After a long drought, it may take Richards equations, respectively. The most important hydrau-
several winter seasons to reestablish the water table at its equi- lic parameters are the soil saturated hydraulic conductivity and
librium height, even though water contents at the soil surface unsaturated hydraulic conductivity function. Laboratory and
are near normal. Stream base flow would not return to nor- field methods have been developed to measure these param-
mal levels until the equilibrium winter water table was fully eters and most of these methods require steady flow conditions.
established. PTFs can be used to predict soil hydraulic properties from more
The shape of the hillslope can also have important effects. easily measurable surrogate properties, such as soil texture.
If the surface is changed from a convex to a concave hillslope Analytical solutions of the Richards equation for soil water
surface, the water table may rise to the surface at the bottom of flow under unsaturated, transient conditions are very few.
the footslope in the concave area. This area can be expected to Numerical methods such as those implemented in the HYDRUS
produce saturation-excess runoff as described earlier in Section models are commonly used to solve the equation. Numerical
5.7.3. In contrast to the previous examples, the water table will be methods can also be used to determine soil hydraulic prop-
deeper higher up the hillslope at the shoulder position. Daniels erties under transient flow conditions in an inverse mode.
and Gamble (1967) noted that the shoulder position in hillslopes Simplifications of the unsaturated flow equations have been
with broad ridges and narrow valleys in the coastal plain region developed to describe infiltration because of the importance
of the southeastern United States were drier than other areas of this transient flow process. However, most of the infiltra-
in the landscape and produced red soils indicative of oxidized tion equations assume 1D vertical flow and do not account for
iron (aerobic conditions). Gray soils indicative of reduced iron saturation-excess runoff. Numerical solutions can be used to
formed at the base of the hillslope and near the center of the understand complex soil water processes such as infiltration,
broad ridge. They attributed these soil formation processes, not evaporation, drainage, transpiration, groundwater recharge,
to differences in parent material but rather to the position of the and groundwater discharge. Preferential flow is one of the most
water table. challenging aspects of predicting soil water movement but vari-
ous methods have been developed to account for the effects of
macropores, fingering, funnel flow, and spatial variability.
5.13  Summary
Soil water movement is a key process that affects both water References
quantity and quality in our environment. Water movement
in soils occurs primarily under unsaturated, transient condi- Abit, S.M., A. Amoozegar, M.J. Vepraskas, and C.P. Niewoehner.
tions, but saturated flow and steady-state conditions can occur. 2008. Solute transport and the capillary fringe and shallow
Although true steady flow may occur only rarely, transient groundwater: Field evaluation. Vadose Zone J. 7:890–898.
flow usually approaches steady flow at long times. The govern- Ahuja, L.R., and C. Hebson. 1992. Root zone water quality model.
ing equations for steady and transient flow are the Darcy and GPSR Tech. Rep. No. 2. USDA-ARS, Fort Collins, CO.
Water Flow in Soils 5-31

Ahuja, L.R., D.L. Nofziger, D. Swartzendruber, and J.D. Ross. Chiang, S.C., D.E. Radcliffe, W.P. Miller, and K.D. Newman. 1987.
1989. Relationship between Green and Ampt parameters Hydraulic conductivities of three southeastern soils as
based on scaling concepts and field-measured hydraulic affected by sodium, electrolyte concentration, and pH. Soil
data. Water Resour. Res. 25:1766–1770. Sci. Soc. Am. J. 51:1293–1299.
Arya, L.M. 2002. Wind and hot-air methods, p. 916–926. In J.H. Clothier, B., and D. Scotter. 2002. Unsaturated water transmis-
Dane and G.C. Topp (eds.) Methods of soil analysis. Part 4. sion parameters obtained through infiltration, p. 878–898.
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 6
Water and Energy Balances in
the Soil–Plant–Atmosphere
Continuum

Steven R. Evett
United States Department
of Agriculture 6.1 Introduction..............................................................................................................................6-1
6.2 Energy Balance Equation........................................................................................................6-1
John H. Prueger Net Radiation  •  Latent Heat Flux  •  Soil Heat Flux  •  Sensible Heat Flux
United States Department 6.3 Water Balance Equation........................................................................................................ 6-31
of Agriculture
Measuring ΔS and ET  •  Estimating Flux across the Lower Boundary  • 
Precipitation and Runoff
Judy A. Tolk
United States Department Acknowledgments..............................................................................................................................6-38
of Agriculture References............................................................................................................................................6-38

6.1  Introduction balance components can be found in ASAE (1988), Campbell

(1985), Richter (1987), Anlauf et al. (1990), Hanks and Ritchie
Energy fluxes at soil–atmosphere and plant–atmosphere inter- (1991), Pereira et al. (1995), and Peart and Curry (1998) to men-
faces can be summed to zero when the surfaces, including plants tion only a few.
and plant residues, have no or negligible capacity for energy
storage. The resulting energy balance equations may be writ-
ten in terms of physical descriptions of these fluxes and have 6.2  Energy Balance Equation
been the basis for problem casting and solving in diverse fields
of environmental and agricultural science such as estimation of A surface energy balance is
evapotranspiration (ET) from vegetated surfaces, estimation of
evaporation from bare soil, rate of soil heating in spring (impor- 0 = Rn + G + LE + H , (6.1)
tant for timing of seed germination), rate of residue decompo-
sition (dependent on temperature and water content at the soil
surface), and many other problems. The water balances at these where
surfaces are implicit in the energy balance equations. So, the R n is net radiation
soil water balance equation, though different from the surface G is soil heat flux
energy balances, is linked to them; a fact that has often been LE is the latent heat flux (evaporation to the atmosphere) and
ignored in practical problem solving. In this chapter the energy is the product of the evaporative flux, E, and the latent heat
balances will be discussed first, followed by the water balance in of vaporization, λ
Section 6.3. H is sensible heat flux (all terms taken as positive when flux is
Computer simulation has become an important tool for toward the surface and in W m−2)
theoretical investigation of energy and water balances at the
earth’s surface, and for prediction of important results of the Each term may be expressed more completely as the sum of sub-
mechanisms involved. This chapter will focus more on the terms that describe specific physical processes, some of which are
underlying principles of energy and water balance processes, shown in Figure 6.1. Note that Equation 6.1 may be written indi-
and will mention computer models only briefly. More informa- vidually for soil, plant, and plant residue surfaces. Net radiation
tion on computer models that include surface energy and water includes the absorption and reflection of shortwave radiation

6-1
6-2 Properties and Processes

1000
R si L
H
P 500

si
L

αR
LE

Flux (W m–2)
0

–500
LE H
R si L –1000
LE Rn G H Rsi
R Rt
si

L
αR

–1500
Soil surface GJw G 0 6 12 18 24 30 36 42 48
Control volume Hour, days 119–120, 1992
I
F Lower boundary Jw FIGURE 6.2  Energy balance components over irrigated winter wheat
at Bushland, Texas.

FIGURE 6.1  Water and energy balance components. Water balance

1000
components are in black, energy balance components in white. The
shared term LE is shaded. Water balance is discussed in Section 6.3.
500
(sunlight, Rsi, and the reflected portion, αRsi), as well as the emis-
Flux (W m–2)
sion and reception of longwave radiation (L↑ and L↓, respec- 0
tively, Figure 6.1). Soil heat flux involves not only diffusion of heat,
G, as expressed by Fourier’s law (see Chapter 9) but also convective –500
heat flux, GJw, as water at temperature T flows at rate Jw into soil
at another temperature T′. Evaporation from both soil and plants –1000
are examples of latent heat flux; but so also is dew formation,
LE Rn G H Rsi
whether it wets the soil surface or plant canopy. Finally, sensible
–1500
heat flux may occur between soil and atmosphere or between 0 6 12 18 24 30 36 42 48
plant and atmosphere, and may be short-circuited between soil Hour, days 254–255, 1997
and plant, for example, when sensible heat flux from the soil
FIGURE 6.3  Energy balance components over irrigated alfalfa at
warms the plant. In the next few paragraphs, these fluxes and
Bushland, Texas.
values they may assume will be illustrated with examples from
some contrasting surfaces under variable weather conditions.
1000
Not shown in Figure 6.1 are energy storage due to photo-
synthesis and that related to temperature and heat capacity of
500
plants. Heat storage in field crops is often ignored as a minor
part of the energy balance, but it may not be trivial for forests
Flux (W m–2)

where heat flux into and out of vegetation can be important, for 0
example, >35 W m−2 with heat storage up to 0.3 MJ m−2 (Meesters
and Vugts, 1996) and >60 W m−2 (Haverd et al., 2007). The latter –500
authors included calculation of vegetative heat fluxes and storage
in a soil–vegetation–atmosphere transfer model. Photosynthesis –1000
is often ignored as a negligible part of the overall energy bal- LE Rn G H Rsi
ance. Further discussion of heat storage and fluxes in vegetation –1500
is beyond the scope of this chapter. 0 6 12 18 24 30 36 42 48
Values of the energy fluxes change diurnally (Figures 6.2 Hour, days 193–194, 1992
through 6.4) and seasonally (Figures 6.5 and 6.6). Regional
FIGURE 6.4  Energy balance components for bare Pullman clay loam
advection is the large-scale transport of energy in the atmosphere soil after 35 mm of rain at Bushland, Texas.
from place to place on the earth’s surface. Regional advection
events can change the energy balance greatly as illustrated with clear sky value of 28.6 MJ m−2 day−1 for this latitude and time of
measurements taken over irrigated wheat at Bushland, Texas year. However, on day 119, strong, dry, adiabatic southwesterly
(35°11′N Lat; 102°06′W Long) for the 48 h period beginning on winds (mean 5 m s−1, mean dew point 4.1°C, mean 2 m air tem-
day 119, 1992 (Figure 6.2). Total Rsi was 26.1 and 26.7 MJ m−2 on perature 20.1°C) caused H to be strongly positive, providing the
days 119 and 120, respectively; close to the expected maximum extra energy needed to drive total LE to −32.8 MJ m−2 day−1, even
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-3

40 cover and moist air was signaled near midnight by the abrupt
change from negative values of R n and LE to near zero values.
30
In the case of net radiation, this was due to the increased long-
20 wave radiation from the clouds, which were warmer and had
Energy (MJ m–2)

10 larger emissivity than the clear sky that preceded them. Also
near midnight, latent heat flux neared zero because the strong
0
vapor pressure gradient from moist crop and soil to dry air was
–10 reduced by the arrival of moist air. Note that after sunset, but
–20
before midnight, latent heat flux was strong, due to continuing
strong sensible heat flux, even though net radiation was negative.
–30 Rsi Rn LE G H Again, due to full crop cover (LAI = 3), G values were small, indi-
–40 cating that very little energy was penetrating the soil surface.
0 60 120 180 240 300 360 For bare soil, G is often larger, becoming an important part of
Day of year, 1996 the energy balance (Figure 6.4). After rain and irrigation totaling
FIGURE 6.5  Daily totals of energy balance terms for a fallow field 35 mm over the previous 2 days, the bare soil was wet on day 193,
(mostly bare Pullman clay loam) at Bushland, Texas. Note some miss- 1992, at Bushland, Texas. Latent heat flux totaled −14.4 MJ  m−2
ing R n and H data in late summer. or 6 mm of evaporation; 77% of Rn. Sensible heat flux was negative
for the first few hours after sunrise because the soil was warmer
40 than the air, which had been cooled by a nighttime thunderstorm.
Rsi Rn LE G H
Later in the day, H and G both approached zero, and near sunset,
30
they became positive, supplying the energy consumed in evapo-
20 ration that continued well into the night hours. Strong radiational
cooling occurred on the nights of days 193 and 194 as indicated
Energy (MJ m–2)

10
by negative values of Rn. Evaporation was probably energy limited
0
on day 193, becoming soil limited on day 194. Latent heat flux
–10 on the second day was reduced to −7.4 MJ m−2, and peak daytime
values were not much larger in magnitude than those for G. The
–20
drying soil became warmer and contributed sensible heat to the
–30 atmosphere during almost all daylight hours.
–40 Seasonal variations in daily total energy flux values occur
0 60 120 180 240 300 360 due to changes of sun angle and day length, of distance from the
Day of year, 1996 earth to sun (about 3% yearly variation), of seasonal weather, and
FIGURE 6.6  Daily totals of energy balance terms for irrigated alfalfa of surface albedo as plant and residue cover changes (Figures 6.5
at Bushland, Texas. and 6.6). A curve describing clear sky solar radiation at Bushland,
Texas, would match the high points of Rsi in Figures 6.5 and 6.6
though both Rsi and Rn levels were reduced in the afternoon due well. Net radiation was similar for alfalfa and bare soil except for
to cloudiness. Total LE was much larger in absolute magnitude a rainy period beginning about day 190 when the soil was wet
than Rsi and Rn totals. The next day, the total LE was 39% smaller and dark and Rn for the fallow field was markedly larger. The big
due to the absence of regional advection, even though total Rsi differences were in LE and H. Latent heat flux from the alfalfa
and Rn values were slightly larger. Values of G were near zero dur- was large, reaching nearly −40 MJ m−2 (16 mm) on day 136 dur-
ing this period of full canopy cover when leaf area index (LAI) ing a regional advection event that allowed LE to be larger than
was 7 (LAI is defined as the single-sided surface area of leaves per Rsi. Sensible heat flux was positive during much of the year. Soil
unit land area). Note that net radiation was negative at night. This heat flux was small during the growing season, becoming larger
is indicative of strong radiational cooling of the surface, which as the soil cooled during the fall and winter. For the bare soil,
radiates heat into the clear, low-humidity nighttime skies com- LE values were small during the first 150 days, the latter end of a
mon to this semiarid location at 1170 m above mean sea level. drought (Figure 6.5). Sensible heat flux was negative during this
Over alfalfa in late summer, Rsi totals were lower (20.1 and period and remained negative after rains began until day 203.
5.4 MJ m−2 day−1, respectively, for days 254 and 255, 1997, Figure Evaporative fluxes were fairly small, rarely reaching 6 mm day−1
6.3). On the very clear day 254, peak Rsi was 798 W m−2; and with even after rains began. In contrast to alfalfa, soil heat flux for bare
regional advection occurring, LE flux was large. The 3 h period soil was larger and more variable throughout the year.
of negative H just after sunrise was due to the sun-warmed crop Methods of measurement and estimation of the energy fluxes
canopy being at greater temperature than the air. The arrival of a are needed to characterize the energy balance. Examples of the
cool front bringing cloudy skies near midnight caused all fluxes instrumentation needed to measure components and subcom-
to be much less on day 255, with Rsi reaching only 220 W m−2, ponents of the energy balance are given in Table 6.1. These will
and H near zero for much of the day. The arrival of the cloud be discussed in the following sections.
6-4 Properties and Processes

TABLE 6.1  Example of Instruments and Deployment Information for Bare Soil Radiation
and Energy Balance Experiments at Bushland, Texas, 1992
Manufacturera
Parameter Instrument (Model) Elevation Description
Rsi Pyranometer Eppley (PSP)b 1 m Solar irradiance
αRsi Pyranometer Eppley (8–48) 1 m (Ic) Reflected solar irradiance
L↓ Pyrgeometer Eppley (PIR) 1 m Incoming longwave radiation
L↑ Pyrgeometer Eppley (PIR) 1 m (I) Outgoing longwave radiation
Rn Net radiometer REBS (Q*6) 1 m Net radiation
Ts IR thermometer Everest (4000; 60° fov) 1 m nadir view angle Soil surface temperature
Ta Thermistor Rotronics Air temperature and relative
humidity
RH Foil capacitor (HT225R) 2 m
U2 DC generator cups R.M. Young (12102) 2 m Wind speed
Ud Potentiometer vane R.M. Young (12302) 2 m Wind direction
Tt Cu–Co thermocouple Omega (304SS) −10 mm and −40 mm Soil temperature (4)d
G50 Plates thermopile REBS (TH-1) −50 mm Soil heat flux (4)
θv-20 3-wire Dynamax −20 and −40 mm Soil water content (2)
θv-40 TDR probe TR-100/20 cm horizontal
Em Lever-scale load cell Interface (SM-50) Below lysimeter box Lysimeter mass change
Source: Adapted from Howell, T.A., J.L. Steiner, S.R. Evett, A.D. Schneider, K.S. Copeland, D.A. Dusek, and A. Tunick.
1993. Radiation balance and soil water evaporation of bare Pullman clay loam soil, p. 922–929. In R.G. Allen and C.M.U.
Neale (eds.) Management of irrigation and drainage systems, integrated perspectives. Proc. Nat. Conf. Irrigat. Drain. Eng.
Park City, UT, July 21–23, 1993. Am. Soc. Civil Eng., New York.
Parameters not shown in Figure 6.1 will be presented later.
a Manufacturers and locations are The Eppley Laboratory, Inc., Newport, RI; Radiation and Energy Balance Systems

(REBS), Seattle, WA; Everest Interscience, Inc., Fullerton, CA; Rotronic Instrument Corp., Huntington, NY; R.M. Young
Co., Traverse City, RI; Omega Engineering, Inc., Stamford, CT; Dynamax, Inc., Houston, TX; Interface, Inc., Scottsdale, AZ.
b The mention of trade names of commercial products in this article is solely for the purpose of providing specific infor-

mation and does not imply recommendation or endorsement by the U.S. Department of Agriculture.
c “I” designates instruments that were inverted and facing the ground.

d Numbers in parentheses indicate numbers of replicate sensors.

6.2.1  Net Radiation Shortwave Longwave

100 25
Net radiation is the sum of incoming and outgoing radiation
Emission power (MW m–2 μm–1)

Emission power (W m–2 μm–1)

80 20
Rn = Rsi (1 − α) − L↑ + L↓ , (6.2)

where 60 15
Rsi is solar irradiance at the surface (W m−2)
α is the albedo or surface reflectance (0–1) 40 10
L↑ is the longwave radiance of the earth’s surface (W m−2)
L↓ is longwave irradiance from the sky (W m−2)
20 5
The sun radiates energy like a black body at about 6000 K, while
the earth radiates at about 285 K. The theoretical maximum 0 0
emission power spectra for these two bodies overlap very little 0.1 1 10 100
(Figure 6.7), a fact that leads to description of radiation from Wavelength (μm)
the earth (including clouds and the atmosphere) as longwave, FIGURE 6.7  Emission power spectra for ideal black bodies at 6000 K (left,
and radiation from the sun as shortwave. Note that the radi- shortwave range) and 285 K (right, longwave range). Note that the units of
ance of the earth is about 4 million times less than that of the the left-hand ordinate are 106 larger than those of the right-hand ordinate.
sun (Figure 6.7). Net radiation may be measured by a net radi-
ometer (Figure 6.8) or its components may be measured sepa- in Table  6.1). Pyranometers and pyrgeometers are thermopile
rately using pyranometers to measure incoming and reflected devices that are sensitive equally across the spectrum. While
shortwave radiation, and pyrgeometers to measure incom- net radiometers are usually much less expensive than four-­
ing and outgoing longwave radiation (first four instruments component suites of pyrgeometers and pyranometers, there have
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-5

FIGURE 6.8  REBS Q*7 net radiometer. FIGURE 6.9  Kipp & Zonen model CM-14 albedometer.

been consistent problems with calibration within a model series as the radiant energy reaching a horizontal plane at the earth’s
and biases between models from different companies leading surface. It may be easily measured by pyranometer with cali-
to inconsistencies of up to 20% (Halldin, S., and A. Lindroth. bration to international standards (Table 6.1) or by solar cells.
1992. Errors in net radiometry: Comparison and evaluation of Silicon photodetector solar radiation sensors such as the LI-COR
six radiometer designs. J. Atmos. Ocean. Tech. 9:762–783; Kustas, model LI-200SA are sensitive in only part of the spectrum but
W.P., J.H. Prueger, L.E. Hipps, J.L. Hatfield, and D. Meek. 1998. are calibrated to give accurate readings in most outdoor light
Inconsistencies in net radiation estimates from use of several conditions. Silicon sensors are much cheaper than thermopile
models of instruments in a desert environment. Agr. Forest pyranometers and have found widespread use in field weather
Meteorol. 90:257–263). Since no international standard exists stations. Measurement of both incident (Rsi) and reflected (Rsr)
for longwave radiation measurement and calibration, users are shortwave allows estimation of the albedo from
left with the options of cross-calibration of multiple instru-
ments and comparisons with four-component pyrgeometer and Rsi (1 − α) = Rsi − Rsr . (6.4)
pyranometer measurements. Continuing problems with net
radiation measurement have made estimation of R n from Rsi a This is done using upward and downward facing matched
common practice that is discussed in Section 6.2.1.6. pyranometers (Table 6.1). Specially made albedometers are
available for this purpose (e.g., Kipp & Zonen model CM-14;
6.2.1.1  Outgoing Longwave Radiation
Figure 6.9).
The longwave radiance of the earth’s surface, L↑, is given by the In the absence of measurements, solar irradiance may be esti-
Stefan–Boltzmann law for radiance from a surface at tempera- mated from the sun’s brightness above the atmosphere Ra(W m−2)
ture T (K) and with emissivity ε (0–1). and reductions in surface irradiation mediated by latitude, time
of day and year, and elevation. Such estimates also provide a use-
L↑= εσT 4 , (6.3) ful check on measurements by providing an upper bound to Rsi,
the clear sky solar irradiance, Rso. The “solar constant” is the flux
where σ is the Stefan–Boltzmann constant (5.67 × 10−8 W m−2 density of solar radiation on a plane surface perpendicular to
K−4). An inverted pyrgeometer (Table 6.1) may be used to mea- the direction of radiation and outside the earth’s atmosphere. It
sure L↑ and, if accompanied by suitable surface temperature is 1366 W m−2 on average, with a within-year variation of about
measurements, may allow estimation of surface emissivity, ε, by ±3.5%, being largest in January when the sun is closest to the
inversion of Equation 6.3. Surface temperature is often measured earth and smallest in July (Jones, 1992). Several satellite obser-
by suitably placed and shielded thermocouples, or remotely by vation platforms have recorded the value of solar irradiance, Ra,
infrared thermometer (IRT). There are problems with either over a >20 year span (Figure 6.10) and clearly show the average
type of measurement (radiational heating of the thermocou- solar cycle of 11 years (Fröhlich and Lean, 1998). The data range
ples, and uncertainty of the emissivity needed for accurate IRT over about 0.36% of the mean value when corrected for earth–
measurements). sun distance. Thus, considering the “solar constant” to be 1366
Values of α and ε for soil and plant surfaces may be estimated W m−2 will introduce a <1% error in calculations when corrected
from published values relating them to surface properties (see for earth–sun distance.
Section 6.2.1.3 and Table 6.4). For soil, the dependence of α on water Irradiance at the earth’s surface is somewhat less, due to
content is strong, but nearly linear, and amenable to estimation. absorption and scattering in the atmosphere and due to sun
angle effects, not often exceeding 1000 W m−2. The further the
6.2.1.2  Solar Irradiance sun is from the zenith the longer the transmission path through
Solar irradiance, Rsi, includes both direct beam and diffuse the atmosphere, and the more absorption and scattering occurs.
shortwave radiation reaching the earth’s surface and is defined Also, as sun angle above the horizon, β (radians), decreases (it is
6-6 Properties and Processes

1369 In the United States, the meridians for Eastern Standard Time
(EST), Central Standard Time (CST), Mountain Standard
1368
Total solar irradiance (W m–2)

Time (MST), and Pacific Standard Time (PST) are 75°, 90°, 105°,
1367 and 120°, respectively. Local or true solar time (t LS, h) for any
local standard time (tST) may be calculated with
1366

1365 (longitude − local meridian)

t LS = t ST − 4 + t EQ . (6.9)
60
1364

1363 The declination (radians) may be calculated from (Rosenberg

1362
et al., 1983)
1978.8 1983.8 1988.8 1993.8 1998.8 2003.8
Year ⎡ 2π( J − 172) ⎤
δ = 0.4101cos ⎢ ⎥, (6.10)
FIGURE 6.10  Composite of observations of total solar irradiance ⎣ 365 ⎦

(Ra) outside the earth’s atmosphere from six satellites: NIMBUS-7,
SMM, ERBS, UARS, SOHO, and ACRIM-Sat (corrected for earth– where J is the day of the year.
sun distance). (ftp://ftp.ngdc.noaa.gov/STP/SOLAR_DATA/SOLAR_ List (1971) gave “equation of time” values to the nearest sec-
IRRADIANCE/composite_d25_07_0310a.dat. Graph constructed ond for the first of each month and every 4 days after that for
using version d25_07_0310a of the dataset from PMOD/WRC, Davos, each month (95 values for the year). The following equation
Switzerland, including unpublished data from the VIRGO experiment
reproduces those values with a maximum error of 6 s and can be
on the cooperative ESA/NASA Mission SoHO; Fröhlich, C., and J. Lean.
used to estimate t EQ (h) for any day of the year.
1998. The sun’s total irradiance: Cycles, trends and related climate
change uncertainties since 1976. Geophys. Res. Lett. 25:4377–4380.)
⎛ J⎞ ⎛ J⎞ ⎛ J ⎞ ⎛ J ⎞
t EQ = b0 + b1 sin ⎜ ⎟ + b2 cos ⎜ ⎟ + c1 sin ⎜ ⎟ + c2 cos ⎜ ⎟
greatest at solar noon) the radiation density, I, on a horizontal ⎝ P1 ⎠ ⎝ P1 ⎠ ⎝ P4 ⎠ ⎝ P4 ⎠
surface decreases according to Lambert’s law
⎛ 2J ⎞ ⎛ 2J ⎞ ⎛ 3J ⎞ ⎛ 3J ⎞
I = I o sin(β), (6.5) + c3 sin ⎜ ⎟ c4 cos ⎜ ⎟ + c5 sin ⎜ ⎟ + c6 cos ⎜ ⎟
⎝ P4 ⎠ ⎝ P4 ⎠ ⎝ P4 ⎠ ⎝ P4 ⎠
where Io is the flux density on a surface normal to the beam.
⎛ 4J ⎞ ⎛ 4J ⎞
Sun angle (β) changes with time of day and year, and can be + c7 sin ⎜ ⎟ + c8 cos ⎜ ⎟ , (6.11)
⎝ P4 ⎠ ⎝ P4 ⎠
calculated from

β = sin −1[sin(δ)sin(φ) + cos(δ)cos(φ)cos(t sa )], (6.6)

where the coefficients b1 and c1 are given in Table 6.2, and P1 =
where 182.5/(2π) and P4 = 365/(2π).
ϕ is latitude Jensen et al. (1990) gave a simpler method for t EQ:
δ is solar declination
tsa is solar time angle (all radians) t EQ = 0.1645 sin(2b) − 0.1255 cos(b) − 0.025 sin(b), (6.12)

Solar time angle is defined as where b = 2π(J − 81)/364. The maximum error compared against
(t − t SN )2π List’s t EQ values is 88 s.
t sa = , (6.7) Disregarding air quality, solar irradiance is affected by lati-
24
tude, time of year and day, and elevation. Latitude and time
where affect the sun angle, β, and so affect both the path length of radi-
t is time (h) ation through the atmosphere (and thus absorption and scatter-
tSN is the time (h) of solar noon ing losses) and the flux density at the surface through Equation
6.5. Elevation affects the path length. Methods for calculating
The time of solar noon varies with time of year and longitude
extraterrestrial, Rsa, and clear sky solar irradiance at the sur-
according to (recall that 1° longitude = 4 min):
face, Rso, are given by ASCE (2005), Campbell (1977, Chapter 5),
4(longitude − local meridian)
t SN = 12 + − t EQ , (6.8)
60 TABLE 6.2  Coefficients for Calculating the “Equation

of Time” Value from Equation 6.11
where
b0 4.744 × 10−5 c2 9.19 × 10–3 c6 −1.29 × 10−3
t EQ is the “equation of time” value (h)
b1 −0.157 c3 −5.78 × 10–4 c7 −3.23 × 10−3
longitude is in degrees
b2 −0.0508 c4 3.61 × 10–4 c8 −2.1 × 10−3
the local meridian is the longitude (°) for which standard
c1 −0.122 c5 −5.48 × 10–3
time is calculated for the time zone in question
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-7

Jensen et al. (1990, Appendix B), Jones (1992, Appendix 7), and Equation 6.13 can be rewritten for total daily Rsa as
McCullough and Porter (1971). Calculation of Rsa depends on
latitude and time of day. Once Rsa is calculated, Rso may be esti- ⎡ 24(60) ⎤
mated from considerations of absorption and scattering in the Rsa = ⎢ ⎥ GSCdr[cos(φ)cos(δ)sin(ω s ) + ω s sin(φ)sin(δ)].
⎣ π ⎦
atmosphere, which depend mainly on the path length through
the atmosphere and its density. Thus latitude, time of day, and (6.19)
elevation are factors in estimating Rso from Rsa. The value of Rso is
an important quantity against which to check measured Rsi; and For example, on day 119 at latitude 35°11′N, longitude 102°6′W,
it can be used in estimates of R n, either to replace Rsi in Equation Rsa calculated using Equation 6.13 on a half-hourly basis totaled
6.2 or to use location-specific regression relationships of R n = 38.097 MJ m−2 compared with 38.100 MJ m−2 calculated with
f(Rso) (see Jensen et al., 1990, Appendix B). Duffie and Beckman Equation 6.19.
(1991) presented the following method of calculating R sa (MJ Jensen et al. (1990) recommended estimating daily total clear
m−2 h−1) for any period, τ (h), sky solar irradiance as

⎡ 24(60) ⎤ Rso = 0.75Rsa (6.20)

Rsa = ⎢ ⎥ GSCdr {cos(φ)cos(δ)[sin(ω 2 ) − sin(ω1 )]
⎣ 2π ⎦
+ (ω1 − ω 2 )sin(φ)sin(δ)}, (6.13) Somewhat in agreement with this, Monteith and Unsworth
(1990) stated that direct beam radiation rarely exceeded 1030
where W m−2, about 75% of the solar constant.
GSC is the solar constant (0.08202 MJ m−2 min−1) Jones (1992) and Monteith and Unsworth (1990) suggested
dr is the relative earth–sun distance
ω1 and ω2 are the solar time angles at the beginning and end ⎛ πt ⎞
Rsi = Rsi_ max sin ⎜ ⎟ , (6.21)
of the period, respectively (all angles in radians) ⎝N⎠

The term 24(60)/(2π) is the inverse angle of rotation per minute. for instantaneous values of Rsi on clear days, where Rsi_max is the
The relative earth–sun distance, dr, is given by maximum instantaneous irradiance occurring at solar noon, t is
time after sunrise (h), and N is day length (h).
⎛ 2πJ ⎞ Rather than Rsi_max, it is more common to know daily total Rsi.
dr = 1 + 0.033 cos ⎜ , (6.14)
⎝ 365 ⎟⎠ Collares-Pereira and Rabl (1979) gave the ratio of hourly irradi-

ance, Rsi,h to daily irradiance, Rsi,d as
where J is the day of year. The solar time angles at the beginning
and end of the period in question are given by Rsi,h ⎛ π ⎞ (cos ω − cos ω S )
= (a + b cos ω) , (6.22a)
Rsi,d ⎜⎝ 24 ⎟⎠ (sin ω S − ω S cos ω S )

π
ω1 = ω − , (6.15)
(24 /τ) where
π
ω2 = ω + , (6.16) ⎛ π⎞
(24 /τ) a = 0.409 + 0.5016 sin ⎜ ω S − ⎟ (6.22b)
⎝ 3⎠

where
ω is the solar time angle at the center of the period (radians) and
τ is the length of the period in hours
⎛ π⎞
b = 0.6609 + 0.4767 sin ⎜ ω S − ⎟ (6.22c)
Calculation of Rsa for an entire day requires knowledge of ⎝ 3⎠

the sunrise and sunset times. The sunset time angle (angle from
solar noon to sunset, radians) is given by Equation 6.22 performed well when applied to data from
Bushland, Texas (Figure 6.11).
ω s = cos −1[− tan(φ)tan(δ)], (6.17) More complex methods of estimating Rso account for attenu-

ation of direct beam radiation using Beer’s law, coupled with
from which it is clear that day length, t D (h), is Lambert’s law to calculate irradiance on a horizontal sur-
face, plus an accounting of diffuse irradiance (see, e.g., List,
24ω s 1971; Rosenberg et al., 1983; Jones, 1992). Beer’s law describes
tD = . (6.18)
π the intensity I of radiation after passing a distance x through
6-8 Properties and Processes

1000 measured air mass number is less than that given by Equation
800
6.24 due to refraction and reflection at these low angles. List
Days 119–120, (1971) gives corrections and notes also that for pressures, p, less
600 1992
than standard sea-level pressure, p0, that m should be corrected
400 by m = m(p/p0). Rewriting Equation 6.23, we have
200
Irradiance (W m–2)

k sec( π / 2 − β )
Io = Ia e , (6.25)

0
1000 where Io is direct beam radiation at the earth’s surface. Monteith
800 and Unsworth (1990) give a range of values of k for England as
Days 254–255,
1997 0.07 for very clean air and 0.6 for very polluted air.
600
Assuming that both direct, Io, and diffuse, Id, radiation are
400 known, the total irradiance at the surface is
200 Rsi = I o (sin β) + I d . (6.26)

0
0 6 12 18 24 30 36 42 48 Diffuse radiation is difficult to estimate because it is so depen-
Time (h) dent on cloud cover and aerosol concentration in the air. Yet,
FIGURE 6.11  Solar irradiance measured at Bushland, Texas, in 1992 summarizing several data sets, Spitters et al. (1986) found that
and 1997 on clear and cloudy days (open circles) and Equation 6.22a the proportion of Rd to Rsi is a function of the ratio of Rsi to Rsa
half-hourly predictions (lines). (Figure 6.12) described for daily total Rsi by

a medium in terms of an extinction coefficient, k, and the initial Rsi,d

Rd,d = 1, < 0.07 (6.27a)
intensity, Ia, as Rsa,d

I = I a ekx . (6.23) 2
Rd,d ⎛R ⎞ R
= 1 − 2.3 ⎜ si,d − 0.07 ⎟ , 0.07 ≤ si,d < 0.35 (6.27b)
For solar radiation, the distance is expressed in terms of air mass Rsi,d ⎝ Rsa,d ⎠ Rsa,d

number, m, as (List, 1971)
Rd,d ⎛R ⎞ R
⎛π ⎞ = 1.33 − 1.46 ⎜ si,d ⎟ , 0.35 ≤ si,d < 0.75 (6.27c)
m = sec ⎜ − β⎟ . (6.24) Rsi,d R
⎝ sa,d ⎠ Rsa,d
⎝2 ⎠

The air mass is referenced to the length of the path when the Rd,d ⎛R ⎞ R
= 0.23 ⎜ si,d ⎟ , 0.75 ≤ si,d , (6.27d)
sun is directly overhead. For β less than 0.175 radians (10°), the Rsi,d ⎝ Rsa,d ⎠ Rsa,d

1.0

0.8

0.6
Rd/Rsi

0.4
57 9
1
6 5
3
4 82
0.2

0.0
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
(a) Rsi/Rsa (b) Rsi/Rsa

FIGURE 6.12  Daily (a) and hourly (b) relationships between Rd/Rsi and Rsi/Rsa. (Reprinted from Spitters, C.J.T., H.A.J.M. Toussaint, and
J. Goudriaan. 1986. Separating the diffuse and direct component of global radiation and its implications for modeling canopy photosynthesis. Part
I. Components of incoming radiation. Agr. Forest Meteorol. 38:217–229.)
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-9

and for hourly values by surfaces are often considered optically rough, but in some cases,
specular (mirror-like) rather than diffuse reflection may occur.
Rsi,h Some plant leaves are shiny and reflect specularly when the
Rd,h = 1, ≤ 0.22 (6.28a) angle of incident radiation is small. Wet soil surfaces may also
Rsa,h
reflect specularly. These mechanisms lead to larger albedo when
sun angle is smaller. The albedo of plant stands is also smaller
2
Rd,h ⎛R ⎞ R in midday because more sunlight penetrates deeply within the
= 1 − 6.4 ⎜ si,h − 0.22 ⎟ , 0.22 < si,h ≤ 0.35 (6.28b) canopy and is trapped by multiple reflections. Wilting and other
Rsi,h R
⎝ sa,h ⎠ Rsa,h
physiological changes during the day may also contribute to
changes in albedo.
Rd,h ⎛R ⎞ R Soil albedo decreases as water content increases. Bowers and
= 1.47 − 1.66 ⎜ si,h ⎟ , 0.35 < si,h ≤ K (6.28c) Hanks (1965) found the relationship to be curvilinear, as did
Rsi,h ⎝ Rsa,h ⎠ Rsa,h
Skidmore et al. (1975). Working with thinner soil layers, Idso
and Reginato (1974) found that bare soil albedo changed lin-
Rd,h R early with water content of the surface 2 mm of soil (smooth clay
= R, K < si,h , (6.28d)
Rsi,h Rsa,h loam; Figure 6.14). For thicker layers, the relationship was curvi-

linear. The maximum albedo, 0.3, occurred for air dry soil, but
the minimum albedo, 0.14, occurred at about 0.23 m3 m−3 water
where
content, much less than saturation. This represents field capacity
(soil water tension of 30 kPa) for this soil; and Idso and Reginato
R = 0.847 − 1.61sin β + 1.04sin2 β (6.29) (1974) postulated that the minimum albedo would occur at field

capacity for all soils. Kondo et al. (1992) found a similar relation-
and ship for a bare loam with a maximum albedo of 0.24 and mini-
mum of 0.13, and with the minimum attained when soil water
content reached about 0.22 m3 m−3. Data of Idso et al. (1974,
(1.47 − R)
K= (6.30) 1975) show that the difference between wet and dry soil albedos
1.66 was constant despite the diurnal variation of albedo or the day of
year. Similarly, Monteith (1961) measured albedo of clay loam to
be 0.18 when dry, decreasing to 0.11 when at field capacity water
6.2.1.3  Surface Albedo and Emissivity
content of 0.35 m3 m−3.
Because Rsi provides most of the energy that is partitioned at the The interaction of sun angle and soil drying causes complex
earth’s surface, albedo plays a major role in the energy balance. patterns of soil albedo change over time. Figure 6.13 illustrates
The mean albedo of the earth is 0.36 ± 0.06 (Weast, 1982). But low daytime wet soil albedos of 0.11 after irrigation and rain
albedo varies diurnally (Figure 6.13) with larger albedo corre- on days 191 and 192, 1992, at Bushland, Texas. Rapid soil sur-
sponding to lesser sun angle (see also bare soil data of Monteith face drying on day 193 caused albedo to rise sharply during the
and Szeicz, 1961; Idso et al., 1974; Aase and Idso, 1975). Soil and plant day. Additional drying on day 194 completed the change, and

0.32
0.4

0.28
Normalized albedo

o 0.2 0.5 1 2 4 6 8 10 cm
0.3 0.24
Surface to

0.20
Albedo

0.2
Dry 0.16
g
yin
0.1 Dr 0.12
Wet 0 0.04 0.08 0.12 0.16 0.2 0.24 0.28 0.32
Water content (m3 m–3)
0
191 192 193 194 195 196 197 FIGURE 6.14  Albedo, normalized according to sun angle, versus soil
Day of year, 1992
water content for different surface layer thicknesses of Avondale clay
loam at Phoenix, AZ. Solid circles describe albedo versus water content
FIGURE 6.13  Albedo plotted as a function of time for smooth, bare at the surface. Data for shaded areas are uncertain. (From Idso, S.B.,
Pullman clay loam at Bushland, Texas, in the daytime, when wet, dur- and R.J. Reginato. 1974. Assessing soil-water status via albedo measure-
ing drying, and dry. ment. Hydrol. Water Resour. Arizona SW 4:41–54.)
6-10 Properties and Processes

diurnal albedo changes on days 195 and 196 reflected only sun 0.6 100
Wheat, u < 4.5 m s–1 Wheat, u > 4.5 m s–1
angle effects, with a minimum albedo of 0.2 for this smooth soil Cotton, u < 4.5 m s–1 Cotton, u > 4.5 m s–1
surface. The same surface in a roughened condition earlier in the 0.5
Sun angle 80
year never reached midday albedo values larger than 0.13.
0.4
Other than water content, major determinants of soil albedo

Sun angle (°)

60

Albedo
are color, texture, organic matter content, and surface rough- 0.3
ness. Dvoracek and Hannabas (1990) presented a model of 40
albedo dependence on sun angle, surface roughness, and color 0.2

20
(c sin β +1) 0.1
α= p , (6.31)

0 0
0 3 6 9 12 15 18 21 24
where Time (h)
p is a color coefficient
FIGURE 6.15  Albedo for wheat and cotton versus sun angle and wind
c is a roughness coefficient
speed (u) according to Equation 6.31.
β is solar angle

They demonstrated good fits with measured data (Table 6.3). 1.0
Albedo values modeled using p and c values from Table 6.3 for Fallow Alfalfa
wheat and cotton (day of year 192, latitude 41°N) appear realistic 0.8 Snow
(Figure 6.15). However, the physical meaning of the p and c coef-
4th cut
ficients is not well understood. 0.6 3rd cut
Daily mean albedos may be calculated as the ratio of daily
Albedo

2nd cut
total reflected shortwave energy to daily total Rsi. Using data 1st cut
0.4
from Figures 6.5 and 6.6, daily mean albedos for fallow (soy-
bean residue) and alfalfa differ by about 0.10 when the soil is
very dry (Figure 6.16). The gradual decline in fallow albedo in 0.2
early 1996 may be due to decomposition of the soybean residue.
0.0
0 60 120 180 240 300 360
Day of year, 1996
TABLE 6.3  Color (p) and Roughness (c) Coefficients
for Equation 6.31 FIGURE 6.16  Daily mean albedos for irrigated alfalfa and fallow after
Color Roughness
soybean on Pullman clay loam at Bushland, Texas.
Surface and Condition Coefficient p Coefficient c Mean r2
Lakes and ponds, clear water
Waves, none 0.13 0.29 0.82
Albedo for the alfalfa field declined at each cutting to nearly
Waves, ripples up to 2.5 cm 0.16 0.70 0.74
that of the fallow field, which was initially rougher than the soil
Waves, larger than 2.5 cm with 0.23 1.25 0.83
under the alfalfa. But, during heavy rains in the latter part of
occasional whitecaps the year, the fallow soil surface was slaked and smoothed and its
Waves, frequent whitecaps 0.30 2.00 0.85 albedo increased to near that of the alfalfa. Thus, after the fourth
Lakes and ponds cut, the alfalfa field albedo was lower than that of the fallow field
Green water, ripples up 0.22 0.70 0.90 for a brief time, probably because the alfalfa was irrigated and
to 2.5 cm the fallow field had dried out again. Peaks of albedo exceeding
Muddy water, no waves 0.19 0.29 0.76 0.8 were due to snow early and late in the year. In contrast to
Cotton soil, albedo of closed canopies (well watered) is relatively con-
Winds, calm to 4.5 m s−1 0.27 0.27 0.80 stant (Table 6.4).
Winds, over 4.5 m s−1 0.27 0.43 0.88 Albedo values for many plant covers may be found in Gates
Wheat
(1980). For surfaces with plants, the amount of radiation reach-
Winds, calm to 4.5 m s−1 0.31 0.92 0.85
ing the soil surface, Rt (Figure 6.1), depends on the LAI and the
Winds, over 4.5 m s−1 0.37 1.30 0.85
canopy structure. Numerical models have been developed that
take into account leaf orientation and distribution in the can-
Source: Dvoracek, M.J., and B. Hannabas. 1990. Prediction of albedo for use opy to calculate absorption of radiation at different levels in the
in evapotranspiration and irrigation scheduling. In Visions of the future, pro-
ceedings of the third national irrigation symposium held in conjunction with
canopy (Goudriaan, 1977; Chen, 1984). Lascano et al. (1987)
the 11th annual international irrigation exposition, October 28–November 1, used Chen’s model to calculate polynomials representing the
Phoenix, AZ. ASAE, St. Joseph, MI. dependence of albedo on LAI, as well as the dependence of the
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-11

TABLE 6.4  Some Albedo and Emissivity Values for Various Soil and Plant Surfaces
(Most are Daily Averages)
Surface Albedo Emissivity Source
Soils, dark, wet to light, dry 0.05–0.50 0.90–0.98 Oke (1978)
Dry sandy soil 0.25–0.45 Rosenberg et al. (1983)
Bare dark soil 0.16–0.17 Rosenberg et al. (1983)
Dry clay soil 0.20–0.35 Rosenberg et al. (1983)
Quartz sand 0.35 Van Wijk and Scholte Ubing (1963)
Sand, wet 0.09 0.98 Van Wijk and Scholte Ubing (1963)
Sand, dry 0.18 0.95 Van Wijk and Scholte Ubing (1963)
Dark clay, wet 0.02–0.08 0.97 Van Wijk and Scholte Ubing (1963)
Dark clay, dry 0.16 0.95 Van Wijk and Scholte Ubing (1963)
Fields, bare 0.12–0.25 Van Wijk and Scholte Ubing (1963)
Fields, wet, plowed 0.05–0.14 Van Wijk and Scholte Ubing (1963)
Dry salt cover 0.50 Van Wijk and Scholte Ubing (1963)
Snow, fresh 0.80–0.95 Rosenberg et al. (1983)
Snow, old 0.42–0.70 Rosenberg et al. (1983)
Snow, fresh 0.95 0.99 Oke (1978)
Snow, old 0.40 0.82 Oke (1978)
Snow, fresh 0.80–0.85 Van Wijk and Scholte Ubing (1963)
Snow, compressed 0.70 Van Wijk and Scholte Ubing (1963)
Snow, melting 0.30–0.65 Van Wijk and Scholte Ubing (1963)
Grass, long (1 m) 0.16 0.90 Oke (1978)
Short (0.02 m) 0.26 0.95 Oke (1978)
Grass, green 0.16–0.27 0.96–0.98 Van Wijk and Scholte Ubing (1963)
Grass, dried 0.16–0.19 Van Wijk and Scholte Ubing (1963)
Prairie, wet 0.22 Van Wijk and Scholte Ubing (1963)
Prairie, dry 0.32 Van Wijk and Scholte Ubing (1963)
Stubble fields 0.15–0.17 Van Wijk and Scholte Ubing (1963)
Grain crops 0.10–0.25 Van Wijk and Scholte Ubing (1963)
Green field crops full cover, LAI > 3 0.20–0.25 Jensen et al. (1990)
Leaves of common farm crops 0.94–0.98 Jensen et al. (1990)
Most field crops 0.18–0.30 Rosenberg et al. (1983)
Field crops, latitude 22°–52° 0.22–0.26 0.94–0.99 Monteith and Unsworth (1990)
Field crops, latitude 7°–22° 0.15–0.21 0.94–0.99 Monteith and Unsworth (1990)
Deciduous forest 0.15–0.20 0.96a Rosenberg et al. (1983)
Deciduous forest, bare 0.15 0.97 Oke (1978)
Leaved 0.20 0.98 Oke (1978)
Coniferous forest 0.10–0.15 0.97 Rosenberg et al. (1983)
Coniferous forest 0.05–0.15 0.98–0.99 Oke (1978)
Vineyard 0.18–0.19 Rosenberg et al. (1983)
Mangrove swamp 0.15 Rosenberg et al. (1983)
Grass 0.24 Jones (1992)
Crops 0.15–0.26 Jones (1992)
Forest 0.12–0.18 Jones (1992)
Water, high sun 0.03–0.10 0.92–0.97 Oke (1978)
Water, low sun 0.10–1.00 0.92–0.97 Oke (1978)
Sea, calm 0.07–0.08 Rosenberg et al. (1983)
Sea, windy 0.12–0.14 Rosenberg et al. (1983)
Ice, sea 0.30–0.45 0.92–0.97 Oke (1978)
Ice, glacier 0.20–0.40 Oke (1978)
Ice, lake, clear 0.10 Rosenberg et al. (1983)
Ice, lake, w/snow 0.46 Rosenberg et al. (1983)
a Van Wijk and Scholte Ubing (1963).
6-12 Properties and Processes

view factor (proportion of sky visible from the soil) on LAI, much recent work on multispectral sensing of radiation reflected
and incorporated these into their ENergy and WATer BALance and emitted from vegetation and soil surfaces (Van Toai et al.,
model (ENWATBAL). Monteith and Unsworth (1990) pre- 2003). This spectral sensing may be done for only a few relatively
sented equations describing the albedo of a deep canopy with narrow bands of radiation in the visible and infrared (IR), or may
a spherical distribution of leaves for sun angles greater than involve hyperspectral scanning that provides sensing of radia-
25°. More discussion of these concepts can be found in Russell tion for every nanometer of the spectrum across a wide range.
et al. (1989). For field studies we can either measure albedo, The advent of fiber optics capable of transmitting both visible
directly measure the components of net radiation, or use a net and IR light and the development of miniaturized spectrometers
radiometer (Table 6.1). (e.g., Ocean Optics, Inc., model S2000) has revolutionized the
Because of the largely unpredictable and time-varying posi- way researchers view plant and soil surfaces.
tion of sun flecks below the canopy, transmitted radiation can An example of multispectral sensing is the use of red and
be measured below the canopy most effectively with one of the near infrared (NIR) reflectance from a cotton canopy (Figure
linear radiation sensors rather than with point sensors. Linear 6.17). The ratio of NIR/red reflectances is clearly related to LAI.
sensors are typically 1 m long and integrate radiation over their However, the relationship is not stable from year to year and
entire length. Some are equipped with diffusers. The tube solar- research continues. Other uses include sensing of the onset and
imeter is enclosed in a clear envelope and accepts radiation from progression of plant disease and insect infestation, and sensing
all directions. Some other linear sensors are configured to accept of plant water status. Much work remains to be done to make
only down welling radiation; for example, transmitted photo- these techniques useful.
synthetically active radiation (400–700 nm) can be measured
below the canopy with a “line quantum sensor” (LI-Cor, Lincoln, 6.2.1.5  I ncoming Longwave Radiation
Nebraska, USA) or with a “crop canopy absorption meter” (ICT Methods of estimating longwave irradiance from the sky, L↓,
International, Armidale, New South Wales, Australia). For usually take the form
either, the results may be usefully related to total shortwave irra-
diance through a linear regression, or the latter sensor may be
L↓ = ε a σ (Ta + 273.16)4 , (6.32)
ordered with sensitivity across the shortwave spectrum from
400 to 950 nm.
where Ta (°C) is air temperature at the reference measurement
level (often 2 m), and the emissivity (εa) may be estimated from
6.2.1.4  Spectral Reflection and Radiation the vapor pressure of water in air at reference level (ea) (kPa) or
The discussion of emissivities and albedos of surfaces given here from both ea and Ta.
is based on a broadband view of irradiance, reflection, and emis- The vapor pressure is
sion that recognizes only shortwave and longwave radiation as
presented in Figure 6.7. Although these are arguably the most RH
ea = es , (6.33)
important features from an energy balance perspective, there is 100

0.8 5 18
LAI=4.4, 16 August
0.7 16
LAI=3.9, 12 July 4 14
0.6
Leaf area index (LAI)

12
Reflectance factor

0.5 3
LAI=1.6, 23 June
NIR/Red

10
0.4
8
2
0.3
6
0.2 4
Bare soil 1 LAI
0.1 NIR/Red 2

0 0 0
300 500 700 900 1100 120 140 160 180 200 220 240 260
(a) Wavelength (nm) (b) Day of year, 1994

FIGURE 6.17  Reflectance factor versus wavelength for bare soil and cotton at three levels of LAI (a), and the relationship between the ratio of
NIR to red reflectance and LAI (b) for cotton in Arizona. (Personal communication from P.J. Pinter Jr. and E.M. Barnes, U.S. Water Conservation
Laboratory, USDA-ARS, Phoenix, AZ, May 2000.)
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-13

where 1.0
RH is the relative humidity of the air A B
es is the saturation vapor pressure (kPa) at Ta (°C) given by C 1:1 line
0.9 A B
(Murray, 1967)
C

Predicted, ε
⎛ 17.269Ta ⎞
es = 0.61078 exp ⎜ . (6.34) 0.8
⎝ 237.3 + Ta ⎟⎠

0.7
If the dew point temperature, rather than the RH, is known then

⎛ 17.269Tdew ⎞ 0.6
ea = 0.61078 exp ⎜ . (6.35) 0.6 0.7 0.8 0.9 1.0
⎝ 237.3 + Tdew ⎟⎠
Emissivity, ε

FIGURE 6.18  Comparison of predictions with measured emissivity

Hatfield et al. (1983) compared several methods for estimat- for two periods in 1992 at Bushland, Texas. Points plotted at extreme
ing ε and concluded that methods using only air temperature right were associated with nighttime and overcast conditions. A,
performed less well than those that used vapor pressure or both Equation 6.37; B, Equation 6.38; C, Equation 6.36. Lines are for regres-
vapor pressure and air temperature. Among the best methods sions shown in Table 6.5.
was Idso’s (1981) equation
TABLE 6.5  Regressions of Predicted Emissivity (εp) versus
Measured Values (ε) for data from Day 133 through 140
⎡ 1500 ⎤ and 192 through 197, 1992, at Bushland, Texas
ε a = 0.70 + 5.95 × 10 −4 ea exp ⎢ ⎥, (6.36)
⎣ Ta + 273.1 ⎦ Method Regression Equation r2 SE
Brunt, Equation 6.37 εp = 0.505 + 0.325ε 0.33 0.024
where ea is in kPa. Idso showed fairly conclusively that ε is a Brutsaert, Equation 6.38 εp = 0.556 + 0.311ε 0.32 0.024
function of both ea and Ta. Idso, Equation 6.36 εp = 0.522 + 0.398ε 0.37 0.027
Howell et al. (1993) measured L↓ (Table 6.1) and calculated εa
by inverting Equation 6.32. Applying Equation 6.36 as well as Despite the difficulty of estimating sky emissivity well,
Brunt’s (1932) equation uncertainty in the value of L↓ usually causes little difficulty in
estimating net radiation for daytime; but L↓ can be seriously
ε a = 0.52 + 0.206ea0.5 (6.37) underestimated at night with important consequences for mod-

els of chill stress or frost.

and Brutsaert’s (1982) equation 6.2.1.6  Comparison of Net Radiation Estimates

with Measured Values
ε a = 0.767e1a/7 (6.38) It has become commonplace to have data from field weather
stations that include R si (W m−2), and air temperature, Taz (°C),
to their data shows that all three equations gave good predic- wind speed, u z (m s−1), and relative humidity, RH z (%), mea-
tions for clear sky conditions but probably underestimated εa for sured at some reference height, z (often 2 m). Measurement of
cloudy and nighttime conditions (Figure 6.18). For regressions R n is still not common, probably due to several factors includ-
of predicted versus measured ε, the Idso equation gave a slightly ing additional expense, fragility of the plastic domes used on
greater correlation coefficient and a slope closer to unity (Table some models of net radiometer, and problems with calibra-
6.5). Under heavy clouds, sky emissivity approaches unity; and tion, including wind speed effects. Net radiometer calibration
none of these models predicts this well. changes with time; and experience shows that even new radi-
Choi et al. (2008) found similar results in a humid climate ometers may not agree within 10%. If a net radiometer is used,
(Florida), where the Brunt and Brutsaert models both per- it is prudent, as with all instruments, to check measured R n
formed well under clear sky conditions, but L↓ was underesti- values against estimated ones. Methods presented in previous
mated under cloudy conditions. They compared seven methods sections can be used to estimate R n, but simpler methods exist
of estimating down welling longwave radiation under clouds, that are adequate for most cases. Jensen et al. (1990) compared
L↓c, and found that the Crawford and Duchon (1999) model four methods of estimating R n, including those of Wright
(L ↓c = L ↓ (1 − cc ) + ccσTa4 ) worked best where cc was fractional and Jensen (1972), Doorenbos and Pruitt (1977), a combina-
cloud cover. tion of Brutsaert (1975) and Weiss (1982), and Wright (1982),
6-14 Properties and Processes

against values measured at Copenhagen, Denmark, and Davis, pressure at dew point temperature was estimated from mean
California. The Wright (1982) method was overall best, but daily dew point temperature, Td (°C)
underestimated R n in the peak month at Copenhagen by 9%.
The Wright and Jensen (1972) method was almost as good.
These methods all assume that surface temperature is not mea- ⎡ 17.27Td ⎤
ed = 0.611exp ⎢ ⎥. (6.43)
sured, so that only air temperature is used in the calculations. ⎣ Td + 237.3 ⎦
Jensen et al. (1990) calculated net longwave radiation, R nl, as

Additionally, half-hourly R n estimates were calculated from

⎡ ⎛R ⎞ ⎤
Rnl = − ⎢a ⎜ si ⎟ + b ⎥ (a1 + b1ed0.5 )σTaz4 , (6.39) half-hourly measured values of Rsi, Ta, and Td using equations
⎣ ⎝ Rso ⎠ ⎦ given by Allen et al. (1994a, 1994b) equivalent to Equations 6.7,
6.8, 6.10, and 6.12 through 6.16 to estimate half-hourly Rsa, and
where Equation 6.42 to estimate half-hourly Rso. Equation 6.43 was
ed is the saturation vapor pressure of water in air at dew point applied to half-hourly dew point temperatures to estimate half-
temperature (kPa) hourly ed values. Equation 6.41 was written for half-hourly val-
the term (a1 + b1ed0.5) is a “net emittance,” ε′, of the surface ues of air temperature, Ta, as

The “net emittance” attempts to compensate for the fact that

surface temperature is not measured, the assumption being that ⎡ ⎛R ⎞ ⎤
Rn = (1 − α)Rs − ⎢ac ⎜ si ⎟ + bc ⎥ (a1 + b1ed0.5 )σ(Ta4 ), (6.44)
Taz can substitute reasonably well for both sky and surface tem- ⎣ ⎝ Rso ⎠ ⎦
perature. The coefficients a, b, a1, and b1 are climate specific, with
a and b being cloudiness factors. Some values are presented by
Jensen et al. (1990, Table 6.3.3). where the ratio of Rsi to Rso was set to 0.7 for nighttime estimates
Many weather stations report only daily totals of solar radia- of R n.
tion; and maximum and minimum of air temperature, Tx and Tn, Comparison of daily R n estimates, calculated using half-
respectively (K). If this is the case, the term σT4 can be estimated as hourly data means, with measurements made with a Radiation
and Energy Balance Systems (REBS) Q*5 (Seattle, Washington)
σ(Tx4 − Tn4 ) net radiometer over irrigated grass show excellent agreement for
σT 4 ≅ . (6.40)
2 alfalfa (Figure 6.19) and grass (Figure 6.20) at Bushland, Texas.
But, there was a consistent bias for R n estimated from daily
If mean dew point temperature is not available, it may be esti- means, with underestimation of R n at large measured values,
mated as equal to Tn in humid areas.
Allen et al. (1994a, 1994b) gave slightly modified versions of 20
the methods presented by Jensen et al. (1990) in a proposed FAO Estimated Rn = 0.3 + 1.02 Rn
standard for reference ET estimation. As an example, estimates r2 = 0.96
of daily total net radiation were made for Bushland, Texas, using SE = 0.7 MJ m–2 day–1
Estimated Rn (MJ m–2 day–1)

15
the following equations

⎡ ⎛R ⎞ ⎤ ⎛ T 4 + Tn4 ⎞
Rn = (1 − α)Rs − ⎢ac ⎜ si ⎟ + bc ⎥ (a1 + b1ed0.5 )σ ⎜ m ,
⎣ ⎝ Rso ⎠ ⎦ ⎝ 2 ⎟⎠ 10
Alfalfa, 1996
(6.41)
Bushland, Texas
where the cloud factors were ac = 1.35 and bc = −0.35, the emissiv- 5
ity factors were a1 = 0.35 and b1 = −0.14, the albedo was α = 0.23,
Rsi was measured, ed was calculated from mean dew point tempera-
Calculated with 0.5 h means
ture, and Rso was calculated from
0
0 5 10 15 20
Rso = (0.75 + 0.00002EL msl )Rsa , (6.42) Measured Rn (MJ m–2 day–1)

FIGURE 6.19  Daily net radiation, estimated with methods from

where
Allen, R.G., M. Smith, A. Perrier, and L.S. Pereira. 1994a. An update for
Rsa is from Equation 6.19 the definition of reference evapotranspiration. ICID Bull. 43:1–34; Allen,
ELmsl is elevation (m) above mean sea level R.G., M. Smith, A. Perrier, and L.S. Pereira. 1994b. An update for the
calculation of reference evapotranspiration. ICID Bull. 43:35–92. Using
This is similar to Equation 6.20 but with a correction increas- half-hourly data, compared with measurements with a REBS Q*5 net
ing Rso for higher elevation sites. The mean daily saturated vapor radiometer over sprinkler irrigated alfalfa in 1996 at Bushland, Texas.
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-15

20
800 Estimated Rn Rn
Estimated Rn = 0.87 + 0.95Rn
r2 = 0.96
SE = 0.66 MJ m–2 day–1 600
Estimated Rn (MJ m–2 day–1)

15

Rn (W m–2)
400

10 200

Grass, 1996
0
Bushland, Texas
5 Grass, 1996, Bushland, Texas
–200
184 185 186 187
Calculated with 0.5 h means Day of year, 1996
0
FIGURE 6.22  Half-hourly measured net radiation compared with
0 5 10 15 20
values estimated with methods of Allen et al. (1994a, 1994b) using half-
Measured Rn (MJ m–2 day–1)
hourly data for drip irrigated grass at Bushland, Texas, 1996.
FIGURE 6.20  Net radiation estimated with methods from Allen et al.
(1994a, 1994b) compared with measurements over drip irrigated grass 6.2.2  Latent Heat Flux
in 1996 at Bushland, Texas.
Latent heat flux, LE (W m−2), is the product of the evaporative
20
flux, E (kg s−1 m−2), and the latent heat of evaporation, λ (2.44 ×
Estimated Rn = 2.47 + 0.76Rn 106 J kg−1 at 25°C). The value of λ is temperature dependent, but
r2 = 0.95
is well described (in J kg−1 × 106) by
SE = 0.62 MJ m–2 day–1
Estimated Rn (MJ m–2 day–1)

15
λ = 2.501 − 2.370 × 10 −3T (r 2 = 0.99995), (6.45)

where T is in °C. Methods of E measurement include weighing

10
lysimeters (including microlysimeters), and other mass balance
Grass, 1996 techniques that rely on measurements of change in soil water
Bushland, Texas storage, ΔS. Evaporative flux may also be estimated from other
5 measurement methods such as eddy covariance (EC) and Bowen
ratio measurements or from models ranging from the relatively
Calculated with daily means simple analytical form of the Penman–Monteith (P–M) equation
0 to complex field surface energy balance (FSEB) models. The sur-
0 5 10 15 20 face renewal method is also a possibility (Snyder et al., 1997), but
Measured Rn (MJ m–2 day–1) may be biased in some conditions (Zapata and Martinez-Cob,
2002) and depends on measurements above the crop and knowl-
FIGURE 6.21  Daily net radiation, estimated with methods of Allen
edge of the measurement height and crop height. Castellví (2004)
et al. (1994a, 1994b) using daily means and maxima and minima, com-
pared with measurements with a REBS Q*5 net radiometer over drip addressed problems with surface renewal analysis by combining
irrigated grass in 1996 at Bushland, Texas. it with similarity theory. The surface renewal approach has so far
not become widely used in agricultural micrometeorology and
and overestimation at small measured values (Figure 6.21). The will not be further discussed herein. Because ΔS is a component
bias evident when daily means and maximum/minimum tem- of the soil water balance, and weighing lysimetry is a key tool
peratures were used is probably tied to both poor estimates of for investigations of soil water balance, discussion of lysimetric
vapor pressure from the max/min temperature data, and the techniques will be deferred to Section 6.3.
inadequacy of Equation 6.40.
Estimates of half-hourly net radiation for alfalfa at Bushland, 6.2.2.1  Boundary Layers
Texas, made using half-hourly data and these methods also Evaporative fluxes move between plant or soil surfaces and the
gave good results (Figure 6.22). Allen et al. (1994a, 1994b) give air by both diffusion and convection. Diffusive processes pre-
detailed methods for estimating R n when measurements are vail in the laminar sublayer close (millimeters) to these surfaces.
missing for Rsi and/or ed. Irmak et al. (2003) give useful methods In this layer, air movement is parallel to the surface and little
for estimating R n when only measured Tx, Tn, and Rsi are avail- mixing occurs. Vapor flux across the laminar sublayer is well
able, or when only measured Tx, Tn, and RH are available and Rsi described by a Fickian diffusion law relating flux rate to vapor
is estimated. pressure gradient factored by a conductance term. But in the
6-16 Properties and Processes

turbulent layer beyond the laminar layer, the flux is mostly con- elements (wheat plants in this schema) upward, within which
vective in nature so that water vapor is moved in parcels of air air flow is more turbulent due to the influence of the rough-
that are emitted and mixed into the atmosphere in turbulent ness elements. This is called the roughness sublayer (Monteith
flow. These moving parcels of air are often referred to as eddies and Unsworth, 1990). For any measurement of air temperature,
and are analogous to eddies seen in a stream. Usually the eddies humidity, or wind speed, its fetch is the distance upwind from
are not visible; but in foggy, smoky, or dusty conditions, they the point of observation to the edge of the new surface. The ratio
may be apparent. Certainly, anyone who has felt the buffeting of of the fetch to the value of δe is dependent on the roughness of
the wind can attest to the force of eddies and the turbulence the surface, the stability of the air, and the wind speed. For many
of the airstream in which they occur. As wind speeds increase, crop surfaces, it may be as small as 20:1 or as large as 200:1. For
the depth of the laminar sublayer decreases. Surface roughness smooth surfaces such as bare soil, the ratio may well be larger
enhances this process, resulting in thinner laminar sublayers. than 200:1. See Section 6.2.2.4 for further discussion of fetch.
Because the resistance to vapor transport across the laminar Measurements should be made in the constant flux layer but
airstream is much larger than the resistance across a turbulent above the roughness sublayer.
airstream of similar dimension, increasing roughness and wind
speed both tend to enhance vapor transport. If the air is still, 6.2.2.2  Eddy Covariance
then eddies due to turbulent flow do not exist, but eddies due The observation of turbulent flow and concept of eddies lead to
to free convection may well be present. Free convection occurs the EC (also referred to as eddy correlation) method of turbu-
when an air parcel is warmer (or colder) than the surrounding lent flux measurement, including latent heat flux measurement.
air and thus moves upward (or downward) because it is lighter It has been described as the most physically correct method of
(or heavier). These buoyancy effects can predominate at very low providing a direct measurement of the vertical turbulent flux
wind speeds when the surface is considerably warmer than the across the mean horizontal streamlines (Swinbank, 1951), pro-
air. As opposed to free convection, transport in eddies due to vided that fast response sensors (10–20 Hz) are available for the
wind is called forced convection. A full discussion of the fluid velocity vector and scalar entity of interest. Conceptually, the
mechanics of laminar and turbulent flow, Fickian diffusion, and vertical velocity component (w) of upward moving eddies cova-
forced and free convection is well beyond the scope of this chap- ries with a scalar or mass density (s) and the same is true for
ter. Discussions relevant to soil and plant surfaces are presented the vertical velocity component and scalar of downward moving
in Chapters 7–9 of Monteith and Unsworth (1990), Chapters 3 eddies; so, if the instantaneous product ws is on average larger
and 4 of Rosenberg et al. (1983), and Chapter 3 of Jones (1992). for the upward moving eddies than for the downward moving
Relevant micrometeorological measurement methods are ones, then the net flux of the scalar or mass of interest is upward.
explained in detail in Chapters 16–21 of Hatfield and Baker In this method, fast response sensors are used to measure w and
(2005). Here we will concentrate on some results and methods s simultaneously at a rate of, for example, 10–20 Hz, producing
of measurement. These methods are valid within the constant estimates of the instantaneous deviations w′ and s′. This pro-
flux layer (Figure 6.23), a layer of moving air that develops from vides an estimate of the vertical flux at the measurement height
the point at which the airstream first reaches a surface of given (but note fetch requirements below). The generic expression for
condition, for example, the wheat field shown in Figure 6.23. The EC can be described as
air mixes as it moves over the field, equilibrating with the new
surface condition, and forming a layer of gradually increasing Fs = wʹsʹ, (6.46a)
thickness, δe, within which the vertical flux of heat and vapor
is constant with height. This is the fully adjusted or equilibrium
layer. Within this layer is a layer, extending from the roughness where
Fs is the flux of a scalar or mass of interest, normally water
vapor, sensible heat, or carbon dioxide
Wind w and s are vertical velocity and scalar measurements,
respectively
δe
Inertial sublayer
Primes represent instantaneous deviations from a mean and
the over bar indicates a time average operator, typically 30 min.
Roughness sublayer
With respect to the turbulent fluxes of the energy balance equa-
h d tion, Equation 6.46a can be recast to represent evaporation, LE,
and sensible heat, H, fluxes as

FIGURE 6.23  Schematic of sublayers of the surface boundary layer

LE = λw ʹρvʹ (6.46b)
over a wheat crop. The height (h) of the crop and the depth (δe) of the
constant flux layer are noted. The height (d) is the zero plane displace-
ment height, which is the height to which a logarithmic wind profile,
H = ρa cpw ʹTaʹ, (6.46c)
measured above the crop, would extrapolate to zero wind speed.
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-17

respectively, where 800

λ is the latent heat of vaporization 700
w′ has been defined above
ρʹv is the estimate of instantaneous water vapor density 600
ρa is the density of air 500

LE + H (W m–2)
cp is the specific heat of moist air
400
Ta�is the estimate of instantaneous air temperature
300
The rate of data acquisition must be faster for measurements 200
nearer the surface. Monteith and Unsworth (1990) state that eddy Correlation: 0.90
100 Slope: 0.89
sizes increase with surface roughness, wind speed, and height
above the surface; and they suggest 1 kHz rates may be needed 0
near a smooth surface, while 10 Hz or less may be adequate at
–100
several meters above a forest canopy. Because the measurements –100 0 100 200 300 400 500 600 700 800
should take place within the fully adjusted boundary layer, sim- –[Rn + G] (W m–2)
ply increasing sensor height will not eliminate the need for fast
sensor response. EC methods are challenging to conduct due FIGURE 6.24  Check of eddy correlation system LE and H val-
to the data handling and sensor requirements. Data-processing ues against measured R n and G values, all measured at the Walnut
requirements are large, but modern data logging and computing Gulch Experimental Watershed, Lucky Hills Site, on days 194–225,
1996. (Adapted from Houser, P.R., C. Harlow, W.J. Shuttleworth, T.O.
equipment are capable of handling these. Commercial systems
Keefer, W.E. Emmerich, and D.C. Goodrich. 1998. Evaluation of mul-
including data-processing software are now available, although
tiple flux measurement techniques using water balance information
expensive (Campbell Scientific Inc., Logan, Utah; and The at a semi-arid site, p. 84–87. In Proc. Spec. Symp. Hydrol. American
Institute of Ecology and Resource Management at the University Meteorological Society, Phoenix, AZ.)
of Edinburgh, Scotland). The sonic anemometer is the wind sen-
sor of choice for EC work due its fast response and sensitivity. layer of the atmosphere and in practice is relatively straightfor-
At this time, a single-axis unit costs about $2500 and a 3D sonic ward to make, there are a number of important assumptions that
anemometer costs about $8000. Suitable vapor pressure sen- must be considered prior to and during data acquisition. These
sors include the krypton hygrometer and infrared gas analyzer assumptions are well described by Foken and Wichura (1996) and
(IRGA) available at this writing in the $6,000–$15,000 range. should always be considered prior to any field campaign. Equally
When LE and H are measured by EC, the performance of this important are the corrections applied to the turbulent fluxes after
approach may be evaluated (Houser et al., 1998) by rearranging the measurements are made. It is significantly beyond the scope of
Equation 6.1 to this chapter to describe in detail the corrections now considered
standard for turbulent flux measurements using EC but we list the
LE + H = −Rn − G (6.47) more important corrections with references. These include coor-
dinate rotation of the velocity and scalar components (Tanner
and measuring R n and G (Figure 6.24). This is referred to as and Thurtell, 1969; Kaimal and Finnigan, 1994; Paw et al., 2000;
evaluating the energy balance closure. If all measurements in Wilczak et al., 2001; Lee et al., 2004), the proportionality of a
Equation 6.47 are perfectly made, then the sum of the turbulent gas concentration to density effects due to changes in tempera-
fluxes (LE + H) will equal the available energy (R n + G). But in ture and humidity commonly referred to as the WPL correction
reality, turbulent flux estimates are usually less than the avail- or adjustment (Webb et al., 1980; Webb, 1982; Leuning, 2004;
able energy. The degree of energy imbalance is an indication of Massman, 2004), and frequency response and sensor separation
how well the EC measurements were made. Energy balance clo- corrections (Moore, 1986; Leuning and Judd, 1996; Massman,
sure can also be expressed as the ratio of the sum of the turbulent 2000; Finnigan et al., 2003; Massman and Clement, 2004). All
fluxes to the available energy, where the typical range considered these need to be considered and implemented to ensure the best
as generally achievable for LE and H fluxes is 0.8–0.9. possible data quality. Note that Thurtell questioned the use of
Fast response thermocouples for measuring air temperature coordinate rotations at a 2002 symposium in his honor.
are used in EC systems for measuring H. Because these are very Despite 40 years of advances in EC equipment and theory
much less expensive than fast response vapor pressure sensors, it since the work of Tanner and Thurtell (1969), including the cor-
is sometimes sensible to measure R n and G, and H by EC, and to rections described above, closure errors of 10%–30% are still
compute LE as the residual common and the error is a systematic underestimation of fluxes,
particularly LE and CO2 fluxes (Twine et al., 2000; Norman and
LE = −Rn − G − H. (6.48) Baker, 2002). This outcome leads one to question either (1) the
description of this method by Swinbank (1951) as the most phys-
While EC is in principle a physically correct approach to measur- ically correct method of providing a direct measurement of the
ing turbulent flux exchange between a surface and the boundary vertical turbulent flux across the mean horizontal streamlines or
6-18 Properties and Processes

(2) the relevance of such a measurement to determination of LE. Ta and ea may become small at the same time that R n becomes
Some of the mechanisms possibly causing lack of closure, such small, leading to instability in Equation 6.50 and irrational
as flux divergence and nonstationarity of flow, are intractable, estimates of LE. Also near sunset, the value of βr may approach
leading Twine et al. (2000) to recommend that closure be forced −1, leading to a near-zero denominator in Equation 6.49 and
routinely in order to avoid cumulative errors in flux estimates poorly defined LE (Todd et al., 2000). Bowen ratio systems
over time. Closure can be forced either by calculating LE as the tend to underestimate LE when regional and local sensible heat
residual of Equation 6.1 or by using the measured Bowen ratio; advection occurs (Blad and Rosenberg, 1974; Todd et al., 2000),
Twine et al. (2000) preferred the latter, but see the next section probably because K H/KV > 1 under the stable conditions that
for possible problems. Comparisons of EC and Bowen ratio sys- prevail then (Verma et  al., 1978). Four Bowen ratio systems
tems are found in Dugas et al. (1991) and Houser et al. (1998). were compared by Dugas et al. (1991) who discuss the merits
Some specifics of EC system design are given in Unland et al. of different designs. Three EC systems agreed well with each
(1996) and Moncrieff et al. (1997). other; but LE measurements from them were consistently lower
than those from the four Bowen ratio systems. Note that R n
measurement errors can have a large impact on LE calculated
6.2.2.3  Bowen Ratio using Equation 6.49.
The Bowen ratio is the ratio of sensible to latent heat flux, βr =
H/LE (Bowen, 1926). Introducing this into Equation 6.1 and
rearranging gives the Bowen ratio method for estimating LE 6.2.2.4  Fetch Requirements
Both EC and Bowen ratio methods are sensitive to upwind sur-
−(Rn + G) face conditions. The LE and H values from these methods rep-
LE = . (6.49)
βr + 1 resent an areal mean for a certain upwind surface area, often

called the “footprint.” Both methods require considerable repre-
sentative upwind surface or fetch, often extending to hundreds
In the constant flux layer, it is possible to measure temperature
of meters, of surface that is similar to that where the measure-
and water vapor pressure differences at two heights, z1 and z2 and
ment is made, if the measurement is to be representative of that
to evaluate βr from a finite difference form
surface. Also, the longer the same-surface fetch is, the deeper is
the fully adjusted layer, and the higher the instruments can be
placed above the surface. Issues of instrument height and fetch
K Hρa cp (Ta_z2 − Ta_z1 )/(z 2 − z1 )
βr = are discussed by Savage et al. (1995, 1996) who recommended
K V (M w /( Ma P ))ρa λ(ea_z2 − ea_z1 )/(z 2 − z1 )
placing the sonic anemometer of an EC system no closer than
(6.50) 0.5 m above a short grass cover. Because eddies are smaller
c p (Ta_z2 − Ta_z1 ) (T − Ta_z1 )
≈ = γ a_z2 , nearer the surface, placement of the sonic anemometer too near
(M w /(M a P ))λ(ea_z2 − ea_z1 ) (ea_z2 − ea_z1 )
the surface may lead to eddies being smaller than the measure-
ment window of the anemometer. Fetch requirements may be
where the second and third entities assume equivalency of the stated as a ratio of fetch distance to instrument height. Heilman
exchange coefficients for sensible heat flux, KH, and latent heat et al. (1989) studied fetch requirements for Bowen ratio systems
flux, KV; and γ = cp P/(λMw/Ma) is the psychrometric “constant,” and concluded that a fetch to height ratio of 20:1 was adequate
so-called because its value changes little with temperature, for many measurements, down from the 100:1 ratios reported
humidity, and normal variations in air pressure. Commonly, earlier. Fetch requirements increase as measurement height, zm,
values of Ta and ea are half-hourly or hourly means. Because increases. This poses some additional problems for Bowen ratio
the sensor response time does not have to be very short, Bowen systems because these incorporate two sensors and the sen-
ratio equipment is much less expensive than that for EC, with sors must be sufficiently separated vertically so that the vapor
complete systems available for under $10,000. Bowen ratio sys- pressure and temperature gradients between them are large
tems are available from REBS, Seattle, Washington; Campbell enough to be accurately determined. The rougher the surface is,
Scientific, Inc., Logan, Utah, and others. the smaller the gradients are. For many surfaces, and common
Because slight differences in instrument calibration may lead instrument resolution, this results in separation distances on the
to large errors, it is advisable to switch instruments between order of a meter. The lower measurement should be above the
the measurement heights. The moving arm system popularized roughness sublayer, typically at least 0.5 m above a crop (more for
by REBS is one way to do this. Bowen ratio measurements are a very rough surface such as a forest), so the upper measurement
usually valid only during daylight hours. Near sunset and at may well be nearly 2 m above the crop surface. This could easily
night, the sum of R n and G in Equation 6.49 approaches zero lead to a fetch requirement of 100 m. Analysis of relative flux and
even though LE may continue at considerable rates, particu- cumulative relative flux for an alfalfa field under moderately sta-
larly in advective environments (Tolk et al., 2006), in which ble conditions using the methods of Schuepp et al. (1990) leads to
most of the irrigated western United States is included. For rather large fetch requirements (Todd et al., 2000; Figure 6.25).
periods just after sunrise and before sunset, the gradients of For unstable conditions, mixing is enhanced and the boundary
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-19

0.04 1.0 vertical flux divergence. However, we see from footprint analy-
zm = 1 m sis that, for nonzero wind speeds, the upwind area contributes
0.8 to the measured flux. Even in supposedly uniform fields, there

Cumulative relative flux

0.03
is spatial variability in soil properties and plant responses, so
that there is almost always some horizontal flux divergence, and
Relative flux

0.6
0.02 therefore necessarily some vertical flux divergence. Although
0.4 both methods have been described as “point” measurements,
they are really averages over an area, with closer upwind sub-
zm = 2 m
0.01
0.2
areas being weighted more heavily and with wind speed and
Relative flux
atmospheric stability causing changes in the relative weighting
Cumulative relative flux
of subareas and the total area involved.
0 0.0
0 100 200 300 400 Interest in the spatial variability of the energy balance, par-
Fetch (m) ticularly the LE component, and in precision farming tech-
nologies aimed at addressing crop requirements for water and
FIGURE 6.25  Relative and cumulative relative flux of an alfalfa field
nutrients at scales well below the field size, has led to a need
for measurement heights (zm) of 1 and 2 m, moderately stable thermal
to measure the spatial variability of LE at scales smaller than
conditions, and canopy height of 0.5 m. Cumulative relative flux reaches
0.8 at 65 m for zm = 1 m, and at 225 m for zm = 2 m. (Courtesy of Richard can reasonably be addressed with Bowen ratio and EC systems.
W. Todd, personal communication.) The radiometric surface temperature can be remotely sensed
to provide the spatial variability of LE based on Equations 6.1
layer becomes adjusted more quickly over a new surface so that and 6.87 (in Section 6.2.4). However, this approach is chal-
fetch requirements are decreased. However, stable conditions lenged by difficulties in quantifying surface and aerodynamic
often prevail for irrigated crops in semiarid and arid regions, resistances and discriminating between crop and soil contri-
suggesting that EC and Bowen ratio methods are ill-suited for butions to the radiometric temperature. There remains a need
estimating ET in these settings. Schmid (1997) concluded that for ground truth measurements giving LE for a well-defined
fetch requirements are more severe for Bowen ratio than for EC area. The water balance methods discussed in Section 6.3.1 are
measurements. However, Stannard (1997) argues that Schmid’s capable in many cases, but costs of deployment are practically
analysis ignored the gradient measurement approach of Bowen insurmountable. Thus, there remains a need for inexpensive,
ratio systems and that the fetch requirements are similar for EC accurate, unattended soil profile water content measurement
and Bowen ratio. methods for implementation of the water balance method of
EC methods are sometimes described as making direct mea- LE measurement.
surements of fluxes, and thus are stated to be the only “direct”
measure of latent (or sensible) heat flux, particularly of areal 6.2.2.5  Field Surface Energy Balance
extent greater than a few square meters. However, the humid- and Remote Sensing
ity sensors in EC and Bowen ratio systems do not measure ea
The FSEB has long been recognized for its promise in calculat-
directly, but infer it from measurements of other physical
ing the latent heat flux, LE, due to ET, from the other energy
properties, typically light absorption or capacitance changes.
balance terms in Equation 6.1. When R n, G, Ts, Ta, hc, and uz are
Moreover, consideration of fetch requirements leads to a con-
measured in the field, Kimball et al. (1999) found that ET (m s−1,
clusion that both EC and Bowen ratio measurements are repre-
positive toward the atmosphere) can be estimated with fair accu-
sentative only for a constantly changing footprint area upwind
racy for full-cover crop surfaces as the residual in
of the measurement location. The footprint area and the “true”
flux are ill-defined because the location and size of the footprint
−LE (Rn + G + H )
change with wind direction and speed. There is strength in this ET = = , (6.51)
(λρw) (λρw)
kind of areal averaging because it reduces noise due to the spatial
variability of evaporation. But the measurement cannot be said
to be true for any specific location. Indeed, as wind direction where
changes, the area contributing to the measurement may change H = ρacp(Ts – Ta)/ra
completely. By contrast, the soil water balance methods of esti- Ts is assumed equal to the aerodynamic surface temperature,
mating E, discussed in Section 6.2, provide measures for specific To (°C)
locations. In the case of weighing lysimeters, these are in fact ra is aerodynamic resistance, which is calculated as a function
direct measurements of E, specific to a well-defined location, for of crop height, hc, and wind speed, uz (m s−1), measured at
all times during which precipitation and runoff are not occur- an elevation z (m)
ring (neglecting the negligible change in plant mass over short cp is the heat capacity of air (∼1003 kJ kg−1 K−1)
periods). Both EC and Bowen ratio measurements are based on λ is the latent heat of vaporization (∼2.45 × 106 J kg−1)
the assumption that, within the fully adjusted layer, the vertical ρw is the density of water (∼1000 kg m−3)
mass or energy fluxes are uniform with height, that is, there is no ρa is air density (kg m−3, ρa ≈ 1.291–0.00418Ta)
6-20 Properties and Processes

In field research, many or all of these fluxes are measured; but 6.2.2.6  Penman–Monteith Estimates
from a remote sensing perspective, the surface brightness in the of Latent Heat Flux
thermal IR (used to estimate Ts) and the brightness in the NIR Since Penman (1948) published his famous equation describ-
and visible bands are used to estimate R n and H. The value of ing evaporation from wet surfaces based on the surface energy
G is taken as a fraction of R n or some function of R n and plant balance, there have been developments, additions, and refine-
cover, which in turn is estimated from a vegetative index based ments of the theory too numerous to mention. Notable examples
on reflectance in discrete NIR and visible bands. The ET is evalu- are the van Bavel (1966) formulation, which includes a surface
ated as the residual. roughness length term, zo, and the P–M formula (Monteith,
Remote sensing–based approaches to FSEB evaluation for ET 1965), which includes aerodynamic and surface resistances. The
include both single-surface approaches (e.g., Bastiaanssen et al., van Bavel equation tends to overestimate in windy conditions
2005; Allen et al., 2007a, 2007b) and two-surface approaches and is very sensitive to the value of zo (Rosenberg, 1969). Howell
that evaluate the energy and water balances for both canopy et al. (1994) compared several ET equations for well-watered,
and soil surfaces and thus must estimate the crop cover frac- full-cover winter wheat and sorghum and found that the P–M
tion (e.g., Norman et al., 1995; Kustas and Norman, 1999). formula performed best. Because it is widely used in agricultural
While providing useful knowledge of regional ET and its spa- and environmental research, and because it has been presented
tial and temporal distribution, FSEB predictions that rely on by ASCE (Jensen et al., 1990; ASCE, 2005) and FAO (Allen et al.,
satellite images are not used for infield management due to 1994a, 1994b, 1998) as a method of computing estimates of refer-
lack of daily data with sufficient resolution to match appropri- ence crop water use, we will discuss the P–M equation, which is
ate scales for management (Gowda et al., 2008). Attempts to expressed as
resolve this problem with existing satellite data involve using
infrequent, greater resolution data such as that from Landsat Δ(Rn + G) + ρa cp (es − ea)/ra
(90 m resolution in the thermal IR, 16 d repeat time) in com- LE = − , (6.52)
Δ + γ ((1 + rs )/ra )
bination with lower resolution more frequent data such as that
from MODIS (1000 m resolution in the thermal IR, daily). Such
a combination was demonstrated with the DisALEXI (disag- where
gregated atmosphere land exchange inverse) model (Norman LE is latent heat flux
et al., 2003; Anderson et al., 2007; Kustas et al., 2007), but no R n is net radiation
testing of this approach for management has ensued. While G is soil heat flux (all in MJ m−2 s−1)
aircraft platforms could resolve some of these problems, cost Δ is the slope of the saturation vapor pressure–temperature
has prevented widespread use of aircraft platforms to provide curve (kPa °C−1) commonly evaluated at air temperature
imaging for management. ρa is air density (kg m−3)
The FSEB using remotely sensed data typically provides an cp is the specific heat of air (kJ kg−1 °C−1)
instantaneous value of ET, which must be scaled to daily ET ea is vapor pressure of the air at reference measurement
using various methods such as the evaporative fraction (which height zm
is assumed constant during daylight hours) or reference ET es is the saturated vapor pressure at a dew point temperature
(which is also assumed constant relative to latent heat flux dur- equal to the air temperature at zm (kPa)
ing daylight hours; Colaizzi et al., 2006). Models of the FSEB (es − ea) is the vapor pressure deficit
that use remote sensing include the two-source model (TSM, ra is the aerodynamic resistance (s m−1)
Norman et al., 1995; Kustas and Norman, 1999), the surface rs is the surface (canopy) resistance (s m−1)
energy balance algorithm for land (SEBAL, Bastiaanssen γ is the psychrometric constant (kPa °C−1)
et al., 1998), and the mapping ET with internalized calibra-
tion model (METRIC, Allen et al., 2007a, 2007b). Gowda Penman’s equation and those derived from it eliminated can-
et al. (2008) reviewed these and several other approaches and opy temperature from energy balance considerations. Besides
reported that daily ET estimation errors ranged from 3% to measurements of R n and G, the user must know the vapor
35% but that almost all studies compared FSEB ET with ET pressure of the air, ea, and air temperature (from which es
sensed by Bowen ratio or EC methods, which themselves may may be calculated) at reference measurement height, zm (often
have large errors. 2 m). The use of es as a surrogate for the (unknown) substo-
Estimates of ET from regional FSEB models using remotely matal vapor pressure introduces the assumptions that osmotic
sensed data are often inaccurate for particular field locations due potential of the leaf water has little affect on the substomatal
to problems with correctly estimating the surface radiation bal- vapor pressure and that the difference between air and canopy
ance components (Berbery et al., 1999). However, studies using temperature does not introduce much error in the estima-
either ground-based or airborne sensor platforms to achieve tion of vapor pressure. To the extent that these assumptions
suitable spatial scales (i.e., a few meters or less), have shown some are not true, the errors are merged into the resistance terms in
success with energy balance models for ET (Colaizzi et al., 2003; Equation 6.52. The values of ra and rs may be difficult to obtain.
French et al., 2007). The surface or canopy resistance is known for only a few crops
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-21

and is dependent on plant height, leaf area, irradiance, water 14

status of the plants, species, and probably variety.
Jensen et al. (1990) and Allen et al. (1994a, 1994b) presented 12
methods of calculating LE for well-watered, full-cover grass
and alfalfa. The following example, drawn from recent studies 10
at Bushland, Texas (Evett et al., 1998, 2000; Todd et al., 2000),

PM ET (mm)
employs those methods. Aerodynamic resistance was estimated 8
for neutral atmospheric conditions from
6

ln((z m − d )/z om ) ln((z H − d )/z oH ) 4

ra = , (6.53)
k 2u z
2 Measured Rn and G
Calculated Rn and G
where 0
zm (m) is the measurement height for wind speed, uz (m s−1) 0 2 4 6 8 10 12 14
Grass ET (mm)
zH (m) is measurement height for air temperature and relative
humidity FIGURE 6.26  Daily P–M estimates of ET using both measured and
k is 0.41 estimated values of R n and G were not significantly different from each
zom and zoH are the roughness length parameters for momen- other for well-watered, full-cover mixed fescue grown at Bushland,
tum (wind) and sensible heat transport Texas, in 1996. Both P–M and ET values were less than values measured
d is the zero plane displacement height by a weighing lysimeter for values above 4 mm day–1.

The value of ra calculated from Equation 6.53 will be too large for Net radiation was calculated as shown in Section 6.2.1.6.
highly unstable conditions and too small for very stable condi- All calculations were on a half-hourly basis. For well-watered
tions. Stability corrections should be made to Equation 6.53 for mixed fescue grass in 1996, the P–M equation underestimated
those conditions (see Monteith and Unsworth, 1990, p. 234 for ET, as measured by a weighing lysimeter, at ET rates exceeding
some examples) but were not made for this example. 4 mm day−1 (Figure 6.26), even though R n and G were well esti-
Surface resistance was calculated from mated. The underestimation of ET was due to systematic error
in the surface and/or aerodynamic resistances. For well-watered,
rl full-cover alfalfa in 1996, the P–M estimates of ET were close
rs = , (6.54) to values measured with a weighing lysimeter (Figure 6.27).
(0.5LAI)
Because R n and G were well estimated, it is presumed that ra and
rs were predicted well also. Examination of diurnal dynamics
where r l is the stomatal resistance taken as 100 s m−1, and the LAI showed that the P–M method was capable of closely reproducing
was taken as those dynamics.

LAI = 5.5 + 1.5ln(hc ), (6.55) 20

PM ET = 1.03 (Alfalfa ET) - 0.2
r2 = 0.89, SE = 1.0 mm
where the crop height, hc, was taken as 0.12 cm for grass and Alfalfa, 1996
15
0.5 m for alfalfa. Bushland, Texas
The zero plane displacement height, d, was calculated as
PM ET (mm)

2 10
d = hc . (6.56)
3

5
The roughness length for momentum, zom, was calculated as
1:1 line
z om = 0.123hc (6.57) Linear (regression)

0
0 5 10 15 20
and the roughness length for sensible heat transport was Alfalfa ET (mm)

FIGURE 6.27  Daily P–M estimates of ET using estimated R n and G

z oH = 0.1z om . (6.58) for well-watered, full-cover (LAI > 3) alfalfa at Bushland, Texas, in 1996.
6-22 Properties and Processes

Although important as a research model, the P–M method is

not much used for direct prediction of LE due to the difficulty
of knowing ra and rs. However, it is commonly used to predict a eo*
theoretical reference ET, ETo for grass and ETr for alfalfa, for use

Vapor pressure
in irrigation scheduling (Allen et al., 1994a, 1994b, 1998). In this
Δ
application, crop water use or ET is estimated from daily values Δ(To – Tz)
of ETr and a dimensionless crop coefficient (Kc), which is depen-
dent on the crop variety, crop growth, and the reference ET (ETo
e*z
or ETr) used, and which is often cast as a function of time since
e*z – ez
planting or growing degree days.
ez

ET = K cETr . (6.59)
Tz To
Temperature
The crop coefficients are determined from experiments that
measure daily crop water use, ET, and that measure or, more FIGURE 6.28  Quantities used in the derivation of Penman’s (1948)
commonly, estimate ETr and then compute combination equation.

ET the slope of the saturation vapor pressure versus temperature

Kc = . (6.60)
ETr curve (Figure 6.28), which is

Many details on this methodology are found in Jensen et al.

(eo* − ez* )
(1990) and ASCE (2005). Δ= . (6.62)
(To − Tz )
6.2.2.7  Limitations of the Penman Approximation
At the time that Penman (1948), Monteith (1965), and van Bavel From Equation 6.62 and Figure 6.28, we see that
(1966) developed their equations for LE, it was very difficult to
measure surface temperature of water or plant canopies. All of
eo* − ez = ez* − ez + Δ(To − Tz ). (6.63)
these equations are called combination equations because they
derive from the combination of the energy balance terms given
in Equation 6.1 with heat and mass transfer mechanisms. The Rearranging to find (Tz − To) and substituting into Equation 6.61
transfer mechanisms are usually stated as flux equations in terms gives
of resistance(s) or conductance(s) and a gradient of temperature
or vapor pressure from the surface to the atmosphere. Penman
⎡ ⎛γ⎞ ⎤
(1948) stated Equation 6.1 for a wet surface and used transport f (u)(ez − eo* ) = − ⎢ Rn + G + ⎜ ⎟ f (u)(ez − eo* + ez* − ez )⎥
⎣ ⎝ Δ ⎠ ⎦
mechanisms for LE and H to derive a combination equation
(6.64)
LE = f (u)(ez − eo* ) = − ⎡⎣ Rn + G + γ f (u)( Tz − To)⎤⎦ , (6.61)

or
where
f(u) is a wind speed dependent conductance or transport ⎡ ⎛γ⎞ ⎛γ⎞ ⎤
coefficient f (u)(ez − eo* ) = − ⎢Rn + G + ⎜ ⎟ f (u)(ez − eo* ) + ⎜ ⎟ f (u)(ez* − ez )⎥ ,
⎣ ⎝ Δ⎠ ⎝ Δ⎠ ⎦
γ is the psychrometric constant (cpP/(0.622λ)
eo* is the saturation vapor pressure at the surface temperature (6.65)
ez is the air vapor pressure at measurement height zm
Tz is the air temperature at measurement height both sides of which hold the identity for LE = f (u)(ez − eo* ).
To is the surface temperature Rearranging gives
the transport mechanism for H is analogous to Equation 6.89

The equation can use eo* because it is assumed that the surface is [Δ(Rn + G) + γ f (u)( ez* − ez)]
LE = − , (6.66)
“wet,” that is, a free water surface. With an appropriate choice of (Δ + γ )

f(u), the surface can be the canopy of a crop that is full cover and
well supplied with water and thus freely transpiring. Because which is the Penman equation and is analogous to Equation
surface temperature was difficult to measure, Penman (1948) 6.52. Rather than using wind functions of the transport coeffi-
introduced an approximation for To − Tz that was derived from cient, Monteith recognized the importance of surface resistance
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-23

and derived the equation in terms of the aerodynamic and sur- of evaluating ra in Equation 6.89 for many surfaces (e.g., partial
face resistances shown in Equation 6.52. or mixed canopies), and the spatial heterogeneity of surfaces that
Although there is much evidence that the Penman equation leads to spatial heterogeneity of air temperature. However, the
and Equation 6.52 are useful for estimating LE from free water continued development of IRTs has led to easy and reliable sur-
and from well-watered, full-cover crops, the results have been face temperature measurement with solid state devices such as
disappointing for transfer of wind functions and rs and ra for- the thermocouple IRT (e.g., the model IRt/c from Exergen, Inc.).
mulations between different regions and crops. Some facts about Meanwhile, the technology for net radiation measurements has
the underlying assumptions should lend insight. First, the value improved, but calibration standards do not exist and it is still
of Δ is usually evaluated at the air temperature, Tz. In humid common to find differences of 10% or more between compet-
climes, there may be little difference between canopy and air ing instruments. Just as the lack of adequate instrumentation
temperatures, particularly if skies are often overcast. But in for measurement of surface temperature affected the develop-
more arid regions, the canopy temperature of a freely transpir- ment of theory and practice in the mid-twentieth century, the
ing crop may be several degrees cooler than air temperature, shift in instrumentation capabilities is now affecting much of the
causing Δ to be overestimated—more so at the hottest part of the experimental physics and development of theory and practice
day, when transpiration rates are greatest, than near sunrise and for calculation of surface energy and water balances as discussed
sunset. Second, the net radiation and soil heat fluxes are modi- in Section 6.2.2.5.
fied by the quotient (1 + γ/Δ). This is fundamentally incorrect.
The value of γ/Δ ranges from 0.80 at 10°C to 0.17 at 40°C; so the 6.2.2.8  Recursive Estimates of Latent Heat Flux
modification of R n and G is not small and will change with air In order to avoid the limitations of the Penman (1948) approxi-
temperature over the course of a day. Third, the surrogate in the mation for (To − Tz), several efforts have focused on iterative
Penman equation for sensible heat flux, γ f (u)(ez* − ez )/(Δ + γ ), or recursive solution of the surface energy balance equations,
is parameterized by vapor pressure terms defined at the same which are implicit in To, without resorting to any assumptions.
height. Thus, unlike real sensible heat flux, the surrogate quan- It has long been recognized that only by iterative solution of
tity γ f (u)(ez* − ez )/(Δ + γ ) can never reverse sign (necessarily, the implicit energy balance equations can these be solved with
ez* ≥ ez ). Also, over the range from 10°C to 40°C, the value of γ complete accuracy (Budyko, 1958; Tracy et al., 1984; McArthur,
varies from 65.5 to 67.5 Pa K−1, while the value of Δ varies from 1990, 1992; Milly, 1991). Iterative solutions have been used in
85 to 402 Pa K−1. To the extent that γ is constant, the division of computer models of the general surface energy balance (Bristow,
the vapor pressure deficit by (Δ + γ) causes the surrogate term to 1987), of evaporation from bare soil (Lascano and van Bavel,
vary as H would vary. To the extent that the sum (Δ + γ) varies 1983, 1986), and of ET from plant and soil surfaces (Lascano
from Δ, and to the extent that ez* differs from eo*, the surrogate et al., 1987; Evett and Lascano, 1993).
differs in value from H. Even though iterative solutions have long been available on
In Equation 6.52, the sum of R n and G is further modified by personal computers and even possible on hand-held calculators,
the surface and aerodynamic resistances to mass and heat trans- they have not yet supplanted the P–M approach for calculating
fer, even though those resistances have negligible effect on the reference ET, ETo, although that is changing. As an alternative
fundamental mechanisms affecting either quantity. (The effect to the P–M equation, Lascano and van Bavel (2007) applied a
of rs and ra on canopy surface temperature has a negligible effect recursive method, attributed to Budyko (1958), in which ET and
on R n.) These facts have much to do with the difficulties encoun- To were found by iteration, satisfying the surface energy bal-
tered in determining appropriate values of ra and rs and in trans- ance. Particularly, when Ta >> To and evaporative demand was
ferring these values from one region to another. Also, the fact large, the P–M method underestimated reference ET by as much
that wind functions for the Penman equation have been deter- as 25%. They concluded that the P–M method will underesti-
mined to be different for different climates is certainly related to mate ET in most cases, with the error increasing as evaporative
the approximations used in the derivation of the Penman and demand increases (larger values of Ta – To and smaller values of
related equations. RH). Widmoser (2009) compared an iterative solution with the
At the time that the combination equations were being devel- P–M method and found the P–M solutions for ET to deviate by
oped, the instrumentation for measuring net radiation was as much as −40% to +9% and deviation was greater for smaller
crude but, compared with that for measuring surface tempera- time steps (e.g., hourly versus daily). Negative errors were larger
ture, effective. In the 1960s, the development of infrared radi- when Ta was larger, RH was smaller and the available energy
ometers allowed the first radiometric measurements of surface (R n + G) was smaller. Positive errors increased when RH and
temperature on a large scale, leading to much research on the use Ta were both large while (R n + G) was small, or when (R n + G)
of surface temperatures to solve H using forms of Equation 6.89 and Ta were both large and the ratio rs/ra was large (large surface
(see Section 6.2.4), and thus to estimate LE from Equation 6.1. resistance and small aerodynamic resistance, for example, tall,
McNaughton (1988) pointed out problems with this method that stressed plants, and windy conditions).
persist to this day. They include the fact that radiometric surface These analyses give further insight into the problems encoun-
temperature often differs from aerodynamic surface temperature tered when transferring crop coefficients between regions with
(the surface temperature that works in Equation 6.89), the difficulty different climates when those Kc values were determined using
6-24 Properties and Processes

P–M based reference ET values. Allen et al. (1994a) provided showed that consideration of the soil albedo change with drying
evidence for this lack of transferability by comparing the esti- could improve the ES estimates. Qiu et al. (1999) replaced the
mated ratio of alfalfa to grass reference ET across six arid and aerodynamic resistance with a soil evaporation transfer coeffi-
five humid locations. The ratio varied considerably across loca- cient: ha = (Ts − Ta)/(Td − Ta), where Ts is the surface temperature
tions, most dramatically between arid and humid locations. For of a drying soil, Td is the surface temperature of a dry soil, and
most locations, there was also a difference between the ratio for Ta is air temperature. They found good agreement dynamically,
the peak month and the mean ratio for that location. Note that although their model consistently overestimated soil ES by 5%.
this variance of ratios applies equally as well to the ratio of a par- Although the method shows promise, it does not provide an
ticular crop ET to reference ET (i.e., the crop coefficient, ET/ETr) estimate of surface soil water content that would be needed to
thus calling into question the transferability of crop coefficients. calculate the albedo change.
Evett et al. (2000) compared alfalfa and grass P–M reference ET When soil is wet, the evaporative flux can be estimated using
formulas to measured ET for alfalfa and grass grown under ref- the Penman or P–M equations with surface resistance set to an
erence ET conditions and found that the ratio of alfalfa to grass appropriate low value (Howell et al., 1993). This wet period is the
reference ET was not well predicted by the P–M formulations energy-limited stage of evaporation. As the soil dries, ES becomes
for their windy, semiarid advective environment, thus support- limited by soil properties. Van Bavel and Hillel (1976) addressed
ing the findings of Allen et al. (1994a). Shuttleworth (2006) pre- this using a finite difference model of soil water and heat flux
sented an analysis of Kc as used with the P–M method in which that later was developed into the CONSERVB model of evapora-
he showed that Kc values depend explicitly on the climatic condi- tion from bare soil (Lascano and van Bavel, 1986). This model
tions at the time of Kc determination. For a variety of different described 1D soil water movement with Darcy’s law, including
plant heights and canopy resistances, Annandale and Stockle the dependence of hydraulic conductivity, K (m s−1), on soil water
(1994) used an energy balance model to study variability of full- potential, h (m), and the soil water retention function, θv(h). The
canopy-cover Kc, as influenced by changes in solar radiation, surface energy balance was solved implicitly for surface tem-
air temperature, the vapor pressure deficit (ez − eo*), and wind perature (Ts), resulting in calculated values of ES, H, R n, and G at
speed. Variability in Kc increased as crop height increased and each time step. The value of ES was used as the upper boundary
as rs decreased. Variability in Kc decreased if an alfalfa reference condition for soil water flux at the next time step. The elements
ET was used rather than a grass reference ET; and they recom- of CONSERVB were included in the ENWATBAL model by
mended (1) using alfalfa reference ET and (2) development of Lascano et al. (1987) who included a vapor transport algorithm
methods for directly estimating crop ET. In light of the discus- as a function of soil drying. The latter model was upgraded to
sion in Sections 6.2.2.7 and 6.2.2.8, we add to this list a recom- model albedo changes dependent on surface soil water content
mendation to pursue a reference ET based on iterative solution by Evett and Lascano (1993). The 1993 version of ENWATBAL
of the energy balance equations. was shown to more accurately predict ES than either the Penman
or P–M equations (Howell et al., 1993). These detailed models of
6.2.2.9  Bare Soil Evaporation Estimates the soil–plant–atmosphere continuum include numerical simu-
Evaporation from bare soil (ES) may be estimated using the EC lation of soil heat and water fluxes that depend on detailed infor-
and Bowen ratio methods previously described with consider- mation on the soil hydraulic properties (characteristic curves)
ation given to the reduced surface roughness of many bare soil and property changes with depth.
surfaces when compared with vegetated surfaces. Also, Section Kustas (2002) summarizes the bulk transport approaches to Es
6.3 describes measurements of ES using weighable lysimeters estimation that depend on the vapor pressure gradient between
of various sizes. Here we describe some alternatives based on the soil surface and the air and may include a drying front algo-
energy balance solutions. rithm; and he contrasts these more mechanistic approaches with
Fox (1968) and later Ben-Asher et al. (1983) and Evett et al. several analytical methods that involve a bulk soil resistance and
(1994) described a bare soil evaporation (ES) prediction method are more amenable to inclusion in models using remotely sensed
based on subtracting the energy balance equations (Equation data for large area estimation of evaporation.
6.1) written for a dry and a drying soil. Because ES is zero for a
dry soil, this gives an expression for ES from the drying soil in 6.2.2.10  T ranspiration
terms of the other energy balance terms. The method requires a Transpiration, the water evaporated from the plants primarily
column of dry soil embedded in the field of drying soil and mea- through stomata, is a significant contributor to total latent heat
surements of the surface temperatures of the dry soil and of the flux and is directly related to the total dry matter production
drying field soil. The surface temperature difference between the of plant communities (de Wit, 1958). Methods of determining
dry and drying soils explains most of ES, but prediction accuracy transpiration (ET) vary widely. The simplest approach has been
is only moderately good (r2 = 0.82 for daily predictions, Evett to weigh single plants in sealed containers (Briggs and Shantz,
et al., 1994). Evett et al. showed that the aerodynamic resistance 1913, 1914). Canopy level measurement of the total evaporative
over the dry soil surface was reduced and that the resistance was flux (ET) using such methods as lysimetry, Bowen ratio, and
relatively independent of wind speed, probably due to buoyancy EC requires that soil water evaporation (ES) be determined,
of air heated over the relatively hot, small surface. They also so that ET can be estimated as the residual, or ET = ET − ES.
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-25

The ES component may be measured using soil microlysimeters 6.2.3  Soil Heat Flux
(see Section 6.3.1). This is the most direct method of determin-
ing ET without sealing the soil surface. Soil heat flux is discussed in detail in Chapter 9. Additional
Another method has been to estimate ET using equations based information related to the surface energy balance is given here.
on the surface energy balance and gradients in water vapor concen- Briefly, heat conduction in one dimension is described by a dif-
trations and resistances to vapor and heat exchange between the fusion equation:
plant canopy and the air. A representative equation is the widely
used P–M formula (1965). The difficulty in using such equations ∂T ∂ ⎡ ∂T ⎤
C = kT ⎢ ⎥ , (6.67)
is derivation of bulk canopy resistances to vapor and heat trans- ∂t ∂z ⎣ ∂z ⎦

port that also exclude contributions from the soil. One approach
to measure canopy resistance has been to first make stomatal
where the volumetric heat capacity, C (J m−3 K−1), and the ther-
resistance measurements on a portion of a leaf using a porometer
mal conductivity, k T (J s−1 m−1 K−1), are assumed constant in
(Turner, 1991) or gas analyzer system (Rochette et al., 1991). The
space; and vertical distance is denoted by z, time by t, and tem-
measurement strategy must somehow capture the totality of the
perature by T.
water loss from the plant canopy as affected by differences in leaf
The 1D soil heat flux, G, for a homogeneous medium is
illumination, leaf angles, microclimates, and aerodynamic resis-
described by
tances throughout the canopy. The stratified measurements must
then be integrated to a whole canopy resistance, which is a process
that has met with limited success (Baldocchi et al., 1991; Rochette ∂T
G = − kT . (6.68)
et al., 1991). The bulk aerodynamic resistance must also be cor- ∂z
rectly estimated for the P–M equation, which is also complicated
by its possible interactive relationship with bulk canopy resistance The thermal conductivity is a single-valued function of water
(Paw and Meyers, 1989). Furon et al. (2007) used numerical sim- content and is related to the thermal diffusivity, D T (m2 s−1), by
ulations to assess the leaf-to-canopy scale translation of surface
resistances and their impact on the performance of the P–M equa- kT = DTC, (6.69)

tion. Raupach and Finnigan (1988) investigated both single- and
multilayer models of evaporation.
where the volumetric heat capacity, C (J m−3 K−1), can be calcu-
Because of these difficulties, techniques to measure plant
lated with reasonable accuracy from the volumetric water con-
sap flow as an approximation of whole plant transpiration have
tent, θv (m3 m−3), and the soil bulk density, ρb (Mg m−3), by
advanced. Sap flow measurement systems use the application of
heat to the plant stem to serve as a tracer of the sap movement
through the xylem tissue. Currently, there are three groups of 2.0 × 106 ρb
C= + 4.2 × 106 θ v + 2.5 × 106 f o (6.70)
heat systems to determine sap flow: stem heat balance, heat dis- 2.65
sipation, and heat pulse (Gonzalez-Altozano et al., 2008). The
stem heat balance method is the most suitable method for her- for a soil with a volume fraction, fo, of organic matter (Hillel,
baceous annual plants with smaller stem diameters, while the 1980).
heat pulse and heat dissipation methods are primarily used for Table 6.6 lists thermal conductivities at “wet” and “dry” points
woody plants, especially those with large trunk diameters. In the for several soils. For coarse soils, the thermal conductivity versus
stem heat balance method, a heater strip constantly heats a small water content curve is S-shaped (see e.g., Campbell et al., 1994),
section of the entire plant stem, and temperature sensors below with a rapid rise at water contents corresponding to about 33 kPa
and above the strip measure how much heat is moved away soil water tension (about “field capacity”). For fine soils, the rela-
from the region by the sap. The specific heat capacity and den- tionship is more linear; and the thermal conductivity between
sity of the sap are then used to convert the measurements into dry and wet conditions in Table 6.6 can be linearly interpolated
volumetric mass sap flow. Over- or underestimating sap flow from the values given, with reasonably small errors. But for water
can occur during periods of small or large flow rates. The heat contents below the “dry” value, the thermal conductivity should
pulse and heat dissipation methods use probes inserted into the be taken as the value corresponding to the “dry” state.
stem, with the heat applied either as a pulse or at a constant rate. De Vries (1963) developed a method of estimating soil ther-
Temperature sensors in the probes determine sap velocity. Probe mal conductivity from soil texture, bulk density, and water
location and cross-sectional area and geometry of the stem content. The method, while including most important soil prop-
must be accounted for to extrapolate probe measurements into erties affecting conductivity, is limited in that it requires knowl-
whole plant sap flow for both methods, and calibration may be edge of parameters called shape factors that describe how the
required. In all methods, a strategy for transforming single plant soil particles are packed together. The shape factors are specific
measurements to field scale ET must be developed. Commonly to a given soil and perhaps pedon and must be measured. They
used strategies include weighting by leaf area or stem or trunk are, in effect, fitting parameters (e.g., Kimball et al., 1976). De
diameter (Cohen and Li, 1996). Vries’ method tends to overestimate thermal conductivity at
6-26 Properties and Processes

TABLE 6.6  Thermal Conductivity, k T, of Some Soil Materials

Soil Dry θv kT W m−1 K−1 Wet θv kT W m−1 K−1 ρb Mg m−3 Source
Fairbanks sand 0.003 0.33 0.18 2.08 1.71 de Vries (1963)
Quartz sand 0.00 0.25 0.40 2.51 1.51 de Vries (1963)
Sand 0.02 0.9 0.38 2.25 1.60 Riha et al. (1980)
Sand 0.00 0.27 0.38 1.77 1.64 Watts et al. (1990)
Sand 0.003 0.32 0.38 2.84 1.66 Howell and Tolk (1990)
Gravelly coarse sand (pumice) 0.02 0.13 0.40 0.52 0.76 Cochran et al. (1967)
Medium and coarse gravel (pumice) 0.01 0.09 0.43 0.39 0.44 Cochran et al. (1967)
Loamy sand 0.01 0.25 0.40 1.59 1.69 Sepaskhah and Boersma (1979)
Loam 0.01 0.20 0.60 1.05 1.18 Sepaskhah and Boersma (1979)
Avondale loam 0.08 0.46 0.23 0.88 1.35–1.45 Kimball et al. (1976)
Avondale loam 0.03 0.31 0.30 1.20 1.40 Asrar and Kanemasu (1983)
Silt loam 0.09 0.40 0.50 1.0 1.25 Riha et al. (1980)
Yolo silt loam 0.14 0.49 0.34 1.13 1.25 Wierenga et al. (1969)
Muir silty clay loam 0.03 0.30 0.30 0.90 1.25 Asrar and Kanemasu (1983)
Silty clay loam 0.01 0.20 0.59 1.09 1.16 Sepaskhah and Boersma (1979)
Pullman silty clay loam 0.07 0.16 0.29 0.89 1.3 Evett (1994)
Healy clay 0.04 0.30 0.30 0.91 1.34 de Vries (1963)
Fairbanks peat 0.03 0.06 0.61 0.37 0.34 de Vries (1963)
Forest litter 0.02 0.10 0.55 0.40 0.21 Riha et al. (1980)

water contents above about 0.15 (Asrar and Kanemasu, 1983; between thermal properties and water content, probably
Evett, 1994). Campbell et al. (1994) developed modifications of due to a paucity of depth-dependent soil water content data
de Vries’ theory that allowed them to match measured values (Nassar and Horton, 1989, 1990). Soil water content often
well. They showed that, as temperature increased, the thermal changes quickly with depth, time, and horizontal distance.
conductivity versus water content curve assumed a pronounced Moreover, diffusivity is not a single-valued function of soil
S-shape for the eight soils in their study, with the curve deviat- water content and so is difficult to directly use in modeling.
ing from monotonicity at temperatures above 50°C. The ability of time domain reflectometry (TDR) to measure
Horton et al. (1983) developed a measurement method for water contents in layers as thin as 0.02 m (Baker and Lascano,
D T based on harmonic analysis. The method entailed fitting a 1989; Alsanabani, 1991) provided the basis for design of a sys-
Fourier series to the diurnal soil temperature measured at 1 h tem that simultaneously measures water contents and tem-
intervals at 0.01 m depth followed by the prediction of temper- peratures at several depths.
atures at a depth, z (0.1 m), based on the Fourier series solu- Evett (1994) used measurements of soil temperature at several
tion to the 1D heat flux problem using an assumed value of depths (e.g., 2, 4, 6, 8 … cm), coupled with TDR measurements
D T. The value of D T was changed in an iterative fashion until of soil water content at the same depths, to find a relationship
the best fit between predicted and measured temperatures at between thermal conductivity and water content in a field soil.
z was obtained. The best fit was considered to occur when a He used the minimum SSE method of Horton to find the thermal
minimum in the sum of squared differences between predicted diffusivity for each soil layer between vertically adjacent mea-
and measured temperatures was found (i.e., minimum sum of surements of water content and temperature. The water content
squared error, [SSE]). Poor fits with this and earlier methods for this layer was used to calculate C and thus λ corresponding to
are often due to the fact that field soils usually exhibit increas- that water content. A function of k T versus θv was developed by
ing water content with depth and changing water content with regression analysis on the k T and θv data (Figure 6.29). Because
time, while the method assumes a homogeneous soil. Costello both C and k T were known for each layer, this method also gave
and Braud (1989) used the same Fourier series solution and a the soil heat flux.
nonlinear regression method, with diffusivity as a parameter The complicated methods of measuring thermal diffusivity
to be fitted, for fitting the solution to temperatures measured at and conductivity mentioned here use computer programs and
depths of 0.025, 0.15, and 0.3 m. nonlinear regression fitting of multiterm sine series in order to
Neither Horton et al. (1983) nor Costello and Braud (1989) handle diurnal temperature waves that differ from simple sinu-
addressed the dependency of diffusivity on water content or soidal waves, as well as to incorporate measurements of soil
differences in water content between the different depths. water content that vary with depth. However, rough estimates
Other papers have dealt with thermal diffusivity in non- of the thermal parameters may be made from phase differences
uniform soils but did not result in functional relationships and amplitude differences observed for temperatures measured
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-27

1.2 13
TDR/TC
Depths (cm)
Regression 12
Forest litter
Silt loam 20
11
0.8
kT (W m–1 K–1)

15

Temperature (°C)
10

10
9

0.4 6
8

4
7
2
6
0.0
0 0.1 0.2 0.3
5
Water content (m3 m–3) 308 308.5 309 309.5 310
Day of year, 1993
FIGURE 6.29  Thermal conductivity (k T) of Pullman silty clay loam,
determined from TDR probe and thermocouple arrays, compared with FIGURE 6.30  Temperatures at six depths in a Pullman clay loam for
functions from Campbell (1985) for forest litter and silt loam. 2 days in 1993.

at only two depths, with the application of simplifying assump- When z equals zd, the amplitude is 1/e = 0.37 of the amplitude at
tions of homogeneous water content and soil properties, and a depth zero. Writing Equation 6.72 for two depths, z1 and z2, and
simple sinusoidal diurnal temperature wave describing the tem- solving for k T/C gives
perature T at depth z and time t
kT π(z 2 − z1 )2 (6.74)
= .
C τ[2.3log(A1 /A2 )]2
T (z , t ) = T + Az sin[ωt + φ(z )], (6.71)

Figure 6.30 shows measured diurnal temperature waves for sev-
where eral depths in a Pullman clay loam on two different days. Table 6.7
−
T is the mean temperature (i.e., the mean of maximum and gives the mean water content as measured by TDR for each depth.
minimum for a sine wave) Also shown are the thermal conductivities obtained by fitting a sine
Az is the amplitude of the wave (i.e., the difference between series to each depth and evaluating the thermal conductivity of the
maximum and minimum temperatures) layer between depths by using the coefficients of the sine series in a
ω is 2π/τ, where τ is the period (e.g., 24 h) sine series solution to T(t) at the next depth and then performing
ϕ(z) is the phase angle at depth z (difference in time between a nonlinear fit of that solution to obtain the thermal conductivity.
the occurrence of the maxima or minima at depth 0 and Single-probe heat pulse methods have been developed to mea-
depth z, units of radiance) sure thermal diffusivity; and a dual-probe heat pulse method
(Campbell et al., 1991) can measure the thermal diffusivity,
Equation 6.67 can be solved using the above equation for T(z, t) D T, as well as k T and C (Kluitenberg et al., 1995). Noborio et al.
yielding (1996) demonstrated a modified trifilar (three-rod) TDR probe
that measured θv by TDR, and k T by the dual probe heat pulse
A0 sin[ωt − (z/z d )] method. Their measured k T compared well with values calcu-
T (z , t ) = T + , (6.72) lated from de Vries (1963) theory.
e z /zd
Soil heat flux is more commonly determined using heat flux
plates (Table 6.1). These are thermopiles that measure the tem-
where perature gradient across the plate, and, knowing the conductiv-
A0 is the amplitude at depth zero ity of the plate, allow calculation of the heat flux from Equation
zd is called the damping depth and is a function of the ther- 6.74. Heat flux plates are impermeable and block water move-
mal conductivity and volumetric heat capacity ment. Because of this, the plates should be installed a minimum
of 5 cm below the soil surface, so that the soil above the plate
1/ 2 does not dry out or wet up appreciably more than the surround-
⎛ 2k ⎞
zd = ⎜ T ⎟ . (6.73) ing soil. Typical installation depths are 5 or 10 cm. Even at these
⎝ Cω ⎠
shallow depths, the heat flux is greatly reduced from its value at
6-28 Properties and Processes

TABLE 6.7  Mean Soil Water Contents, θ (m3 m−3), and Thermal 250
Conductivities, k T (J m−1 s−1 K−1), Calculated from a Nonlinear Fit Equation 6.77
of a Sine Series Solution Compared with k T Estimated using 200 Equation 6.80
Equation 6.74 for a Pullman Clay Loam for 2 Days in 1993 Equation 6.81
150 Equation 6.83
Amplitude Based, Nonlinear Fit—Sine Plates

Flux (W m–2)
Equation 6.74 Series Soln. 100

Depth (cm) θ (m m ) 3 −3 kT at θ=interlayer mean kT at θ=0.23 kTθ 50

Day 308
0
2 0.09
0.176 0.232 0.138 –50
4 0.14
–100
0.518 0.577 0.485
194 195 196
6 0.22 Day of year, 1992
0.74 0.717 0.709
10 0.27 FIGURE 6.31  Four methods of correcting heat flux, measured with
1.128 1.003 1.221 plates at 5 cm depth, to surface heat flux.
15 0.31
1.295 1.151 1.271
where θvzj, ρbzj, and fozj are the water contents, soil bulk densi-
20 0.27
ties, and volume fractions of organic matter, respectively, at
Day 309 depths zj. The estimate of G is not much changed by the exact
2 0.08 form of the combination equation as shown by data from
0.082 0.111 0.117 Bushland, Texas, for four forms of Equation 6.75 (Figure 6.31).
4 0.13 For situations where water content and temperature change rap-
2.273 2.566 0.363 idly with depth, or bulk density or fo changes rapidly with depth,
6 0.22 the multiple layer approach will work better.
3.85 3.772 0.596 As an example, we compare four methods of combining tem-
10 0.26 perature and water content data to correct heat flux for bare soil at
3.008 2.7 0.916 Bushland, Texas, in 1992 (Figure 6.31). Temperatures were mea-
15 0.31 sured at 2 and 4 cm depths (two replicates) with thermocouples, T2
2.006 1.784 1.098 and T4; at the surface with a single IRT, T0; and as a mean tempera-
20 0.27 ture of the surface to 5 cm depth soil layer using thermocouples
wired in series and buried (four replicates) at 1 and 4 cm depths,
T1_4. Water contents were measured by TDR probes (two repli-
the soil surface; and corrections must be applied to compute sur-
cates) inserted horizontally at 2 and 4 cm depths, θ2 and θ4. Soil
face heat flux. The most common correction involves measuring
heat flux at 5 cm depth, G5, was measured with heat flux plates
the temperature and water content of the soil at midlayer depths,
(four replicates). For all methods, the product of soil bulk density
zj, in N layers (j to N) between the plate and surface and applying
and heat capacity of soil solids were set to 1.125 MJ m−3. For the
the combination equation over some time period, τt, defined by
first method, the surface heat flux, G0, was described as
beginning and ending times ti and ti+1
(1.125 + 4.2θ w ) × 106 (0.05)(Tw +1 − Tw )
N G0 = G5 + , (6.77)
G = Gz +
∑ j =1
(Tzj_i +1 − Tzj _ i )Δz jCzj
, (6.75)
1800

(t i +1 − t i ) where 1800 was the period in seconds; the weighted water con-
where tent for the surface to 5 cm depth layer, θw, was
G is the surface heat flux during τt
3θ 2 2θ 4
Gz is the flux at depth z θw = + (6.78)
Tzj are temperatures at the N depths, zj, at times ti and ti+1 5 5
Δzj is the depth of the layer with midpoint zj
the weighted temperature for the surface to 5 cm depth layer, Tw,
was
where the volumetric heat capacities, Czj, at depths zj are calcu-
lated from Equation 6.70, rewritten as 3T2 2T4 (6.79)
Tw = +
5 5
2.0 × 106 ρbzj and Tw+1 was calculated the same way, but for the previous
C zj = + 4.2 × 106 θ vzj + 2.5 × 106 f ozj , (6.76)
2.65 measurement.
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-29

For the second method, θw and the series-wired thermocouple For  row crop investigations, at least four soil heat flux plates
temperature were used: should be used to obtain a representative mean. Spatial and tem-
poral variation of G will depend on row orientation, crop height
(1.125 + 4.2θ w ) × 106 (0.05)(T1 _ 4 +1 − T1 _ 4 ) and cover factor, and the time since wetting and the pattern of
G0 = G5 + . (6.80) soil water uptake by roots. For sparse canopies, G measurement
1800
may require many more heat flux plates (Kustas et al., 2000).

For the third method, θw was used: 6.2.3.1  Bernoulli, Soil Air, and Convective Heat Flux
In addition to diffusive heat flux, convective heat flux plays an
(1.125 + 4.2θ w ) × 106 (0.05)(T024 +1 − T024 ) important and often overlooked role in soil heating or cooling.
G0 = G5 + , (6.81)
1800 This is the heat transported by moving air or water, the latter
denoted in Figure 6.1 by GJw for heat transported by infiltrating
but the depth-weighted mean, T024, of IRT temperature and the water. Convective heat flux due to infiltration of water can be
temperatures measured at 2 and 4 cm was used. much larger than that due to diffusion on a diurnal basis. For
example, irrigation with 5 cm of water at 15°C on a soil at 25°C
⎡ (T0 + T2 )/2 + T0 ⎤ with an initial water content of 0.1 m3 m−3 and a bulk density
⎢ 2 ⎥ of 1.48 would immediately lower the temperature of the 11.6 cm
T024 =⎣ ⎦ + 2T2 + 2T4 .
(6.82) deep, wetted layer to 20°C (assuming negligible heat of wetting,
5 5 5
the soil brought to saturation, and a heat capacity of 1.54 MJ
m−3 K−1). Although soil temperature may be changed strongly
For the fourth method, a modified layer approach was used: by infiltration of water, there is another mechanism for soil
temperature changes, the heat of wetting. The heat of wetting
is heat energy released when a soil is wetted and is usually not
(1.125 + 4.2θ2 ) × 106 (0.05)(T02 +1 − T02 ) large enough to be important in heat balance calculations. It can
G0 = G5 +
1800 be large for clays with large surface area if they are extremely
(1.125 + 4.2θ 4 ) × 106 (0.05)(T4 +1 − T4 ) dry, ranging from 40 J g−1 for kaolinitic clays to 125 J g−1 for allo-
+ . (6.83) phanic clays (Iwata et al., 1988). But, it decreases quickly as the
1800
initial water content of the soil increases and is not likely to be
important for the normal range of field water contents.
where the depth-weighted mean temperature in the surface to Convective heat flux due to air movement into and out of soil
3 cm deep layer, T02, was surfaces is commonly ignored in energy balance considerations.
Most people do not see any reason for air to move into or out
⎡ (T2 + T0 )/2 + T0 ⎤ of soil other than changing atmospheric air pressure. However,
⎢ ⎥ there are other forces at play that may significantly increase air
2 ⎦ + 2T2 .
T02 = ⎣ (6.84) flow into or out of soil surfaces. Consider Bernoulli’s theorem,
3 3

v12 p v2 p
All of these methods produced similar values of G 0, but those + 1 + z1 = 2 + 2 + z 2 , (6.85)
2g ρa g 2g ρa g
using a depth-weighted water content tended to overestimate
extreme values, probably because the 2 cm water content
was less than that at 4 cm (Figure 6.31). The weighted mean which is an equation of conservation of energy where v1 and
approach for both water content and temperature, with sur- v2 are fluid (e.g., air) velocities at two points, p1 and p2 are the
face temperature included (Equation 6.81), produced gener- respective fluid pressures normal to the fluid flow direction, ρa is
ally the largest diurnal swing in G 0. Methods that did not the density of air, g is the acceleration due to gravity, and z1 and
include the surface temperature, but used the weighted mean z2 are the elevations of the two points. Placing point 1 in the soil
approach for both water content and temperature (Equations and point 2 in the atmosphere directly above the soil, we see that
6.77 and 6.80), produced intermediate results. The layer v1 ≈ 0, and v2 ≥ 0, so that the equation may be rewritten as
approach (Equation 6.83), produced the smallest diurnal
swing in G 0, despite using the surface temperature, and is ρa v22
p1 − p2 = + (z 2 − z1 )ρa g . (6.86)
probably the most accurate approach. All methods corrected 2
both the amplitude and the phase of the diurnal cycle of G 0
appropriately. That is, the pressure differential from soil to air is equal only
Spatial variability of G can be considerable due to shad- to the elevation difference multiplied by ρa g when wind speed
ing of soil by vegetation and due to micro-relief that both lead is zero, and it increases above that value as the square of wind
to variable soil wetness, thermal conductivity, and E s rates. speed. During sustained winds across flat surfaces, there is a
6-30 Properties and Processes

sustained pressure gradient driving air movement from soil to where

air. For air movement over nonplanar surfaces, the situation is ρa is the density of air (ρa = 1.291 – 0.00418Ta, with less than
complicated by other aerodynamic effects such as drag, which 0.005 kg m−3 error in the −5°C to 40°C range, Ta in °C)
may increase or decrease the pressure gradient at various places cp is the heat capacity of air (1.013 × 103 J kg−1 K−1)
over the surface. This has implications for soil gas efflux rates and Tz is the air temperature at measurement height
measurements (Rudolf et al., 1996). Turbulent air flow across soil raH is the aerodynamic resistance to sensible heat flux (s m−1)
was investigated by Farrell et al. (1966), who showed with field T0 is the temperature of the surface
measurements and theoretical analysis that the effective gaseous
diffusion coefficient in soil could be increased by 100 times for For vegetation, the “surface” for aerodynamic resistance is the
wind speed of 7 m s−1. Bulk air movement into and out of soils height at which the logarithmic wind speed profile, established
can substantially alter the energy balance as evidenced by such by measurements of wind speed above the surface, extrapolates
phenomena as ice caves in permeable lava rocks overlain by soils. to zero. This height is d + z om and is often well below the top
of the canopy, typically at 2/3 to 3/4hc. Measurements of sur-
face temperature (with, for instance, an IRT) may not be the mean
6.2.4  Sensible Heat Flux
temperature at the same height as the aerodynamic “surface,”
Sensible heat flux is the transfer of heat energy away from or thus introducing bias in the raH estimation. Also, the roughness
to the surface by conduction or convection. Because air is a length for momentum, zom, may be different from that for sen-
poor conductor of heat, most sensible heat flux is by convec- sible heat, zoH.
tion (movement) of air. This occurs in eddies of different scales A general form for aerodynamic resistance to sensible, latent
depending on the turbulence of the atmosphere near the sur- energy, and momentum fluxes is
face. Turbulence is influenced by the aerodynamic roughness
of the surface, the wind speed, and the temperature differen- 1 ⎡ ⎛ zm − d ⎞⎤
2

tial between the surface and the air. Perhaps the most common ra = ⎢ ln ⎜ ⎟⎥ , (6.90)
k 2uz ⎣ ⎝ zo ⎠⎦
method of evaluating sensible heat flux is to measure the other
terms in Equation 6.1 as accurately as possible and then set H
equal to the residual where
k is the von Kármán constant = 0.41
H = −Rn − G − LE. (6.87) zo is the roughness length (m)
zm is the reference measurement height (m)
Of course, this approach lumps all the errors in the other terms uz is the wind speed (m s−1) at that height
into H. More importantly, it does not allow for a check on the d is the zero plane displacement height (m)
accuracy of the energy balance. By definition, if H is defined by
Equation 6.87 then Equation 6.1 will sum to zero. Only an inde- Equation 6.90 only holds for neutral stability conditions.
pendent measure of H can provide a check sum for Equation Unstable conditions occur when the temperature (and thus air
6.1. As noted in Section 6.2.2.2, EC is a direct method of mea- density) gradient from the surface upward is such that there is
suring H. warm air rising through the atmosphere (forced convection).
The Bowen ratio method can be applied to sensible heat Stable conditions prevail when the air is much cooler and denser
flux as well as to latent heat flux as outlined in Section 6.2.2.3. near the surface, thus inhibiting turbulent mixing due to forced
Sensible heat flux is calculated from the Bowen ratio as (follow- convection. Neutral conditions obtain when neither stable nor
ing Rosenberg et al., 1983, p. 256) unstable conditions do.
For bare soil, Kreith and Sellers (1975) simplified Equation
−(Rn + G) 6.90 as follows:
H= . (6.88)
(1 + (1/βr ))
2
1 ⎡ ⎛ zm ⎞⎤
ra = 2 ⎢ ln ⎜ ⎟⎥ . (6.91)
The considerations of fetch, measurement height, equipment, k uz ⎣ ⎝ z o ⎠⎦

etc., mentioned in Section 6.2.2.4 for Bowen ratio and EC mea-
surements apply as well to sensible heat flux measurements made
They found a value of zo = 0.003 m worked well for smooth bare
with these methods.
soil.
Though obviously a dynamic and complex process, sensible
For nonneutral conditions, a variety of stability corrections
heat flux, H (W m−2), is sometimes estimated using a straightfor-
have been proposed. See Rosenberg et al. (1983, pp. 140–144)
ward resistance equation
and Monteith and Unsworth (1990, pp. 234–238). Because many
models of the soil–plant–atmosphere continuum use Equation
ρa cp( Tz − T0)
H= , (6.89) 6.89 to model H, it is important to note that, while stability
raH corrections can improve model predictions of H and surface
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-31

temperature, the stability corrections are implicit in terms of H. Units are typically millimeter depth of water per unit time,
This leads to a requirement for iterative solution of sensible heat equivalent to volume of water per unit area per unit time. The
flux at each time step in these models. value of P is always positive or zero, but values of ΔS, R, F, and
Knowledge of appropriate values for d and zo in the above LE/(λρw) may have either sign. By convention, R is taken to be
equations can be hard to come by since their determination positive when there is more runoff than runon. As in Equation
involves measurements of wind speed and temperature at 6.1, LE/(λρw) is positive when flux is toward the surface of
multiple heights within and above the canopy (Monteith and the soil. The equation is often rearranged to provide values of
Unsworth, 1990). Campbell (1977) suggests estimating these LE/(λρw) when suitable measurements or estimates of the other
from plant height, hc, as terms are available; but it can and has been used to estimate run-
off, soil water available for plants, and deep percolation losses
d = 0.64hc (6.92) (flux downward out of the control volume). Here, we take F as
positive when flux is upward across the lower boundary into the
for densely planted agricultural crops and control volume. The term F is used rather than P for deep perco-
lation, both to avoid confusion with precipitation, and to avoid
z om = 0.13hc (6.93)
the common misconception that deep flux is only downward
since P is often used to indicate deep percolation.
for the roughness length for momentum for the same condition.
In the case of LE/(λρw), the units of LE (W m−2) are conve-
Campbell (1977) gives the roughness length parameters for sen-
niently converted to depth of water in mm s−1 by dividing by
sible heat, zoH, and vapor transport, zov, as
the latent heat of vaporization (λ, ∼2.45 × 106 J kg−1) and by the
z oH = z ov = 0.2z om . (6.94) density of water (ρw, ∼1000 kg m−3), with little loss of accuracy
because the changes in density of water and the latent heat of
Note that Equation 6.94 differs from Equation 6.58, where vaporization with temperature are small. For precise work,
Jensen et al. (1990) used zoH = 0.1 zom. For coniferous forest, Jones both parameters can be temperature corrected. The change in
(1992) gives storage (ΔS) is often determined by measuring soil water con-
tent changes by methods that give volumetric water content,
d = 0.78hc (6.95) θv (m 3 m−3). Multiplying the water content by the depth of the

layer gives the depth of water stored, and the first derivative
and of storage over time is ΔS. In the United States, the term ET is
used to represent the sum of evaporative fluxes from the soil and
z om = 0.075hc (6.96) plant. By convention, ET is taken as positive for fluxes from plant
or soil surface to the atmosphere. Thus, ET = −LE/(λρw) and the
for these parameters. As wind speeds increase, many plants water balance may be rearranged as
change form and height, with resulting decrease in h, d, and zom.
It  is unlikely that the relationships given in Equations 6.92 ΔS = P − R + F − ET. (6.98)
through 6.96 hold true for large wind speeds.
This provides a use for the ET term for those who prefer to say
6.3  Water Balance Equation evaporation rather than ET. Examination of Equation 6.98 will
satisfy the reader that soil water storage increases with precipi-
The water balance equation is written for a control volume of tation, decreases if runoff from precipitation occurs, decreases
unit surface area and with a vertical dimension that extends with increasing ET, and increases with flux upward into the
from the soil surface to a lower boundary that is commonly control volume. Although Equations 6.97 and 6.98 are instan-
assigned a depth below the bottom of the root zone (Figure 6.1) taneous rate equations, they are often written for an assumed
but may be much deeper: period of time such that the variables are in units of depth of
water for that time period.
LE
0 = ΔS − P + R − F − , (6.97)

(λρw ) 6.3.1  Measuring ΔS and ET
where Probably the most accurate method of measuring ΔS is the weigh-
ΔS is the change in soil water storage in the profile (taken as ing lysimeter (Wright, 1991). Although large weighing lysimeters
positive when water storage increases over time) involve considerable expense, they can give very precise measure-
P is precipitation and irrigation ments (0.05 mm = 0.05 kg m−2) (Howell et al., 1995). An excellent
R is the sum of runoff and runon review of the use of weighing lysimeters is given by Howell et al.
F is flux across the lower boundary of the profile (1991). Careful design, installation, and operation will overcome
LE/(λρw) is water lost to the atmosphere through evaporation any of the serious problems reported with some lysimeters includ-
from the soil or plant or gained by dew formation ing disturbance of the soil profile (less with monolithic lysimeters),
6-32 Properties and Processes

1.5 m Soil surface temperature swing of 1°C, reducing temperature-induced errors

in low-level measurements such as load cell transducer bridges
and thermocouples. Other equipment that may be installed in the
Bolted chamber includes a system for TDR measurements of soil water
connection Anti-seep
collar
content and bulk electrical conductivity and concurrent measure-
ments of soil temperature, and an automatic vacuum drainage
system that continuously monitors drainage rate. The drainage
tanks were suspended by load cells from the bottom of the lysim-
2.4 m eter tank, allowing measurement of tank mass change without
changing the mass of the lysimeter until the tanks are drained
(manual but infrequent). The design illustrated in Figure 6.33
overcomes the main disadvantages of the design of Marek et al.
Drainage (1988), which were the shallow soil depth over the ceiling around
system the periphery of the chamber and the nearness of the entrance
hatch to the lysimeter surface. The shallow soil depth can cause
uneven plant growth next to the lysimeter, but this problem can
Platform scale be eliminated with the installation of a drip irrigation system to
four load beams apply additional water to this area. Access to the lysimeter must
be carefully managed to avoid damage to the crop.
Figure 6.32 shows a weighing lysimeter design that minimizes
Scale Drainage
sump
disturbance to the field during both installation and operation.
base
plate Fine
The monolith was collected a short distance away, and the outer
gravel box was installed in a square hole that disturbed only a 15 cm
perimeter of soil outside the lysimeter. Because there is no access
FIGURE 6.32  Cross-sectional view of simplified weighing lysim- to the sides or bottom of the lysimeter, there is no reason for
eter installed for grass reference ET measurements at Bushland, Texas. personnel to visit the lysimeter area except for crop management
(From Schneider, A.D., T.A. Howell, A.T.A. Moustafa, S.R. Evett, and and the occasional manual drainage accomplished with a vac-
W.S. Abou-Zeid. 1998. A simplified weighing lysimeter for monolithic uum pump and collection bottle. Disadvantages of this design
or reconstructed soils. Appl. Eng. Agr. 14:267–273.) are considerable, and include the lack of continuous drainage
data, the fact that manual drainage may not be timely or com-
interruption of deep percolation and horizontal flow components, plete, and the fact that the weighing system is impossible to
uneven management of lysimeter compared with field soil (Grebet repair without disassembling the entire lysimeter, which can be
and Cuenca, 1991), and other sources of bias (Ritchie et al., 1996). costly and time consuming (sometimes months; e.g., Schneider
Other drawbacks include heat flux distortions caused by greatly et al., 1998; Marek et al., 2006). This lower cost, direct weigh-
conductive steel walls (Black et al., 1968; Dugas and Bland, 1991), ing lysimeter built with no access below the surface at Bushland,
but minimal for large lysimeters, and high cost, for example, Texas (Howell et al., 2000), experienced a weighing system fail-
$65,000 (Lourence and Moore, 1991), $80,000 (Marek et al., 1988), ure due to lightning that required removal of the soil container
and $65,000 (Evett et al., 2009a). All lysimeters have walls, one and scale, which took many weeks, was costly, and disrupted an
that retains the soil and is part of the soil container, and another entire measurement season. A scale failure in a similar lysimeter
that separates the soil container from the surrounding field soil. at Uvalde, Texas, caused Marek et al. (2006) to point out that
A gap between the walls is necessary to allow weighing. The wall- this “closed” type of design has the potential to result in costly
gap surface area is the sum of inside and outside wall horizontal repairs and lengthy loss of data when scales fail. In addition, the
surface areas plus the gap horizontal surface area. Well-designed remote location of the data logger for the “closed” design can
lysimeters may have a wall-gap surface area as little as 1.5% of the cause problems of electrical interference or signal degradation.
lysimeter soil surface area (Howell and Tolk, 1990). The long cable lengths to the external data logger used with the
Schneider et al. (1996) described simplified monolithic weigh- lysimeter in Figure 6.32, and the large diurnal temperature swing
ing lysimeters (Figure 6.32) that were considerably less expensive to which cables and data logger were exposed, both caused a six-
than, and nearly as accurate as, the monolithic weighing lysimeter wire bridge to be needed to reduce errors due to temperature-
described by Evett et al. (2009a) (Figure 6.33). These two designs induced resistance changes when reading the platform scale
represent contrasts in mode of operation and each presents some load cells. By contrast, the location of the data logger inside the
advantages and disadvantages. The design in Figure 6.33 allows lysimeter chamber in Figure 6.33 results in diurnal temperature
access to all sides and the bottom of the lysimeter for installation variations being <1°C, allowing a four-wire bridge to be used for
or repair of sensors and weighing or drainage systems. The data reading the weighing system load cell. Measurement precision
logger that handles all measurements is installed in the under- with the lever beam scale in Figure 6.33 is 0.06 mm, while that with
ground chamber and typically is subject to only a small diurnal the platform scale in Figure 6.32 is 0.1 mm.
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-33

Section through lysimeter 5.0 m

A B
Soil surface
0.01-m gap between soil tank
Ship’s ladder and outer enclosure at top
continuous to 1.5 m 3.0 m
floor with hand
rail. Place to 1.79 m
Soil tank
one side
0.05 m gap between soil
tank and outer enclosure

4.0 m 4.23 m
2.34 m
3.0 m
Continuous 75 by 40
2.44 m by 6 mm channel
embedded in concrete
floor around perimeter Final lever Scale
for welding of and load support
steel walls cell support piers
stand

A΄ B΄
0.15 m concrete slab 0.50 m concrete w/12 16 mm 3.75 m
w/16 mm steel on horizontal steel on 0.10 m O.C.
0.30 m O.C. square w/6 6 mm ties at 0.30 m O.C.
grid over 0.20 m w/double ties at 0.05 m spacing at
compacted gravel ends, over 0.20 m compacted 0 1 2 3 4 5m
base coarse gravel base coarse (see
foundation plan)

FIGURE 6.33  Cross-sectional view of the large weighing lysimeter at Dayr Alla in the Jordan Valley, Jordan. (From Evett, S.R., N.T. Mazahrih,
M.A. Jitan, M.H. Sawalha, P.D. Colaizzi, and J.E. Ayars. 2009a. A weighing lysimeter for crop water use determination in the Jordan Valley, Jordan.
Trans. ASABE 52:155–169.)

Weighing lysimeters measure mass change over a given time. to the operations defined by the +P and +F in Equation 6.98; result-
If mass is measured in kilograms, then dividing the mass change ing in the monotonically decreasing storage shown in Figure 6.35.
by the surface area in meter squares of the lysimeter will give Taking the first derivative of the adjusted storage with respect to
the change in water storage, ΔS, of the lysimeter as an equivalent time gives the adjusted ΔS rate, and thus ET rate (Figure 6.36) (R
depth of water in millimeter, with only slight inaccuracy due to the assumed to be zero). In order to compute ET rates on the same
density of water not being quite equal to 1 Mg m−3. If evaporation time interval as lysimeter mass measurements are made, we must
from bare soil is being measured, then the surface area of the soil have concurrent measurements of irrigation, precipitation, and
within the lysimeter should be used in the calculation. However, drainage on the same or a finer recording interval.
if a closed crop canopy is present, then the surface area to be used Weighing lysimeters are subject to wind loading, more so when
should be representative of the canopy surface that is supported the soil surface is bare, as evidenced by Figure 6.37. In windy
by the lysimeter. This may be equal to the sum of the lysime- 15
ter soil surface area plus one half of the wall-gap surface area,
depending on the lysimeter design and crop planting pattern. 10
If only daily ET values are needed, then ΔS is computed from
Relative storage (mm)

Irrigation Irrigation
the 24 h change in lysimeter mass, usually midnight to midnight. 5
26.7 mm 22.3 mm
Some averaging of readings around midnight may be needed to
0
smooth out noise. The daily ET is computed by summing ΔS with
any precipitation or drainage. Data from a continuously weigh- –5
ing lysimeter may be presented as a time sequence of mass (or
depth of water storage) referenced to an arbitrary zero (Figure –10
6.34). Irrigation or precipitation events often will appear as obvi-
ous increases in storage (Figure 6.34), and drainage events will –15
95 96 97 98 99 100 101 102 103
show up as decreases in storage. Adjusting the sequential record
Day of year, 1992
of storage amount by subtracting the rainfall or irrigation depth,
and adding the depth of drainage water, at the time that these FIGURE 6.34  Unadjusted weighing lysimeter storage for winter wheat
occurred, will remove these changes in storage, and is equivalent at Bushland, Texas, showing storage increases due to two irrigations.
6-34 Properties and Processes

10 regions, it may be necessary to smooth the data to remove noise

when calculating the ET rate. Gorry (1990), following Savitsky and
0
Golay (1964), described a method for general least squares smooth-
Corrected storage (mm)

–10 ing that allowed application of different levels of smoothing to both

the raw data and their first derivative. Application of this method
–20
to post-processing of data is preferable to real-time smoothing
–30 that may eliminate detail in the data. With post-processing, we
can apply only the amount of smoothing needed to reduce noise
–40
to acceptable levels. A computer program to apply Savitsky–Golay
–50 smoothing is available (http://www.cprl.ars.usda.gov/programs/).
Microlysimeters are lysimeters small enough to be installed
–60 and removed by hand for weighing daily or more often. They
95 96 97 98 99 100 101 102 103
have been used to measure the water use of short grass, but
Day of year, 1992
lack the soil depth needed for soil water redistribution and
FIGURE 6.35  Lysimeter storage values from Figure 6.34 adjusted by drainage that would reproduce the soil profile water content
subtracting irrigation amounts. in the adjacent field over the long term. They can give good
precision but are sensitive to spatial variability of soil water
characteristics, soil profile water content distribution, and sur-
1.4
face condition. Lascano and Hatfield (1992) showed that 182
1.2 microlysimeters were required to measure field average E with
1.0 precision of 0.1 mm day−1 at a 90% confidence level when their
soil was wet but only 39 when dry. This was due to the greater
0.8
ET (mm h–1)

variability of E for wet soil. For a precision of 0.5 mm day−1,

0.6 only seven microlysimeters were required for any soil wetness.
0.4 To avoid heat conduction to and from the surface, microlysim-
eter walls should be made of low thermal conductivity materi-
0.2
als such as plastic; and, to avoid trapping heat at the bottom of
0.0 the microlysimeter, the bottom end cap should be made of a
–0.2 thermally conductive material such as metal (Evett et al., 1995).
95 96 97 98 99 100 101 102 103 Plastic pipe makes good microlysimeters. Typical dimensions
Day of year, 1992 are 7.6 or 10 cm in diameter and from 10 to 40 cm in height.
FIGURE 6.36  ET rate calculated by taking the negative of the first Beveling the bottom end eases insertion into the soil. Typical
derivative of adjusted storage from Figure 6.35. The negative ET rates practice is to insert the microlysimeter vertically until its top is
shown for some nights are caused by dew formation. level with the soil surface; then dig it out, or rotate it to shear
the soil at the bottom, and pull it out. After capping the bot-
tom with a water-tight seal, it is weighed before reinsertion
into the original or a new hole; sometimes lined with a mate-
Bare soil rial (e.g., plastic sheet or bag) to prevent sticking of the soil
0.3
Alfalfa to the microlysimeter outside surface. After a period of time,
the microlysimeter is reweighed and the difference in initial
Standard deviation (mm)

and final weights is the evaporative loss. Short microlysimeters

0.2
should be replaced daily, as the water supply is soon used up to
the point that the soil inside the lysimeter is no longer at the
same water content as the soil outside, biasing the measured E.
In a study of spatial variability of evaporation from bare soil,
0.1 Evett et al. (1995) used 30 cm high microlysimeters to avoid
daily replacement so that the spatial relationship would not be
changed. They showed that for their clay loam soil the 30 cm
height was adequate for 9 days. If plant roots are present, it is
0.0 recommended to replace microlysimeters daily to lessen errors
0 2 4 6 8 10 12 associated with root water uptake that occurs elsewhere in the
Wind speed (m s–1) field but not in the microlysimeters.
FIGURE 6.37  Half-hourly standard deviations of lysimeter stor- Alternatives to weighing lysimetry include soil water mea-
age (mm) as affected by wind speed over contrasting surfaces for days surement methods for assessing ΔS for a soil profile of given
97–105 at Bushland, Texas, in 1994. depth over a given time. In this case, the soil volume of interest is
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-35

unbounded below the surface and F is, strictly speaking, uncon- 20

trolled. Measurements of soil water content can give the change Lysimeter
in soil water stored in a profile of given depth with good accu- 10 TDR

Relative storage (mm)

racy; and can give good values for E if water flux across the bot-
tom of the profile is known or can be closely estimated. Baker 0
and Spaans (1994) described a microlysimeter with TDR probe
installed vertically to measure the water content. Comparison of
–10
E calculated from the change in storage determined with TDR
closely matched the E measured by weighing the microlysim-
–20
eter. Young et al. (1997) showed that a single 800 mm long probe
installed vertically from the surface could account for 96% of ET
from weighing lysimeters irrigated on a 6 day interval; but stan- –30
100 101 102 103 104 105 106 107 108
dard error for the probe was about four times larger than that
Day of year, 1992
for the lysimeter (0.46 and 0.07 mm, respectively). In a container
study with a sorghum plant, Wraith and Baker (1991) showed FIGURE 6.38  Soil water storage in the upper 35 cm of the soil pro-
that a TDR system could measure ET with good resolution and file, as measured by two TDR probe arrays, compared with storage in
provide measurements of change in storage on a 15 min interval a 2.4 m deep weighing lysimeter. Zero reference is arbitrary. Winter
that compared very well with those measured by an electronic wheat, Bushland, Texas, 1992.
scale. Despite the good laboratory performance of TDR for soil E
and ET determinations, outdoor installations are limited by the
depth to which TDR probes can be installed without disturbing
20
the soil profile unduly, and the diurnal and seasonal tempera- Lysimeter
ture effects on TDR derived water contents, which can bias E and TDR
ET determinations.
Evett et al. (1993) showed that change in storage in the upper 10
35 cm of the profile under winter wheat could be accurately
ΔS (mm)

tracked with horizontally placed TDR probes, with an average of

88% of daily ΔS occurring in the upper 30 cm. But, E estimates
were incorrect (compared with a weighing lysimeter) when flux 0
across the 35 cm lower boundary occurred. However, combina-
tion of the TDR system with neutron moisture meter (NMM)
measurements of deeper soil moisture allowed measurement –10
of E to within 0.7 mm of lysimeter measured ET over a 16 day 100 101 102 103 104 105 106 107
period; five times better than the accuracy achieved using only Day of year, 1992
NMM measurements.
FIGURE 6.39  Daily change in storage for the 35 cm and 2.4 m profiles
Figure 6.38 shows the soil water storage (referenced to arbi- from Figure 6.38.
trary zero) as measured for winter wheat by weighing lysimeter
and two TDR arrays. Each TDR array consisted of seven probes
inserted horizontally into the side of a pit and the pit backfilled
after wheat planting. Probe depths were 2, 4, 6, 10, 15, 20, and 14
30 cm, and the probes were read every half hour. Rains on days Lysimeter
12
101, 104, and 106 can be seen as increases in the storage amount. TDR
Changes in storage as measured by the two systems were nearly 10
identical in the 7 day period shown (Figure 6.39); and ET
ET (mm)

amounts were closely similar (Figure 6.40). 8

Water balance measurement intervals commonly range 6
between hours and weeks and are usually no smaller than the
required period of ET measurement. Measurement of each vari- 4
able in Equation 6.97 presents its own unique problems. These 2
include measurement errors in determination of lysimeter mass
or ΔS, and errors in P and R measurements. Problems of P and R 0
100 101 102 103 104 105 106 107
measurement are essentially identical for either weighing lysim-
Day of year, 1992
etry or soil profile water content methods because the surface
area of the control volume can be defined for both methods with FIGURE 6.40  Daily ET as calculated from the TDR and weighing
a water-tight border, often consisting of a sheet metal square lysimeter data shown in Figure 6.38 and assuming F = 0.
6-36 Properties and Processes

or rectangle pressed into or partially buried in the soil surface. other practices. Many farming efforts are aimed at increasing
When the soil volume is unbounded below the surface, as in the surface storage through practices like plowing to roughen the
soil profile water content method, there are additional errors soil surface or furrow diking to create infiltration basins and
due to uncontrolled horizontal flow components and deep per- decrease runoff, to name two. Soil conservation measures such
colation that are difficult to measure or estimate. Nevertheless, as terraces, contour bunds, etc., are aimed at decreasing runoff
the profile water balance technique is applicable in many situa- or runoff velocity, and thus increasing the opportunity time for
tions for which lysimetry is inappropriate or impossible and is, infiltration. On the other hand, water harvesting is a practice
in addition, much less expensive. In many cases, the horizon- of increasing runoff by reducing both surface storage and infil-
tal flow components may be assumed to sum to zero; and deep tration rate, with the aim of using the runoff water elsewhere.
percolation may be nil if the soil profile water content measure- Among the oldest artifacts of human cultivation are water
ments are made to sufficient depth (Wright, 1990). harvesting systems that included the removal of gravel from
When the NMM alone is used to measure soil water content, desert surfaces to improve runoff, terrace systems for guiding
the soil water balance method is suitable for periods of several and reducing runoff, and in some cases, the combined use of
days or more if closure (F ≈ 0) at the bottom of the measured both technologies to concentrate water on an area chosen for
soil profile can be obtained (Wright, 1990). The NMM has been cultivation (Shanan and Tadmor, 1979). To the extent that such
commonly used (Cuenca, 1988; Wright, 1990) but due to the practices influence infiltration, they will affect the timing,
small changes in water content associated with daily ET, this magnitude, and spatial patterns of such energy balance terms
water balance method has usually been restricted to determina- as sensible and latent heat fluxes, and the convective heat flux
tion of ET over several-day periods (Carrijo and Cuenca, 1992). accompanying infiltrating water.
Evett et al. (1993) showed that TDR measurements of soil water
content near the surface could be coupled with deeper water
6.3.2  Estimating Flux across the
content measurements by NMM to close the water balance con-
Lower Boundary
siderably more precisely than with the NMM alone, opening up
the prospect for daily ET measurements by this method. One of the great advantages of lysimeters is that they control
Although several alternatives to the NMM have been the soil water flux, F, into and out of the control volume. To
introduced, all depending on sensing a change in the soil’s date, a reliable soil water flux meter has not been developed,
electrical properties due to water content changes, none of so F must be estimated if it is not controlled. If water flux
these has proven useful for ET determinations due to interfer- across the lower boundary of the control volume is vertical,
ence from soil temperature, bulk electrical conductivity, and it may sometimes be estimated by measurements (preferably
bound water effects on the soil dielectric permittivity, which multiple) of soil water potential, h, at different depths sepa-
are particularly important in superactive clay soils but pres- rated by distance, Δz, and knowledge of the dependence of
ent in nearly all soils (Evett et al., 2008), the limited measure- hydraulic conductivity, K (m s−1), on soil water potential, the
ment depth of some of the available sensors (Mazahrih et al., K(h) curve. The potential difference, Δh, coupled with the
2008), and the problems with small-scale spatial variability unit hydraulic gradient for vertical flux, gives the hydraulic
and nonrepresentativeness of readings uncovered by Evett head difference, ΔH, driving soil water flux. Averaging the
et al. (2009b). The latter authors found that, in the field, the measurements allows estimation of the mean hydraulic con-
dielectric sensors used in access tubes were less precise than ductivity for the soil layer between the measurement depths
either the NMM or gravimetric sampling. Mazahrih et al. from the K(h) curve, and thus estimation of the soil water
(2008) pointed out several studies in which soil water uptake flux, Jw (m s−1), from a finite difference form of Darcy’s law
was substantial to depths >3 m for crops such as corn, cotton,
sugar beet, and winter wheat. A soil water sensing system for ⎛ ΔH ⎞
ET determination must be capable of determining the water J w = −K ⎜ . (6.99)
⎝ Δz ⎟⎠
content of the entire soil profile from the surface to well below
the zone of root water uptake if the control volume is to be
closed and ET estimates assured without errors due to deep F. Soil water potential may be measured by tensiometer or other
Surface storage has been ignored in the discussion of soil means described in Chapter 3 (or see van Genuchten et al., 1991).
water balance here, but it not only has a large influence on the Methods of measuring or estimating the K(h) curve may be
amount of water infiltrated from a precipitation or irrigation found in Chapter 4. For fluxes across boundaries too deep for the
event, but it is also one of two factors that are the most amenable installation of tensiometers, the soil water content may be mea-
to human control both on a small and large scale. The other is sured at two or more depths by the NMM (see Chapter 3) and
infiltration rate, a soil property that may be increased by soil the soil water potential inferred by inverting the θv(h) relation-
tillage over the short term, and decreased by tillage in the long ship, which may be estimated or measured (see Chapter 3 or van
term, and also may be influenced by no-tillage or minimum- Genuchten et al., 1991). Due to the hysteresis of the θv(h) rela-
tillage practices, by tree plantings and ground covers designed tionship, there is more room for error when basing Jw estimates
to protect the soil surface from slaking and crusting, and many on θv measurements. But, for many cases, the soil water potential
Water and Energy Balances in the Soil–Plant–Atmosphere Continuum 6-37

will be in the range where hysteresis is not a large source of error

(drier soils), and hydraulic conductivity is not large either. Thus,
both the value of Jw and the error in Jw may be small enough for
practical use in determinations of ET.

6.3.3  Precipitation and Runoff

An in-depth discussion of precipitation and runoff measurement
and modeling is beyond the scope of this chapter. A classic and
still valuable reference on field hydrologic measurements is the
Field Manual for Research in Agricultural Hydrology (Brakensiek
et al., 1979). A more up-to-date and extensive reference is the
ASCE Hydrology Handbook, 2nd edition (ASCE, 1996). Flow FIGURE 6.42  Wind shield installed around a heated, tipping bucket
measurement in channels is detailed in Flow Measuring and rain gauge.
Regulating Flumes (Bos et al., 1983). The monograph Hydrologic
Modeling of Small Watersheds (Hann et al., 1982) included use-
ful chapters on stochastic modeling, precipitation and snowmelt standard equipment on field weather stations. These are capa-
modeling, runoff modeling, etc., and listed some 75 hydrologic ble of providing precipitation data needed to solve the soil
models available at that time. For soil water balance measure- water balance for short intervals. Two problems are sometimes
ments, runoff is often controlled with plot borders or edging associated with tipping bucket type gauges. First, most of these
driven into the ground or included as the above-ground exten- devices count the tips using a Hall-effect sensor for detecting
sion of a lysimeter. Steel borders driven into the soil to a depth of the magnetic field of a magnet attached to the tipping bucket;
20 cm will suffice in many situations. Sixteen gauge-galvanized and the sensing system is sometimes susceptible to interfer-
steel in rolls 30 cm wide is useful for this and can be reinforced ence from sources of electromagnetic noise such as vehicle
by rolling over one edge. If runoff must be measured, this can ignition systems, generators, lightning strikes, etc. Second,
be done with flumes such as the H-flume and recording station tipping bucket gauges do not keep up with very large rainfall
shown in Figure 6.41. rates. In regions with predominantly small rainfall events, a
Precipitation varies so much from location to location that third error due to the water left in the tipping bucket at the
it is rarely useful to attempt estimating it. Measurement meth- end of precipitation may result in significant accumulative
ods include standard U.S. Weather Bureau rain gauges read errors in seasonal precipitation. At Bushland, Texas, we have
manually, various tipping bucket rain gauges, heated gauges to observed tipping bucket errors of 10%–15% for totals of rain-
capture snow fall (e.g., Qualimetrics model 6021, Sacramento, fall from high intensity convective thunderstorms compared
CA), snow depth stations, etc. A rain gauge should be located with amounts collected in standard rain gauges and sensed
as close to the surface as possible and be surrounded by a wind by weighing lysimeters. If accuracy is very important, then a
shield to avoid catch loss associated with wind flow over the tipping bucket gauge should be supplemented with a standard
gauge (Figure 6.42). A standard for the capture area or throat gauge that captures and stores all the rainfall. For solving the
of a rain gauge is that it should be 20 cm in diameter because soil water balance, experience shows that the rain gauge(s)
smaller throats lead to more variability in amount captured. should be placed directly adjacent to the location of ΔS mea-
Various designs of tipping bucket rain gauge have become surement. Separation of even 100 m can lead to large errors due
to the spatial variability of precipitation.
For studies and operations at scales larger than small field
size, there are now precipitation estimates from Doppler radar-
based systems that offer calibrated rainfall data on a 24 h basis
(Figure 6.43; see also Legates et al., 1996; Vieux and Farajalla,
1996). Although Figure 6.43 shows large grid sizes and only 16
levels of precipitation, grid sizes of 4 km on a side, with 256 lev-
els of rainfall, are available. Data for these maps are generated
by the WSR-88D radar system, usually known as the NEXRAD
weather radar system, in widespread use in the United States.
The Center for Computational Geosciences at the University
of Oklahoma has developed a radar-based precipitation inter-
face (RPI) for the radar data to generate the maps. Radar data
FIGURE 6.41  H-flume and recorder (in white box) for measuring are used from two or more stations and calibrated against rain
runoff rate from a graded bench terrace at Bushland, Texas. Note dike gauge measurements available from, for example, the Oklahoma
diverting flow from uphill flume. MESONET system of weather stations.
6-38 Properties and Processes

Allen, R.G., M. Tasumi, and R. Trezza. 2007a. Satellite-based

energy balance for mapping evapotranspiration with inter-
nalized calibration (METRIC)-model. J. Irrigat. Drain. Eng.
133:380–394.
Alsanabani, M.M. 1991. Soil water determination by time domain
reflectometry: Sampling domain and geometry. Ph.D.
Thesis. Department of Soil and Water Sciences, University
of Arizona, Tucson, AZ.
Anderson, C.M., W.P. Kustas, and J.M. Norman. 2007. Upscaling
flux observations from local to continental scales using
thermal remote sensing. Agron. J. 99:240–254.
Anlauf, R., K.Ch. Kersebaum, L.Y. Ping, A. Nuske-Schüler,
J. Richter, G. Springob, K.M. Syring, and J. Utermann. 1990.
FIGURE 6.43  Map of 24 h rainfall accumulation over Oklahoma.
Models for processes in the soil—Programs and exercises.
From NEXRAD radar data processed by the RPI. (Image downloaded Catena Verlag, Cremlingen, West Germany.
from http://ccgwww.ou.edu/rip_images and converted to gray scale. Annandale, J.G., and C.O. Stockle. 1994. Fluctuation of crop
With permission.) evapotranspiration coefficients with weather: A sensitivity
analysis. Irrigat. Sci. 15:1–7.
Acknowledgments ASAE. 1988. Modeling agricultural, forest, and rangeland hydrol-
ogy. Proceedings of the 1988 International Symposium,
Much of the data presented in this chapter was collected by the December 12–13, 1988, Chicago, IL. American Society of
ET Research Team at the USDA-ARS Conservation & Production Agricultural Engineering, St. Joseph, MI.
Research Laboratory at Bushland, Texas, of which the author is ASCE. 1996. Hydrology handbook. 2nd edn. American Society of
a member. Other past and present team members are (alphabeti- Civil Engineers, New York.
cally) Paul D. Colaizzi, Karen S. Copeland, Donald A. Dusek, ASCE. 2005. The ASCE standardized reference evapotranspi-
Prasanna H. Gowda, Terry A. Howell, Arland D. Schneider, Jean ration equation. American Society of Civil Engineers,
L. Steiner, Richard W. Todd, and Judy A. Tolk. Many techni- Reston, VA.
cians supported the data collection efforts, including Brice B. Asrar, G., and E.T. Kanemasu. 1983. Estimating thermal diffusiv-
Ruthardt and Jim L. Cresap among many others. Some of the ity near the soil surface using Laplace transform: Uniform
data shown here have not yet been published and may appear at initial conditions. Soil Sci. Soc. Am. J. 47:397–401.
a later date in a peer reviewed journal. “Everything can be taken Baker, J.M., and R.J. Lascano. 1989. The spatial sensitivity of time-
from a person except the freedom to choose one’s attitude in any domain reflectometry. Soil Sci. 147:378–384.
situation”—a favorite quote of Ruby O. Crosby. Baker, J.M., and E.J.A. Spaans. 1994. Measuring water exchange
between soil and atmosphere with TDR-microlysimetry.
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 7
Solute Transport
7.1 Introduction.............................................................................................................................. 7-1
7.2 Advection–Dispersion Equation............................................................................................ 7-1
Solute Spreading  •  Advection–Dispersion Equation  •  Adsorption  • 
Nonequilibrium Transport
7.3 Solutions of the Advection–Dispersion Equation............................................................. 7-11
Basic Concepts  •  Analytical Solutions  •  Numerical Solutions
Feike J. Leij 7.4 Stream Tube Models............................................................................................................... 7-20
California State University, Model Formulation  •  Application
Long Beach
7.5 Nonaqueous Phase Liquids................................................................................................... 7-23
Antonella Sciortino Dissolution Process  •  Numerical Modeling  •  Remediation  •  Inverse Modeling
California State University, to Locate Contaminant Sources
Long Beach References............................................................................................................................................ 7-28

7.1  Introduction equation (ADE) will be introduced in Section 7.2. This equa-
tion, also known as the convection–dispersion equation, is
Soil scientists and agricultural engineers have traditionally most often used to model solute transport in porous media.
been interested in the behavior and effectiveness of agricul- The movement of a solute that undergoes adsorption by the soil
tural chemicals (fertilizers and pesticides) applied to soils for requires modifications of the ADE, particularly if several solute
enhancing crop growth, as well as in the effect of salts and other species are present that may participate in a number of differ-
dissolved substances in the soil profile on plant growth. More ent reactions. Section 7.3 is devoted to analytical and numerical
recently, concern for the quality of the vadose zone and possible methods for quantifying solute concentrations as a function of
contamination of groundwater has provided a major impetus for time and space. The traditional advection–dispersion concept
studying solute transport in soils. is not always adequate to describe solute transport in field soils.
The movement and fate of solutes in the subsurface are Section 7.4 describes the stream tube model as an example of an
affected by a large number of physical, chemical, and micro- alternative transport model that may be better suited to model
biological processes requiring a broad array of mathematical transport in real-world situations. Finally, Section 7.5 deals
and physical sciences to study and describe solute transport. with the dissolution of nonaqueous phase contaminants into
A range of experimental and mathematical procedures may be the aqueous phase.
employed to quantify transport in soils. Transport of a dissolved
substance (solute) depends on the magnitude and direction of
the solvent (water) flux; considerable experimental and numeri- 7.2  Advection–Dispersion Equation
cal effort may be needed to determine the transient flow regime
in unsaturated soils. Furthermore, the determination of solute Consider the transport of a chemical species in a three-phase
concentrations is not always straightforward, particularly if the soil–air–water system, and assume that the chemical species
solute is involved in partitioning between different phases or (the solute) is completely miscible with water (the solvent). At
subject to transformations. Solute transport in porous media the macroscopic level and for one-dimensional flow, the mass
is studied in many scientific disciplines such as soil science, balance equation for a solute species subject to arbitrary reac-
civil and environmental engineering, geology, and chemistry. tions is given as
A vast body of literature exists on the subject, and this chapter
provides a somewhat subjective introductory treatment of the
solute transport in soils. First, the standard transport mecha- ∂(θC) ∂J
= − s + θRs , (7.1)
nisms pertaining to the fundamental advection–dispersion ∂t ∂x

7-1
7-2 Properties and Processes

where the result of diffusion as described by Fick’s first law. Diffusive

θ is the volumetric water content (L3 L−3) transport in the free or bulk solution is given by
C is the solute concentration expressed as solute mass-per-
∂C
solvent volume (M L−3) J dif = −Do , (7.3)
∂x
t is time (T)
x is position (L) where
Js is the solute flux expressed in solute mass-per-cross- Jdif is the one-dimensional mass flux (M L2 T−1)
sectional area of soil-per-unit time (M L−2 T−1) Do is the coefficient of molecular diffusion for a free or bulk
Rs denotes arbitrary solute sinks (<0) or sources (>0) due to solution (L2 T−1)
zero- or higher-order rate processes in the aqueous phase
or transfer to another phase (M L−3 T−1) Many publications exist that provide data on Do (Kemper, 1986;
Lide, 1995).
For a conservative or nonreactive solute, Rs equals 0. Similar The experimentally observed proportionality between Jdif and
equations may be derived for multidimensional flow and trans- the concentration gradient can be described at the molecular or
port. The solute flux is composed of an advective and a dispersive ionic level with a balance of forces. The driving force for particle
component according to movement from higher to lower concentrations is the gradient
in the chemical potential. For mixtures with ideal behavior, the
J s = JwC + J D , (7.2) chemical potential can be expressed in terms of its mole fraction.
For solutions with nonideal mixing behavior, the activity coef-
where ficient of the solute needs to be determined. Ionic activity coeffi-
Jw is the volumetric water flux (L T−1), that is, the Darcian cients can be estimated with the extended Debye–Hückel equation
velocity expressed as volume of water-per-cross-sectional or the Davies extension for solutions up to 0.5 M. Activity coef-
area of soil-per-unit time ficients for a greater concentration range up to 16 M can be esti-
JD is a solute flux to quantify transport caused by a gradient in mated with the Pitzer virial equations (Pitzer, 1979; Harvie and
the solute concentration (M L−2 T−1), also per unit area of soil Weare, 1980). Codiffusion or counterdiffusion occurs in systems
with multiple ion species. Diffusion rates for individual species as
7.2.1  Solute Spreading predicted solely by Fick’s model would violate the electroneutrality
principle. The ionic diffusion flux consists then of a term for ordi-
The movement of a solute with flowing water, described by the nary Fickian diffusion and a term accounting for electric transfer-
solute flux (JwC), is referred to as advection or convection. Because ence of ions. The corresponding diffusion coefficient is related to the
dissolved substances move in a passive fashion, advective trans- ionic mobility using the Nernst–Planck equation (Helfferich, 1962).
port can be readily quantified when the solvent flux (Jw) is known. To characterize diffusion in soils, the coefficient for diffusion
The water flux is generally a function of time and position. of a substance in a free solution is typically adjusted with terms
However, for transport in laboratory soil columns, it is often con- accounting for a reduced solution phase (a smaller cross-­sectional
stant while simplifications may also be possible for field studies. area available for diffusion) and an increased path length. A gen-
Even if the macroscopic water flux is known or can be mea- eral treatment of diffusion in soils can be found in Olsen and
sured, the velocity at smaller pore scales is not easily determined. Kemper (1968) and Nye (1979). The macroscopic diffusive flux
Variations in the microscopic velocity will lead to unequal solute per unit area of soil can be written as
movement in the direction of flow. This movement is quantified
∂C
by means of the dispersive solute flux. If, during steady water J dif = −θDdif , (7.4)
flow, the solute concentration of the solution at the inlet of a ∂x
water-saturated soil column is changed abruptly at time t = 0,
with Ddif as the coefficient of molecular or ionic diffusion for the
the observed breakthrough of a solute at the column outlet at
liquid phase of the soil. Diffusion coefficients for the soil liquid
times t > 0 will not exhibit an equivalent abrupt change (Nielsen
and a free liquid are related by (Epstein, 1989)
and Biggar, 1961). The solute concentration will change more
gradually with time as a result of (hydrodynamic) dispersion,

which quantifies the effects of both mechanical dispersion and Do D
Ddif = ≡ o ≡ Do τ o , (7.5)
diffusion. Molecular diffusion and mechanical dispersion will (Ldif /L)2 τ 2

be discussed first for “free” solutions and then for soil solutions.
where
7.2.1.1  Diffusion Ldif  and L are the actual and the shortest path lengths for dif-
Molecular or ionic diffusion is an important mechanism for fusion (L)
solute transport in soils in directions where there is little or no τ = Ldif /L is known as the tortuosity
water flow. A net transfer of molecules of a solute species usu- τ2 is the tortuosity factor, while τa = (L/Ldif)2 is often desig-
ally occurs from regions with higher to lower concentrations as nated as an apparent tortuosity factor
Solute Transport 7-3

The tortuosity Ldif/L is squared in Equation 7.5 because the con- and the approximate boundary conditions
centration gradient along the streamline diminishes and the
travel distance increases in the soil solution compared with dif- C(−∞, t ) = Co , C(∞, t ) = Ci . (7.9)

fusion along a straight path with length L in a free solution (Olsen
and Kemper, 1968). It should be noted that the terms tortuosity The solution for this problem is given by (Crank, 1975)
and tortuosity factor have not been used consistently in the lit-
erature. Furthermore, some authors include the water content ⎛ x ⎞
in their definition of tortuosity (Dykhuizen and Casey, 1989) or C(x , t ) = Ci + 0.5(Co − Ci )erfc ⎜ ⎟, (7.10)
⎜⎝ 4Ddif t ⎟⎠
solute adsorption (retardation) in the expression for either τ or
Ddif (Nye, 1979; Robin et al., 1987).
For unsaturated conditions, it is convenient to quantify  the where erfc is the complementary error function (Gautschi, 1964).
dependency of the diffusion coefficient on water content. Assuming
that the tortuosity affects diffusion in the liquid phase in the same 7.2.1.2  Dispersion
way as in the gaseous phase, the tortuosity term previously derived Local variations in water flow in a porous medium will lead to
for gaseous diffusion in soils by Millington (1959) and Millington mechanical dispersion. Several mechanisms that are commonly
and Quirk (1961) can be adapted to describe aqueous diffusion used to contribute to mechanical dispersion are illustrated with
in variably saturated soils. The following expressions then result: hypothetical tracer particles in Figure 7.1. Dispersion may occur
because of (a) the development of a velocity profile within an
θ10 /3 individual pore such that the highest velocity occurs in the cen-
Ddif = Do , (7.6a)
ε2 ter of the pore and presumably little or no flow at the pore walls;
(b) different mean flow velocities in pores of different sizes;
θ2
Ddif = Do , (7.6b) (c) the mean water flow direction in the porous medium being
ε2/3 different from the actual streamlines within individual pores,

which differ in shape, size, and orientation; and (d) solute par-
where ε is the soil porosity (L3 L−3). An equivalent of the first ticles converging to or diverging from the same pore. All these
expression, using a volumetric air content instead of θ, has been processes contribute to solute spreading, in which initially steep
used frequently to describe gaseous diffusion in soils although concentration fronts become smoother during movement along
Jin and Jury (1996) reported that the lesser known second ver- the main flow direction.
sion provided a better description. Taylor (1953) analyzes dispersion of a solute injected in a cylin-
Diffusion coefficients in soil systems are usually determined drical tube with laminar flow; this study is often used to elucidate
by mathematically analyzing solute concentration profiles in the dispersion in porous media. For laminar flow in a cylindrical tube
soil as a function of time or position. Results and procedures for filled with water, the parabolic velocity profile is
diffusion in soils have been summarized by Flury and Gimmi
(2002). van Rees et al. (1991) measured diffusivities by allowing ⎛ r2 ⎞
diffusion from a spiked solution or soil sample into a solute-free q(r ) = qo ⎜ 1 − 2 ⎟ , (7.11)
⎝ ro ⎠
medium. Typically, two blocks of soil with different concentra-
tions are brought together at time t = 0 (Kemper, 1986; Oscarson
et al., 1992). After sufficient time has elapsed for solute diffusion where
to occur from the block with the higher to the lower concen- qo is the maximum velocity at the center of the tube (L T−1)
tration, the joined soil blocks are sectioned. The solute con- r is the radial distance from the axis (L)
centration of each section is determined, for example, by using ro is the tube radius (L)
extraction, centrifugation, and chemical analysis of the superna-
tant liquid. This approach yields a concentration profile versus The mean velocity over a cross section of the tube equals qo/2.
distance from which the diffusion coefficient may be estimated If a solute is injected in the tube, the velocity profile tends to
using an appropriate analytical solution of the governing solute stretch its concentration profile while diffusion will mitigate
diffusion equation. Consider the diffusion equation, the large (transverse) concentration gradients caused by the
velocity distribution. Taylor skillfully analyzed the governing
∂C ∂ 2C two-­dimensional transport problem. He obtained the following
= Ddif , (7.7)
∂t ∂x 2 dispersion coefficient assuming proportionality between the lon-
gitudinal solute flux and the concentration gradient (i.e., Fick’s
subject to the initial condition, law is applicable):

⎪⎧Co −∞ < x < 0 ro2 vo2

C(x , 0) = ⎨ , (7.8) Ddis = . (7.12)
⎩⎪ Ci 0<x<∞
192Do
7-4 Properties and Processes

(a) (b) (c) (d)

FIGURE 7.1  Schematic concepts contributing to mechanical dispersion.

Note that Ddis (L2 T−1) is inversely proportional to the coefficient of rate increases. Hydrodynamic dispersion is often simply referred
molecular diffusion Do after sufficient time has elapsed for equi- to as dispersion, as will be done in the remainder of this chapter.
librium to be established. The results by Taylor were later derived The effects of dispersion can be illustrated with a hypotheti-
for more general conditions by Aris (1956) using moment cal laboratory experiment in which water and a dissolved tracer
analysis. are applied to an initially tracer-free, uniformly packed soil col-
The Taylor–Aris model has been widely applied to describe dis- umn of length L = 1 m (Figure 7.2a). The column is subjected to
persion in porous media. It was adapted early on in soil physics by steady-state water flow with uniform water content. The average
Nielsen and Biggar (1962). Research to further elucidate dispersion pore water or interstitial velocity v = 0.5 m day−1. Note that v is
phenomena in porous media has continued along the lines of the the actual travel-time velocity, which is given per unit area of
original theory (e.g., Gupta and Bhattacharya, 1983). At the early fluid. It is determined by the ratio of the Darcian water flux den-
stage, dispersion in soils cannot be described as a Fickian process, sity (Jw) and the volumetric water content (θ), where Jw is defined
and other models may need to be employed (Jury and Roth, 1990). per unit area of (bulk) soil. There is a step change in solute con-
The one-dimensional solute flux due to mechanical dispersion centration at the inlet (Figure 7.2b), and the solute front becomes
in a uniform isotropic soil may be approximated using Fick’s law: smoother because of solute spreading during passage of the soil
column (Figure 7.2c). A smooth effluent curve can be monitored
∂C at the column exit as shown in Figure 7.2d. In the absence of dif-
J dis = −θDdis , (7.13)
∂x fusion and dispersion (D = 0), the front of a perfectly inert tracer
will travel as a square wave through the column (a process often
where Jdis is the dispersive solute flux (M L−2 T−1). Because of the called piston flow) to reach the bottom of the column at time
similarity between Equations 7.4 and 7.13, solute spreading dur- t = L/v. For piston flow, a conservative tracer reaches the column
ing transport in soils is typically described with a single coef- exit exactly after one pore volume of tracer solution has been
ficient of hydrodynamic dispersion, that is, D = Ddis + Ddif . As injected (or collected at the column exit). Pore volume is defined
is often noted, this is done for convenience in spite of the con- as the volume of water stored in that column.
ceptual differences between the diffusion and dispersion mecha- The degree of spreading is usually related to the solute travel
nisms (Scheidegger, 1974). The practice is consistent with results time, although some constraints do exist on the amount of
from laboratory and field experiments, which do not permit a spreading. Dispersion, as sketched in Figure 7.1a, is limited
distinction between mechanical dispersion and molecular diffu- because of transverse molecular diffusion, which causes solutes
sion. The hydrodynamic dispersive flux (JD) (Equation 7.2) con- to move from the center of a tube to areas near the pore walls,
sists of contributions from molecular diffusion (Equation 7.4) or vice versa, in response to local concentration gradients. Such
and mechanical dispersion (Equation 7.13): transverse diffusion counteracts spreading caused by variations
in the longitudinal flow velocity. Dispersion is also limited since
capillaries in a porous medium generally are not independent
J D = J dif + J dis . (7.14)
cylindrical tubes, but branch and join or rejoin each other at dis-
tances characteristic of the pore or particle size distribution of
Since diffusion is independent of flow, the contribution of diffu- the medium. This branching and rejoining promote lateral mix-
sion to hydrodynamic dispersion diminishes if the soil water flow ing of solutes from different pores as sketched in Figure 7.1d.
Solute Transport 7-5

1 For a one-dimensional system, Equation 7.15 reduces to Ddis =

αL|v|. Mechanical dispersion, as sketched in an idealized fashion
in Figure 7.1a, can be reversed by changing the flow direction to

C/Co
0.5
make a smooth front steep again. In soils, however, dispersion
is not reversible since mixing erases antecedent concentration
0 distributions, as illustrated in Figure 7.1d. Absolute values are,
Influent
0 therefore, used for v in Equation 7.15. In case of uniform water
(b) Time (days) flow parallel to the x-axis of a Cartesian coordinate system, only
the following three main components of Equation 7.15 need to
be considered:
C/Co
0 0.5 1
0.0 Dxx = α Lv, D yy = αT v , Dzz = αT v , (7.16)

t = 0.2 days
0.25
0.6 where
Depth (m)

Dxx is the coefficient of longitudinal (mechanical) dispersion

0.50 1.0
Dyy and Dzz are the coefficients of transverse dispersion
1.4
0.75 Dispersion coefficients may be determined by fitting a mathe-
matical solution to observed concentration (Toride et al., 1995).
1.00 Additional procedures to determine dispersion coefficients are
(c) given by Fried and Combarnous (1971) and van Genuchten
and Wierenga (1986). Values of the longitudinal dispersivity
(a)
(αL) for laboratory experiments typically vary between 0.1 and
10 cm with 6–20 times smaller values for αT (Klotz et al., 1980).
Effluent Dispersivities for field soils are generally much higher. Gelhar
1
v = 0.5 m day–1 et al. (1992) reviewed published field-scale dispersivities deter-
mined in aquifer materials that are typically one or two orders
C/Co

0.5 D = 0.005 m2
day–1 of magnitudes larger, even more so for relatively large experi-
D=0 mental scales.
0
1 2 3 4
(d) Time (days) 7.2.2  Advection–Dispersion Equation
FIGURE 7.2  Hypothetical laboratory tracer experiment: (a) column of The expressions for the advective and dispersive solute fluxes
soil, (b) influent curve, (c) concentration distributions inside the column, can be substituted in mass balance Equation 7.1. The one-dimen-
and (d) breakthrough curves with and without dispersion. (Modified after sional ADE for solute transport in a homogeneous soil becomes
van Genuchten, M.Th. 1988. Solute transport, p. 360–362. In S.P. Parker
(ed.) McGraw-Hill yearbook of science and technology. McGraw-Hill
∂(θC) ∂ ⎛ ∂C ⎞
Book Co., New York.) = − ⎜ J wC − θD + θRs . (7.17)
∂t ∂x ⎝ ∂x ⎟⎠

Three-dimensional dispersion is quantified with a dispersion In the case where the water content is invariant with time and
tensor. The components of the symmetric dispersion tensor for space, the ADE may be simplified to (v = Jw/θ),
an isotropic soil are given as (Bear and Verruijt, 1987)
∂C ∂2C ∂C
= D 2 −v + Rs . (7.18)
 (α L + αT )viv j ∂t ∂x ∂x
Dij = δ ij αT | v | +  , (7.15)
|v | This is a parabolic differential equation similar to the diffusion
equation. To complete the mathematical formulation of the trans-
where port, several concentration types and mathematical conditions will

| v | denotes the magnitude of the pore water velocity with vi be reviewed in Section 7.3.1.
as the ith component (L T−1) A variety of solute source or sink terms may be substituted
δij is the Kronecker delta (δij = 1, if i = j and δij = 0, if i ≠ j) for Rs. The most common source/sink term is due to ­adsorption/
αL and αT are, respectively, the longitudinal and transverse desorption and ion exchange stemming from chemical and
dispersivity (L) physical interactions between the solute and the soil solid phase.
7-6 Properties and Processes

Many  other processes such as radioactive decay, aerobic A single-valued isotherm for equilibrium adsorption Γ(C) is
and anaerobic transformations, volatilization, photolysis, used to define h(C, S) according to
­precipitation/dissolution, reduction/oxidation, and complexation
may also affect the solute concentration. A further refinement of h(C, S) = Γ(C) − S. (7.21)

the transport model is necessary in the case of nonuniform inter-
actions between the solute and the soil, or if there is adsorption For equilibrium adsorption k → ∞, and hence h(C, S) → 0, which
on moving particles and colloids. In the following, only interac- implies that S = Γ(X). For a linear adsorption isotherm, the rela-
tions at the solid–liquid interface will be considered. tion between Γ and C can simply be given as

Γ = K d C, (7.22)
7.2.3  Adsorption
Dissolved substances in the liquid phase can interact with sev- where Kd is a partition coefficient, often referred to as the distri-
eral soil constituents such as primary minerals, oxides, and bution coefficient, expressed in volume of solvent per mass of soil
inorganic or organic colloids. Dissolved ions in the soil solu- (L3 M−1). For S = Γ, substitution of Equation 7.22 into Equation
tion counterbalance the surface charge of soil particles caused 7.19 leads to the following ADE commonly used to describe
by isomorphous substitution of one element for another in the transport of a solute that undergoes linear equilibrium exchange:
crystal lattice of clay minerals, by the presence of hydronium
∂C ∂2C ∂C
or hydroxyl ions at the solid surface, or other mechanisms. The R = D 2 −v , (7.23)
∂t ∂x ∂x
net surface charge of an assemblage of soil particles produces an
electric field that affects the distribution of cations and anions in which the retardation factor R is given by
within water films surrounding the soil particles.
Adsorption of solute (adsorbate) by the soil (adsorbent) is an ρb
R =1+ Kd , (7.24)
important phenomenon affecting the fate and movement of sol- θ
utes. The ADE for one-dimensional transport of an adsorbed
with ρb as soil bulk density. The advective and dispersive fluxes
solute may be written as
are reduced by a factor R as a result of adsorption. The movement
of the solute is said to be retarded with respect to the average sol-
∂C ρb ∂S ∂2C ∂C
+ = D 2 −v , (7.19) vent movement. If there is no interaction between the solute and
∂t θ ∂t ∂x ∂x
the soil (Kd = 0), the value for R is equal to unity. The value for R
where S is the adsorbed concentration, defined as mass of solute may be calculated from Kd as obtained from chemical analyses
per mass of dry soil (M M−1). The above equation can be expressed of the solution and adsorbed phases. Frequently, R is obtained by
in terms of one dependent variable by assuming a suitable rela- optimizing a mathematical solution to observed concentrations.
tionship between the adsorbed and liquid concentrations. This For step application of a solute to a soil column (cf. Figure 7.2),
is typically done with a simple adsorption isotherm to quantify the net solute flux into the column should be equal to the change
the adsorbed concentration as a function of the liquid concen- in the amount of solute in the soil column. The following mass
tration at a constant temperature. In addition to temperature, balance can hence be formulated to estimate R:
the adsorption isotherm is generally also affected by the solution
L
composition, total concentration, the pH of the bulk solution, and
sometimes the method used for measuring the isotherm. A math- ∫
v ⎡⎣ g (t ) − Ce ⎤⎦ = R ⎡⎣C(x , t ) − f (x )⎤⎦ dx , (7.25)
ematically pertinent distinction is often made between linear and 0
nonlinear adsorption. Although most adsorption isotherms are
nonlinear, the adsorption process may often be assumed linear for where
low solute concentrations or narrow concentration ranges. Ce is the effluent concentration
f(x) and g(t) are the initial and influent concentrations,
7.2.3.1  Linear Adsorption respectively
Consider the general case of nonequilibrium adsorption, where
a change in C is accompanied by a delayed change in S. The The effects of linear adsorption on solute transport in a homo-
adsorption rate can be described assuming first-order kinetics: geneous soil profile are shown in Figure 7.3. Analytically pre-
dicted solution and adsorbed concentrations are plotted 4 days
∂S after the start of a 1-day application of influent with a unit solute
= kh(C, S), (7.20)
∂t concentration (units may be selected arbitrarily, e.g., g m−3) to an
initially solute-free soil profile subject to steady saturated water
where flow. Other parameters for this example are Jw = 10 cm day−1,
k is a rate parameter (T−1) θ = 0.40 cm3 cm−3, and D = 62.5 cm2 day−1. The pore water velocity
h is a function to quantify how far the adsorption or desorption (v = Jw/θ) is hence 25 cm day−1 and αL = 2.5 cm. Solute distributions
process is removed from equilibrium are plotted for three values of the retardation factor, R (Figure 7.3).
Solute Transport 7-7

0 0

20 R=4 20

R=4
40 40
R=2
Soil depth (z) (cm)
60 60 R=2

80 80
R=1
100 100
R=1

120 120

140 140

160 160
0.1 0.2 0.3 0.4 0.5 0.6 0.05 0.10 0.15 0.20 0.25 0.30
(a) Solution concentration (C ) (b) Adsorbed concentration (S)

FIGURE 7.3  Effect of adsorption, as accounted for by the retardation factor R, on (a) solution (C) and (b) adsorbed (S) concentration distributions
in a homogeneous soil profile.

When R is increased from 1.0 to 2.0, the apparent solute veloc- Instead of using R < 1, anion transport may be modeled with R = 1,
ity (v/R) is reduced by one-half (Figure 7.3a), causing a shallower which restricts the accessible liquid volume (Krupp et al., 1972).
penetration of the solute pulse into the profile. At the same time, Anions are also adsorbed by the soil through surface complex-
the area under the curve in Figure 7.3a is also reduced by one-half. ation and adsorption onto positively charged areas of the solid
When R = 4, the apparent solute velocity and the area under the matrix. If the effect of adsorption exceeds exclusion, the anion
curve are again reduced by half. The distribution for the adsorbed will be retarded. The retardation factor should be viewed as an
concentration S, which may be expressed as mg kg−1 soil, increases effective parameter since it quantifies a variety of adsorption
from 0 (no adsorption) when R = 1 to a maximum when R = 4 are and exclusion processes to which the solute (anion) is subjected.
similar (Figure 7.3b). Assuming a soil bulk density (ρb) of 1.25 g Breakthrough curves typical for the transport of an excluded
cm−3 and the same water content as before (θ = 0.40 cm3 cm−3), anion (Cl−), a nonreactive solute (tritiated water, 3H2O), and an
one may calculate, using Equation 7.24, that the distribution coef- adsorbed cation (Ca 2+) are presented in Figure 7.4. The first two
ficient Kd = 0, 0.32, and 0.96 cm3 g−1 for R = 1, 2, and 4, respectively. tracers pertain to transport through 30 cm columns contain-
Anion exclusion occurs when negatively charged surfaces ing disturbed Glendale clay loam soil (P.J. Wierenga, personal
of clays and ionizable organic matter are present; anions are
repelled from such surfaces and accumulate in the center of
1.0
pores. Because water flow velocities are 0 at pore walls and
maximum in the center of pores (Figure 7.1a), the average anion 3
H2O
Cl– Ca2+
movement will be faster than the average water movement. Many 0.8
Relative concentration (C/Co)

displacement experiments also suggest faster anion than water

movement simply because the apparent displacement volume is
smaller for anions than water. The quantity (1 − R) is the relative 0.6
anion exclusion volume. The exclusion volume-per-unit mass of
soil can also be estimated as
0.4

⎛ c ⎞

Vex = ⎜ 1 − ⎟ dV
⎝ Co ⎠ ∫ (7.26)
0.2

where 0.0
0.0 2.0 4.0 6.0 8.0 10.0
Vex is the exclusion volume (L3 M−1)
Pore volumes (T )
c is the local concentration of the anion (M L−3)
Co its bulk concentration (M L−3) FIGURE 7.4  Observed and fitted ADE breakthrough curves for three
V is the entire volume encompassing the liquid phase per unit tracers typifying the transport of anions (Cl−), a (nearly) nonreactive
mass of soil solute (3H2O), and an adsorbing solute (Ca 2+).
7-8 Properties and Processes

communication; van Genuchten and Cleary, 1982), while the 0.7

Ca 2+ data are for transport through a 30 cm long column con-
taining a Troup loam and a Savannah fine loam (Leij and Dane, k = 0.64
0.6
1989). Optimizing the solutions of the ADE to the three break-
through curves yielded R values of 0.681, 1.027, and 4.120 for Cl−,

Adsorbed concentration (S ) (mg kg–1)

3H O, and Ca 2+. Hence, the Cl− curve was strongly affected by
2 0.5
anion exclusion, while 3H2O transport was subject to very minor
adsorption/exchange.
0.4

7.2.3.2  Nonlinear Adsorption

0.5
n=
In many cases, adsorption, and hence, the retardation factor, 0.3

1.0
cannot be described using a simple Kd approach. For nonlinear

n=

1.5
equilibrium adsorption, R is given as

n=
0.2

ρb ∂Γ
R(C) = 1 + . (7.27)
θ ∂C 0.1

Two common nonlinear adsorption isotherms are the Langmuir

0
and Freundlich equations: 0 0.2 0.4 0.6 0.8 1.0
Solution concentration (C ) (g m–3)
k1C FIGURE 7.5  Freundlich equilibrium plots for k3 = 0.64 and three val-
Γ= (Langmuir), (7.28)
1 + k2C ues of the exponent n.

0 0
Γ = k3C n (Freundlich), (7.29)

20 20
where k1, k2, k3, and n are empirical constants. Many other equa-
40 40
tions for adsorption exist, including some that account for dif-
Soil depth (z) (cm)

ferences between adsorption and desorption isotherms (van 60 60

Genuchten and Sudicky, 1999).
The Freundlich isotherm will be used in the following to illus- 80 80
trate the effects of nonlinear equilibrium adsorption on solute
100 100
transport. In order to keep the calculations simple, the value of
k3 in Equation 7.29 is taken to be 0.64. Three different values of 120 k = 0.64 120
the exponent n are used, viz., 0.5, 1.0, and 1.5, to demonstrate n = 0.5 t = 8 days
n = 1.0 140 to = 4 days
favorable, linear, and unfavorable adsorption isotherms (Figure 140
n = 1.5
7.5). Calculated distributions of the solution (C) and adsorbed
160 160
(S) concentrations versus soil depth (z) 8 days after application of 0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8
a 4-day long solute pulse to the soil surface are shown in Figure Solution concentration Adsorbed concentration
7.6. The same pore water velocity is used as for the example illus- (a) (C) (μg cm–3) (b) (S) (mg kg–1)
trated in Figure 7.4 but with a smaller dispersion coefficient of FIGURE 7.6  Effect of nonlinear adsorption on (a) solution (C) and (b)
D = 25 cm2 day−1 (αL = 1 cm). Notice that, as in Figure 7.4, the adsorbed (S) concentrations in a deep homogeneous soil profile during
solution concentration distribution for n = 1 (linear adsorption) steady-state flow. The distributions were obtained for the three isotherms
has a nearly symmetrical shape versus depth. The other two n shown in Figure 7.5.
values yield nonsymmetric profiles.
If n = 0.5, a very sharp concentration front develops, while cannot move faster than lower concentrations; front sharpening
the curve near the soil surface becomes more dispersed. The sharp will lead to a steep solute front. This front never becomes a step
front can be explained by considering the retardation factor (R) function because the large concentration gradient across the
for nonlinear adsorption (Equation 7.27), which for n =  0.5, front will create a large diffusion/dispersion flux. If n << 1, the
ρb  = 1.25 g cm−3, θ = 0.40, and k3 = 0.64 leads to R = 1  +  1/C. front may be determined from the average slope of the isotherm
This shows that R increases rapidly when C decreases with the between the initial and the maximum aqueous concentration.
extreme R  →  ∞, if C =  0. Consequently, the apparent solute In this example, those concentrations are zero and approximately
velocity va = v/R is very small at the lower liquid concentrations 1 g m−3. The average slope of the isotherm is therefore exactly
but increases at higher values. Of course, higher concentrations the same as the linear distribution coefficient (dΓ/dC  =  0.64).
Solute Transport 7-9

Substituting this value into Equation 7.27 yields R = 3. Hence, of solutes by various domains of the solid phase may lead to
the apparent solute velocity (va) equals 25/3 or 8.33 cm day−1, chemical nonequilibrium transport. This may also be described
and the solute front after 8 days is located at a depth of about with a two-domain model; sorption occurs instantaneous in
67 cm (Figure 7.6). Transport of favorably adsorbed solutes is the equilibrium domain and is a rate-limited process for the
frequently modeled with traveling wave solutions (van der Zee, remainder of the sorption sites of the solid phase. It is not always
1990; Simon et al., 1997). possible to differentiate between physical and chemical nonequi-
A reverse scenario occurs if n > 1 (unfavorable exchange). librium since many sorption sites are only accessible after diffu-
Adsorption at the lower concentrations is now relatively small sion through the immobile region of the liquid phase.
and, as displayed in Figure 7.6, the toe of the front moves through In the following, nonequilibrium transport will be described
the profile at a velocity nearly equal to that of an inert solute. with a two-domain model with a separate liquid or sorbed con-
Adsorption at the higher concentrations, on the other hand, is centration for each domain, that is, the two-region model for
much more extensive, resulting in a lower apparent solute veloc- physical and the two-site model for chemical nonequilibrium.
ity in the higher range of concentrations. As a result, the concen- The equilibrium ADE (Equation 7.19) can be readily modified
tration front becomes increasingly dispersed over time. Ignoring for this purpose. The same dimensionless mathematical formu-
dispersion, the velocity of the solute front (va = v/R) at any given lation can be used for physical and chemical nonequilibrium
value of C is given by models. If necessary, the ADE can be modified to incorporate
additional nonequilibrium processes and continua.
v (7.30)
va = ,
1+ 3 C 7.2.4.1  Physical Nonequilibrium
Consider one-dimensional solute movement in an isotropic soil
while the depth of the solute front can be approximated by with uniform flow and transport properties during steady flow
and assume that the solute is subject to linear retardation, that
z(C, t ) = z(C, 0) + vat , (7.31) is, equilibrium sorption can be described with a linear exchange
isotherm. The physical nonequilibrium approach is based on a
partitioning of the liquid phase into a mobile or flowing region
where z(C, 0) is the location of a solute concentration with value
and an immobile or stagnant region. Solute movement in the
C at t = 0.
mobile region occurs by both advection and dispersion, whereas
Cation exchange processes during solute transport will
solute exchange between the two regions occurs by first-order
involve at least two species. The simplest case arises when two
diffusion (Coats and Smith, 1964). Following van Genuchten
cations of the same valency and total concentration such as
and Wierenga (1976), the governing equations for the two region
Ca 2+ and Mg2+ are considered. The resulting exchange process
model are as follows:
is then approximately linear for relatively small changes in the
composition of the soil solution, that is, a change in aqueous
concentration will involve a commensurate change in adsorbed ∂ Cm ∂2Cm ∂C
(θm + f ρb K d ) = θm Dm − θmvm m − α(Cm − Cim ),
concentration. Exchange between Na+ and Ca 2+, on the other ∂t ∂x 2 ∂x
hand, is considerably more nonlinear. Equations that quan- (7.32)
tify the exchange reaction have been proposed by Gapon, Kerr,
Vanselow, Eriksson, and others. Typically, the soil solution will ∂Cim
contain many different species, and their interactions with the ⎡⎣θm + (1 − f )ρb K d ⎤⎦ = α(Cm − Cim ), (7.33)
∂t
solid soil phase will have to be simulated numerically.

where
7.2.4  Nonequilibrium Transport f represents the fraction of sorption sites in equilibrium with
Solute breakthrough curves for aggregated soils will exhibit the fluid of the mobile region
asymmetrical distributions or nonsigmoidal concentration fronts. α is first-order mass transfer coefficient (T−1)
The difference in water flow in the inter- and intra-aggregate subscripts m and im, respectively, refer to the mobile and
regions leads to nonequilibrium conditions for solute trans- immobile liquid regions (with θ = θm + θim), while ρb and
port due to (transversal) gradients in the solute concentration Kd are the soil bulk density and distribution coefficient for
between the regions. Depending upon the exact pore structure linear sorption
of the medium, asymmetry is sometimes enhanced by desatura-
tion when the relative fraction of water residing in the marginally Transport Equation 7.32 follows directly from addition of
continuous immobile region increases. Physical nonequilibrium a source/sink term (Rs) to Equation 7.19.
transport due to different flow regimes is often modeled by par- Anion exclusion can be viewed as a particular example of
titioning the liquid phase into two flow domains with diffusive physical nonequilibrium, the exclusion volume roughly corre-
solute transfer between them. Similarly, differences in sorption sponds to the immobile region (Krupp et al., 1972). The physical
7-10 Properties and Processes

nonequilibrium concept may, therefore, be adapted to describe ∂S2

transport of excluded anions (van Genuchten, 1981) instead of = α [(1 − f )K dC − S2 ], (7.39)
∂t
using a retardation factor of less than 1.

7.2.4.2  Chemical Nonequilibrium where the subscript for α has been dropped. This two-site
Sorption of solute, especially for organic chemicals, has often chemical nonequilibrium model reduces to a one-site kinetic
been described with a combined equilibrium and kinetic sorption nonequilibrium model by setting f = 0. The two-site chemical
expression so as to better simulate transport in soils with a wide nonequilibrium model was applied successfully to describe sol-
variety of soil constituents (clay minerals, organic matter, and ute breakthrough curves by Selim et al. (1976), van Genuchten
oxides). The lack of an instantaneous equilibrium for the sorption (1981), and Nkedi-Kizza et al. (1983), among others.
process is sometimes referred to as chemical nonequilibrium. This
terminology is somewhat misleading since the rate of adsorption 7.2.4.3  General Nonequilibrium Formulation
or exchange is usually determined mostly by physical phenom- The two-site and the two-region nonequilibrium models can
ena such as diffusion through the liquid film around soil particles be cast in the same (dimensionless) model according to Nkedi-
and inside the aggregates (Boyd et al., 1947; Sparks, 1989). Kizza et al. (1984):
The simplest and by far most popular approach distinguishes
between type 1 sites, with instantaneous adsorption, and type 2
sites, where adsorption obeys a kinetic rate law (Selim et al., 1976). ∂C1 1 ∂2C1 ∂C1
βR = − + ω (C2 − C1 ), (7.40)
In the case of first-order kinetics, the general adsorption rates can ∂T P ∂X 2 ∂X
be given with a model similar to Equations 7.20 and 7.21 as
∂ C2 (7.41)
∂S1 (1 − β)R = ω(C 1 − C2 ),
= α1 [ Γ1 (C) − S1 ], (7.34) ∂T
∂t
∂S2 where
= α2 [ Γ2 (C) − S2 ], (7.35)
∂t β is a partition coefficient
R is a retardation factor
C1 and C2 are dimensionless equilibrium and nonequilibrium
where
concentrations
α is again a rate constant (T−1)
T is time
S is the actual adsorbed concentration (M M−1)
X is distance
Γ is the final adsorbed concentration at equilibrium as pre-
P is the column Peclet number
scribed by the adsorption isotherm
ω is a mass transfer coefficient
subscripts 1 and 2 refer to the type of adsorption site Γ1 +
subscripts 1 and 2 refer to the equilibrium and nonequilib-
Γ2 = Γ
rium phases, respectively
Because type 1 sites are always at equilibrium, S1 = Γ1 and Equation
7.34 can further be ignored. The transport equation becomes
The common dimensionless parameters are defined using an
arbitrary characteristic concentration (Co) and length (L):
∂C ρb ∂Γ α 2ρb ∂2C ∂C
+ + (Γ 2 − S2 ) = D 2 − v . (7.36)
∂t θ ∂t θ ∂x ∂x
vt x vL ρK (7.42)
T= , X= , P= , R = 1+ b d .
If the fraction of exchange sites that is at equilibrium (type 1) L L D θ
equals f and if equilibrium adsorption is governed by the same
linear isotherm for both types 1 and 2 (Γ1 = Γ2) then For the physical nonequilibrium model, the remaining dimen-
sionless parameters are
Γ1 + Γ2 = fK d C + (1 − f )K d C. (7.37)

θm + f ρb K d αL C C
β= , ω= , C1 = m , C2 = im , (7.43)
Of course, nonlinear equilibrium isotherms may also be used θ + ρb K d θv Co Co

in nonequilibrium transport models. The complete transport
problem can now be written as whereas for the chemical nonequilibrium model:

⎛ ρb fK d ⎞ ∂C ∂2C ∂C αρb θm + f ρb K d α(1 − β)RL C S2

⎜⎝ 1 + θ ⎟⎠ ∂t = D ∂x 2 − v ∂x − θ ⎡⎣(1 − f )K dC − S2 ⎤⎦ , β= , ω= , C1 = , C2 = .
θ + ρb K d v Co (1 − f )K dCo

(7.38) (7.44)
Solute Transport 7-11

In the chemical engineering literature, αL/v is known as the Conversely, the resident concentration may also be determined
Damköhler number; it quantifies the rate of the reaction or from the flux-averaged concentration. For solute application
exchange relative to advective transport. to an initially solute-free medium, the transformation is (van
Genuchten et al., 1984)
7.3  Solutions of the Advection– ∞

Dispersion Equation v ⎛ vx ⎞ ⎛ vξ ⎞
D ⎝ D⎠ ⎝ D⎠ ∫
CR (x , t ) = exp ⎜ ⎟ exp ⎜ − ⎟ CF (ξ, t )dξ. (7.48)

The research and management of solute behavior in soils almost x

invariably require that the temporal and spatial solute distribu-
The difference between CR and CF is usually small, except when
tion be known. Solute distributions as a function of time and/or
the second term on the right-hand side of Equation 7.46 is
space can be estimated with a variety of analytical and numeri-
relatively large. It should be noted that a distinction between
cal solutions of the ADE, some of which will be briefly reviewed
flux and resident type can be made for both the application
in the following.
and the detection of solutes (Kreft and Zuber, 1978, 1986).
Resident concentrations are used for solute detection with,
7.3.1  Basic Concepts for example, time domain reflectometry, and to specify most
initial conditions. Flux-averaged concentrations, on the other
A complete mathematical formulation of the transport problem
hand, are used for effluent samples, and to specify the influent
requires that the pertinent-dependent variable or concentra-
concentration in most boundary value problems. Unless stated
tion type is used and that the proper auxiliary conditions are
otherwise, it is assumed that solute concentrations are of the
specified.
resident type.
7.3.1.1  Concentration Types Averaged concentrations can also be defined in terms of the
observation scale, the latter exceeding the macroscopic scale
Concentration is conventionally defined as the amount of solute-
associated with using the ADE. A time-averaged concentration
per-unit volume of the liquid. Since microscopic concentrations
(Ct) is obtained by averaging over a time interval (Δt) about a
are based on a relatively small scale, a concentration at a larger
discrete time (to) (Fischer et al., 1979):
scale needs to be introduced to allow use of the ADE, which is
based on larger macroscopic variables and parameters. For this to + Δt / 2
purpose, a macroscopic resident or volume-averaged concentra- 1
tion (CR) is defined as
Ct (x , t o ) =
Δt ∫
to − Δt / 2
C(x , t )dt , (7.49)

1

CR =
ΔV ∫∫∫ c dV , (7.45) where C is a continuous solution of the solute concentration, which
can be obtained by solving the ADE. This type of concentration
where occurs if solute breakthrough curves are measured using, for
c is the variable local-scale (microscopic) concentration (M L−3) example, fraction collectors or gamma-ray attenuation. Similarly,
ΔV is some representative elementary volume (Bear and a one-dimensional spatial average can be defined as
Verruijt, 1987)
xo + Δx / 2
1
A different concentration type may be encountered at soil bound-
C x (xo , t ) =
Δx ∫
xo − Δx / 2
C(x , t )dx. (7.50)
aries where the concentration is implicitly determined or defined
as the ratio of the solute flux (Js) and water flux (Jw) densities,
This concentration may be used to describe experimental results
J obtained for samples with centroid (xo) and length (Δx). This situa-
CF = s , (7.46)
Jw tion occurs, for example, when the measured concentration of a large
core sample is to be modeled as a point value (Leij and Toride, 1995).
with CF as the flux-averaged concentration. This concentration
represents the mass of solute-per-unit volume of fluid passing 7.3.1.2  Boundary and Initial Conditions
through a soil cross section during an elementary time inter- Initial and boundary conditions need to be specified in order to
val (Kreft and Zuber, 1978). For a one-dimensional solute flux obtain a meaningful solution of the ADE. For a finite or semi-
consisting of an advective and a dispersive component, the flux- infinite soil, the initial condition can be formulated as
averaged concentration can be derived from the resident con-
centration according to the transformation: C(x ,0) = f (x ) x ≥ 0, (7.51)

D ∂C R where f(x) is an arbitrary function. Initial concentrations are
CF = CR − . (7.47)
v ∂x almost invariably of the resident type.
7-12 Properties and Processes

The selection of the most appropriate boundary conditions The formulation of the boundary and inlet conditions should
for a transport problem is a somewhat esoteric topic that has account for the injection and detection modes in order to arrive
received considerable attention in the literature. This is partly at a mathematically consistent formulation of the problem with
due to a lack of detailed experimental information for evaluating the same concentration type as independent variable (Parker
and applying boundary conditions, and inherent shortcomings and van Genuchten, 1984; Leij and Toride, 1995). Normally,
of the transport equation itself at boundaries. Many transport observed or predicted resident (volume-averaged) concentra-
problems involve the application to the soil of a solute, whose tions require the use of a third-type inlet condition (also in
influent concentration may be described by a function g(t). The terms of the resident concentration) whereas a first-type inlet
application method may be pumping, ponding, or sprinkling. condition is used in conjunction with flux-type concentrations.
Two different types of inlet conditions are used, which assume
either continuity in solute concentration or solute flux density.
Simultaneous use of both conditions is seldom possible. It is gen- 7.3.2  A nalytical Solutions
erally more desirable to ensure mass conservation in the whole
Analytical solutions can formally be obtained only for linear
system than a continuous concentration at the inlet. The solute
transport problems. It would appear that analytical solutions
fluxes at the inlet boundary are, therefore, equated to obtain the
are not very useful for transport in field soils where there is
following third or flux-type inlet condition:
(1)  spatial and temporal variability of flow and transport
parameters, (2) transient flow, especially for unsaturated soils,
⎛ ∂C ⎞ and (3) nonuniformity in the boundary and initial condi-
⎜⎝ vC − D ∂x ⎟⎠ = vg (t ) t ≥ 0, (7.52)
x = 0+ tions. However, analytical solutions can still be quite valuable.
A nonlinear transport problem may be linearized through a
where 0+ indicates a position just inside the soil. It is assumed that suitable transformation to obtain a problem for which an ana-
there is no dispersion outside the soil. The alternative condition lytical solution is available. Also, analytical solutions provide
requires the concentration to be continuous across the interface quick estimates of solute behavior over large temporal and
at all times. At smaller scales, such continuity will likely exist. spatial scales while they may offer insight into the underlying
However, at the scale of the ADE, it appears difficult to maintain transport processes. Moreover, there is usually a lack of input
a constant concentration at the interface, particularly during the parameters for field problems, which diminishes the advan-
initial stages of solute displacement for low influent fluxes and tage of numerical over analytical model results. Analytical
high dispersive fluxes in the soil. Mathematically, the first or solutions are also routinely used to evaluate the performance
concentration-type condition is expressed as of numerical schemes. Finally, the mathematical and physical
conditions tend to be well defined for laboratory settings and
C(0, t ) = g (t ) t ≥ 0. (7.53) an analytical solution can often be used, especially to estimate
transport parameters by fitting analytical solutions to experi-
mental data (Parker and van Genuchten, 1984; van Genuchten
The outlet condition can be defined as a zero gradient at a finite and Parker, 1987).
or infinite distance from the inlet. The infinite outlet condition,

∂C 7.3.2.1  Variable Transformation

(∞, t ) = 0 t ≥ 0, (7.54)
∂x One straightforward way to obtain an analytical solution is to
transform the ADE to an equation for which a solution already
is more convenient for mathematical solutions than the finite exists. As an example, consider transport in an infinite system
condition, given by

∂C − ∂C ∂2C ∂C (7.56)
(L , t ) = 0 t ≥ 0. (7.55) R = D 2 −v ,
∂x ∂t ∂x ∂x

The use of Equation 7.54 implies that there is a semi-infinite fic- ⎧⎪Co x<0
C(x ,0) = ⎨ . (7.57)
titious soil layer beyond x = L, with identical properties as the ⎪⎩ 0 x>0

actual soil. Such a layer does not affect the movement of the sol-
ute in the actual soil upstream of the exit boundary. Since the
The new coordinates
transport at the outlet cannot be precisely described, the intuitive
contradiction of an infinite mathematical condition to describe
ξ = x − vt , (7.58a)
a finite physical system is often more acceptable than using
Equation 7.55, which precludes dispersion inside the soil near
the outlet. τ = t, (7.58b)
Solute Transport 7-13

transform the ADE into a heat or solute diffusion problem given by subject to

∂C ∂ 2C D d C Co
R =D 2 , (7.59) C−δ = , (7.66)
∂τ ∂ξ v dx s

⎪⎧Co ξ < 0 (7.60)

C(ξ,0) = ⎨ . dC
⎩⎪ 0 ξ < 0 (∞, s) = 0, (7.67)
dx

The solution for this and many other cases can be readily found
in the literature on diffusion problems (Carslaw and Jaeger, where the bar denotes a transformed variable. The following
1959; Crank, 1975): solution for the concentration in the Laplace domain is obtained
with the help of the inlet condition:
Co ⎛ Rx − vt ⎞
(7.61)
C( x , t ) = erfc ⎜ . 1/ 2
2 ⎝ 4DRt ⎟⎠ v Co v ⎡⎛ v ⎞
2
sR ⎤
C( x , s) = exp(λ − s), λ − = − ⎢⎜ ⎟ + ⎥ .
v − δλ D s
−
2D ⎢ ⎝ 2D ⎠
⎣
D⎥
⎦
Warrick (2003) reviews the use of a transformation similar to
Equation 7.58a for solute transport in a three-dimensional (7.68)
porous medium of infinite extent. Other transformations to the
diffusion problem have been employed as well (Brenner, 1962; Inversion of this solution may be done with a table of Laplace
Selim and Mansell, 1976; Zwillinger, 1989). Transformation of transforms, by applying the inversion theorem or by using
time to a time-integrated flow variable sometimes also allows a numerical inversion program. The solution in the Laplace
one to derive an analytical solution of the nonlinear ADE for domain is also convenient to obtain transformations between
transient flow (Wierenga, 1977; Parker and van Genuchten, resident and flux-averaged concentrations such as given by
1984; Huang and van Genuchten, 1995). Equation 7.48. Finally, it should be noted that the solution for
a finite outlet condition is also possible with the Laplace trans-
7.3.2.2  Laplace Transformation form, although a bit more cumbersome (Brenner, 1962; Leij and
The ADE is commonly solved directly with the method of van Genuchten, 1995).
Laplace transforms. The solution procedure will be illustrated
here for an initially solute-free semi-infinite soil with a constant 7.3.2.3  Equilibrium Transport
solute flux (vCo) or concentration (Co) at the inlet boundary. The van Genuchten and Alves (1982) provided a compendium of
mathematical problem consists of solving the ADE given by available analytical one-dimensional solutions for a variety of
Equation 7.56 subject to mathematical conditions and physical processes. Four com-
mon analytical solutions for a zero initial condition involving a
D ∂C ⎧⎪0 first type first- or third-type inlet condition and an infinite or finite outlet
C−δ = vCo δ = ⎨ , (7.62)
v ∂x ⎪⎩1 third type condition are listed in Table 7.1. The solutions may be expressed

in terms of the dimensionless variables P, T, and X (Equation
7.42). Typically, L is equal to the position of the outlet (the col-
∂C
(∞, t ) = 0, (7.63) umn length) for a finite system, whereas for a semi-infinite soil
∂x system an arbitrary length may be used.
Figure 7.7 contains solute profiles C/Co(X) according to the
with δ as a coefficient depending on the type of inlet condition.
solutions listed in Table 7.1 using R = 1, P = 5 or 20, and T = 0.25
The Laplace transform of the solute concentration with respect
or 1. Curves are for a first- (A1) or a third-type (A2) inlet con-
to time is defined as (Spiegel, 1965)
dition assuming an infinite outlet condition, or a first- (A3) or
∞
third-type (A4) inlet condition in case of finite outlet condition.
The predicted profile for a first-type condition (A1, A3) for the
∫
C(x , s) = L ⎡⎣C(x , t )⎤⎦ = C(x , t )exp(− st )dt , (7.64)
lower Peclet number (P = 5) lies considerably above the line pre-
0
dicted for a third-type condition (A2, A4). The effect of the outlet
condition is initially minor, but when the solute front reaches the
where s is the (complex) transformation variable (T−1). This outlet (L), a clear difference between a finite and an infinite outlet
transformation changes the transport equation from a partial to condition can be observed for both a first- (A1, A3) and a third-
an ordinary differential equation: type (A2, A4) inlet condition. The simpler solution for a semi-
infinite system can, in many cases, be used to approximate the
d 2 C v dC sR solution for a finite condition; van Genuchten and Alves (1982)
− − C = 0, (7.65)
dx 2 D dx D formulated the empirical restriction X < 0.9 − 8/P on the position
7-14 Properties and Processes

TABLE 7.1  Analytical Solutions of the ADE for Different Boundary Conditions
Outlet
Case Inlet Condition Condition Analytical Solution C(x, t)/Co

∂C 1 ⎛ Rx − vt ⎞ 1 ⎛ vx ⎞ ⎛ Rx + vt ⎞
A1 C(0, t) = Co (∞, t ) = 0 erfc ⎜ + exp ⎜ ⎟ erfc ⎜
∂x 2 ⎝ 4 DRt ⎟⎠ 2 ⎝ D⎠ ⎝ 4 DRt ⎟⎠

⎛ ∂C ⎞ ∂C 1 ⎛ Rx − vt ⎞ v 2t ⎛ (Rx − vt )2 ⎞ 1 ⎛ vx v 2t ⎞ ⎛ vx ⎞ ⎛ Rx + vt ⎞
A2 ⎜⎝ vC − D ∂x ⎟⎠ = v Co (∞, t ) = 0 erfc ⎜ + exp ⎜ − ⎟ − 2 ⎜ 1 + D + DR ⎟ exp ⎜⎝ D ⎟⎠ erfc ⎜⎝ ⎟
x = 0+
∂x 2 ⎝ 4 DRt ⎟⎠ πDR ⎝ 4 DRt ⎠ ⎝ ⎠ 4 DRt ⎠

⎛β x⎞ ⎛ vx v 2t β2 Dt ⎞
∞ 2βn sin ⎜ n ⎟ exp ⎜ − − n 2 ⎟
∂C ⎝ L ⎠ ⎝ D 4 DR RL ⎠ vL
A3 C(0, t) = Co
∂x
(L, t ) = 0 1− ∑ ⎛ vL ⎞ vL
2
βn cot (βn ) +
2D
=0
n=1
βn2 + ⎜ +
⎝ DR ⎟⎠ 2D

2vL ⎡ ⎛ β x ⎞ vL ⎛ β x⎞⎤ ⎛ vx v 2t β2 Dt ⎞
∞ βn ⎢βn cos ⎜ n ⎟ + sin ⎜ n ⎟ ⎥ exp ⎜ − − n 2 ⎟
⎛ ∂C ⎞ ∂C D ⎣ ⎝ L ⎠ 2 D ⎝ L ⎠ ⎦ ⎝ D 4 D R RL ⎠ β2 D vL
A4
⎝⎜
vC − D
∂x ⎠⎟ x = 0+
= v Co
∂x
(L, t ) = 0 1− ∑
n=1
⎡ ⎛ vL ⎞
2
vL ⎤ ⎡ 2 ⎛ vL ⎞ ⎤
2
βn cot (βn ) − n +
vL 2D
=0
⎢βn2 + ⎜ + ⎥ ⎢βn + ⎜ ⎥
⎢⎣ ⎝ DR ⎟⎠ 2D ⎥ ⎢ ⎝ 2D ⎟⎠ ⎥
⎦⎣ ⎦

1.0 1.0
A1 T = 1.0
T = 1.0 A3
0.8 0.8
A3
A1
Concentration (C)

Concentration (C)

A2
0.6 T = 0.25 0.6
A2
A4
A4
0.4 0.4 T = 0.25
A1, A3
A1, A3
0.2 0.2 A2, A4
P=5 A2, A4 P = 20

0 0.2 0.4 0.5 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
Reduced distance (x) Reduced distance (x)

FIGURE 7.7  Plot of the concentration (C/Co) as a function of distance (X) calculated for four different combinations of boundary conditions
according to the solutions in Table 7.1 at two different times for a Peclet number of 5 and 20. (After van Genuchten, M.Th., and W.J. Alves. 1982.
Analytical solutions of the one-dimensional convective–dispersive solute transport equation. USDA Tech. Bull. 1661. USDA, Washington, DC, 1982.)

for which such an approximation is reasonable. For smaller times The greatest difference occurs for small Peclet numbers, namely,
when the solute has not reached the outlet, the finite and infinite when hydrodynamic dispersion is relatively important. The
outlet conditions obviously lead to a similar solution. nature of hydrodynamic dispersion suggests that C/Co should be
For a third-type inlet condition, the concentration at X = 0 just approximately 0.5 for X = T = R = 1, the average of the zero ini-
inside the soil is not equal to the influent concentration, even at tial concentration and the influent concentration (Co). Because
time T = 1. Although the jump in concentration is physically of the effect of the boundary conditions, this only happens when
odd, mass conservation is ensured. For the higher Peclet number the Peclet number exceeds 10 or more, depending on the type of
(P = 20), deviations between a first- and a third-type inlet condi- solution. For the first-type inlet condition (A1, A3), C/Co exceeds
tion are considerably reduced. 0.5 at low Peclet numbers since a considerable amount of solute
Large differences in the predicted concentration may occur if the is forced to diffuse into the column to establish a constant inlet
solute front approaches the outlet at X = 1 or x = L. Calculated con- concentration.
centrations according to solutions A1, A2, A3, and A4 versus the Finally, for displacement experiments involving finite col-
Peclet number at the outlet for T = 1 are illustrated in Figure 7.8. umns, it may be of interest to quantify the amount of solute
Solute Transport 7-15

1.0 ∂C1
(∞,T ) = 0. (7.72)
T = 1.0 ∂X
0.9 R = 1.0
A3 Solutions for the equilibrium and nonequilibrium concentra-
0.8 tions are
A1
Concentration (C)

0.7 T

0.6 A4 ∫
C1 = J (a, b)G( X , τ)d τ, (7.73)
0

0.5 T

0.4
∫
C2 = ⎡⎣1 − J (b, a)⎤⎦ G( X , τ)d τ, (7.74)
0

A2
0.3
where the auxiliary (equilibrium) function G(X, τ) for resident
0.2 concentrations is defined as
0.1 1 10 100 1000
Peclet number (P)
P ⎛ (βRX − τ)2 ⎞ P ⎛ βRX + τ ⎞
FIGURE 7.8  Solute concentration predicted with solutions A1, A2, G( X , τ) = exp ⎜ − − erfc ⎜ − ⎟,
πβRτ ⎟
A3, and A4 as a function of the Peclet number at T = 1 and X = 1. (After ⎝ 4βRτ / P ⎠ 2βR ⎜⎝ 4βRτ /P ⎟⎠
van Genuchten, M.Th., and W.J. Alves. 1982. Analytical solutions of
the one-dimensional convective–dispersive solute transport equation. (7.75)
USDA Tech. Bull. 1661. USDA, Washington, DC, 1982.)
and for flux-averaged concentrations by
that can be stored in the liquid and sorbed phases of the soil
(Equation 7.24). When, beginning at t = 0, a solution with con- βRPX 2 ⎛ (βRX − τ)2 ⎞
G( X , τ) = exp ⎜ − 4 βRτ/P ⎟ . (7.76)
centration (Co) is applied to a soil column, holdup can be defined 4πτ 3 ⎝ ⎠

as (Nauman and Buffham, 1983)

∞ Furthermore, J denotes Goldstein’s J function (Goldstein, 1953),

v ⎡ C (L, t ) ⎤ which is given by
H=
∫
L ⎢⎣
1−
Co ⎥⎦
dt . (7.69)
0
a

The holdup is determined by the area above the breakthrough ∫

J (a, b) = 1 − exp(−b) exp(− x )I 0 (2 ab )dξ , (7.77)
curves, that is, by integrating the “complementary” solute con- 0

centration versus dimensionless time. van Genuchten and
Parker (1984) showed that H = R for solutions A1 and A4, H = with I0 as the zero-order modified Bessel function. The variables
R[1 + (1/P)] for solution A2, and H = R{1 − (1/P) [1 − exp(−P)]} a and b are given by
for solution A3. In case of anion exclusion, the relative exclusion
volume equals 1 − R and the column holdup will be less than 1. ωτ
a= , (7.78a)
7.3.2.4  Nonequilibrium Transport βR

Analytical solutions for two-domain nonequilibrium trans- ω (T − τ)

port have been presented by, among others, Lindstrom and b= . (7.78b)
(1 − β)R
Narasimhan (1973), Lindstrom and Stone (1974), Lassey (1988),
and Toride et al. (1993). The boundary value problem involving
solute application with a constant concentration may be specified The above solution for a flux-averaged concentration was used
by Equations 7.40 and 7.41 subject to the following conditions: to describe breakthrough data for the pesticide 2,4,5-trichloro-
phenoxyacetic acid (2,4,5-T) as observed from a 30 cm long col-
C 1( X ,0) = C2 ( X ,0) = 0, (7.70) umn containing a Glendale clay loam with soil aggregates with

a diameter of up to 6 mm (van Genuchten and Parker, 1987). The
⎛ 1 ∂C1 ⎞ two-region model (TRM) three adjustable parameters (P, R, ω)
⎜⎝ C1 − p ∂X ⎟⎠ = 1, (7.71) provided an excellent description of the data (Figure 7.9b).
X = 0+ The retardation factor (R) was estimated independently, using
7-16 Properties and Processes

1.0 1.0
2, 4, 5-T 2, 4, 5-T

Relative concentration (C1)

Relative concentration (C1)

0.8 <6 mm 0.8 <6 mm

0.6 Observed 0.6 Observed

Fitted TRM
Fitted CDE
0.4 0.4

0.2 0.2

0 0
0 1.0 2.0 3.0 4.0 5.0 6.0 0 1.0 2.0 3.0 4.0 5.0 6.0
(a) Pore volume (T ) (b) Pore volume (T )

FIGURE 7.9  Observed and fitted effluent curves for 2,4,5-T movement through Glendale clay loam. The fitted curves were based on (a) the equi-
librium ADE or CDE and (b) the nonequilibrium ADE or TRM.

the distribution coefficient obtained from batch experiments, third moment quantifies the asymmetry or skewness of the
according to Equation 7.23. Using the ADE fit with P (Figure breakthrough curve. Normalized moments (μp) are obtained as
7.9a), or P and R (not shown), as adjustable parameters resulted follows:
in a poor description of the data.
mp
As pointed out by van Genuchten and Dalton (1986), the main μp = . (7.80)
disadvantage of the first-order physical nonequilibrium approach m0
is the obscure dependency of the transfer coefficient (α or ω) on
the actual diffusion process in the aggregate, particularly the The mean breakthrough time is given by μ1. Central moments
value for the diffusion coefficient and the aggregate geometry. are defined with respect to this mean according to
The diffusion process may be modeled for well-defined struc- ∞
tured or aggregated porous media to allow a better description of 1
the concentration distribution inside the aggregate. Analytical
μ ʹp (L) =
m0 ∫
(t − μ1 ) p C(L, t )dt . (7.81)

solutions are available for several aggregate geometries. The 0

simplified immobile concentration, which is used in the general
The variance of a breakthrough curve, which can be used to
nonequilibrium formulation, can always be obtained by averag-
assess solute dispersion, is given by the second central moment
ing the more detailed solution over the aggregate volume.
μʹ2. The degree of asymmetry of the breakthrough curve is indi-
7.3.2.5  T ime Moments cated by its skewness μ ʹ3 /(μ ʹ2 )3/2.
The previous definitions are employed to obtain numerical
Moments are frequently used to characterize statistical distribu- values for moments from experimental results. Substitution of
tions such as those of solute particles (concentrations) versus time an analytical solution for the solute concentration into the defi-
or position. Analytical expressions for lower order moments are nitions allows the derivation of algebraic expressions for time
sometimes derived for deterministic transport models, espe- moments. Values for transport parameters can be obtained by
cially when a direct analytical solution may be difficult to obtain. equating numerical and algebraic moments (Jacobsen et al.,
Moment analysis is more widely employed in stochastic than deter- 1992; Leij and Dane, 1992). This procedure is not reliable if
ministic transport models since the uncertainty in both model experimental moments of higher order (p > 2) are needed since
parameters and predicted results is most conveniently quantified even small deviations, at larger times, between experimental and
with moments. Only time moments will be considered here. modeled concentrations will greatly bias such moments.
The pth (time) moment of the breakthrough curve, as Algebraic moments are normally obtained using the solu-
obtained, say, from effluent samples collected from a soil col- tion for the concentration in the Laplace domain. The following
umn (with length x = L) to which a solute pulse is applied during equality can be established from properties of the Laplace trans-
steady water flow, is defined as form (cf. Aris, 1958; van der Laan, 1958):
∞

d p C( x , s)
∫
mp (L) = t p C(L , t )dt ( p = 0,1,2,. . .). (7.79)
mp (x ) = (−1) p lim
s →0 ds p
, (7.82)
o

The zero moment is proportional to the total solute mass, the where, as before,
─
first moment quantifies the mean displacement, the second C (x, s) is the concentration in the Laplace domain
moment is indicative of the variance (dispersion), whereas the s is the (complex) transformation variable
Solute Transport 7-17

Expressions for moments can hence be obtained by differentiat- TABLE 7.2  Mean Breakthrough Time (μ1) and Variance (μ 2ʹ )
ing the solution in the Laplace domain and evaluating the result for the Equilibrium and Nonequilibrium Solution of the ADE
for s = 0. This task is conveniently handled by mathematical at a Distance x from the Inlet as a Result of a Dirac Delta
software. Input Described with a First-Type Inlet Condition
Time moments will now be considered for three different Mean
transport problems. First, the mathematical problem for physi- Breakthrough
cal nonequilibrium transport can be written as ADE Model Time, μ1 Variance, μ 2ʹ
2
Rx 2DR x
Equilibrium
∂C ∂C ∂2Cm ∂C v v3
θm R m + θim R im = θm Dm − θv m , (7.83)
∂t ∂t ∂x 2 ∂x Nonequilibrium

∂Cim Two-region Rx 2θm Dm R2 x 2θ(1 − β)2 R 2 x

θim R = α(Cm − Cim ). (7.84) v θv 3
+
αv
∂t
Rx 2DR 2 x 2(1 − β)Rx
Two-site +
v v3 αv
The conditions for instantaneous solute application to a soil are

C(x, 0) = 0 0 ≤ x < ∞, (7.85) 7.3.3  Numerical Solutions

The solution of many practical transport problems requires the
m use of numerical methods because of changes in water satura-
C (0, t ) = 0 δ(t ), (7.86)
v tion (as the result of irrigation, evaporation, and drainage),
spatial and temporal variability of soil properties, or compli-
∂C
(∞, t ) = 0, (7.87) cated boundary and initial conditions. Numerical methods are
∂X
based on a discretization of the spatial and temporal solution
domain and subsequent calculation of the concentration at dis-
where crete nodes in the domain. This approach is in contrast with
m0 is the solute mass that is applied per unit area of soil solu- analytical methods, which offer a continuous description of the
tion at t = 0 concentration. In some cases, a combination of analytical and
δ(t) is the Dirac delta function (T−1) numerical techniques may be employed (Sudicky, 1989; Moridis
and Reddell, 1991; Li et al., 1992).
The first-type inlet condition is used to describe flux-averaged con- The accuracy of the numerical results depends on the input
centrations such as effluent samples from column displacement parameters, the approximation of the governing partial differ-
experiments. Second, the equilibrium problem is defined by the ential equation, the discretization, and implementation of the
same set of equations by setting θm = θ, θim = 0, and α → 0. Third, numerical solution in a computer code solving the simulated
the chemical nonequilibrium transport equations are as follows: problem. Numerous texts exist on the numerical modeling of
flow and transport in porous media (Pinder and Gray, 1977;
∂C ρb ∂S ∂2C ∂C Huyakorn and Pinder, 1983; Campbell, 1985; van der Heijde
+ = D 2 −v , (7.88) et al., 1985; Istok, 1989).
∂t θ ∂t ∂x ∂x
The many numerical methods for solving the ADE can be
classified into three groups (Neuman, 1984): (1) Eulerian, (2)
∂S Lagrangian, and (3) mixed Lagrangian–Eulerian. In the Eulerian
= α(K dC − S). (7.89)
∂t approach, the transport equation is discretized by the method
of finite differences or finite elements using a fixed mesh. For
These equations are also subject to boundary and initial conditions the Lagrangian approach, the mesh deforms along with the flow
in Equations 7.85 through 7.87. while it is stable in a moving coordinate system. A two-step pro-
Formulas for the mean breakthrough time (μ1) and the cedure is followed for a mixed approach. First, advective trans-
variance (μ2) of the breakthrough curve predicted for these port is solved using a Lagrangian approach and concentrations
three models are presented in Table 7.2 for a first-type inlet are obtained from particle trajectories. Subsequently, all other
condition, which should be employed if effluent samples are processes including sinks and sources are modeled with an
analyzed (i.e., flux-averaged concentrations). The expressions Eulerian approach using finite elements, finite differences, etc.
suggest that nonequilibrium conditions do not affect the mean The method of finite differences (Bresler and Hanks, 1969;
travel time but they do increase solute spreading. Since only Bresler, 1973) and the Galerkin method of finite elements (Gray
the solution in the Laplace domain is needed, moment analysis and Pinder, 1976; van Genuchten, 1978) belong to the first group
is particularly useful for more complex transport problems to as do the previously mentioned combination of analytical and
study the general behavior of the breakthrough curve. numerical techniques. The finite difference and finite element
7-18 Properties and Processes

methods were the first numerical methods used for solute trans- Consider the simulation of the one-dimensional ADE for steady
port problems and, in spite of their problems discussed below, flow of a conservative tracer as given by Equation 7.56 with R = 1.
are still the most often utilized methods. Numerical experi- Temporal and spatial derivatives are approximated with Taylor
ments have shown that both methods give very good results series expansions. Assume that the concentrations are known at
if significant dispersion exists as quantified with the Peclet the current time (t = jΔt) and that the objective is to calculate
number. If advection is dominant, however, numerical oscilla- the concentration distribution {C[iΔx, (j + 1)t]} at the next time.
tions may occur for both methods and small spatial increments A forward-in-time finite difference scheme where the unknown
should be used. It may not always be possible to decrease the concentration is given explicitly in terms of known concentra-
spatial step size due to the associated increase in computations, tions is written as
and a variety of approaches have been developed to overcome
the oscillations (Chaudhari, 1971; van Genuchten and Gray, Ci , j +1 − Ci , j Ci +1, j − 2Ci , j + Ci −1, j Ci +1, j − Ci −1, j
1978; Donea, 1991). ≈D 2
−v . (7.91)
Δt (Δx ) 2(Δx )
Lagrangian solution methods will result in very few numeri-
cal oscillations (Varoglu and Finn, 1982). However, Lagrangian
methods, which are based on the method of characteristics, suf- On the other hand, a backward-in-time or implicit scheme is
fer from inherent diffusion and do not conserve mass. They are given by
difficult to implement for 2D and three-dimensional problems.
Instabilities resulting from inadequate spatial discretization Ci , j +1 − Ci , j Ci +1, j +1 − 2Ci , j +1 + Ci −1, j +1 Ci +1, j +1 − Ci −1, j +1
may occur during longer simulations due to deformation of the ≈D 2
−v ,
Δ t ( Δx ) 2(Δx )
stream function, especially if the solute is subject to sorption,
(7.92)
precipitation, and other reactions.
The mixed approach has been applied by several authors
which contains several concentrations at the next time level.
(Konikov and Bredehoeft, 1978; Yeh, 1990). In view of the different
The problem is solved implicitly after combining the difference
behaviors of the diffusive (parabolic) and advective (hyperbolic)
schemes of all nodes, and subsequently using a matrix equation
terms of the ADE, the problem is decomposed into an advec-
solver. Finally, a weighted scheme can be defined as
tion and a diffusion problem. Advective transport is solved with
the Lagrangian approach while all other terms are solved
with the Eulerian approach. The trajectories of flowing particles Ci , j +1 − Ci , j
are obtained using continuous forward particle tracking (to fol- Δt
low a set of particles as they move through the flow domain), sin- w(Ci +1, j +1 − 2Ci , j +1 + Ci −1, j +1 ) + (1 − w)(Ci +1, j − 2Ci , j + Ci −1, j )
gle-step reverse particle tracking (the initial position of particles ≈D
(Δx )2
arriving at nodal points was calculated for each time step), and a
combination of both approaches. Ahlstrom et al. (1977), among w(Ci +1, j +1 − Ci −1, j +1 ) + (1 − w)(Ci +1, j − Ci −1, j )
−v , (7.93)
others, used the random walk model to describe the movement 2(Δx )
of individual solute particles by viewing the travel distance for a
particular time step as the sum of a deterministic and a stochas- with w being a weighting constant between 0 and 1. The scheme is
tic velocity component. said to be fully explicit for w = 0 and fully implicit for w = 1, while
In the following, only a brief introduction to the finite dif- a Crank–Nicolson central-in-time scheme is derived if w = 0.5.
ference and finite element methods to solve transport problems For transient flow, the scheme becomes more complicated; the
is provided. Both methods encompass a wide variety of more velocity (v) and water content (θ) are usually obtained by solv-
specific numerical approaches. As a rule of thumb, the finite ing the Richards equation prior to solving the transport problem.
difference method is attractive because of its simplicity and the Errors associated with the discretization and the solution pro-
availability, at least early on, of handbooks and computer pro- cedure can be evaluated by comparison with analytical results,
grams simulating flow and transport in porous media. On the provided that the problem can be sufficiently idealized (linear-
other hand, the finite element method has proven to be more ized) to permit the use of such solutions. This is true for other
suitable for problems involving irregular geometries of the flow numerical solutions as well. For a convergent scheme, the dif-
and transport problem, such as situations involving flow to ference between the numerical and analytical solutions should
drainage pipes and along sloping soil surfaces. decrease if smaller space and time steps are used in the numeri-
cal solution; the difference should become zero if Δx → 0 and
7.3.3.1  Finite Difference Methods Δt → 0, barring round off and computational errors.
An even more important question relates to the stability of
For one-dimensional transient solute transport, the dependent the finite difference approximation, namely, the degree to which
variable can be discretized according to the numerical solution is affected by errors that occur dur-
ing the simulation. Such errors can usually not be eliminated
C(x , t ) = C(i Δx , jΔt ) = Cij (i = 0,1, 2,…, n; j = 0,1, 2,…, m). (7.90) completely; they depend on the implemented discretization,
Solute Transport 7-19

the values of the input parameters, and the type of numerical An approximate or trial solution for the concentration in each
scheme used for approximation of the governing transport equa- element is formulated as the weighted sum of the unknown
tion. Errors are damped during the course of a simulation when concentration at the nodes of that element. A wide variety of
a stable scheme is used, while unstable schemes allow such errors so-called basis functions can be selected to assign weights to
to grow without bounds. the nodes; the functions depend on the type of element being
Implicit systems are unconditionally stable, but their results selected. The approximation for the element concentration will
may not be as amenable to changes in grid sizes as is the case not be exact; substitution of the element concentration in the
with explicit systems. The Crank–Nicolson method offers an ADE yields an expression for this error (residual). The objective
attractive compromise of being unconditionally stable and is to minimize the residual over the entire domain with some
having a truncation error of order O[(Δx)2 + (Δt)2]. These prop- kind of weighting procedure for the elements. The method of
erties imply, among other things, that a variable time step can weighted residuals forces the weighted average of the residuals at
be used independently of the spatial step to effectively balance the nodes to be 0 and gives an expression for the residual of each
the needs of an accurate approximation and a limited number element. After applying Green’s theorem for each element, the
of computations. However, oscillations near the concentration residual can be written in matrix form.
front may develop even for unconditionally stable methods The third step is the assembly of all element matrices into a
due to the hyperbolic (convection) term in the solute transport global matrix system that contains the nodal concentrations and
equation. To avoid these oscillations, stability criteria in terms its temporal derivative as unknown variables.
of the grid Peclet (Pe) and Courant (Cr) numbers are frequently The last step involves the solution of this global matrix equa-
formulated. Huyakorn and Pinder (1983) provided the follow- tion. Since there are, in general, no obvious advantages for also
ing conservative guidelines for one-dimensional transport of a using a finite element approximation for the temporal deriva-
nonreactive solute: tive, the latter is normally dealt with using the (simpler) finite
difference method. The time step may be constant or variable.
v Δx As noted earlier, the explicit or forward scheme (w = 0) is con-
Pe = < 2, (7.94a)
D ditionally stable whereas the implicit or backward (w = 1) and
the centered or Crank–Nicolson (w = 0.5) schemes are uncondi-
tionally stable. The nodal concentration can then be solved using
v Δt
Cr = < 1. (7.94b) standard numerical procedures.
Δx
7.3.3.3  Application
For transport of a reactive solute, the retardation factor R must Numerical oscillations and dispersion are illustrated for sev-
be included in the denominator of the Courant number. eral numerical schemes using results by Huang et al. (1997).
The numerical solution of the ADE is particularly difficult for
7.3.3.2  Finite Element Methods relatively sharp concentration fronts with advection-dominated
The application of the finite element methods for modeling sol- transport characterized by small dispersivities (i.e., large Pe). As
ute transport in soils involves several steps, which will be briefly mentioned earlier, undesired oscillations can often be prevented
reviewed in a qualitative manner. The specifics of the method with judicious space and time discretizations. A smaller grid
can be found in, among others, Huyakorn and Pinder (1983) size with Pe < 2 will virtually eliminate numerical oscillations.
and Istok (1989). The (spatial) solution domain should first be However, acceptable results may still be obtained for local Peclet
discretized. The finite element mesh, consisting of nodal points numbers as high as 10 (Huyakorn and Pinder, 1983). The time
marking the elements, is usually tailored to the problem at hand. step is selected based upon the Courant number.
The selection of mesh size is a somewhat subjective process that Consider one-dimensional, steady-state flow in a soil column
considers the required degree of accuracy, the geometry of the with v = 4 cm day−1. The column was initially free of any solute; a
problem, the ease of mesh generation, and the mathematical nonreactive solute (Co = 1) was subsequently applied for 20 days.
complexity associated with the use of a particular mesh. The For negligible molecular diffusion and a longitudinal disper-
shape of the finite elements is determined by the dimensionality sivity (αL = 0.02 cm), the grid Pe = 100 for a spatial increment
and the geometry of the transport problem. One-dimensional Δx = 2 cm. This grid Peclet number indicates that advection is
elements consist of lines between nodal points along the coor- the dominant mechanism for solute transport. In all calcula-
dinate where (one-dimensional) transport occurs. Examples of tions, the Courant number was less than 1, which is the stability
two-dimensional elements are triangles, rectangles, and paral- condition for Eulerian methods.
lelograms, while many different three-dimensional elements can The concentration predicted with four different finite element
be constructed. methods and with the analytical solution is shown in Figure
A second step in implementing the finite element method 7.10. The first numerical method is based on the central Crank–
is the description of the transport problem for each element. Nicolson scheme for time with weighting constant (w = 0.5).
Generally, the method of weighted residuals is used to arrive at Second, the analytical solution is shown as a solid line. Third, an
an integral formulation for the governing transport equation. implicit scheme (w = 1.0) is used. The last two numerical methods
7-20 Properties and Processes

1.0
1.0
Central
Analytical 0.8
0.8
Implicit

Concentration (C)
Central-UW
Concentration (C)

0.6
0.6 Implicit-UW t = 30
t = 20
0.4
0.4

0.2
0.2

40 0 20 40 60 80 100 120 140 160 180 200

0 20 60 80 100 120 140 160 180 200
(b) Distance (x)
(a) Distance (x)

FIGURE 7.10  Concentration profiles predicted with different numerical schemes for (a) solute infiltration (t = 20 days) and (b) solute leaching
(t = 30 days).

implement upstream weighting (Huyakorn and Pinder, 1983) in V3 Vn

the central and the implicit schemes, respectively. The results V2
Vn–1
obtained with the Crank–Nicolson method have significant
V1
numerical oscillations (both overshoot and undershoot) Figure
7.10). This is not surprising given the large value for Pe. The
oscillations are reduced by using an implicit scheme. Upstream
weighting leads to very similar results for the central and implicit
schemes. The oscillations are virtually eliminated but the solute
profile exhibits more numerical dispersion; there is a greater dis-
crepancy with the steep analytical profile than for the regular
implicit scheme.

7.4  Stream Tube Models

Considerable errors may be made when applying deterministic FIGURE 7.11  Schematic of the stream tube model.
methods to the field since model parameters are actually sto-
chastic due to spatial and temporal variability, measurement either deterministic or stochastic. The problem may be solved
errors, and different averaging scales. Usually, it is not possible analytically at the scale of the tube and the field. The stream tube
or important to obtain discrete values for parameters in deter- model is suitable for inverse procedures to estimate transport
ministic models of field-scale transport. Instead, transport and statistical properties (Toride et al., 1995).
properties and model results are described with statistical func-
tions. Stochastic modeling is no substitute for data collection or 7.4.1  Model Formulation
model development but merely a method to deal with uncer-
tainty of model parameters and complexity of flow and trans- For one-dimensional transport, the solute concentration at the
port processes. The scale at which solute movement is observed outlet of a stream tube of length (L) may be written with the
or modeled is important. The averaging process associated with transfer function approach as (Jury and Roth, 1990)
larger field-scale descriptions tends to filter out the variability at
t
smaller scales.
The stochastic modeling of actual field problems is seldom ∫
C(L, t ) = C(0, t − τ) f (L, τ)d τ. (7.95)
possible. The stream tube model provides a possible exception 0
(Dagan and Bresler, 1979; Amoozegar-Fard et al., 1982; Rubin
and Or, 1993). The field is conceptualized as a system of parallel The outlet concentration is a convolution of the input signal and
tubes illustrated in Figure 7.11. A process-based model is used the residence time distribution f(L, τ). The latter is, in effect, a
to describe a one-dimensional, autonomous transport in each probability density function (pdf) of the time a solute parti-
tube as a function of time and depth. Transport parameters are cle resides in the soil between x = 0 and L. The pdf, which has
Solute Transport 7-21

dimension of inverse time, can be determined from experimen- with

tal results or it may be a theoretical expression derived from a
process-based model such as the ADE. The pdf depends mostly ∞ ∞

on the transport properties of the soil and, to a lesser extent,

on the mode of solute application and detection, but not on the
ρvK d = <YvYK d > =
∫ ∫Y Y v Kd f (v, K d )dv dK d , (7.100)
0 0

input and initial concentrations. For the equilibrium problem
involving instantaneous solute application to a solute-free soil, ln(v) − μ v
the flux-averaged concentration and hence the pdf is given by Yv = , (7.101a)
σv
x ⎛ (x − vt )2 ⎞
f (x , t ) = exp ⎜ − . (7.96) ln(K d ) − μ K d
4πDt 2 ⎝ 4 Dt ⎟⎠ YK d = , (7.101b)
σKd

Note that this is a Gaussian pdf. Expressions for f(x, t) derived at
a particular depth can be readily used for predicting concentra- where
tions at other depths if the soil is homogeneous. μ and σ are the mean and standard deviation of the log-trans-
The stochastic approach is implemented by considering the formed variable, respectively
(constant) column parameters as realizations of a random dis- ρνK d is the correlation coefficient between Yv and YK d (Kd tends
tribution. The (horizontal) field-averaged solute concentration is to increase with v for positive ρvK d and to decrease with v
considered the ensemble average over the probability distribution. for negative correlation)
It is assumed that each random parameter obeys a distribution
function that is independent of location and that the ensemble of Ensemble averages of v and Kd are given by (Aitcheson and
possible concentrations may be estimated from a sufficient num- Brown, 1963),
ber of samples taken at different locations. The average concentra-
tion across the field is then identical to the ensemble average: ⎛ 1 ⎞
<v > = exp ⎜ μ v + σv2 ⎟ , (7.102a)
n ⎝ 2 ⎠
1 1

< C( x , t ) > =
A ∫ ∫ C(x,t )dA = lim n ∑ C (x,t ),
n →∞
i =1
i (7.97)
⎛ 1 ⎞ (7.102b)
<K d > = exp ⎜ μ K d + σ2K d ⎟ ,
⎝ 2 ⎠
where
A denotes the area of the field with coefficients of variation (CV):
n is the number of samples
< > indicates an ensemble average
CV(v) = exp(σ2v ) − 1, (7.103a)

7.4.2  Application
Solute transport in a local-scale stream tube may be described CV(K d ) = exp ( σ2K d ) − 1. (7.103b)
with the one-dimensional ADE. Following Toride and Leij
(1996a), the effects of heterogeneity are studied using pairs of
random parameters (v and Kd). Note that the water content (θ) Based upon the detection mode of the local-scale concentration,
and bulk density (ρb) are the same for all stream tubes. The three types of field-scale concentrations can be defined: (1) the
field-scale mean concentration (denoted by ∧) is equal to the ensemble average of the flux-averaged concentration (<CF>); (2)
ensemble average: the field-scale resident concentration ĈR, which is equal to the
ensemble average of the resident concentration (<CR>); and (3)
∞ ∞ the field-scale flux-averaged concentration (ĈF), which is defined
Cˆ (x , t ) = <C(x , t )> = as <vCF>/<v>. The second type of concentration is obtained
∫ ∫ C(x,t; v, K ) f (v, K )dv dK ,
d d d (7.98)
from averaging values of the resident concentration at a par-
0 0

ticular depth across the field. The third type is defined as the
ratio of ensemble solute and water fluxes in a similar manner as
where the bivariate lognormal joint probability density function
for deterministic transport. It should be noted that <vCF>/<v> ≠
f(v, Kd) is given by
<CF> because v is a stochastic variable.
The use of the stream tube model for field-scale transport is
1 ⎛ Y 2 − 2ρ Y Y + Y 2 ⎞ illustrated in Figure 7.12. The local-scale concentration only depends
f (v, K d ) = exp ⎜ − v v Kd v Kd Kd
⎟, on the particular realizations of the two stochastic parameters
2πσv σ K d vK d 1 − ρv2K d ⎜⎝ 2 1 − ρv2K d( ) ⎟⎠
(v and Kd) after the independent variables (t and x) have been
(7.99) specified. The solution for the ADE, the resident concentration
7-22 Properties and Processes

0.05

f (v, Kd )
1.0
0.5
Cr

0.0 0.00
150 150
2 2
100 100
K 1 –1 ) K –1 )
1
d (cm 3 50 ay d (cm 3 50 day
md m
(a)
g –1
) 0 0 v (c (b)
g –1
) 0 0 v (c

0.04
Cr f (v, Kd )
0.02

0.00
150
2
100 1
K 1 – )
d (cm 50 day
3 m
(c) g –1 0 0 v (c
)

FIGURE 7.12  Illustration of the stream tube model for field-scale transport for a two-dimensional solute application with D = 20 cm2 day−1 and
ρb/θ = 4 g cm−3: (a) the local-scale resident concentration as a function of v and Kd at x = 100 cm and t = 5 days; (b) a bivariate lognormal pdf for
ρvKd = 0.5, <v> = 50 cm day−1, σv = 0.2, <Kd> = 1 cm3 g−1, and σKd = 0.2; and (c) the expected concentration at x = 100 cm and t = 5 days.

at x = 100 cm and t = 5 days as a function of v and Kd is shown where the lognormal pdf for the single stochastic variable (v) is
in Figure 7.12a and the bivariate lognormal pdf for v and Kd in given by
Figure 7.12b; the distribution is skewed with respect to v since
σv is fairly high; the smaller σKd results in a more symmetric
1 ⎛ ⎡ ln(v) − μ v ⎤ 2 ⎞
distribution for Kd. The negative ρνK d results in an increasing v f (v) = exp ⎜ − ⎣ ⎦ ⎟. (7.106)
with a decreasing Kd, and vice versa. The expected concentration— 2πσv v ⎜⎝ 2σ2v ⎟⎠
again a resident or volume-average—is shown in Figure 7.12c. It
is obtained by weighting the local concentration (Figure 7.12a)
by multiplying it with the joint pdf (Figure 7.12b). The peak The mean (Figure 7.13a) (ĈR = <CR>) and the variance (Figure
in Figure 7.12c suggests that stream tubes with approximately 7.13b) are shown as a function of depth for three values of σv
v  = 25 cm day−1 and Kd = 1 cm3 g−1 contribute the most to sol- at t = 3 days for a nonreactive solute. More solute spreading
ute breakthrough when x = 100 cm and t = 5 days. The volume occurs in the ĈR profile when σv increases (Figure 7.13a). The
of the distribution in Figure 7.12c corresponds to the ensemble variation in the local-scale CR also increases with σv, indicat-
average (<CR>). ing a more heterogeneous solute distribution in the horizontal
Variations in the local-scale concentration between stream plane (Figure 7.13b). Because flow and transport become more
tubes, at a particular depth and time, can be characterized by heterogeneous as σv increases, more observations are needed to
its variance. The variance across the horizontal plane is given by estimate ĈR for σv = 0.5 than for σv = 0.1. The double peak in the
(Bresler and Dagan, 1981; Toride and Leij, 1996b): variance profiles of Figure 7.13b is due to the relative minimum
for this pulse application at around x = 30 cm, where the highest
∞ ∞ concentration occurs.
2
Var ⎡⎣C(x , t )⎤⎦ =
∫ ∫ ⎡⎣C(x,t )− < C(x,t )>⎤⎦ f (v, K )dv dK
0 0
d d For reactive solutes, the variability in the distribution coeffi-
cient (Kd) must also be considered. The field-scale resident con-
centration (ĈR) at t = 5 days is plotted versus depth in Figure 7.14
= <C 2 (x , t )> − <C(x , t )> 2 . (7.104)
for perfect and no correlation between v and Kd. The figure shows
that the negative correlation between v and Kd causes additional
For a deterministic distribution coefficient (Kd), Equation 7.99 spreading. Such a negative correlation seems plausible since
reduces to coarse-textured soils generally have a relatively high v, due to their
higher hydraulic conductivity, and a small Kd, due to their lower
∞ exchange capacity. The opposite may hold for fine-textured soils.
∫
<C(x , t )> = C(x , t ; v ) f (v )dv , (7.105) Robin et al. (1991) reported a weak negative correlation between
Kd and the saturated hydraulic conductivity for a sandy aquifer.
0

Solute Transport 7-23

1.2 0.20
Resident concentration (CR)

‹ 1.0 σv = 0.1 σv = 0.5

0.3 0.15
0.8

Variance (CR )
0.5
0.6 0.10
0.3
0.4
0.05 0.1
0.2 t = 3 days

0.0 0.00
0 50 100 150 200 0 50 100 150 200
(a) Distance (x) (cm) (b) Distance (x) (cm)

FIGURE 7.13  The effect of variability in the pore-water velocity, v, on (a) the field-scale resident concentration profile, and (b) the distribution of
the variance for ĈR in the horizontal plane; for a two-dimensional application of a nonreactive solute (R = 1) assuming <v> = 20 cm day−1 and
D = 20 cm2 day−1.

0.25 eventually reach the water table. LNAPLs will accumulate on the
water table and in the capillary fringe and, if a sufficient amount is
ρv K = 1 t = 5 days spilled, the contaminant will spread on the water table. DNAPLs,
Resident concentration (CR)

‹ 0.20 d

σv = 0.5, σK = 0.2 on the other hand, will penetrate across the groundwater table
0
d
and through the saturated porous medium if the spill volume
0.15
is sufficient to feed the flow. Further vertical migration will be
halted if the penetrating liquid encounters layers of fine-grained
0.10 –1
material such as silt or clays. In this case, the DNAPL will deflect
horizontally until it reaches a more permeable vertical path or
0.05 it forms a pool. Most NAPLs are slightly soluble in water and,
either as entrapped in the soils or as a pool, will constitute a long-
0.00 term source of groundwater pollution. The slow degradation and
0 50 100 150 the extreme toxicity of many NAPLs found in groundwater make
Distance (x) (cm) them a persistent and serious threat to human health.
FIGURE 7.14  The field-scale resident concentration profile, ĈR(x), for Transport of NAPLs in porous media is a complex multiphase,
three different correlations between v and Kd with <v> = 50 cm day−1, multidimensional, and multicomponent problem (Willson et al.,
D = 20 cm2 day−1, <Kd> = 1 g−1 cm3, σKd = 0.2, <R> = 5, and ρb/θ = 4 g cm−3. 2006). Further details pertaining to the multiphase transport of
NAPL compounds can be found in Bear and Verruijt (1987),
Miller et al. (1998), and Charbeneau (2000). Several researchers
7.5  Nonaqueous Phase Liquids have developed mathematical models for multiphase flow and
transfer between nonaqueous and aqueous phase (e.g., Kueper
Contamination of soil and water resources by nonaqueous phase
and Frind, 1988; Huyakorn et al., 1994; Imhoff et al., 2003;
liquids (NAPLs) has received considerable attention over the past
Willson et al., 2006; Fagerlund et al., 2008). Numerical models
few decades. These organic liquids have a low aqueous solubility.
such as TOUGH2 (Pruess et al., 1999) and STOMP (White and
They are classified according to density as LNAPLs and DNAPLs,
Oostrom, 2000) are available to describe the multiphase trans-
that is, lighter and denser than water. Oil and gasoline represent
port of NAPLs in saturated and unsaturated media. The concern
LNAPLs while many DNAPLs are chlorinated solvents used as
here is dissolution of static NAPL from both residual ganglia and
cleaning (degreasing) agents or in manufacturing processes.
pools and subsequent transport of the dissolved constituents in
NAPLs may be accidentally released to the soil through spill-
the aqueous phase by the same mechanisms of a (generic) solute
age during transport and handling operations or leakage from
that were previously reviewed.
underground storage tanks, or they could have been disposed in
the past when there was less awareness about any risks. NAPLs
7.5.1  Dissolution Process
move downward through the vadose zone due to gravity as a sep-
arate liquid phase. A portion of the liquid will remain entrapped Schwarzenbach et al. (1993) define dissolution as a thermo-
in the soil pores due to capillary forces forming isolated gan- dynamic process by which the molecules of an organic solute
glia known as residual NAPL. The contaminant may partition in its pure liquid phase are transferred into water. When an
among the solid, water, and air phases. The remaining liquid will organic liquid is in contact with pure water, some of the organic
7-24 Properties and Processes

molecules will transfer from the organic into the water phase concentration (Powers et al. 1992). The proportionality factor kf
while some water molecules will transfer from the water into is often referred to as the mass transfer coefficient, that is:
the organic phase. Upon equilibrium, the concentration of the
organic molecules in the water phase equals the aqueous solu- J = k f (Cs − C ), (7.107)

bility of the compound. Partitioning of NAPL pollutants in the
water phase has been described according to the local equilib-
rium assumption. Hence, if the organic concentration is known where
for one phase, it may be inferred for other phases by equilibrium J is the mass flux [M L−2T−1]
partitioning relationships. Cs [M L−3] is the solubility of the compound
Several early laboratory experiments (van der Waarden et al., C [M L−3] is the concentration in the aqueous phase
1971; Dietz, 1978; Duffy et al., 1980) suggested the validity of kf is the mass transfer coefficient [L T−1]
the local equilibrium assumption in groundwater systems.
Other studies however (Feenstra and Coburn, 1986; Sitar et al., Imhoff et al. (2003) pointed out that the mass transfer coefficient
1987; Mercer and Cohen, 1990) note that observed concentra- depends on the morphology of the entrapped NAPL as deter-
tions can be several orders of magnitude lower than the aque- mined by pore structure (Powers et al., 1992) and wettability
ous solubility suggesting that no equilibrium conditions exist. (Bradford et al., 2003), the velocity in the aqueous phase, viscos-
Powers et  al. (1991) found that nonequilibrium mass transfer ity, density (Miller et al., 1990), and NAPL saturation (Imhoff
conditions must be assumed for small contact times, large et al. 1994). The mass transfer coefficient may be predicted from
NAPL blobs, and low NAPL saturations. In terms of ground- regression equations, and interfacial area may be inferred or
water contamination, this implies that the duration of contami- measured (Powers et al., 1991; Geller and Hunt, 1993; Bradford
nation and the volume of contaminated groundwater are much and Leij, 1997; Dobson et al., 2006). A lumped mass transfer rate
larger than that predicted by the local equilibrium assump- constant equal to the product of the specific interfacial area and
tion (Mackay et al., 1985). Powers et al. (1992) pointed out that the mass transfer coefficient may also be used (Miller et al., 1990;
the lower observed concentrations may be due to rate-limited Powers et al., 1992; Imhoff et al., 1994). Various correlations have
mass transfer between the NAPL and the aqueous phase or to been developed, which relate dimensionless groups, such as the
a bypassing of the water flow around the low permeability area Reynolds, Schmidt, and Peclet numbers, and residual NAPL sat-
contaminated with NAPL ganglia (Kueper and Frind, 1988). uration to the Sherwood number, which represents the dimen-
Other causes could be NAPL morphology and available surface sionless concentration gradient at the interface. Once the total
contact area (Cho and Annable, 2005; Dobson et al., 2006; Zhao mass transfer flux is evaluated, the term is incorporated into the
and Ioannidis, 2007), heterogeneities in the aquifer (Miller classical ADE.
et al., 1998), or multicomponent dissolution effects (Geller
and Hunt, 1993; Garg and Rixey, 1999; Brahma and Harmon, 7.5.1.2  NAPL Pools
2003). Several studies have attempted to quantify the dissolu- The description of the dissolution of NAPLs from a planar
tion kinetics and the NAPL–water interfacial area using pho- source (pools) poses special challenges. The low cross-sectional
tography of frozen or polymerized NAPL blobs (Powers et al., area with respect to pool volume implies slow dissolution. The
1992; Kennedy and Lennox, 1997; Jia et al., 1999), gamma radia- merits of different conditions at the interface of pool and porous
tion (Brusseau et al., 2002), magnetic resonance (Baldwin and medium have been reviewed for mass transfer into pure fluids
Gladden, 1996; Zhang et al., 2007), and x-ray microtomography (Sherwood et al., 1975). A comparison of boundary conditions
(Brusseau et al., 2008). for dissolution in porous media has been lacking, in part because
of a paucity of experimental data (Schwille, 1988; Voudrias and
7.5.1.1  Entrapped NAPL Yeh, 1994; Whelan et al., 1994; Dela Barre, 1999).
In view of the inadequacy of the local equilibrium assumption, For a NAPL pool located at the water table (LNAPL) or an
several researchers have further examined rate-limited disso- effectively impermeable layer (DNAPL), a concentration bound-
lution of NAPL in saturated porous media. Most of the stud- ary layer develops at the organic–water interface. The thickness
ies dealt  with NAPL at residual saturation (Miller et al., 1990; of the concentration boundary layer depends on the intersti-
Powers et al., 1991, 1992; Geller and Hunt, 1993; Sahloul and tial groundwater velocity, hydrodynamic dispersion, and pool
Chatzis, 2002). A detailed discussion of the residual NAPL dis- size (Dela Barre, 1999). After a hydrodynamic boundary layer
solution mechanisms in porous media can be found in Powers is established for water flow, a concentration gradient develops.
et al. (1991, 1992) and in Khachikian and Harmon (2000). In general, the NAPL–water interface and the geometry of the
Dissolution from a single-component source may be described porous medium are difficult to determine accurately, and the
with a linear driving force model, and dissolution of an organic dissolution process at the macroscopic scale is described via
species from a multicomponent source will be more compli- mass transfer coefficients. For flow over a NAPL pool, the local
cated to model. For a single component, the mass flux from the mass transfer coefficient decreases with distance from the front
organic to the ­aqueous phase is proportional to the difference end of the pool and has a maximum value at the upstream edge
between the solubility of the compound and its actual aqueous (Chrysikopoulos and Lee, 1998). However, due to the complexity
Solute Transport 7-25

of the subsurface environment and associated scale dependency pool, and therefore the concentration in the medium, depends
of modeling parameters, the NAPL dissolution process is com- strongly on the mass transfer coefficient.
monly described with an average mass transfer coefficient or
rate constant.
7.5.2  Numerical Modeling
Johnson and Pankow (1992) used experimental results from
Schwille (1988) and the analytical solution from Hunt et al. Numerical modeling of NAPL dissolution in saturated porous
(1988) to calculate a surface-area-averaged mass transfer rate media has been widely investigated in the past decades. Several
whose value decreases as the length of the pool increases to numerical techniques have been applied in order to enhance the
reproduce the decreasing dissolution rate across the top of the performance of computer codes designed to simulate contami-
pool. The mass transfer term was then included in the steady- nant transport in the subsurface. A distinction is again made
state ADE, which was solved analytically for a homogeneous between dissolution from NAPL blobs entrapped in the pores of
semi-infinite medium with a square pool of negligible thickness. a saturated porous medium and from a DNAPL pool at the bot-
Local equilibrium was assumed by selecting the aqueous solubil- tom of a saturated porous medium.
ity as boundary condition at the pool–water interface while the In the first case, the NAPL blobs are incorporated in the
remaining boundary conditions away from the pool where of the domain of interest. Therefore, the dissolution term, expressed by
Dirichlet type with fixed zero concentration. a first-order rate-limited relationship used by Geller and Hunt
Holman and Javandel (1996) also used the local equilib- (1993) and Powers et al. (1991), among others, will be added to the
rium assumption in the transient two-dimensional ADE that ADE as a point source term. In the second case, the pool is just
describes the dissolution and transport of a mixture of slightly outside the solution domain, and NAPL dissolution is accounted
soluble compounds from a LNAPL pool into the groundwater. for by formulating the appropriate boundary conditions.
Their model describes the dissolution and transport of the con- Examples of numerical models developed to describe ground-
taminant as a heterogeneous reaction involving three steps: water plumes emanating from entrapped NAPL in the subsur-
molecular diffusion of the compound inside the pool toward face can be found in Guiguer (1991) and Clement et al. (2004).
the LNAPL–water interface, dissolution of the compound at the Christ et al. (2009) simulated dissolution of a DNAPL (tetra-
interface, and transport of the dissolved compound from the chloroethylene or PCE) and mass recovery in two- and three-­
interface into the aquifer. dimensional nonuniform permeability fields using a modified
Chrysikopoulos et al. (1994) developed a mathematical model version of the popular MT3D numerical code to assess the influ-
for dissolution of a single-component rectangular DNAPL ence of model dimensionality on the mass recovery predictions.
pool of negligible thickness in a two-dimensional semi-infinite The numerical simulation of NAPL blobs dissolving in a
homogeneous porous medium with steady-state flow, equilib- saturated porous medium does not present particular difficul-
rium sorption, and first-order decay. The boundary condition ties when the mass transfer coefficient is considered indepen-
at the DNAPL–water interface was a second-type boundary dent of the aqueous concentration. In this case, the governing
condition. It is represented by a mass transfer relationship in partial differential equation is linear and its solution can be
which the fixed diffusive flux is related to the saturated aqueous achieved by using one of the numerical techniques available to
concentration through a time-varying mass transfer coefficient. solve the classical ADE. For dispersion–diffusion-dominated
Lee and Chrysikopoulos (2002) applied the same boundary con- problems, the classical Eulerian approach either by using finite
ditions to the analysis of the dissolution of a circular trichlo- difference techniques or using Galerkin finite element meth-
roethylene (TCE) plume. The authors developed correlations ods on a fixed grid in space has performed quite satisfactorily.
between the time invariant overall Sherwood number and the For advection-dominated transport problems and for pure
Peclet number, which were found in good agreement with the advection problems, however, the Eulerian methods produce
experimental data. inaccurate solutions due to oscillation and numerical disper-
Leij et al. (2000) used the ADE to model the three-­dimensional sion. As mentioned in Section 7.3, a way to obviate this prob-
equilibrium solute transport in a homogeneous porous medium lem is to use refined grids or higher order finite difference and
generated from the dissolution of planar and parallelepipedal finite element methods or, alternatively, to use the upstream
sources of persistent contamination. Analytical solutions weighted finite difference or finite element method (Settari and
were formulated based upon Green’s functions for a first-, sec- Aziz, 1975; Dalen, 1979). Lagrangian and mixed Lagrangian–
ond-, and third-type boundary condition in the case of a pla- Eulerian approaches have also been popular to solve advection-
nar source. A third-type or Cauchy-type boundary condition, dominated transport problems (Huyakorn and Pinder, 1983).
which imposes a fixed total flux (diffusive and advective) at the The method of characteristics and the random walk method
DNAPL–water interface, more realistically predicts the concen- belong to these classes of techniques. Yeh (1990) proposed an
tration profiles compared with either the first-type or fixed con- Eulerian–Lagrangian method with a zoomable hidden fine-
centration or a second-type boundary condition. Leij and van mesh approach, which eliminates the numerical oscillations
Genuchten (2000) extended Green’s function method to obtain and reduces the numerical dispersion. A variety of approaches
analytical solutions for nonequilibrium transport from a rect- exist to combine numerical methods with analytical solutions
angular pool. The authors observed that the solute flux from the (e.g., Hwang et al., 1985).
7-26 Properties and Processes

When the contamination in the aquifer is produced by the adopted by the authors to solve the governing equation is the
dissolution of NAPL pools, the process is described by the clas- classical implicit finite difference approximation, which yielded
sical two or three-dimensional ADE where the presence of the a band diagonal system of algebraic equations.
pool is accounted for in the boundary conditions. This problem
is also known as the patch-source problem. According to Segol
(1994), the term “refers to the transport of a solute from a bound- 7.5.3  Remediation
ary source of finite extent into a rectangular domain subjected to
Over the past decades, researchers have aimed to develop effi-
a uniform, unidirectional velocity field.”
cient techniques to remediate soil and groundwater. The simplest
The boundary conditions applied to simulate the source term
and commonly applied technique is known as pump-and-treat,
are the Dirichlet or first-type boundary condition, the Neuman-
where contaminated groundwater is extracted and treated
or second-type boundary condition, or the Cauchy- or third-type
above ground. This technique promotes a decline in contami-
boundary condition. Numerically, the problem of modeling sol-
nant concentrations over time, but it requires the treatment of
ute transport with a dissolving source on the boundary is some-
large volumes of water. A combination of optimization meth-
what different than dissolution from a source inside the domain
ods and simulation models has been proposed to determine
of integration. Segol (1994) reviewed several studies where the
more efficient cleanup design strategies (Gorelick et al., 1993). In
patch-source problem has been used to illustrate numerical
particular, these optimization techniques have been developed
techniques developed to solve the convection–­dispersion equa-
to determine the location and number of pumping wells, the
tion. Daus and Frind (1985) formulated the patch-source prob-
optimal pumping rate (which will maximize the contaminant
lem using either Dirichlet or Cauchy boundary conditions. The
removal at the lowest energy cost) and treatment strategies.
governing equation is then solved numerically by the alternat-
Among the remediation techniques are hot-water flush-
ing direction Galerkin technique, which consists in splitting the
ing (Imhoff et al., 1995; O’Carroll and Sleep, 2007), air sparg-
governing equation into two one-dimensional ADEs coupled
ing (Adams and Reddy, 2000), cosolvent flushing (Imhoff et al.,
with cross derivatives terms. For both boundaries, the technique
1995), the use of surfactants (Childs et al., 2006), and in situ bio-
produces accurate results, and it is more efficient than the clas-
remediation (Zoller and Rubin, 2001). The effectiveness of the
sical finite-element method due to the decoupling procedure.
remediation may be substantially improved if the location and
The cell analytical–numerical method was successfully applied
extent of the NAPL source are known.
by Elnawawy et  al. (1990) to the patch-source problem with a
Dirichlet boundary condition at the source. The results showed
to be accurate but were obtained at the expenses of geometrical
7.5.4  Inverse Modeling to Locate
flexibility. Leismann and Frind (1989) solved the patch-source
Contaminant Sources
problem by applying the ­symmetric-matrix time integration
technique. They used the Dirichlet-type boundary condition at The problem of defining the location of the DNAPL pool and the
the source. The method applied by the authors uses an integra- release history of the contaminant (the time period and the mass
tion technique for the time derivative, which produces an alge- at which the contaminant was released) is important to design
braic system of equations whose coefficient matrix is symmetric of the most efficient cleanup strategy but also from a legal and
and positive definite. In this case, the resulting algebraic system regulatory point of view. Remediating a contaminated soil or
can be efficiently solved. Sudicky (1989) used the patch-source aquifer is typically costly and cumbersome. Therefore, as Skaggs
problem with the source described by Dirichlet-type boundary and Kabala (1994) noted, a model capable of backtracking a con-
conditions to illustrate the Laplace transform Galerkin method. taminant plume in space and time would help to individuate the
In this method, the Laplace transform is first applied to the ADE responsible parties and to distribute the cleanup costs accord-
to eliminate the temporal derivatives. The transformed equation ingly. Unfortunately, the dispersive nature of the contaminant
is then solved for a discretized spatial domain using the stan- transport problem makes it an irreversible problem. Modeling
dard Galerkin finite element procedure. Finally, the inversion of the contaminant release history by simply reversing time will
the transformed concentration values is obtained using Crump’s result in an ill-posed problem with a nonunique or unstable
method. According to the author, the method has the advantage solution (Skaggs and Kabala, 1994).
of producing accurate and robust solutions, but it is restricted to Another obstacle in the development of a model to identify
linear mass transport in a steady flow field. contaminant release history is the scarcity of historical data.
In the four studies reviewed by Segol (1994), the source term Due to this lack of data, reconstruction must be based on obser-
is perpendicular to the flow direction. Lee and Chrysikopoulos vations of the existing contaminant plume. Usually, an exten-
(1995) used a Neuman or second-type boundary condition for sive number of observations are required in order to obtain a
dissolution from a multicomponent DNAPL pool at the bottom detailed description of the concentration profiles. Recently, sev-
of an aquifer with steady flow. The boundary condition corre- eral parameter identification techniques coupled with numerical
sponding to the pool location is described by a relationship in models have been developed to minimize the number of loca-
which the diffusive flux is specified using a time- and position- tions (wells) where the NAPL concentration needs to be observed
dependent mass transfer coefficient. The numerical scheme (Yeh and Sun, 1984; McCarthy and Yeh, 1990).
Solute Transport 7-27

Several researchers have dealt in the past with the problem of In the first step, a nonlinear optimal source identification model
contaminant source characterization (Gorelick et al., 1983; Skaggs with embedded flow and transport simulation constraints is
and Kabala, 1994). Much emphasis has been given to the temporal employed to identify source fluxes using concentration data
reconstruction of the source release while the problem of locating for arbitrary locations. The results from this preliminary step
existing DNAPL contaminant sources has been neglected, espe- are then perturbed statistically, to account for uncertainties in
cially for those cases involving heterogeneous flow and transport measurements, and incorporated into a groundwater monitor-
fields. Hwang and Koerner (1983) explored the performance of ing network design model with an integer-programming-based
two different approaches: nonsequential and sequential optimi- optimization model. The concentration data generated by the
zation. In the former the optimization process is applied to the monitoring network are then fed back to the source identifica-
partial differential equation describing solute transport. In the tion model to obtain more accurate predictions.
sequential optimization approach, the partial differential equa- Skaggs and Kabala (1994) applied Tikonov regularization in
tion is discretized and a linear dynamic system is developed that one-dimensional numerical experiments to recover the release
may subsequently be optimized. Hwang et al. (1988) applied their history of a contaminant originated from a known site. Their
methods to two field cases with pollution due to surface ponding method was found to be very sensitive to observation errors. In
of organic waste and a landfill. In both cases the estimated source a subsequent paper, Skaggs and Kabala (1995) attempted to solve
location was relatively close to the actual location but the proce- the same problem by applying the method of quasi-reversibility
dure was limited to two-dimensional geometries. to the convection–dispersion equation. The method was prefer-
Gorelick et al. (1983) combined least-square regression and able to Tikonov regularization due to its simple implementa-
linear programming to obtain the least absolute error to identify tion and its capacity to include nonconstant flow and transport
the location, magnitude, and disposal period of underground parameters, although it was not as accurate.
pollutant point sources. The authors examined the case of steady Snodgrass and Kitanidis (1997) proposed Bayesian analysis
and transient scenarios. The solution procedure was based on and a geostatistical approach to the problem. Their method pro-
the response matrix approach, which assumes a linear system vides a measure of the error associated with the best estimate of
response. Their results showed that at steady state both the lin- the release history and helps to identify sources of uncertainties.
ear programming and the multiple regression formulations One limitation is that the location of the contaminant source
produced accurate results only when data were relatively noise has to be known a priori. The same assumption was made by
free. In the transient case, both procedures were successful in Kondisetty et al. (1996) in an inverse optimization approach to
estimating the location and magnitude of pollutant sources due analytically track instantaneous point-source releases in the sat-
to the abundance of concentration data. urated zone. The inverse approach, based on the minimization
Uffink (1989) and Bagtzoglou et al. (1992) applied the Random- of the error in the difference between calculated data and obser-
walk method, which is based on reversing the advective part of vations, was coupled with a two-dimensional transport model
the transport model while the dispersive part is left positive. The using the method of characteristics.
results provide a probability distribution of the contaminant An attempt to extend the release history problem to three-
initial position, but the approach is not able to define a contami- dimensional domains and spatially distributed sources was
nant release history. Simultaneous estimation of aquifer param- presented by Woodbury et al. (1998). The authors applied the
eters and a distributed pollutant source term was attempted by minimum entropy method to recover the source-release his-
Wagner (1992) by combining nonlinear maximum likelihood tory of a three-dimensional plume generated by a rectangular
estimation with groundwater flow and transport models. first-type patch source. Their work is carried out in an analytical
Sidauruk et al. (1998) presented an inverse method based on framework, and it is limited to steady flow in a uniform porous
analytical solutions of contaminant transport problems to esti- medium. Liu and Ball (1999) applied inverse modeling to estimate
mate mass transport parameters such as dispersion coefficients the contaminant plume history from observed concentrations
and flow velocities as well as the amount of pollutant, its initial at a field site that was being remediated. The authors estimated
location, and time origin. The inverse procedure is based upon the contaminant boundary concentration by assuming a simple
the method of correlation coefficient optimization. By mini- mass-conserving two-layer diffusion model. They used least-
mizing the correlation coefficient of the linear regression, the square minimization where the objective function was regular-
parameters of interest are determined by explicit formulas simi- ized by adding a term to smooth the boundary concentration.
lar to linear regression equations. The method was applied to the Sciortino et al. (2000) developed an inverse model procedure
two-dimensional cases of a plume generated by instantaneous to determine the size and the location of a single-component
and continuous point sources. As the authors pointed out, the DNAPL pool in a saturated homogeneous porous medium for
method is restricted to simple problems involving a homoge- steady flow. The inverse problem was solved using least-squares
neous porous medium, and simple geometries and flow fields. minimization with a search procedure based on the Levenberg–
Mahar and Datta (1997) combined optimal groundwater Marquardt method. A three-dimensional analytical model was
quality monitoring network design and point-source identifica- used to describe the transport of solute from a dissolving DNAPL
tion algorithms to estimate the magnitude, location, and active pool. The algorithm was tested to predict the location and size
duration of a pollutant source using a three-step procedure. of a DNAPL pool placed in a controlled three-dimensional
7-28 Properties and Processes

bench-scale experiment. The Levenberg–Marquardt algorithm Bear, J., and A. Verruijt. 1987. Modeling groundwater flow and
was used to minimize (1) ordinary residuals, (2) residuals with pollution. Kluwer Academic Publishers, Norwell, MA.
weights equal to the square of the inverse of the observations, Boyd, G.E., A.W. Adamson, and L.S. Meyers. 1947. The exchange
and (3) residuals with weights obtained by adding a constant adsorption of ions from aqueous solutions by organic zeo-
term to the observed concentrations. The results were found to lites. II. Kinetics. J. Am. Chem. Soc. 69:2836–2848.
be sensitive to the location of the observation wells and to the Bradford, S., and F.J. Leij. 1997. Estimating interfacial areas for
type of residuals minimized. The inverse problem is nonunique multi-fluid soil systems. J. Contam. Hydrol. 27:83–105.
and nonconvex even in the absence of observation errors. Bradford, S.A., K.M. Rathfelder, J. Lang, and L.M. Abriola. 2003.
Neupauer and Wilson (1999, 2001) developed a backward loca- Entrapment and dissolution of DNAPLs in heterogeneous
tion and travel-time probabilistic model to characterize source porous media. J. Contam. Hydrol. 67:133–157.
of groundwater contamination and their prior location. The Brahma, P.P., and T.C. Harmon. 2003. The effect of multicompo-
authors derived the governing equation of the backward proba- nent diffusion on NAPL dissolution from spherical ternary
bilities using the adjoints of the ADE modified with the addition mixtures. J. Contam. Hydrol. 67:43–60.
of a load term that depends on both the type of probability that it Brenner, H. 1962. The diffusion model of longitudinal mixing
describes (location or travel time) and the type of well (pumping in beds of finite length. Numerical values. Chem. Eng. Sci.
or monitoring) used to detect pollution. Michalak and Kitanidis 17:229–243.
(2004) proposed a geostatistical approach combined with the Bresler, E. 1973. Simultaneous transport of solutes and water
adjoint state method that was able to reconstruct the historical under transient unsaturated flow conditions. Water Resour.
multidimensional contaminant distribution in porous media. Res. 9:975–986.
Recently, Yeh et al. (2007) presented the SATS-GWT approach, Bresler, E., and G. Dagan. 1981. Convective and pore scale disper-
which consists of a combination of simulated annealing (SA), sive solute transport in unsaturated heterogeneous fields.
tabu search (TS), and a three-dimensional groundwater flow Water Resour. Res. 17:1683–1693.
and solute transport model (MODFLOW-GWT). Source loca- Bresler, E., and R.J. Hanks. 1969. Numerical method for estimat-
tion, release concentration, and release period of groundwater ing simultaneous flow of water and salt in saturated soils.
contaminants may be estimated using the proposed model. The Soil Sci. Soc. Am. Proc. 33:827–832.
authors applied their model to different contamination scenar- Brusseau, M.L., H. Janousek, A. Murao, and G. Schnaar. 2008.
ios, and they claim that the approach yields accurate estimates, Synchrotron X-ray microtomography and interfacial parti-
even in the presence of measurement errors. tioning tracer test measurements of NAPL–water interfacial
areas. Water Resour. Res. 43:3619–3625.
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characteristics to solve accurately two-dimensional trans- nutrient-surfactant. J. Environ. Sci. Health A 36:1451–1471.
port problems by finite elements. Int. J. Numer. Methods Zwillinger, D. 1989. Handbook of differential equations. Academic
Fluids 2:173–184. Press, San Diego, CA.
 8
Gas Transport in Soils
8.1 Introduction..............................................................................................................................8-1
8.2 Soil-Air Composition...............................................................................................................8-2
8.3 Mechanisms of Gas Transport...............................................................................................8-2
Diffusion Processes and Definitions  •  Gas Flux Definitions  •  Gas/Liquid/Solid
Partitioning  •  Gas Reactions
8.4 Gas Transport Theory..............................................................................................................8-5
Stefan–Maxwell Equations  •  Fick’s Equations  •  Dusty Gas Model  • 
Darcy’s Equation  •  Convection–Dispersion Equation
8.5 Measuring Gas Transport Parameters..................................................................................8-7
Soil-Gas Diffusion Coefficient  •  Air Permeability  •  Dispersion Coefficient
8.6 Predictive Equations................................................................................................................8-9
Soil-Gas Diffusion Coefficient  •  Air Permeability and Soil-Gas Dispersion Coefficient
Dennis E. Rolston 8.7 Applications.............................................................................................................................8-15
University of California, Davis Soil Aeration  •  Greenhouse Gas Emissions  •  Soil Fumigation  •  Volatile Organic
Compounds and Vapor Extraction  •  Radon Transport into Structures  •  Volatile Organic
Per Møldrup Vapor Transport into Structures
Aalborg University References............................................................................................................................................ 8-17

8.1  Introduction decay products in soils and into buildings (Nazaroff, 1992) is
important for evaluating the possible adverse health effects of
Understanding gas transport in soils and the vadose zone is radon gas. In a longer-term perspective, design of optimal plant
important for evaluation of soil aeration, which is the inter- growth media for use on earth or in space requires detailed
change of various gases between the atmosphere and the soil knowledge of the gas diffusivity behavior in aggregated porous
and the various processes that either produce or consume gases media including soils at both normal gravity and microgravity
in the soil. Soil aeration is important for plant growth since O2 (Jones et al., 2003).
is required for root respiration. The two major gases associated Gas transport in soils occurs due to two processes: diffu-
with aeration are oxygen (O2) and carbon dioxide (CO2) where sion and advection. Diffusion is considered to be the principal
O2 moves from the atmosphere to soil and is consumed and CO2 mechanism in the interchange of gases between the soil and the
is produced in soil and moves from the soil to the atmosphere. atmosphere, although advection may be responsible for moving
Oxygen transport through the capillary fringe in regard to significant amounts of gas but generally over short time peri-
reaeration of groundwater is another important area of soil-gas ods. The interchange due to diffusion results from concentration
transport. A thorough discussion of soil aeration is given in a gradients established within soil by respiration of microor-
book by Glinski and Stepniewski (1985), Scott (2000), Jury and ganisms, macrofauna, and plant roots; by production of gases
Horton (2004), and Rolston (2005). associated with biological reactions, such as fermentation, nitri-
In solid waste landfills, methane and carbon dioxide transport fication, and denitrification; and by incorporation of chemicals,
through the cover soil will likely be by both diffusion and advec- such as fumigants, anhydrous ammonia, pesticides, and volatile
tion affected by variations in soil moisture conditions, soil type, organic compounds (VOCs) from toxic waste sites. The diffusion
and soil structure, while oxygen diffusion into the cover layer of water vapor within the soil also occurs due to differences in
will be a main control of atmospheric methane oxidation and vapor pressure gradients induced by temperature differences or
uptake. Movement of gaseous radionuclides from radioactive by evaporative conditions at the soil surface.
waste sites is important in many areas. Understanding gas trans- Whereas diffusion is driven by concentration gradients,
port is also important for estimating movement of volatile organic advection is driven by pressure gradients. Pressure gradi-
chemicals from contaminated waste sites within the vadose zone ents may develop due to barometric pressure changes in the
(Baehr et al., 1989). Understanding transport of radon and its atmosphere; wind blowing across the soil surface or against

8-1
8-2 Properties and Processes

a hill or other landscape feature; infiltration of water into the for clayey soils than for sandy soils due to the ability of sandy
soil due to rainfall or irrigation; soil-water redistribution and soils to transmit gases at a higher rate (larger soil-gas diffusion
evaporation; temperature gradients near the soil surface; and coefficients and air permeability) and maintain more constant
differences in gas density due to high concentrations of gases concentrations.
that have densities greater than air. Soil-gas pressure gradi-
ents are also created artificially using soil venting, or soil-
vapor extraction, as techniques for removing harmful volatile 8.3  Mechanisms of Gas Transport
gases from contaminated waste sites in the unsaturated zone
8.3.1  Diffusion Processes and Definitions
(Rathfelder et al., 1995).
The molecular transport of one gas relative to another is known
8.2  Soil-Air Composition as diffusion. Diffusion in porous media consists of several kinds
of movement: ordinary or continuum diffusion (also known as
The composition of soil air depends on the relative magnitude molecular, mass, or concentration diffusion); Knudsen diffusion
of both the sources and sinks of the various gas components, and configurational diffusion (free-molecule diffusion; Ho and
the interchange between soil air and atmospheric air, and the Webb, 2006); pressure diffusion; thermal diffusion; forced diffu-
partitioning of the gases between the gaseous, liquid, and solid sion; and surface diffusion. For the first of these, ordinary dif-
(mineral and organic matter) phases of the soil. If a soil were fusion, molecules of a given species transfer momentum to the
completely “aerated,” the concentrations of the gases in the soil molecules of other species, and if a concentration or mole frac-
air would be similar to that in the atmosphere. Oxygen concen- tion gradient exists, there will be a net movement of a gas spe-
trations in the soil air will be somewhat below that in the atmo- cies from the more-concentrated region to the less-concentrated
sphere (approximately 20% by volume), since O2 is consumed region. The probability of molecule–molecule collisions is much
in soil by plant root and microbial respiration (including soil greater than molecule-wall collisions or, in other words, the
mezofauna) and through chemical reactions. Under some con- distance that a molecule moves before it collides with another
ditions, O2 concentrations can go to zero and the soil becomes molecule (i.e., the mean free path), is much smaller than the soil-
anaerobic (anoxic). It is now widely accepted that under some pore diameter.
conditions soil profiles do not have to be either fully aerated or For Knudsen diffusion, the probability of molecule–molecule
fully anaerobic but may be partially aerobic and partially anaer- collisions is negligible compared to molecule-wall collisions,
obic. Anaerobic pockets or “hot spots” may exist within the soil or in other words, the mean free path is much larger than the
due to pockets of very high O2 consumption such as around soil-pore diameter. In this case, gas molecules transfer momen-
incorporated carbon materials and/or due to very slow diffusion tum predominately to the pore walls rather than to other gas
to regions of O2 consumption. For example, the interior of large molecules. The driving force for flow is due to a concentration
aggregates may be anaerobic due to slow diffusion to microbial gradient just as in ordinary diffusion. As the pore size gets even
“hot spots.” smaller, approaching that of single gas molecules, the flow mech-
Carbon dioxide concentrations in the soil air can be as high anism changes and configurational diffusion (Ho and Webb,
as 10 times larger than in the atmosphere (0.036% by volume). 2006) becomes important.
Since nitrogen gas (N2) is more abundant than other gases in Pressure diffusion is the separation of gases of different molec-
the atmosphere (∼76%) and there are generally no sources or ular weight under a pressure gradient (Chapman and Cowling,
sinks for N2 in the soil (except N2 produced during denitrifica- 1970). Pressure diffusion causes the heavier molecules to diffuse
tion), the concentration of N2 in the soil air will be similar to toward the regions of greater pressures. Under the natural gravi-
that in the atmosphere, varying only slightly depending on the tational pressure gradient, the heavier molecules tend to diffuse
production and consumption of other soil gases. The soil air will downward along the direction of gravity. Pressure diffusion is
also contain varying amounts of nitric oxide and nitrous oxide generally negligible for vadose zone depths of less than 100 m
(from nitrification and denitrification); methane, hydrogen sul- (Amali and Rolston, 1993).
fide, and ethylene (from anaerobic processes); water vapor; and Thermal diffusion is the movement of gases due to a tempera-
trace amounts of inert gases such as argon. Human activities ture gradient. This process appears to be minimal (Grew and
also result in the accidental or intentional introduction of gases Ibbs, 1952; Bird et al., 2007) because it requires large tempera-
in the soil profile such as fumigants, anhydrous ammonia, pes- ture gradients of 200°C or more, which are not possible under
ticides, and various organic chemicals that exist partially in the normal conditions in soils. Another diffusion process due to
gas phase. external forces such as a gravitational, electric, or magnetic field
The concentrations of O2 and CO2 that occur in the soil-pore of some kind is called forced diffusion. For a case where gas mol-
space vary widely, especially for CO2, and depend on the rate of ecules are adsorbed by a pore wall or surface, the gas molecule
consumption and production and upon the rate that the soil is may migrate along the surface giving rise to surface diffusion
able to exchange these gases between the soil and the atmosphere where the binding energy is not too great. Since soil particles
through diffusion and advection. The diurnal and annual vari- are generally covered by multiple layers of water, surface dif-
ability in the soil-gas concentrations is generally much greater fusion is either not likely or becomes incorporated into an
Gas Transport in Soils 8-3

effective diffusion coefficient. For diffusion in soil and vadose The  more common case is that diffusing gases differ in their
zone materials, only ordinary and Knudsen diffusion are gen- molecular weights. If one considers two different gases of dif-
erally considered to be of most importance (Thorstenson and fering molecular weight initially separated that are allowed to
Pollock, 1989a, 1989b). diffuse into each other, two inseparable phenomena will occur.
First, the lighter molecules will diffuse faster than the heavier
molecules creating a higher concentration in the region toward
8.3.2  Gas Flux Definitions which they flow. A pressure gradient thus develops that creates a
As with diffusion processes, there are several different kinds of nonsegregative viscous flux in a direction opposite to that of the
fluxes that arise from different driving forces in soils. direction of diffusion of the lighter molecules. Since this non-
segregative viscous flux arises as a result of a difference in con-
8.3.2.1  Ordinary Diffusive Flux centration (nonequimolarity) it is called a “nonequimolar flux”
(Cunningham and Williams, 1980). This flux is also called “diffu-
As mentioned earlier, ordinary or molecular diffusion occurs
sion slip flux.” At some point, a quasi steady state will be reached,
where there are no temperature or pressure gradients in systems
and the pressure gradient will become constant. Macroscopically,
where the pore size is much larger than the mean free path of the
the only observable phenomena would be the equal and opposite
gas molecules or is dominated by molecule–molecule collisions.
net fluxes of the two different gases (Thorstenson and Pollock,
Although gas molecules are constantly in motion, there will only
1989a, 1989b).
be a net flux (mass of gas moving across a cross-sectional area
of soil per unit time) of a gas if a concentration or mole fraction 8.3.2.4  K nudsen Diffusive Flux
gradient exists. Strictly speaking, ordinary diffusive flux only
Knudsen diffusive or free-molecule flux occurs when the gas
occurs for a binary mixture of gases that are of equal or nearly
mean free path is much greater than the pore size. For this case,
equal molecular weights, which results in equal countercurrent
the gas molecules will collide only with the walls and rebound-
diffusion. Diffusion is considered to be “segregative” because the
ing molecules do not collide with other gas molecules. The flux is
diffusing species has a different velocity than that of the gas as a
in response to a concentration gradient, there will be segregation
whole (Cunningham and Williams, 1980).
of species, and specific species fluxes will be independent of one
For a two-component system consisting of gases i and j, the
another and additive.
diffusive flux of gas i is given by Fick’s first law,
The Knudsen flux in a capillary tube can be described by

NiF = −DijC∇y i , (8.1) Nik = −Dik C∇y i , (8.2)

where where
NiF is the molar diffusive flux of gas i (mol m−2 s−1) Nik is the molar Knudsen flux of gas i (mol m−2 s−1)
C is the total molar density (mol m−3) C is the total molar density (mol m−3)
Dij is binary diffusion coefficient (m2 s−1) for the gas pair Dik is Knudsen diffusion coefficient (m2 s−1) for the gas i
∇y i is the gradient in the mole fraction of gas i within the capillary tube
∇y i is the gradient in the mole fraction of gas i (Reinecke and
Discussion of how Fick’s law is adapted for use in porous media Sleep, 2002)
will be presented later.
For unsaturated soils, a whole range of air-filled pore sizes will
8.3.2.2  Viscous Flux (Advection) be available, and some method is needed to obtain an effective
The flow of gas due to a pressure gradient is called viscous or Dik for the porous medium. An approach used by Reinecke and
advective flux. Viscous flux differs from that of diffusive flux in Sleep (2002) is to make use of the Brooks–Corey equation relat-
that the gas molecules lose momentum due to collisions with ing soil-water potential to water-phase saturation (Corey, 1994).
pore walls and there is no segregation of species since a spe- Using the Brooks–Corey relationship gives
cific gas species is moving at the same velocity as the gas as a
whole (Cunningham and Williams, 1980). For soils, a viscous Dik = Dik0 (1 − Se )2 (1 − S(e1+λ )/ λ ), (8.3)
flux is due to the presence of a pressure gradient that arises from
artificially applying a pressure difference in the soil or to such where
effects as barometric pressure changes, wind, and/or infiltration Dik0 is the Knudsen diffusion coefficient for an effective water
of water. saturation of zero (determined empirically)
Se is the effective water saturation
8.3.2.3  Nonequimolar Flux (Diffusion Slip Flux) λ is an empirical parameter called the pore-size distribution
In general, ordinary diffusion of gases with equal molecular wei- index that is determined from the soil-water characteristic
ghts and equal countercurrent diffusion is rare in porous media. for a particular soil or porous medium
8-4 Properties and Processes

8.3.2.5  Total Flux The partitioning of soil gas between the gas and liquid phases is
The total molar diffusive flux, NiD , is the sum of the segregative given by Henry’s law,
ordinary diffusive flux and the nonsegregative nonequimolar
diffusive flux given by C g = K HC l , (8.7)

v
where
NiD = NiF + x i ∑N ,
j=1
D
j (8.4) Cg is mass concentration of gas in the gas phase
K H is the Henry’s law constant

v
Soil gases vary significantly in their solubility in water. A table
where x i • j=1
N Dj is the nonequimolar flux.
giving Henry’s law constants for various soil gases and chemi-
The total molar gas flux is the sum of the total diffusive flux
cals is given by Farrell et al. (2002).
and the molar viscous flux given by

NiT = NiD + NiV . (8.5) 8.3.4  Gas Reactions

8.3.4.1  Respiration
The equations for molar viscous flux will be given in a later Oxygen is continuously consumed and CO2 produced by plant
section. roots and by soil microorganisms and other soil fauna. This
process and the exchange of O2 and CO2 between soil and the
8.3.2.6  Diffusion versus Dispersion atmosphere are called aeration. For a thorough description of
According to the equation for total flux (Equation 8.5) above, soil aeration processes, see the texts of Glinski and Stepniewski
the diffusive and the viscous flux are totally additive. However, (1985) and Scott (2000). The rates of O2 consumption and CO2
it has been shown (Rolston et al., 1969) that when a pressure production are directly related to the rate of plant and micro-
gradient is applied to soil columns inducing both viscous and bial growth, which in turn is related to several environmental
diffusive flow that an additional gas mixing phenomena occurs factors including air and soil temperature, substrate availabil-
called dispersion. Dispersion is a complicated phenomenon due ity, and soil moisture. Many studies have shown that the bulk
to differences in gas velocities within a soil pore and between of the soil respiratory activity (>90%) occurs in regions of high
pores. Dispersion is usually handled mathematically by adding organic matter near the soil surface (Glinski and Stepniewski,
a dispersive flux term to the total advective or viscous flux (Jury 1985). For aerobic conditions, the amount of CO2 produced and
and Horton, 2004). The dispersive flux is usually described by O2 consumed tends to be about equal. For anaerobic conditions,
an equation identical to Fick’s law, except the ordinary diffusion the CO2 production will tend to be larger than the O2 consump-
coefficient is replaced with a dispersion coefficient. tion because other reactions are occurring.

8.3.4.2  Oxidation/Reduction
8.3.3  Gas/Liquid/Solid Partitioning These processes are connected with the transfer of electrons from
During gas transport through soils and vadose zone materials, soil organic matter (or organic contaminants) to oxidized inor-
some of the moving gas will dissolve in the soil water and some ganic compounds catalyzed by enzymes produced by soil micro-
will adsorb onto soil surfaces. For oven-dry soil (no or little water organisms. For well-aerated conditions (aerobic), O2 is the electron
adsorbed on soil surfaces), soils have a high capacity to adsorb acceptor. When O2 becomes limiting (anaerobic), other substances
gas. For example, Petersen et al. (1994, 1995) determined that will accept electrons or be reduced. Examples of compounds that
the adsorption of toluene and trichloroethylene was 4 orders of can be reduced under anaerobic conditions are nitrate, manganic
magnitude higher on oven-dry soil than on moist soil. Water is manganese, ferric iron, sulfate, and perchlorate (a natural and
preferentially adsorbed on soil surfaces over most soil gases, so anthropogenic contaminant). The reduction of nitrate and sulfate
for a moist soil, little gas will be adsorbed or partitioned on soil results in N2 (and N2O) and hydrogen sulfide gases, respectively.
solids, but will be dissolved in soil water. The partitioning of soil Another gas produced from reduction processes is methane (CH4).
gas between the solid and liquid phases is given by Both CH4 and N2O are strong greenhouse gases and contribute to
global warming. For further information on oxidation/reduction
processes in soils, see Glinski and Stepniewski (1985).
C s = K dC l , (8.6)
8.3.4.3  Production and Consumption
where There are a few gases produced in soils that are not necessarily
Cs is the mass concentration of adsorbed gas on the soil solids associated with oxidation/reduction reactions. When fertilizer
Kd is the liquid/solid partitioning coefficient materials such as urea and ammonium salts are applied to the soil,
Cl is the mass gas concentration in the liquid phase reactions can occur, particularly in soils with a pH greater than
Gas Transport in Soils 8-5

about 7.5 or 8 that produces ammonia gas (NH3). Fairly large emis- This equation results in n − 1 independent equations because
sion of NH3 can occur, for instance, if urea is applied to the soil sur-
n
face since urea hydrolysis results in a large increase in pH near the
fertilizer granules, with NH3 being emitted. The deeper the mate- ∑ y = 1.i (8.9)
rial is placed, the lesser the NH3 will be emitted. Ammonia may i =1
also be produced in soil from the incorporation of animal waste.
To use this equation for soils, the binary diffusion coefficient, Dij,
Under aerobic conditions, ammonium-based materials either
would need to be replaced with the soil-gas diffusion coefficient
from fertilizer or mineralization of organic materials will be oxi-
to be discussed later.
dized to nitrite and then to nitrate by microbial processes (nitri-
fication). During nitrification, some N2O and nitric oxide (NO)
can be produced and emitted to the atmosphere (Venterea and 8.4.2  Fick’s Equations
Rolston, 2000). Nitric oxide enters into the tropospheric ozone
Fick’s first law applies to steady-state gas transport, and Fick’s
cycle and can contribute to very small particle (<10 or <5 μm)
second law is for unsteady (transient) transport derived by
generation in the atmosphere.
incorporating Fick’s first law into the mass conservation equa-
Besides O2, gases including hydrocarbons, N2O, NO, CH4,
tion. Fick’s first law for diffusion is considered to be a restric-
and some sulfur gases may move from the atmosphere into the
tive case of the Stefan–Maxwell equations. Jaynes and Rogowski
soil and be consumed by biological processes. Thus, the soil may
(1983) showed that Fick’s law would result in incorrect estima-
act as a significant sink for atmospheric gases under some cir-
tions of mass distributions and fluxes for systems containing
cumstances. At toxic waste sites, the vapors of VOCs may be
two or more vapor components when the concentrations of the
prevalent in the gas phase of soil and may undergo various con-
diffusing species are not small compared to the bulk gas. They
sumption and production processes. In other cases, fumigants,
showed that in ternary systems, the Fickian diffusion coeffi-
herbicides, and pesticides are added to soil for agricultural pur-
cient depends not only on the binary diffusion coefficient and
poses, and the vapors of these chemicals may undergo consump-
flux ratios but also on the mole fraction of the diffusing species.
tion processes due to biodegradation.
Leffelaar (1987) found that when the binary diffusion coeffi-
cients are different by a factor of two, the diffusion of gases in
8.4  Gas Transport Theory multicomponent gas mixtures could not accurately be described
8.4.1  Stefan–Maxwell Equations with Fick’s law. Amali and Rolston (1993) showed that if the total
mole fraction of VOC vapors in air exceeded about 0.05, Fick’s
In general, the diffusion velocities of gas mixtures in porous law fluxes deviated from the true diffusive flux for each species
media are related to each other in a complex manner dependent by up to 5%. This indicated that the total mole fraction of the
upon the mole fraction of each gas, the molar fluxes of each gas, diffusing species also needs to be considered in addition to the
and the binary diffusion coefficient of each gas pair. Bird et al. requirement of Leffelaar (1987) that the binary diffusion coef-
(2007) indicate that the Stefan–Maxwell equations are simply an ficients of the diffusing species must be sufficiently different for
extension of Fick’s law for multicomponent mixtures of gases. multicomponent effects to be observed.
Curtiss and Hirschfelder (1949) gave the general equations for Thus, Fick’s law is generally applicable for only a few spe-
steady transport of a multicomponent mixture of gases, based cial situations. One of these cases is for the diffusion of a trace
on kinetic gas theory. If gravity effects are ignored or diffusion gas in a binary mixture, meaning that the mole fraction of the
occurs only horizontally, the well-known Stefan–Maxwell equa- tracer gas is small. The second special case is for diffusion of
tions provide the theoretical framework for 1D diffusion of gases two gases in a closed system (total pressure remains constant
in soils, given by or there is equimolar countercurrent diffusion). In this case,
neither gas needs to be in trace amounts. A third case where
n
y jNi − y i N j P dy i Fick’s law is applicable is for a three-gas system where there is
∑
j=1,i ≠ j
D ij
=−
RT dz
, (8.8)
equimolar, countercurrent diffusion of two of the gases and the
third gas is stagnant (Jaynes and Rogowski, 1983). The conse-
quences and potential errors of using Fick’s law for situations
where
other than the few special cases above are discussed in the
y i and y j are the mole fractions of gases i and j, respectively
application sections later on.
Ni and Nj are the molar fluxes (mol m−2 s−1) of gas i and j,
To use Fick’s law for describing steady transport of a single
respectively
gas species in soils, one must assume that the above condi-
Dij is the binary diffusion coefficient (m2 s−1) for gas pairs
tions are met. Fick’s first law given in mass fluxes and mass
i and j in the gas phase (no porous media)
concentrations is
P is total pressure (kPa)
R is the universal gas constant (m3 kPa mol−1 K−1)
T is absolute temperature (K) Mg ∂C g
= fgF = −Dp , (8.10)
z is a spatial coordinate (m) At ∂z
8-6 Properties and Processes

where theory (Ho and Webb, 2006). Writing the DGM in terms of total
Mg is the amount of gas diffusing (g gas) molar flux (diffusive plus advective) relative to fixed coordinates
A is the cross-sectional area of the soil (m2 soil) (Thorstenson and Pollock, 1989a) gives
t is time (s)
fgF is the gas flux density (g gas m−2 soil s−1) n
y i N Tj − y jNiT NiT P∇y i ⎛ k gP ⎞ y i ∇P
Cg is concentration in the gaseous phase (g gas m−3 soil air) ∑ e
Dij
− k =
Di
+ ⎜1 + k
⎜
RT ⎝ Di μ g
⎟⎟
⎠ RT
, (8.13)
z is distance (m soil) j =1
j≠i
Dp is the soil-gas diffusion coefficient (m3 soil air m−1 soil s−1)

where
Soil air is considered to consist of a mixture of gases (i.e., N2, O2,
N Tj is the total molar flux of gas species j
CO2, etc.). For unsteady transport of gases in soil, Fick’s second
Dije is the effective ordinary diffusion coefficient of gas species
law, including partitioning of the soil gas in soil water and onto
j in i
soil surfaces and a source/sink term for production/consumption
kg is the air permeability
processes, is
μg is the gas viscosity

∂C g ∂ 2C g The effective ordinary diffusion coefficient, Dije , is equiva-

Rε = Dp − rg , (8.11)
∂t ∂z 2 lent to the soil-gas diffusion coefficient, Dp, in Fick’s equations

above. The first term on the left-hand side of the above equation
considers molecule–molecule interactions and is recognized as
where R is the retardation factor given by the Stefan–Maxwell equations. The second term on the left-hand
side takes into account molecule–particle interactions (Knudsen
θ ρK diffusion). The first and second terms on the right-hand side
R =1+ + b d (8.12) represent the driving forces for diffusion and advection due
εK H εK H
to gradients in gas partial pressure (concentration) and total
pressure, respectively (Ho and Webb, 2006). If Knudsen diffu-
ε is the soil-air content (air-filled porosity; m3 air m−3 soil) sion is negligible and there are no total pressure gradients, the
rg is the sink or source (positive sign) that can be described by DGM simplifies to the Stefan–Maxwell equations. For a more
various kinetic equations thorough description of the DGM, see the books by Mason and
θ is soil-water content (m3 water m−3 soil) Malinauskas (1983) and Ho and Webb (2006), and the papers by
ρb is soil dry bulk density (kg soil m−3 soil) Thorstenson and Pollock (1989a, 1989b).

8.4.4  Darcy’s Equation

8.4.3  Dusty Gas Model
Darcy’s law can be used to describe advective gas transport in
In order to use either the Stefan–Maxwell equations or Fick’s law
soils. For a nonreactive gas, the total molar advective (viscous)
as given above to calculate soil-gas flux and/or concentration dis-
flux is given by
tributions, the equations are modified by inserting empirically
obtained, soil-gas diffusion coefficients for the binary diffusion
coefficients in free air (no porous media). Even without imposed P kg
NV = − ∇P. (8.14)
pressure gradients in the soil, advective or viscous flow may RT μ g

occur in nonequimolar diffusion processes (discussed above).
Only for equimolar gases will diffusion not result in advection.
The phenomena of an advective flux due to diffusion of a non- 8.4.5  Convection–Dispersion Equation
equimolar system of gases have been implicitly included in the If one assumes that for both diffusion and advection that the two
diffusion formulation (Bird et al., 2007), in that diffusion is in processes are simply additive, then the total mass flux is the sum
relation to the molar-average velocity of the gas as a whole (Ho of the flux due to diffusion by Fick’s law and that due to advec-
and Webb, 2006). Coupling of diffusion and advection due to the tion by Darcy’s equation. Thus, the total mass flux is
nonequimolar phenomenon has been formulated with the devel-
opment of the dusty gas model (DGM) by Mason et al. (1967).
fgT = fgF + fgD , (8.15)
The DGM includes the effect of the porous media as a “dusty gas”
component of the gas mixture, where the “dusty gas” is assumed
to be large molecules fixed in space. The DGM combines ordi- where
nary and Knudsen diffusion through kinetic arguments and fgF is the mass flux due to Fick’s first law
advective fluxes are added based on Chapman–Enskog kinetic fgD is the mass flux due to Darcy’s equation
Gas Transport in Soils 8-7

Combining these fluxes and the mass conservation equation C g = Cs t≥0

x=0
(equation of continuity) and assuming that the gas is nonreac-
tive gives

∂C g Dp ∂ 2C g fgD ∂C g Soil
= − . (8.16)
∂t ε ∂z 2 ε ∂z

The term fgD / ε is the “average” velocity of gas v g within pores.

Due to additional mixing from dispersion (see definition above), Cg = Cs t=0
the term Dp /ε = DH becomes somewhat of a fitting parameter x=L
and is called the dispersion coefficient (Rolston et al., 1969). Cg = C0 t=0

8.5  Measuring Gas Transport

Parameters Cg = f(t) t>0

8.5.1  Soil-Gas Diffusion Coefficient

Diffusion chamber
In order to use the models above for calculating soil-gas fluxes x=L+a
and/or soil-gas concentration distributions, the fundamental
FIGURE 8.1  Schematic showing boundary and initial conditions
parameter that must be determined either by measurement or used in the recommended laboratory method for determining the soil-
from predictive equations is the soil-gas diffusion coefficient, Dp. gas diffusion coefficient. (Redrawn from Rolston, D.E., and P. Moldrup.
Field or in situ methods are available, but the most common 2002. Gas diffusivity, p. 1141–1158. In G.C. Topp and J.H. Dane (eds.)
approach is a laboratory method using either undisturbed or Methods of soil analysis, Part 4, Physical methods. SSSA, Madison, WI.
repacked soil cores (Rolston and Moldrup, 2002). As with most With permission from Soil Science Society of America.)
other soil properties, the soil-gas diffusion coefficient is spa-
tially variable, so multiple cores should be collected from each up a binary mixture. Thus, the self-diffusion coefficients are
soil depth of interest. The diffusion coefficient is also strongly very similar. The binary diffusion coefficient of O2 diffusing
dependent upon the soil-air content (air-filled porosity), which into either air or N2 is very similar to the self-diffusion coeffi-
is dependent upon the soil-water content. Thus, diffusion coef- cients of O2 and N2. Based upon these arguments, with O2 as the
ficients should be measured over a range of soil-air contents. tracer gas in measurements of the soil-gas diffusion coefficient
The standard laboratory method is based upon establishing a and using Fick’s law, using O2 as the tracer gas appears to be a
tracer gas concentration, Co, within a chamber (Figure 8.1). One valid approach. Furthermore, Leffelaar (1987) indicated that if
end of a soil core at concentration Cs is placed in contact with the binary diffusion coefficients do not differ by more than a
the gas of the chamber. The other end of the soil core is main- factor of 2, then Fick’s law should be valid. Since O2 is poten-
tained at concentration Cs, usually by exposing the core to the tially consumed in moist soil and CO2 is produced by microbial
atmosphere. The gas of interest diffuses either into or out of the respiration, an additional error may occur. However, since the
chamber depending upon the gas concentration Co compared to diffusion measurements are taken over fairly short time periods
that outside the core. The other gases making up the atmosphere of a few minutes to a few hours, it is assumed that the consump-
will diffuse in an opposite direction to that of the gas of interest. tion of O2 and production of CO2 is small, and the error in using
The rate of change of concentration versus time in the chamber O2 as the tracer gas is considered to be small (<1.5%) (Moldrup
is related to the soil-gas diffusion coefficient. et al., 2000b).
The gases to be used in measuring the soil-gas diffusion coeffi- The method described here is based on solutions to Fick’s
cient should be selected with some care to be sure that Fick’s law second law given by Currie (1960). Similar procedures have
is valid. As discussed above, this means that the gas of interest been used by several investigators (Rust et al., 1957; Gradwell,
should be in trace amounts or that the self-diffusion coefficients 1961; Shearer et al., 1966; Flühler, 1973; Schjønning, 1985;
of the gases in the diffusion apparatus are similar. Also, the gas Resurreccion et al., 2008).
should be basically nonreactive in order to simplify the math- For unsteady diffusion of a gas that is nonreactive (physically,
ematical derivation. For example, a trace gas that has been used biologically, and chemically), Equation 8.11 can be simplified
for this purpose is Freon diffusing into air. Freon is nonreactive to give
and can be measured in trace amounts by gas chromatography
(Rolston and Moldrup, 2002). Another common approach is to ∂C g ∂ 2C g
ε = Dp , (8.17)
use oxygen in air as the gas of interest diffusing into nitrogen ∂t ∂z 2
gas. The two gases, O2 and N2, make up 99% of atmospheric
air and their molecular weights are similar, basically making where ε is the soil-air content (m3 air m−3 soil).
8-8 Properties and Processes

In developing Equation 8.11, it is assumed that the soil is TABLE 8.1  The First Root, α1L, of αL tan αL = hL
uniform with respect to the diffusion coefficient and that ε is and the Roots of This Equation Are All Real If hL > 0
constant in space and time. Equation 8.17 may be solved subject hL α1L hL α1L hL α1L
to the boundary and initial conditions given in Figure 8.1. The
0 0 0.4 0.5932 8.0 1.3978
solution (Carslaw and Jaeger, 1959, p. 128) for the relative con-
0.001 0.0316 0.5 0.6533 9.0 1.4149
centration in the chamber Cr is
0.002 0.0447 0.6 0.7051 10.0 1.4289
∞ 0.004 0.0632 0.7 0.7506 15.0 1.4729
Cg − Cs 2h exp(−Dpα 2n t/ε)
Cr =
Co − Cs
= ∑ L(α 2n + h 2 ) + h
, (8.18) 0.006
0.008
0.0774
0.0893
0.8
0.9
0.7910
0.8274
20.0
30.0
1.4961
1.5202
n =1
0.01 0.0998 1.0 0.8603 40.0 1.5325
where 0.02 0.1410 1.5 0.9882 50.0 1.5400
Cg is the concentration in the chamber (g m−3) 0.04 0.1987 2.0 1.0769 60.0 1.5451
h = ε/(aεc), εc is the air content of the chamber (1.0 m3 air m−3 0.06 0.2425 3.0 1.1925 80.0 1.5514
chamber), a is the length of the chamber or the volume V, 0.08 0.2791 4.0 1.2646 100.0 1.5552
of the chamber per area A, of soil 0.1 0.3111 5.0 1.3138 ∞ 1.5708
αn, with n = 1, 2,…, are the positive roots of 0.2 0.4328 6.0 1.3496
0.3 0.5218 7.0 1.3766
αL tan αL = hL. (8.19) Source: Adapted from Rolston, D.E., and P. Moldrup. 2002.

Gas diffusivity, p. 1141–1158. In G.C. Topp and J.H. Dane
(eds.) Methods of soil analysis, Part 4, Physical methods.
At some time greater than zero, the terms for n ≥ 2 are negligible SSSA, Madison, WI. With permission from Soil Science
with respect to the first term, and Equation 8.18 reduces to Society of America.

2h exp(−Dpα12 t/ε) Cr versus time, t, according to Equation 8.20, and determine the
Cr = , (8.20)
L(α12 + h 2 ) + h slope = −Dp α12 / ε from the linear part of the curve. To get Dp

from this relationship, one must have a measured value of ε, and
where α1 is the first root of Equation 8.19 above. Thus, for a plot the value of α1 must be determined from Table 8.1. For specif-
of ln Cr versus time t, Equation 8.20 becomes linear with the ics on the diffusion apparatus, measurement methodologies,
slope = −Dp α12 / ε for sufficiently large t. and alternative approaches for handling the data, see Rolston
To make the diffusion coefficient measurement, the diffusion and Moldrup (2002). Also, see Rolston and Moldrup (2002) for a
apparatus is set up according to the boundary and initial condi- description of some field methods for measuring Dp.
tions of Figure 8.1 using a diffusion chamber setup similar to
Figure 8.2. The tracer gas is measured within the diffusion cham- 8.5.2  A ir Permeability
ber initially and then at several times after tracer gas is allowed
to diffuse either into or out of the diffusion chamber. Graph ln The fundamental soil property for advective gas transport in
soils is the air permeability. It is similar to hydraulic conductiv-
ity for soil water but differs in that the air permeability of dry
porous media is larger than the corresponding permeability
determined from water flow due to the occurrence of slip flux
L = 4.1 cm
Sample along the pore walls (Klinkenberg, 1941). As with the soil-gas
O-ring
diffusion coefficient, the air permeability differs for various soil
types and is highly dependent upon soil-water content.
In principle, the air permeability is determined by imposing
a pressure gradient across some volume of soil (a soil column
in the simplest case) to induce a steady-state advective flow of
Slide plate
gas through the soil. The steady-state approach is used predomi-
a = 9.5 cm Diffusion nately for laboratory methods where either the pressure gradient
Inlet and
chamber outlet valve is maintained constant and the flow rate is measured or the flow
rate is maintained constant and the pressure is measured. The
pressure gradient across the column and the flow rate through
the soil volume are measured and the air permeability is calcu-
lated from Darcy’s equation (Equation 8.14).
Oxygen electrode
There have been many experimental variations and measure-
FIGURE 8.2  Schematic diagram of a diffusion apparatus that uses ment approaches of steady-state laboratory and field approaches
oxygen as the tracer gas. since the early designs of Grover (1955) as discussed by Ball and
Gas Transport in Soils 8-9

pumping gas through columns, generally of differing soil-water

content. The soil-air content for the column must be known.
The flow rate of the gas is measured precisely, and a switching
mechanism is established on the inflow end of the column
L = 4.1 cm Sample so that the gas flow into the column can be switched from the
background gas to the tracer gas. Initially, the column is flushed
with a background gas such as N2 until the flow becomes steady
and the gas filled pores are completely filled with the back-
ground gas. Then, the inflow gas is switched to the tracer gas,
and the concentration of the tracer gas is measured in the outlet
gas stream. Some investigators have also measured the tracer gas
Flow meter
concentration at various distances along the column in addi-
Valve tion to the outlet gas stream. The concentration of the tracer
gas in the outlet gas stream (and at sampling points along the
Compressor column if applicable) is measured as a function of time, usually
until the tracer gas concentration is equal to the concentration
in the inflow stream. The inflow gas may be switched back to
Manometer the background gas and tracer gas concentration in the outflow
measured until the tracer gas approaches zero.
Solutions of the convective–dispersion equation (Equation
FIGURE 8.3  Schematic of a typical laboratory apparatus to measure
8.16) (Rolston et al., 1969; Costanza-Robinson and Brusseau,
the air permeability of a soil core.
2002, 2006) are then compared with the experimental data with
Schjønning (2002). In a nonsteady-state field method first used the dispersion coefficient being a fitting parameter. Some inves-
by Kirkham (1946), air permeability was calculated from the tigators also curve fit the pore-gas velocity in the convective–
rate of decrease in pressure in a tank supplying the air flowing dispersion equation (Hamamoto et al., 2009b) and then compare
through an in situ soil sample. the fitted pore-gas velocity with the measured velocity deter-
The laboratory technique recommended by Ball and mined from the gas flow rate and the soil-air content.
Schjønning (2002) is the steady-state approach used by Ball et al. Various designs of the experimental apparatus have been
(1981) where the air permeability is measured on an intact or used (Rolston et al., 1969; Costanza-Robinson and Brusseau,
repacked soil core enclosed within a two-chamber apparatus. 2002; Poulsen et al., 2008), but Hamamoto et al. (2009b) con-
The two-chamber apparatus allows good control of the bound- structed a unique apparatus that allows for the measurement of
ary conditions on each end of the soil core. For this technique, a the soil-gas diffusion coefficient, the air permeability, and the
constant flow of air is applied, and the pressure at each end of the dispersion coefficient on the same soil core shown schematically
soil core is accurately measured. For specifics on this technique, by Figure 8.4.
see Ball and Schjønning (2002). A typical apparatus is schemati-
cally shown by Figure 8.3.
The field method recommended by Ball and Schjønning
8.6  Predictive Equations
(2002) is a steady-state, surface-chamber method where pres- 8.6.1  Soil-Gas Diffusion Coefficient
surized air is applied to a sharpened cylinder (recommended
diameter and height of 200 mm) pressed into the soil. The top 8.6.1.1  Repacked, Dry Soil
of the cylinder is sealed to create a closed chamber. Thus, air Prediction of the soil-gas diffusion coefficient (Dp) in dry porous
flows through the soil enclosed within the cylinder and flows media (void of water) normally can be described by the classical
out the bottom of the cylinder into the soil profile. Air flow power law of Buckingham (1904),
rates and the pressure gradient across the cylinder of soil
are measured precisely. Again, the air permeability is calcu- Dp
lated from Darcy’s law. This method is based on that of van = AεB , (8.21)
D0
Groenewoud (1968), Green and Fordham (1975), Liang et al.
(1995), and Iversen et al. (2001). For specifics on this technique,
see Ball and Schjønning (2002). where
Dp is the soil-gas diffusion coefficient (m3 soil air m−1 soil s−1)
D0 is the gas diffusion coefficient in free air (m2 air s−1)
8.5.3  Dispersion Coefficient
ε is the volumetric soil-air content (the air-filled porosity;
The soil-gas dispersion coefficient is generally determined from m3 soil air m−3 soil)
laboratory soil column experiments (miscible displacement). An A and B are empirical constants representing pore connectiv-
undisturbed or repacked soil column is set up with a system for ity, continuity, and tortuosity of the dry porous medium
8-10 Properties and Processes

Slide
Oxygen electrode

Inlet chamber
O-ring

8.3 cm 30 or 60 - cm soil column

8.3 cm

Flow meter
Valve

Air supply
Outlet chamber
N2 supply

FIGURE 8.4  Schematic of a typical apparatus for measuring the dispersion coefficient of a soil core. Schematic simplified from unified measure-
ment system (UMS) setup by Hamamoto et al. (2009b).

In the case of a dry porous medium, the soil-air content will a small amount of water can have a dramatic effect in reduc-
equal the soil total porosity, Φ (m3 pore space m−3 soil). ing D p/D 0 (Papendick and Runkles, 1965; Moldrup et al.,
Moldrup et al. (2000b) tested three widely used models based 2000a). This is illustrated in Figure 8.5 for a sieved, repacked
on Equation 8.21: the Penman (1940) model (A = 0.66, B = 1), fine sand (Toyoura sand, Japan; data from Hamamoto et al.,
the Millington (1959) model (A = 1, B = 1.33), and the Marshall 2009a) at different moisture contents compared with dry
(1959) model (A = 1, B = 1.5). They found that all three models
0.4
performed well against data for a wide range of sieved, repacked
Dry sand materials
dry porous media (sand, soil, glass beads, steel and glass wool, Wet sand material (Toyoura sand)
and various mixtures) in the range of 0.2 < Φ < 0.6. The Marshall Millington (1959)
(1959) model, 0.3 Marshall (1959)
WLR (Marshall) (Moldrup et al., 2000b)
Gas diffusivity, Dp/D0

Dp
= ε1.5 , (8.22)
D0
0.2
performed best across the entire range of air-filled porosities and
is generally recommended to predict the soil-gas diffusion coef-
ficients in dry, nonaggregated soil.
0.1
In the case of aggregated soil with bimodal pore-size distri-
bution, recent studies (Resurreccion et al., 2008, 2010) suggest
that the change of Dp/D0 with ε in the intraaggregate pore space
is linear and often with a slope close to 0.5. Thus, if the soil is 0.0
highly aggregated and with known values of interaggregate 0.0 0.1 0.2 0.3 0.4
porosity (Φ1; m3 interaggregate pore space m−3 soil) and intra- Soil-air content, ε (m3 m–3)
aggregate porosity (Φ2 = Φ − Φ1), which could be determined
from the measured soil-water retention curve (Resurreccion FIGURE 8.5  Prediction of the soil-gas diffusivity in dry and wet (vari-
ably saturated) sand. Models considered are the Millington (1959) and
et al., 2009), the soil-gas diffusion coefficient for dry conditions
Marshall (1959) models for dry soil (void of water) and a WLR type of model
may be estimated from
for variably saturated soil (Moldrup et al., 2000b). (Data from Moldrup, P.,
T. Olesen, J. Gamst, P. Schjønning, T. Yamaguchi, and D.E. Rolston. 2000a.
Dp (ε = Φ) Predicting gas diffusivity in sieved, repacked soil: Water-induced linear
= (Φ1 )1.5 + 0.5Φ 2 . (8.23)
D0 reduction model. Soil Sci. Soc. Am. J. 64:1588–1594; Moldrup, P., T. Olesen,
P. Schjønning, T. Yamaguchi, and D.E. Rolston. 2000b. Predicting the gas
diffusion coefficient in undisturbed soil from soil water characteristics. Soil
8.6.1.2  Repacked, Wet Soil
Sci. Soc. Am. J. 64:94–100; Hamamoto, S., P. Moldrup, K. Kawamoto, and T.
In the case of wet porous media, the soil water will typically Komatsu. 2009a. Effect of particle size and soil compaction on gas transport
be located in the narrow bottlenecks between pores, meaning parameters in variably saturated, sandy soils. Vadose Zone J. 8:986–995.)
 Gas Transport in Soils 8-11

Toyoura sand and different other dry sands from the litera- This model with a high degree of accuracy predicted Dp/D0 in
ture (data compiled by Moldrup et al., 2000a). In the dry state sieved, repacked soil across the entire water content range from
at different levels of compaction (open circles), the measured wet to dry, and with soil texture ranging from 0% to 54% clay
data are mostly placed in between the models by Millington (Moldrup et al., 2000a). Figure 8.6 shows the performance of the
(1959: A  = 1 and B = 1.33 in Equation 8.21) and Marshall WLR (Marshall) model against data for 15 sands and differently
(1959, Equation 8.22). In the wet state at different moisture textured soils from the literature (data compiled by Moldrup
contents (filled-out circles), the D p/D 0 is markedly reduced et  al., 2000a and Hamamoto et al., 2009a), with total porosi-
compared to the dry state at the same air-filled porosity. This ties (Φ) ranging from 0.4–0.5 m3 m−3 (average 0.45 m3 m−3).
leads to the development of the so-called water-induced lin- Also  shown is the still most commonly used model in the lit-
ear reduction (WLR) class of models (Moldrup et al., 2000a; erature for predicting gas diffusivity, the Millington and Quirk
Hamamoto et al., 2009a), where the D p/D 0 model for an (1961) model,
equivalent dry media at a given ε (Equation 8.21) is multiplied
with a water reduction factor, Dp ε 3.33 ⎛ ε⎞
2

= 2 = ε1.33 ⎜ ⎟ . (8.26)
D0 F ⎝ Φ⎠

N
⎛ε⎞
F=⎜ ⎟ , (8.24)
⎝Φ⎠ The Millington and Quirk (1961) model when rewritten like the

right-hand side of Equation 8.26 is recognized as an analogue
to the WLR model, here based on Millington (1959; A = 1 and
where N for repacked soils typically can be taken as 1 (Moldrup B = 1.33) at dry conditions and with N = 2 in Equation 8.24,
et al., 2000b; Hamamoto et al., 2009a; Resurreccion et al., 2009). representing a nonlinear water reduction factor. Both at high
If the Marshall (1959) model (Equation 8.22) is assumed at dry gas diffusivities (see Figure 8.6a with normal-scale Dp/D0 axis)
conditions and N = 1 is applied in Equation 8.24, the resulting and at low gas diffusivities (see Figure 8.6b with log-scale Dp/D0
WLR (Marshall) model becomes axis), the WLR model (Equation 8.25) is more accurate than the
Millington and Quirk model (Equation 8.26). The upper, mid-
dle, and lower prediction curves for each model (WLR solid line,
Dp ⎛ ε⎞
= ε1.5 ⎜ ⎟ . (8.25) Millington and Quirk dotted line) in Figure 8.6a and b represent
D0 ⎝ Φ⎠
Φ = 0.4, 0.45, and 0.5 m3 m−3, respectively.

0.4 100
Sandy (5 soils)
Loamy/sandy (10 soils)
WLR (Marshall)
from Moldrup et al. (2000b) Φ = 0.50
0.3 Millington and Quirk (1961) 10–1
Gas diffusivity, DP/D0
Gas diffusivity, DP/D0

Φ = 0.40

0.2 10–2
Φ = 0.40
Φ = 0.50

Sandy (5 soils)
0.1 10–3
Loamy/sandy (10 soils)
WLR (Marshall)
from Moldrup et al. (2000b)
Millington and Quirk (1961)
10–4
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.1 0.2 0.3 0.4 0.5 0.6
(a) Soil-air content, ε (m3 m–3) (b) Soil-air content, ε (m3 m–3)

FIGURE 8.6  Prediction of the soil-gas diffusivity in variably saturated sands and soils with 0%–54% clay. Models considered are the widely used
Millington and Quirk (1961) model (dotted line) and WLR model (Moldrup et al. 2000b; solid line). Model performance is shown in (a) normal-
scale DP/D0 and (b) log-scale DP/D0 plots, and for values of soil total porosity (Φ) equal to 0.4 (upper line; representing minimum Φ for data), 0.45
(average for all data), and 0.5 (lower line; representing maximum Φ for data). (Data from Moldrup, P., T. Olesen, J. Gamst, P. Schjønning, T. Yamaguchi,
and D.E. Rolston. 2000a. Predicting gas diffusivity in sieved, repacked soil: Water-induced linear reduction model. Soil Sci. Soc. Am. J. 64:1588–1594;
Moldrup, P., T. Olesen, P. Schjønning, T. Yamaguchi, and D.E. Rolston. 2000b. Predicting the gas diffusion coefficient in undisturbed soil from soil water
characteristics. Soil Sci. Soc. Am. J. 64:94–100; Hamamoto, S., P. Moldrup, K. Kawamoto, and T. Komatsu. 2009a. Effect of particle size and soil compaction
on gas transport parameters in variably saturated, sandy soils. Vadose Zone J. 8:986–995.)
8-12 Properties and Processes

The reason why both measured data and predictive models to 2  + (3/b), following the capillary tube model for hydraulic
suggest that the Dp/D0 at a given air-filled porosity (ε) is larger at conductivity by Burdine (1953),
higher compaction (lower Φ) is due to the larger water to solid
2 + (3 / b )
ratio, remembering that increasing water content typically has a Dp ⎛ D*p ⎞ ⎛ ε ⎞
=⎜ ⎟ , (8.28)
dramatic effect on reducing air-filled pathways for gas diffusion, D0 ⎝ D0 ⎠ ⎜⎝ ε* ⎟⎠
since water will form water blockages in bottlenecks between
air-filled pores. For example, a soil with an air-filled porosity of
where
ε = 0.25 m3 m−3 and a total porosity of Φ = 0.4 m3 m−3 will con-
ε* is the air-filled porosity at DP = D*p
tain a volumetric water content of θ = 0.15 m3 H2O m−3 soil and
D*p is the soil-gas diffusion coefficient at a given reference-
a volumetric solids content of VS = 0.6 m3 solids m−3 soil. This
point soil-water content (e.g., zero water content equal to
yields a volumetric water/solids ratio, θ/VS, of 0.25. If the same
air saturation) or a given soil-water matric potential
soil has a higher total porosity of Φ = 0.5 (less compacted), the
same ε as before will give a θ/VS ratio of 0.25/0.5 = 0.5 (double
At pF 2 (−100 cm H2O of soil-water matric potential), where
the ratio), which explains the markedly higher water blockage
only the larger pores of >30 μm equivalent pore diameter are air
effects and smaller Dp/D0 at larger Φ.
filled, a good relation (r2 = 0.97) between Dp/D0 at pF 2 (Dp100/D0)
The Millington and Quirk (1961) model performs well in
and air-filled porosity at pF 2 (ε100) was found for 126 differently
some cases. Equation 8.26 normally predicts Dp/D0 well in uni-
textured, undisturbed soils (Moldrup et al., 2000b),
form, coarse sandy soils (not included in Figure 8.6), since the
water blockage effects will be more pronounced in media with Dp100 3
larger particles and lower number of pores and bottlenecks = 2ε100 + 0.04ε100 . (8.29)
D0
between pores, explaining the sometimes higher N values for
sandy media (Thorbjørn et al., 2008; Hamamoto et al., 2009a;
Using this as reference-point gas diffusivity in the Moldrup
Resurreccion et al., 2009).
et  al. (1999) b-dependent model yields for undisturbed, less-
It is further noted that in the case of aggregated soil (bimodal
aggregated soil (Moldrup et al., 2000b):
pore-size distribution), it will again be necessary to apply a two-
region model, with the gas diffusivity (Dp/D0) in the interaggre- 2 + (3 / b )
Dp ⎛ ε⎞
gate pore space described by Equation 8.24 with Φ set equal to 3
= (2ε100 + 0.04ε100 ) ⎜ ⎟ . (8.30)
the interaggregate porosity Φ1 (Jones et al., 2003) and Dp(ε)/D0 D0 ⎝ ε* ⎠

in the intraaggregate pore space described by a linear relation
(Resurreccion et al., 2009). This macroporosity (ε100) and b-dependent model well predicted
gas diffusivity in differently textured, undisturbed soils across a
8.6.1.3  Undisturbed Soil wide range of soil and moisture conditions (Moldrup et al., 2000b,
In the case of undisturbed soil, Werner et al. (2004) suggested 2004; Rolston and Moldrup, 2002; Kawamoto et al., 2006b).
that the WLR (Marshall) model, Equation 8.25, was the most Recently, Moldrup et al. (2005) developed soil-gas diffusiv-
accurate compared to a number of classical, soil-type inde- ity models for undisturbed soil linked to the van Genuchten
pendent models (including Equation 8.26) when tested against (1980) soil-water retention model to establish a more direct and
field-measured Dp/D0 across soil types and moisture conditions. detailed link between pore-size distribution and soil-gas dif-
However, to some extent soil structure will influence gas dif- fusivity. However, these models are presently more useful for
fusivity in undisturbed soil compared to sieved, repacked soil. description (curve-fitting to measured data) than prediction due
Moldrup et al. (1999) therefore suggested using the Campbell to the combined high number of soil-water retention and pore
pore-size distribution parameter b as a soil structure index for tortuosity–connectivity parameters involved.
gas diffusivity. The Campbell b equals the negative slope of the The above models represent only a few, although likely the
soil-water retention curve in a pF (i.e., log −ψ) versus log(θ) plot, most precise and useful currently, among the numerous predic-
where ψ is soil-water matric potential in cm H2O and θ is volu- tive models available for soil-gas diffusivity. A more thorough
metric soil-water content in m3 H2O m−3 soil (Campbell, 1974; listing and discussion of predictive and descriptive Dp(ε)/D0
Jury and Horton, 2004), models can be found in Tick et al. (2007) and Allaire et al. (2008).
When using the predictive equations for relative gas diffusiv-
ity in simulation models for diffusive gas transport, the D0 needs
−d[log(−ψ(θ))]
b= , (8.27) to be known for the actual gas under consideration at the given
d[log(θ)] temperature. For example, the trace gas diffusion coefficient of
oxygen in air at 20°C equals the trace gas diffusion coefficient of
where b will always be >0. The Campbell soil-water reten- methane in air at 25°C, equal to 0.205 cm2 s−1 (Andrussow and
tion model normally performs best in the pF interval between Schramm, 1969; Kruse et al., 1996). Further values for the binary
1.2 and 3.2. Moldrup et al. (1999) introduced and successfully diffusion coefficients of common gases at standard temperature
tested  a  power law model for Dp/D0 with the exponent equal and pressure are provided by Rolston and Moldrup (2002) that
Gas Transport in Soils 8-13

100 0.30
Narita sand
0.11–0.25 mm
0.25 0.25–0.42 mm
0.42–0.85 mm
Cumulative mass fraction < D (%)

75 WLR (Marshall) (Moldrup et al., 2000b)

Gas diffusivity, DP/D0

0.20 WLR (Millington) (Moldrup et al., 2000b)

50 0.15

0.10
25
Narita sand
0.11–0.25 mm 0.05
0.25–0.42 mm
0.42–0.85 mm
0 0.00
0 0.2 0.4 0.6 0.8 1 0.0 0.1 0.2 0.3 0.4
(a) Particle diameter, D (mm) (b) Soil-air content, ε (m3 m–3)

250
Narita sand m = 2.8
0.11–0.25 mm
0.25–0.42 mm
200 0.42–0.85 mm
Soil-air permeability, ka (μm2)

RPL from Moldrup et al. (1998)

150

100
m = 2.6

50
m = 2.0

0
0.0 0.1 0.2 0.3 0.4
(c) Soil-air content, ε (m3 m–3)

FIGURE 8.7  Relation between basic soil physical properties and gas transport parameters for three size fractions of Narita sand. (a) particle-size
distribution, (b) gas diffusivity, and (c) air permeability. Also shown are predictions by (b) the WLR type of DP/D0 models (Moldrup et al., 2000b),
and (c) a general power law model for ka (Moldrup et al., 1998). (Data from Hamamoto, S., P. Moldrup, K. Kawamoto, and T. Komatsu. 2009a. Effect of
particle size and soil compaction on gas transport parameters in variably saturated, sandy soils. Vadose Zone J. 8:986–995.)

also provides references for additional gas mixtures and an of pore-size distribution and soil structure is minor, especially
equation (Fuller et al., 1966) to calculate D0 for nonpolar gases for repacked soil (Moldrup et al., 2001). This is illustrated in
from molar mass and volume, pressure, and temperature. Figure 8.7 for three different particle-size fractions of a sandy
soil (Narita sand, Japan, data from Hamamoto et al., 2009a). The
particle-size distribution of the three size fractions are shown in
8.6.2  A ir Permeability and Soil-Gas
Figure 8.7a. Despite the differences in particle (and thus pore)-
Dispersion Coefficient
size distribution, the difference in measured gas diffusivity
Robust predictive models for air permeability (ka) and the soil- (Dp/D0) curves between the three size fractions are minor, and
gas dispersion coefficient (DH) are presently not available across the WLR model based on either Millington (1959) or Marshall
soil type and scale. Both convective gas transport parameters (1959) at dry conditions and with N = 1 (Equation 8.25) well pre-
are highly sensitive to small changes in particle and pore-size dict the data (Figure 8.7b). In contrast to this result, the effect of
distribution and soil structure. This is contrary to the behavior particle (and thus pore)-size distribution on air permeability,
for gas diffusivity (Dp/D0, previous section) where the influence k a (μm2), is dramatic (Figure 8.7c).
8-14 Properties and Processes

8.6.2.1  A ir Permeability This ka(ε) model described well the air permeability for differ-
Moldrup et al. (1998, 2003) suggested a reference-point power ently textured undisturbed soils (100 cm3 scale) sampled from
law model for ka(ε), analogous to Equation 8.28 for Dp/D0, two deep vadose zone profiles. If Campbell b is not known, aver-
age b values of 3 for sandy soils (m = 2), 6 for silty soils (m = 1.5),
m and 10 for clayey soils (m = 1.3) are recommended. For coarse
⎛ ε⎞
k a = k *a ⎜ ⎟ , (8.31) porous media like the two largest particle-size fractions of
⎝ ε* ⎠
Figure 8.7, m values significantly higher than 2 can be observed
(Figure 8.7c), and the d100 value (Equation 8.33) likely exceeds
where 150 μm. Compared to soil-gas diffusivity, the prediction inac-
ka is the soil-air permeability (μm2) curacy for ka is high (order of magnitude) and likely highly scale
ε* is the volumetric soil-air content dependent. It is again stressed that reliable models for ka across
k*a is the air permeability at a given reference point of mois- soil types and scales are not available, and this parameter if pos-
ture content or soil-water matric potential sible should be measured in situ.
m is a tortuosity–connectivity parameter for convective gas
transport 8.6.2.2  Dispersion Coefficient
The same lack of models are evident for the soil-gas dispersion
If the reference point is again (like for soil-gas diffusivity, coefficient, DH (m2 s−1) where very limited amount of studies and
Equation 8.30) chosen at pF 2 (−100 cm H2O), the ka(ε) model measurements have been carried out since the first major study
becomes by Rolston et al. (1969). Like for gas diffusivity and air perme-
ability, Hamamoto et al. (2009b) found different behavior and
m
⎛ ε ⎞ DH(ε) curve shapes for structureless (unimodal) and aggregated
k a = k a100 ⎜ ⎟ . (8.32)
⎝ ε100 ⎠ (bimodal) soils packed in 30 or 60 cm columns. They also for the
first time documented quantitative links between the soil-gas
diffusion coefficient, air (gas) permeability, and soil-gas disper-
For the three particle-size fractions in Figure 8.7c, both ka100 and
sion coefficient for structureless soils and in the interaggregate
m markedly increase with particle size and thus median air-
region of aggregated soils. They found that the soil-gas disper-
filled pore size. Kawamoto et al. (2006a) developed a predictive
sivity (λ, in m),
equation for ka100 from ε100, and Dp100 (applying Equation 8.29
for Dp100) by combining Fick’s law for diffusive transport with
Poiseuille’s law for convective fluid transport and assuming soil DH
λ= , (8.36)
pores to be uniform, tortuous and nonjointed tubes of similar vg

diameter to give

where –vg is the pore-gas velocity, was closely related to the soil-
⎛ d 2 ⎞ Dp100 ⎛ d100
2
⎞
k a100 = ⎜ 100 ⎟ =⎜ 3
(2ε100 + 0.04ε100 ) (8.33) gas diffusion coefficient and air-filled porosity. The best-fit rela-
⎝ 32 ⎠ D0 ⎝ 32 ⎟⎠ tion was

where the average equivalent pore diameter for convective gas

⎛ ⎛ εD ⎞ 0.5 ⎞
transport at pF 2 was found to be d100 = 150 μm (i.e., around five λ = 0.0185 ⎜ ⎜ 0 ⎟ − 1⎟ . (8.37)
times the minimum drained pore size at pF 2), Inserting this in ⎝ ⎝ DP ⎠ ⎠
Equation 8.33 gives

3
k a100 = 700(2ε100 + 0.04ε100 ). (8.34) Combining Equations 8.36 and 8.37 with the WLR (Marshall)
model for Dp, Equation 8.25, yields
Kawamoto et al. (2006a) suggested an expression for the
0. 5
tortuosity–connectivity parameter for convective gas transport, ⎛⎛ Φ ⎞ ⎞
m in Equation 8.32, based on the Alexander and Skaggs (1986) DH = v g × 0.0185 ⎜ ⎜ 1.5 ⎟ − 1⎟ , (8.38)
⎝⎝ ε ⎠ ⎠
capillary tube model for unsaturated water permeability, m = 1 +
(3/b), where b is the Campbell pore-size distribution parameter
(Equation 8.27). Combining Equations 8.32 and 8.34 and insert- where
ing m = 1 + (3/b) yield DH is in m2 s−1
–
vg in m s−1
1+ ( 3 / b )
3 ⎛ ε ⎞
k a = 700(2ε100 + 0.04ε100 ) ⎜ ⎟ . (8.35) This relation needs further testing and modification against a
⎝ ε100 ⎠ wider range of soil types, for undisturbed soils, and at different
Gas Transport in Soils 8-15

measurement scales. Presently, Equation 8.38 is therefore sug- 8.7.1  Soil Aeration
gested to be used only as an order of magnitude estimate for DH.
As discussed above, soil aeration is generally considered to be
the exchange of gases between the soil and the atmosphere, but
8.7  Applications more specifically, it is the transport of O2 from the atmosphere to
There have been many studies to evaluate the applicability of the soil microbial and root respiration sites and the exchange of
the various models and equations for simulating the move- generated CO2 from the soil to the atmosphere. The ratio of the
ment of gases within porous media for a whole range of chemi- production of CO2 (moles) to the consumption of O2 (moles) is
cals, porous media type, and applications. For soil science and called the respiration quotient (Freijer and Leffelaar, 1996). The
other disciplines, the bulk of the applications have used Fick’s respiration quotient is determined by the C–H–O ratio and
laws for modeling purposes. However, as noted above, Fick’s the fraction of the carbon sources that is mineralized to CO2.
laws are only applicable under a limited set of conditions. The respiration quotient varies from 0.8 to 1.1 for most constitu-
From the results of multiple studies, some general statements ents of soil organic matter (Freijer et al., 1995).
can be made about the applicability of the various models for Soil respiration is basically a ternary system of diffusion of N2,
various modeling situations. For cases of multinary system O2, and CO2 (Argon neglected). Fick’s first and second laws have
of gases and where the diffusion coefficients of the diffusing often been used in an effort to quantify soil respiration from
gases are very much different from one another, the Stephan– measurements of the concentration gradients of O2 and CO2
Maxwell equations would be more appropriate than Fick’s within soil profiles. For example, de Jong and Schappert (1972)
law. Neither Fick’s law nor the Stephan–Maxwell equations used field-measured CO2 gradients to calculate the flux of CO2
consider Knudsen diffusion. Thus, for porous media with very in order to estimate soil respiration rates. Freijer and Leffelaar
small pores and with small air permeabilities where Knudsen (1996) used the Stefan–Maxwell equations to evaluate soil res-
diffusion may be important, both of these models may be piration. They concluded that only using Fick’s law for a fairly
inadequate to model gas transport. The dividing line between wide range of the respiration quotient and the O2 consumption
molecular and Knudsen diffusion is still quite uncertain, rate that the errors in the CO2 gradients were small (<5%), but
but there is some evidence that Knudsen diffusion becomes that the errors in the O2 gradients were substantial. Freijer and
important and should be included in models for air perme- Leffelaar (1996) showed through comparison of Fick’s law with
ability less than 10 −13 m 2 (Sleep, 1998; Webb and Pruess, 2003). the Stefan–Maxwell calculations that there will be no error in
The air permeability for many natural soils at field-water con- the O2 gradient only when the respiration quotient is close to
tent range from about 10 −10 to 10 −12 m 2 , except for heavy clay 0.789. Thus, using Fick’s law and the gradient of CO2, as did
soils (>20% clay), where the air permeability may be as low as de Jong and Schappert (1972), soil respiration rate may be esti-
10 −14 m 2 (Moldrup et al., 1998; Kawamoto et al., 2006a). Fick’s mated reasonably well, but errors will occur if the gradient of O2
law and the Stefan–Maxwell equations also may prove inad- is used to calculate the flux. Leffelaar (1987, 1988) developed a
equate when nonequimolar fluxes result in large pressure gra- method to correct the Fickian fluxes by considering the diffusive
dients and subsequent large viscous fluxes. For porous media flux to consist of the Fickian component and a correction term
with small air permeability, the DGM is generally considered to account for the effect of the presence of other gases (nonequi-
to be superior over the other models because it not only con- molar diffusion).
siders Knudsen diffusion but also is applicable to multinary
mixtures of counter diffusing gases (Abriola and Pinder,
8.7.2  Greenhouse Gas Emissions
1985; Thorstenson and Pollock, 1989a, 1989b; Massmann and
Farrier, 1992; Sleep, 1998; Webb, 2006). The three most prevalent greenhouse gases that may be emitted
For cases where either naturally occurring or imposed pres- from soils are CO2, N2O, and CH4. The most common method-
sure gradients occur within porous media, both advection and ology to quantify the emissions of these gases is to measure the
diffusion are controlling processes of gas transport. For high surface flux by placing chambers over the soil surface. Transport
permeability and low concentration of the gas of interest, it is in soil is not considered for this methodology except to correct
generally considered that the convection–dispersion equation is the diffusion flux due to nonlinear behavior of the chamber con-
adequate for modeling. However, if concentration of the gas of centration versus time curves (Livingston et al., 2006; Venterea
interest is high and nonequimolar fluxes may occur, the DGM and Baker, 2008). As for soil aeration, one could use Fick’s law
(with an advective component added) may be more appropri- or some other theory to calculate the diffusion fluxes from mea-
ate (Abu-El-Sha’r and Abriola, 1997). For nonisobaric (pressure sured concentration gradients within the soil near the soil sur-
gradients) conditions and low permeability, the DGM is needed face. Since the greenhouse gases are generally in trace amounts
and is generally considered to be superior over the convection– in soil compared to the other soil gases, one may consider a
dispersion equation (Webb, 2006). There is still a debate about binary system comprised of a trace gas diffusing into air (espe-
the applicability of the various models to real porous media, and cially near the soil surface). Thus, the effective diffusion coef-
there is still large uncertainty in the appropriate parameter val- ficient from Fick’s law would be equal to the binary diffusion
ues to use in the models. coefficient (Jaynes and Rogowski, 1983), and Fick’s law could be
8-16 Properties and Processes

used to calculate the fluxes. However, the large spatial variability nonequimolar gases. Investigators also have used the O2 and
of greenhouse gas concentration profiles in soils generally makes CO2 concentration gradients in soil in an attempt to estimate
this estimate of emission very uncertain. the rate that VOCs or hydrocarbons are being biodegraded.
Thus, because of these properties, it is generally considered that
Fick’s law would not be a valid approach to modeling the move-
8.7.3  Soil Fumigation
ment of these gases, and the Stefan–Maxwell equations (Amali
Various fumigants, including methyl bromide and 1, 3-dichlo- and Rolston, 1993; Amali et al., 1996; Evans et al., 2004), the
ropropene, have been extensively used in agriculture to control DGM (Massmann and Farrier, 1992; Sleep, 1998; Webb and
soilborne pests such as nematodes. Fumigants are generally Pruess, 2003; Fen and Abriola, 2004), or “adjusted” Fick’s law
applied by shank injection into the soil and the soil surface often (Freijer and Leffelaar, 1996; van de Steene and Verplancke,
covered with some kind of plastic tarping material in an attempt 2006) are deemed more appropriate. This application will usu-
to slow the transport of the gas from the soil to the atmosphere ally require knowledge of all three gas transport parameters
in order to attain effective control of the pests. Although some of (Dp, ka, and DH). Some studies (Sleep, 1998; Fen and Abriola,
the early models only considered diffusive transport using Fick’s 2004) show that the DGM is superior to the others for modeling
law (Rolston et al., 1982), the process of gas movement within the the movement of VOCs in soils.
soil can be by both diffusion and advection (from the injection
and volatilization process, wind, barometric pressure changes).
A later model (Chen et al., 1995) used a modified convection– 8.7.5  Radon Transport into Structures
dispersion equation to model the transport of a fumigant with
Radon gas is formed in soil from the radioactive decay of naturally
barometric pressure fluctuations. Wang et al. (1997, 2000, 2004)
occurring radium within the upper few meters of the vadose zone.
used a convection–dispersion model coupled to a heat, water,
Radon is a significant human health concern because of radon
and transport model to evaluate the movement of fumigants
entering buildings and the inhalation of the gas that may poten-
in soils. Although Chen et al. (1995) indicate good agreement
tially cause lung cancer. Radon moves through soil primarily by
between model simulations and measurement of surface volatil-
diffusion except in the near proximity to buildings. Near build-
ization of the fumigant, this case of high concentration of fumi-
ings, radon enters buildings primarily through cracks in base-
gant, cotransport of water vapor (Leffelaar, 1987; Petersen et al.,
ment floors and walls by advective gas transport due to pressure
1996), and advective transport due to pressure gradients may be
differences within and below the building (Nazaroff, 1992). This
a situation where the DGM could have been applied.
advective flow is driven by barometric pressure changes, wind,
Model applications include simulating scenarios of injection
temperature differences, and by operation of heating and air-
depth and either plastic film or high soil-water content near the
conditioning systems. It is estimated that diffusion accounts for
soil surface in order to attempt to decrease the flux of fumi-
about 10% of the transport into single family structures and that
gant out of soil and into the atmosphere (Allaire et al., 2004).
advection contributes the other 90% (Nazaroff, 1992). Since radon
Potentially as equally important as using the most appropriate
gas occurs in very small concentrations, it may be considered to be
gas transport model is to use the most appropriate predictive
a trace gas and Fick’s law for describing the diffusion part of the
equation for Dp. For example, the Millington and Quirk (1961)
transport process should be applicable. For advection, Darcy’s law
relation would underestimate the soil-gas diffusion coefficient at
has been used to describe the gas flow into and around buildings
the higher water contents.
(Riley et al., 1996; Robinson et al., 1997). For a thorough discus-
sion of radon transport through porous media and into buildings,
8.7.4  Volatile Organic Compounds see Nazaroff (1992). Again, this application will usually require
and Vapor Extraction knowledge of all three gas transport parameters (Dp, ka, and DH).

In recent years, there has been a lot of interest in the movement

of VOCs from contaminated soil sites to sites where humans
8.7.6  Volatile Organic Vapor Transport
may be exposed to these chemicals. Also, soil-vapor extraction
into Structures
has been used as a means to remediate contaminated sites by
removing and treating the vapor phase (Falta, 2006). The trans- A focus area for soil-gas transport in relation to human health
port mechanism for soil-vapor extraction is primarily advec- stems from the numerous contaminated soil sites around the
tion, and Darcy’s law has been extensively used (Falta, 2006). world, most of which are in urban areas, causing intrusion of vol-
Many VOCs have molecular weights much different than air, atile organic vapors (e.g., gasoline compounds such as benzene
and consequently their diffusion coefficients are much differ- and chlorinated compounds such as trichloroethylene) from
ent than air. Also, the vapor concentration of these chemicals soil into buildings. Moisture conditions below buildings greatly
in soil can also be quite high especially near the contaminated impact vapor intrusion due to moisture controls on the soil-gas
soil or aquifer. Since some of the volatile chemicals are also diffusivity, dispersion coefficient, and air permeability (Tillman
being biodegraded in the subsurface, O2 will be consumed and Weaver, 2007). The pathways and controls will be similar
and CO2 produced, setting up a complex transport system of to those discussed for radon (previous section). Two technology
Gas Transport in Soils 8-17

barriers preventing realistic assessment of indoor air problems Ball, B.C., and P. Schjønning. 2002. Air permeability, p. 1141–
from vapor intrusion are (a) lack of knowledge of actual mois- 1158. In G.C. Topp and J.H. Dane (eds.) Methods of soil
ture conditions and its temporal and spatial variability under analysis, Part 4, Physical methods. SSSA, Madison, WI.
and around buildings and (b) current risk assessment models Bird, R.B., W.E. Stewart, and E.N. Lightfoot. 2007. Transport
for soil contribution to indoor air concentrations (e.g., USEPA, phenomena. Revised 2nd edn. John Wiley & Sons,
1996; DKEPA, 2002) where general simulation tools for predict- New York.
ing diffusive and convective gas transport have only considered Buckingham, E. 1904. Contributions to our knowledge of the
traditional models such as the Millington and Quirk model for aeration of soils. USDA, Bureau of soils Bulletin 25. U.S.
gas diffusivity (Equation 8.26) that do not reflect intact soil con- Government Printing Office, Washington, DC.
ditions across soil types and moisture conditions. However, the Burdine, N.T. 1953. Relative permeability calculations from pore
new generation of simulation models for the soil vadose zone size distribution data. Trans. AIME 198:71–78.
including the HYDRUS-1D and 2D packages (Simunek et al., Campbell, G.S. 1974. A simple method for determining unsatu-
2008) allows for use of more realistic models based on transport rated conductivity from moisture retention data. Soil Sci.
parameters in both soil liquid and gaseous phases and will in 117:311–314.
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intrusion as well as the other key application areas of gas trans- 2nd edn. Clarendon Press, Oxford, U.K.
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Hamamoto, S., P. Moldrup, K. Kawamoto, T. Komatsu, and D.E. Massmann, J.W., and D.F. Farrier. 1992. Effects of atmospheric
Rolston. 2009b. Unified measurement system for the gas pressures on gas transport in the vadose zone. Water Resour.
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media. Springer, Dordrecht, the Netherlands. ids. Trans. Faraday Soc. 57:1200–1207.
Iversen, B.V., P. Schjønning, T.G. Poulsen, and P. Moldrup. 2001. Moldrup, P., T. Olesen, J. Gamst, P. Schjønning, T. Yamaguchi,
In situ, on-site and laboratory measurements of soil air per- and D.E. Rolston. 2000a. Predicting gas diffusivity in sieved,
meability: Boundary conditions and measurement scale. repacked soil: Water-induced linear reduction model. Soil
Soil Sci. 166:97–106. Sci. Soc. Am. J. 64:1588–1594.
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to gas diffusion. Soil Sci. Soc. Am. J. 47:425–430. 2001. Tortuosity, diffusivity, and permeability in the soil liq-
Jones, S.B., D. Or, and G.E. Bingham. 2003. Gas diffusion mea- uid and gaseous phases. Soil Sci. Soc. Am. J. 65:613–623.
surement and modeling in coarse-textured porous media. Moldrup, P., T. Olesen, P. Schjønning, T. Yamaguchi, and
Vadose Zone J. 2:602–610. D.E. Rolston. 2000b. Predicting the gas diffusion coefficient
Jury, W.H., and R. Horton. 2004. Soil physics. 6th edn. John Wiley in undisturbed soil from soil water characteristics. Soil Sci.
& Sons, Hoboken, NJ. Soc. Am. J. 64:94–100.
Kawamoto, K., P. Moldrup, P. Schjønning, B.V. Iversen, T. Komatsu, Moldrup, P., T. Olesen, T. Yamaguchi, P. Schjønning, and
and D.E. Rolston. 2006a. Gas transport parameters in the D.E.  Rolston. 1999. Modeling diffusion and reaction in
vadose zone: Development and tests of power-law models soils: IX. The Buckingham-Burdine-Campbell equation for
for air permeability. Vadose Zone J. 5:1205–1215. gas diffusivity in undisturbed soil. Soil Sci. 164:542–551.
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D.E. Rolston. 2004. Three-porosity model for predicting the houses driven by atmospheric pressure fluctuations—The
gas diffusion coefficient in undisturbed soil. Soil Sci. Soc. influence of soil properties. Atmos. Environ. 31:1487–1495.
Am. J. 68:750–759. Rolston, D.E. 2005. Aeration, p. 17–21. In D. Hillel (ed.)
Moldrup, P., T. Olesen, S. Yoshikawa, T. Komatsu, and D.E. Rolston. Encyclopedia of soils in the environment. Elsevier,
2005. Predictive-descriptive models for gas and solute diffu- Amsterdam, the Netherlands.
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to pore-size distribution: II. Gas diffusivity in undisturbed simulated with measured transport and transformation of
soil. Soil Sci. 170:854–866. methyl bromide gas in soils. Pestic. Sci. 13:653–664.
Moldrup, P., T.G. Poulsen, P. Schjønning, T. Olesen, and Rolston, D.E., D. Kirkham, and D.E. Nielsen. 1969. Miscible dis-
T. Yamaguchi. 1998. Gas permeability in undisturbed soil. placement of gases through soil columns. Soil Sci. Soc. Am.
Measurements and predictive model. Soil Sci. 163: 180–189. Proc. 33:488–492.
Moldrup, P., S. Yoshikawa, T. Olesen, T. Komatsu, and Rolston, D.E., and P. Moldrup. 2002. Gas diffusivity, p. 1141–1158.
D.E. Rolston. 2003. Air permeability in undisturbed volca- In G.C. Topp and J.H. Dane (eds.) Methods of soil analysis,
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Poulsen, T.G., W. Suwarnarat, M.K. Hostrup, and N.V. Prasad. 22:247–256.
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Sci. 173:169–174. solid-, and water-phase resistance in variably saturated soil.
Rathfelder, K., J.R. Lang, and L.M. Abriola. 1995. Soil vapor Vadose Zone J. 7:1230–1240.
extraction and bioventing: Applications, limitations, and Thorstenson, D.C., and D.W. Pollack. 1989a. Gas transport in
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Reinecke, S.A., and B.E. Sleep. 2002. Knudsen diffusion, gas per- quacy of Fick’s laws. Water Resour. Res. 25:477–507.
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medium. Water Resour. Res. 38:1280. unsaturated porous media: The adequacy of Fick’s law. Rev.
Resurreccion, A.C., P. Moldrup, K. Kawamoto, S. Hamamoto, Geophys. 27:61–78.
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gas diffusion in soils contaminated with petroleum hydro- dimensional model simulation of 1,3-dichloropropene
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Soc. Am. J. 44:892–898. methyl bromide volatilization in soil fumigation. J. Environ.
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Venterea, R.T., and D.E. Rolston. 2000. Nitric and nitrous oxide Webb, S.W., and K. Pruess. 2003. The use of Fick’s law for mod-
emissions following fertilizer application to agricultural eling trace gas diffusion in porous media. Transp. Porous
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Res. 105:15117–15129. Werner, D., P. Grathwohl, and P. Höhener. 2004. Review of field
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 9
Soil Thermal Regime
9.1 Introduction.............................................................................................................................. 9-1
9.2 Mechanisms of Heat Transfer in Soil.................................................................................... 9-2
9.3 Surface Energy Balance...........................................................................................................9-4
Net Radiation  •  Sensible and Latent Atmospheric Heat Fluxes  • 
Sensible and Latent Soil Heat Flux
9.4 Soil Thermal Properties...........................................................................................................9-5
Soil Thermal Conductivity  •  Soil Heat Capacity  •  Soil Thermal Diffusivity  • 
Measuring Soil Thermal Properties
9.5 Modeling the Soil Thermal Regime..................................................................................... 9-10
Conduction Models  •  Conduction–Convection Models  •  Coupled Heat
and Water Transfer Models
9.6 Measuring Soil Temperature................................................................................................ 9-14
9.7 Measuring and Interpreting Soil Heat Fluxes.................................................................... 9-14
Measuring Soil Heat Fluxes  •  Interpreting Soil Heat Fluxes
Robert Horton 9.8 Managing the Soil Thermal Regime.................................................................................... 9-17
Iowa State University
9.9 Soil Temperature and Global Climate Change.................................................................. 9-17
Tyson Ochsner 9.10 Concluding Remarks.............................................................................................................. 9-18
Oklahoma State University References............................................................................................................................................ 9-18

9.1  Introduction and evapotranspiration models require accurate submodels of

the soil temperature regime. Climate modeling and remote sens-
What is temperature, and more specifically, what is soil tempera- ing require additional ground-truth data for both soil heat flux
ture? Temperature is a measure of the average kinetic energy of and temperature of the surface soil.
the molecules of a substance. As kinetic energy increases, the Soil temperature is highly dynamic and is influenced by a
temperature increases. At the macroscale, temperature is a phys- multitude of factors. Those factors include soil thermal prop-
ical property that determines the direction of heat flow between erties, surface mulch, tillage, precipitation, air temperature,
two substances in thermal contact. Heat flows from high tem- incoming radiation, fire, vegetation, snow cover, soil color
perature to low temperature. Temperature is not a measure of and organic-matter content, aspect and slope, elevation, and
heat content. In order to specify the heat content of a particular groundwater. All these factors have some influence on soil
substance (e.g., soil), both the heat capacity and the temperature temperature, and they contribute to the great diversity of soil
must be known. temperature regimes.
Why is soil temperature important? Temperature influences Soil temperature may range from highs of near 700°C at the
many biological, chemical, and physical processes that occur surface during an intense forest fire (Neary et al., 1999) to lows
in the soil. Plant germination and growth are closely related to of −20°C during the Arctic winter (Coulson et al., 1995). At the
soil temperature. Below a soil temperature of about 5°C, growth local scale, soil temperature varies horizontally, vertically, and
of roots of most plants is negligible. When a soil freezes, most temporally. Local horizontal variations in soil temperature arise
biological activities and chemical processes essentially cease. from differences in plant cover and surface shading (Figure 9.1),
Pesticide degradation, residue decomposition, soil microbiologi- variability in soil moisture and density, or distance from buried
cal activity, and nutrient cycles are affected by soil temperature. heat sources. Horizontal gradients in soil surface temperature
Soil temperature gradients affect soil moisture and solute move- under a partially developed row crop canopy (or partial mulch
ment. Soil temperature affects soil hydraulic conductivity, trans- cover) can exceed 1°C cm−1 (Horton et al., 1984a).
port properties, and important environmental processes such as Vertical soil temperature variations are primarily driven by the
soil–atmosphere gas exchanges, the global carbon cycle, and the fluctuating temperature of the soil surface. Heat is both absorbed
transformations and transport of contaminants. Crop growth at and lost from the surface of the soil. The soil transmits heat

9-1
9-2 Properties and Processes

30 daily cycles, if seasonal air temperature differences occur. Thus,

Below rows
annual soil temperature cycles are much less pronounced near
20
the equator than in the middle and high latitudes. Seasonal
temperature differences decrease, and the annual cycles lag pro-
(a) gressively as depth increases. The amplitude of the annual tem-
perature cycle at depths >8 m is 5% or less of the amplitude at the
25 cm from
30 west row
soil surface, and the temperature at these depths approximates
the mean annual temperature of the shallower soil (Baker and
Baker, 2002; Smerdon et al., 2003).
20
For soils that freeze in winter, soil temperature is influenced
(b)
by the release of heat when liquid water becomes ice. The amount
of heat released is about 334 J g−1 of water that freezes. The heat
60
At center of fusion energy must be dissipated while soil water freezes. The
between rate of thaw of frozen soils is relatively slow, because heat energy
rows
Temperature (°C)

50 0 cm is required to both warm the soil and melt the ice. In areas of
5 cm heavy snowfall, the snow provides an insulating blanket and
20 cm soils do not freeze as deeply or may not freeze at all.
40
The soil thermal regime is one of the defining characteristics
of a soil. The USDA soil classification system (Soil Survey Staff,
30 1999) includes soil temperature regimes based on temperature
at a depth of 50 cm or at the upper boundary of a root-limiting
20 layer, whichever is shallower. The soil temperature regimes,
defined in terms of the mean annual soil temperature and the
(c) difference between mean summer and mean winter tempera-
40 tures, are determined by the following groupings:
25 cm from Gelisols and gelic suborders and great groups are assigned
30 east row to soil temperature regimes based on their mean annual soil
temperature as follows: hypergelic (−10°C or lower), pergelic
20 (−4°C to −10°C), and subgelic (1°C to −4°C).
0 4 8 12 16 20 24 Other soils that have a difference in soil temperature of 6°C or
(d) Time (h) more between mean summer and mean winter temperatures are
assigned to soil temperature regimes based on their mean annual soil
FIGURE 9.1  Soil temperature with time at 0, 5, and 20 cm below the soil temperature as follows: frigid (lower than 8°C), mesic (8°C–15°C),
surface as measured between two NE–SW-oriented rows of 60 cm tail chili thermic (15°C–22°C), and hyperthermic (22°C or higher).
(Capsicum annuum L.) plants. The rows were 100 cm apart, (a), (b), (c), and
All other soils are assigned to soil temperature regimes based
(d) show diurnal soil temperatures measured at locations beneath rows,
on their mean annual soil temperature as follows: isofrigid
25 cm from the west row, at the center between rows, and 25 cm from the
east row, respectively. (Reprinted from Horton, R., O. Aguirre-Luna, and (lower than 8°C), isomesic (8°C–15°C), isothermic (15°C–22°C),
P.J. Wierenga. 1984a. Observed and predicted two-dimensional soil tem- and isohyperthermic (22°C or higher).
perature distributions under a row crop. Soil Sci. Soc. Am. J. 48:1147–1152.)
9.2  Mechanisms of Heat Transfer in Soil
downward when the temperature near the surface is higher than the
temperature below, and it transmits heat upward when the temper- Three principal mechanisms, radiation, convection, and con-
ature is warmer within the soil than at the surface. During warm- duction, are responsible for the transfer of heat in soil simul-
ing periods, the soil temperature is greatest near the surface and taneously. Radiative energy transfer includes incoming direct
lower at depth. During cooling periods, the reverse is true. Thus, and diffuse solar (shortwave) radiation, as well as longwave sky
for most environments, both the highest and lowest observed soil radiation to the soil surface and longwave radiation emitted
temperatures occur at the surface. Under conditions of dry soil outward from the soil surface. Radiative transfer is a significant
and high incoming radiation, vertical soil thermal gradients near component of heat transfer at the soil surface, but its significance
the surface can exceed 10°C cm−1 (Heitman et al., 2008c). decreases below the soil surface. Convective heat transfer in soil
Soil temperature also changes with time. In many, but not all, is associated with a net flux of fluids. Convection may be respon-
cases, soil temperatures exhibit distinct daily and annual cycles. sible for a major portion of the soil heat transfer during periods of
The cycles deeper in the soil lag behind those near the sur- large water flux (e.g., during rainfall or irrigation). Convection is
face. The daily cycles decrease in amplitude as depth increases, also important via vapor fluxes in shallow unsaturated soil lay-
and below 35 cm, amplitudes become quite small in most soils ers when large thermal gradients occur. Although radiation and
(Figure 9.2). Annual cycles are observable to greater depths than convection are each important mechanisms of soil heat transfer
Soil Thermal Regime 9-3

Temperature with depth in prairie

30
5 cm 10 cm 17.5 cm 35 cm

Temperature (°C)
25

20

15
242 243 244 245
DOY 2008
Temperature with depth in corn
30
5 cm 10 cm 17.5 cm 35 cm
Temperature (°C)

25

20

15
242 243 244 245
DOY 2008
Temperature with depth in soybean
30
5 cm 10 cm 17.5 cm 35 cm
Temperature (°C)

25

20

15
242 243 244 245
DOY 2008

FIGURE 9.2  Soil temperature variation with depth and time for several Iowa fields.

under certain conditions, conduction is typically the dominant simultaneously. This is good because in soil, conduction and
mechanism of heat transfer within the soil. Conduction heat convection often occur together.
transfer involves the transfer of heat at a molecular scale from Transfer of heat and water in soil is generally coupled, which
positions of large kinetic energy (high temperature) to positions is to say that the transfer processes are intertwined. Water mov-
of small kinetic energy (low temperature). ing into and through the soil carries heat with it, and tempera-
We will consider that radiation heat transfer is restricted ture gradients in the soil cause movement of both liquid water
to the surface. That leaves convection and conduction as heat and water vapor. In a typical diurnal cycle, the soil surface loses
transfer mechanisms to be considered within soil. Most authors heat during the night. The surface temperature drops, and the
focus on conduction heat transfer as the primary mechanism of resulting upward thermal gradient results in transfer of heat
heat transfer in soil. They assume that conduction predominates to the surface from the relatively warm soil below. If the sur-
at times other than rainfall or irrigation. Buchan (2001) is some- face temperature drops to the dew point temperature, water
what unique in his presentation of soil heat transfer processes vapor condenses at the cooled soil surface, liberating more heat.
in that he includes conduction and convection heat transfer Throughout the night, liquid water flows upward, rewetting
9-4 Properties and Processes

surface layers that had dried during the previous day and redis- the energy balance are interdependent. The surface temperature
tributing heat upward. In the morning, solar radiation warms affects all four terms, including Rn . The surface temperature, in
the soil surface. As the surface temperature increases, the ther- turn, is a result of the energy partitioning that includes all four
mal gradient shifts direction. Liquid water near the soil surface terms of Equation 9.1. In the following sections, the four terms
vaporizes and is transported into the atmosphere, taking large of Equation 9.1 are briefly considered for the case of a bare soil
quantities of heat with it. Liquid water and water vapor are also surface. We refer readers to Chapter 6 for a more comprehensive
driven by the thermal gradient from the hot surface to the cooler presentation of surface energy balance.
soil below. As the sun goes down, the dynamic and intricate
cycle begins again. 9.3.1  Net Radiation
Net radiation (Rn) is defined as incoming minus outgoing radia-
9.3  Surface Energy Balance tion at the land surface. Net radiation can be described by the
following:
The complexities and significance of the soil thermal regime find
full expression in the deceptively simple and widely used equa- Rn = (1 − a)Rg + Rl − εσTs4 , (9.2)
tion for the energy balance of the land surface:

where
Rn + H + LE + G = 0, (9.1)
a is surface albedo
Rg is global (i.e., direct plus diffuse solar) radiation (W m−2)
where Rl is downward longwave sky irradiance (W m−2)
Rn is net radiation at the surface ε is surface emissivity
H is sensible heat flux between the surface and the atmosphere σ is the Stefan–Boltzmann constant (5.67 × 10−8 W m−2 K−4)
LE is latent heat flux between the surface and the atmosphere Ts is surface temperature (K)
G is the total heat flux (sensible and latent) between the sur-
face and the subsurface The soil surface temperature can be measured with thermocou-
ples or by infrared thermometers (Ham and Senock, 1992).
Here, all the fluxes are positive toward the surface and expressed
in units of watt per square meter. 9.3.2  Sensible and Latent Atmospheric
Comprehensive surface energy balance studies have been con- Heat Fluxes
ducted since the 1950s. Works by Lettau and Davidson (1957)
and Lemon (1963) are early examples of these types of studies. In Horton and Chung (1991) used the following equations to calcu-
recent years, with technical advancement of ground-based and late surface latent and sensible heat fluxes:
remote sensing instrumentation, surface energy balance mea-
L(ρva − ρvs )
surements have become much more common. This trend is evi- LE = , (9.3)
denced by the development of the global energy balance archive rva
(GEBA) for documentation of current climatic conditions and
L = 2.49463 × 109 − 2.247 × 106 (Ts − 273.15), (9.4)
facilitation of the study of past and future climate (Gilgen and
Ohmura, 1999). The spatial scale of energy balance studies has
also expanded with advancing sensor technology. For example, Ca (Ta − Ts )
H= , (9.5)
interest in global climate change has prompted several efforts to rA
estimate the earth’s annual mean energy budget (e.g., Ohmura
and Gilgen, 1993; Kiehl and Trenberth, 1997). where
Some authors have defined H, LE, and G as positive away E is the evaporative flux (m s−1)
from the surface, in which case the “plus” signs are replaced L is the latent heat of vaporization (J kg−1)
with “minus” signs in Equation 9.1. With that convention, ρva is vapor density of the air (kg m−3)
Equation 9.1 is often rearranged to set Rn equal to the sum of ρvs is vapor density of the surface (kg m−3)
the other three terms. Such presentation promotes the idea that rva and rA are the aerodynamic boundary layer resistances (s m−1)
net radiation is partitioned into heating the air, heating the to vapor and heat transfer
soil, and evaporating water. This thinking is only partially Ca is air volumetric heat capacity (J m−3 °C−1)
true. By isolating the net radiation term, proper importance Ta is air temperature
is assigned to the radiative energy that derives from the sun.
However, the net radiation includes more than solar energy. Some studies suggest that an additional soil surface resistance
The implication that Rn is the driver and that the other pro- parameter be added to the numerator in Equation 9.3 to more
cesses are the followers is not completely true. A more accurate accurately represent evaporation when the soil surface is dry
representation is given in Equation 9.1. The four components of (Saito et al., 2006).
Soil Thermal Regime 9-5

The vapor density at the surface, ρvs, can be calculated from 300
the Kelvin equation as Rn
250 G
LE
⎡ (M ψ) ⎤ 200 H
ρvs = ρ*vs exp ⎢ w ⎥ , (9.6)

Flux density (W m–2)

⎣ (RTs ) ⎦ 150

where 100
ρ*vs is the saturated vapor density (kg m−3)
50
Mw is the molecular weight of water (kg mol−1)
ψ is the water potential (sum of osmotic and matric) at the 0
surface (J kg−1)
–50
R is the universal gas constant (8.314 J mol−1 K−1)
–100
Note that Equations 9.2, 9.4 through 9.6 show that Rn, LE, 310.0 310.5 311.0 311.5 312.0
Day of year
and H are each influenced by surface temperature. Therefore,
the terms cannot be considered to be independent of each FIGURE 9.3  Energy balance components measured above a corn
other. Several approaches for solving the surface energy bal- residue-covered soil surface in 1994 at a site near Ames, Iowa. Net radi-
ance equations for Ts have been developed (e.g., Bristow, 1987; ation (Rn) is positive toward the surface. The other terms are positive
Horton and Chung, 1991). away from the soil surface. (Reprinted from Sauer, T.J., J.L. Hatfield, J.H.
Prueger, and J.M. Norman. 1998. Surface energy balance of a corn resi-
due-covered field. Agric. For. Meteorol. 89:155–168, Copyright (1998),
9.3.3  Sensible and Latent Soil Heat Flux with permission from Elsevier.)
The final term in Equation 9.1 is G, the soil heat flux. The amount surface energy balance and has, in some cases, been ignored.
of sensible and latent energy that moves through an area of soil However, there are often significant transfers of energy into and
in a unit of time is the soil heat flux or heat flux density, G. The out of a soil during both day- and nighttime hours, and failure
ability of a soil to conduct heat impacts how fast its temperature to include G in short-term (i.e., hourly) energy balance determi-
changes during a day or between seasons. Soil heat flux is impor- nations can lead to significant errors. Later in this chapter, we
tant because it effectively couples energy transfer processes at the consider methods to estimate and measure G.
surface (surface energy balance) with energy transfer processes
in the soil (soil thermal regime). This interaction between sur-
face and subsurface energy transfer processes has led to detailed 9.4  Soil Thermal Properties
investigations of soil heat flux for a wide variety of agricultural
systems (Sauer, 2002; Sauer and Horton, 2005). The three main soil thermal properties are volumetric heat
The magnitude of G as a component of the surface energy bal- capacity (C), thermal conductivity (λ), and thermal diffusivity
ance varies with surface cover, soil moisture content, and solar (α). Because α ≡ λC−1, knowledge of any two of the three proper-
irradiance (Sauer and Horton, 2005). Daytime peak hourly values ties is sufficient information to calculate the third property. Soil
of G for a bare, dry soil in midsummer, could be in excess of thermal properties are generally expressed as a function of soil
300 W m−2 (Fuchs and Hadas, 1972). By contrast, hourly G for a water content. For example, Ren et al. (1999) reported soil ther-
moist soil beneath a plant canopy, residue layer, or snow cover will mal property values for two soils as a function of water content
often be less than ±20 W m−2. Surface soil heat flux typically repre- (Figure 9.4). Ochsner et al. (2001) studied soil thermal properties
sents 1%–10% of daily Rn for growing crops with full canopy cov- as a function of soil solid, liquid, and gas fractions. For a range of
erage (Denmead, 1969; Szeicz et al., 1973; Brown, 1976; Uchijima, soils, they found that soil air content exerted the most dominant
1976; Baldocchi et al., 1985; Clothier et al., 1986). This percentage influence on soil thermal properties (Figure 9.5). The effective or
can exceed 50% in the fall and spring when Rn is low and the soil is apparent thermal properties of soil at temperatures below freez-
cooling/warming or in arid climates when there is no vegetation ing can also be strongly temperature dependent due to latent
(Monteith, 1958; Idso et al., 1975; Choudhury et al., 1987). heat effects associated with the liquid–solid phase change of soil
Figure 9.3 provides example curves of the energy balance water (Figure 9.6; Ochsner and Baker, 2008).
terms for a corn (Zea mays L.) residue-covered soil in central
Iowa (Sauer et al., 1998). The data in Figure 9.3 were obtained in 9.4.1  Soil Thermal Conductivity
November when the soil and fresh residue layers were dry and
the mean surface temperature was 6.8°C. Daytime G averaged Heat flow in soil has often been considered analogous to heat
14.4% and 16.8% of Rn for days 310 and 311, respectively. Much flow in a solid to which Fourier’s law is applied:
of the energy that enters the soil during the day returns to the
atmosphere at night through terrestrial longwave radiation. dT
G = −λ (9.7)
For this reason, G is often the smallest component of the daily dz
9-6 Properties and Processes

4 12 4 12

10 10
ρc (MJ m–3 °C–1), λ (W m–1 °C–1)

ρc (MJ m–3 °C–1), λ (W m–1 °C–1)

3 3
8 8

α (10–7 m2 s–1)
α (10–7 m s–1)
2 6 2 6

4 4
1 1
α 2 α 2
ρc ρc
λ λ
0 0 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4
(a) θ (m3 m–3) (b) θ (m3 m–3)

FIGURE 9.4  Thermal properties of clay loam soil (a) and silica sand (b) as functions of volumetric water content. (Reprinted from Ren, T., K.
Noborio, and R. Horton. 1999. Measuring soil water content, electrical conductivity, and thermal properties with a thermo-TDR probe. Soil Sci. Soc.
Am. J. 63:450–457. With permission. Soil Science Society of America.)

θ (m–3 m–3) vs (m–3 m–3) na (m–3 m–3)

3.0
Sandy loam
Clay loam
λ (W m–1 K–1)

2.0 Silt loam

Silty clay loam

1.0

0.0

3.0
C (106 J m–3 K–1)

2.0

1.0

0.0

1.0

0.8
α (10–6 m2 s–1)

0.6

0.4

0.2

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
θ (m–3 m–3) vs (m–3 m–3) na (m–3 m–3)

FIGURE 9.5  Thermal conductivity, heat capacity, and thermal diffusivity versus volume fractions of water (θ), solids (vs), and air (na) for four
medium-textured soils. (Reprinted from Ochsner, T.E., R. Horton, and T. Ren. 2001. A new perspective on soil thermal properties. Soil Sci. Soc. Am.
J. 65:1641–1647. With permission. Soil Science Society of America.)
Soil Thermal Regime 9-7

103 TABLE 9.1  Density, Specific Heat and Thermal Conductivity

of Common Soil Constituents at 10°C
Thermal
Ca (MJ m–3 K–1) 2 Density (ρ) Specific Heat (c) Conductivity (λ)
10
Soil Constituent (Mg m−3) (kJ kg−1 K−1) (W m−1 K−1)
Quartz 2.66 0.75 8.8
Clay minerals 2.65 0.76 3
101
Soil organic matter 1.3 1.9 0.3
Water 1.00 4.18 0.57
Ice (0°C) 0.92 2.0 2.2
Air 0.00125 1.0 0.025
Source: After de Vries, D.A. 1963. Thermal properties of soils, p. 210–
102
235. In W.R. van Wijk (ed.) Physics of plant environment. North-Holland
λa (W m–1 K–1)

Publishing Co., Amsterdam, the Netherlands, Table 7.1.

101 materials affect the overall thermal conductivity of soils. Two of

the major factors affecting thermal conductivity of porous mate-
rials are water content (θ) and bulk density (ρb). In general, λ
100 of solid > λ of liquid > λ of gas. Therefore, increasing the bulk
density or water content of a soil should lead to increases in λ.
Al Nakshabandi and Kohnke (1965), for instance, measured an
100 eightfold increase in the thermal conductivity of a silt loam soil as
its water content increased. The thermal conductivity of soil also
varies by composition of the solid fraction (e.g., mineral type,
αa (mm2 s–1)

particle size, and amount of organic matter) (Al Nakshabandi

10–1
and Kohnke, 1965; Abu-Hamdeh and Reeder, 2000). In par-
ticular, the thermal conductivity increases with quartz content
because quartz has a higher thermal conductivity than other
common soil minerals (Bristow, 1998). de Vries (1963) presented
average values of thermal conductivity for various soil constitu-
10–2
–5 0 5 ents and those values are reproduced here in Table 9.1.
Soil temperature (°C) Temperature is another parameter that influences thermal
conductivity. de Vries (1963) found that thermal conductivity of
FIGURE 9.6  Apparent thermal properties of silt loam soil for temper-
a sandy soil increased with increasing water content and with
atures just above and below 0°C. Thermal properties were measured
temperature until 60°C. At a temperature of 75°C, the ther-
in situ (symbols) using an HP method. Thermal properties were mod-
eled (lines) using the approach of Fuchs et al. (1978). (Reprinted from
mal conductivity increased with increasing water content until
Ochsner, T.E., and J.M. Baker. 2008. In situ monitoring of soil thermal 0.1 m3 m−3, but then decreased as water content increased. In
properties and heat flux during freezing and thawing. Soil Sci. Soc. Am. J. unsaturated soil, conduction is not the only heat transfer mecha-
72:1025–1032. With permission. Soil Science Society of America.) nism influencing λ. Evaporation, movement, and condensation
of water vapor in the soil pores also influence λ. These latent heat
where transfer processes become more important as soil temperature
G is the heat flux density (W m−2) increases, but they can be inhibited when liquid water content
λ is thermal conductivity (W m−1 K−1) fills the majority of the pore space.
dT/dz is the temperature gradient (K m−1) The properties that influence λ vary between soils, spatially
at the soil surface for the same soil, between layers within a
Thermal conductivity is a measure of the soil’s ability to soil, and over time. Because of this variability, much effort has
transmit heat. It is the ratio of the magnitude of the heat flux been made to develop λ models based on easily measurable
through the soil to the magnitude of the temperature gradient. soil parameters (Kersten, 1949; de Vries, 1963; Johansen, 1975;
Fourier’s law is easily and directly utilized in many engineer- Campbell; 1985; Côté and Konrad, 2005). The available models
ing applications; however, in a porous, three-phase media like can be divided into two groups: semi-theoretical models and
soil, specifying λ is considerably more difficult. empirical models.
Unsaturated soils consist of three phases: solid, liquid, and gas. The de Vries (1963) model is a physically based, semi-theoretical
The different materials within soils have different thermal con- model, which has been applied in numerous studies, including
ductivities. Both fractional makeup and physical arrangement of predicting the response of λ to temperature change (Hopmans
9-8 Properties and Processes

and Dane, 1986; Campbell et al., 1994). In the de Vries model, The de Vries model has proven useful for many years, but proper
the thermal conductivity of soil is calculated as the weighted (and somewhat subjective) selection of model parameters, such
average of the conductivities of the various soil constituents as critical water content and shape factors, is necessary to predict
according to the formula: λ accurately (Horton and Wierenga, 1984; Ochsner et al., 2001).
There is a great diversity of empirical models for λ. One of
n the earliest is that of Kersten (1949). This model only requires
λ=
∑ i =0
n
ki λ i xi
, (9.8) bulk density as an input parameter, but the model is not suit-
able for predicting λ at lower water contents (Côté and Konrad,

∑ i =0
ki xi
2005). Campbell (1985) introduced an empirical function to
calculate λ. The empirical function has five parameters, some
where of which are difficult to estimate. Johansen (1975) proposed the
xi is the volume fraction of each constituent concept of normalized thermal conductivity and established a
λi is the thermal conductivity of each constituent simple empirical model based on the degree of saturation and
n is the number of soil constituents soil mineral composition. For many soils, the Johansen (1975)
model provides accurate predictions of λ (Farouki, 1981, 1982;
The weighting factors, ki, depend on the shape and orienta- Tarnawski and Wagner, 1992). Nevertheless, the Johansen (1975)
tion of the granules of the soil constituents and on the ratio of model does not cover the entire water content range. Lu et al.
the conductivities of the constituents. The subscript 0 refers (2007) presented an improved model describing the relationship
to the continuous fluid surrounding the solid particles (i.e., between thermal conductivity and volumetric water content. The
air for dry soil and water for moist soil) with k 0 = 1. Other new model was calibrated using measured thermal conductivity
values of ki are calculated from from eight soils, and it was validated by comparing predicted λ
with measured λ on 19 additional soils. The model performed
1
3
⎡ ⎛ λi ⎞ ⎤
−1
well for a wide range of soils and was applicable over the entire
ki =
3 ∑ ⎢1 + ⎜ − 1⎟ g j ⎥ ,
⎣ ⎝ λ0 ⎠ ⎦
(9.9) range of soil water contents. Frozen soil represents a special con-
j =1
dition. Farouki (1986) provides insight on observations and
predictions of thermal properties for frozen soil conditions.
where g j represents the shape factors for the ith constituent, and
g1 + g2 + g3 = 1. Assuming g1 and g2 are equal, only one shape 9.4.2  Soil Heat Capacity
factor needs to be estimated for each constituent.
The thermal conductivity of the air-filled pores is considered Soil heat capacity characterizes the quantity of heat added to
to be the sum of λa and λv , where λa is the thermal conductiv- or removed from soil per unit change in temperature. Heat
ity of dry air (0.025 W m−1 K−1 at 20°C), and λv accounts for heat capacity has an important role in determining the magnitude
transfer across the air-filled pores by water vapor. Above some of diurnal and annual soil temperature variations. In soil with
critical water content, the air-filled pores are assumed to be satu- low heat capacity, the addition or removal of heat causes a rela-
rated with water vapor, and λv is assumed to be 0.074 W m−1 K−1 at tively large soil temperature change, and in soil with large heat
20°C. Below the critical water content, λv is assumed to decrease capacity, the addition or removal of heat causes a relatively
linearly with water content to a value of zero for oven-dry soil. small temperature change.
Assuming a soil solid particle shape factor of 0.144, then for The volumetric heat capacity of soil is calculated as the
water contents above the critical water content, the value of g1 weighted sum of the heat capacities of the various soil constitu-
for the air-filled pores is given by ents (Kluitenberg, 2002). Thus,

na
g 1 = 0.333 − (0.333 − 0.035), (9.10) n n
(1 − v s )
C= ∑ xiCi = ∑x ρc , i i i (9.12)
i =1 i =1
where na and vs are the volume fractions of air and solids,
respectively.
where xi and Ci (J m−3 K−1) represent the volume fractions and
For water contents below the critical water content, the value
volumetric heat capacities, respectively, of n soil constituents.
of g1 for the air-filled pores is given by
This relationship shows that the volumetric heat capacity of each
θ constituent is the product of its density ρi (Mg m−3) and its spe-
g 1 = 0.013 + ( g 1c − 0.013), (9.11) cific heat ci (J kg−1 K−1). Equation 9.12 can be expressed in terms
θc of mass fractions ϕi by using the relationship:
where
φiρb
θc is the critical water content xi = , (9.13)
g1c is the value of Equation 9.10 at the critical water content ρi

Soil Thermal Regime 9-9

where ρb is the soil bulk density. Substituting Equation 9.12 into and soil is a practical inhibitor to accurate results. Bruijn et al.
Equation 9.13 yields (1983) and van Haneghem et al. (1983) presented and tested the
theory for simultaneously determining λ and C by accounting
n for contact resistance between sensor and soil. Other investiga-
C = ρb ∑φ c . i i (9.14) tors have recognized that measurement of temperature (mul-
i =1 tineedle sensors) at a known distance away from a heat source
provides opportunity for simultaneous determination of ther-
In order to use Equation 9.14, knowledge is needed of the specific mal properties (Lubimova et al., 1961; Chudnovski, 1962; Jaeger,
heats of the various constituents present in soil. Approximate 1965; Nix et al., 1967, 1969; Larson, 1988; Kluitenberg et al., 1993,
specific heat values for soil constituents are provided in Table 1995; Bristow et al., 1994; Bilskie et al., 1998).
9.1. Because soil air makes a negligible contribution to C, it is Bristow et al. (1994) showed that using short-duration
common to write Equation 9.14 as heat-pulse (HP) theory, λ, C, and α could be determined from a
single HP measurement using a dual-probe sensor as described
by Campbell et al. (1991). This method is commonly referred to
C = ρb (cmφm + coφo + cw θ g ), (9.15) as the dual-probe HP method or simply the HP method. Figure
9.7 shows diagrams of a typical dual-probe HP sensor. The HP
where method is based on the theory of radial heat conduction of a
the subscripts m, o, and w indicate mineral material, organic short-duration heat pulse from an infinite line source. In an
material, and water, respectively infinite medium, the temperature change as a function of time at
θg is the gravimetric water content a radial distance from the HP source is given by (de Vries, 1952;
Kluitenberg et al., 1993):
The mineral and organic fractions of soil can be lumped to give
an average specific heat of the solid constituents, cs,
Q ⎡ ⎛ −r 2 ⎞ ⎛ −r 2 ⎞ ⎤
ΔT (r , t ) = ⎢ Ei ⎜ − Ei ⎜ ⎥, t > t0 (9.17)
⎟
4 πα ⎢⎣ ⎝ 4α(t − t 0 ) ⎠ ⎝ 4αt ⎟⎠ ⎥⎦
C = ρb (cs + cw θ g ). (9.16)

where
9.4.3  Soil Thermal Diffusivity
ΔT is the temperature change (°C)
Soil thermal diffusivity, α, is defined as the ratio of thermal t is time (s)
conductivity to volumetric heat capacity. Thermal diffusiv- t0 is the HP duration (s)
ity often appears in partial differential equations describing r is the radial distance (m)
soil heat transfer and in the solutions to those equations. Soil –Ei(–x) is the exponential integral
thermal diffusivity is the parameter that describes the rate of
transmission of a temperature change through the soil. The The source strength is defined as Q = q′/C, where q′ is the rate
higher the thermal diffusivity, the more rapid the propagation of heat liberation per unit length of probe (W m−1). Figure 9.8
of temperature changes through the soil. Thermal diffusivity shows a typical temperature rise curve obtained from an HP
can be estimated by using appropriate models to calculate measurement.
thermal conductivity and heat capacity and then taking the Based upon Equation 9.17, soil thermal properties can be
ratio. Procedures for measuring thermal properties, including expressed analytically as (Kluitenberg et al., 1993; Bristow et al.,
diffusivity, are discussed below. 1994):

9.4.4  Measuring Soil Thermal Properties (r 2/4)[(1 /(t m − t 0 )) − (1/t m )]

α= , (9.18)
ln[t m /(t m − t 0 )]
Considerable effort has gone into developing methods for
measuring soil thermal properties. The line-source thermal sen-
sor (with single needle or multiple needles) has been the primary qʹ ⎡ ⎛ −r 2 ⎞ ⎛ −r 2 ⎞ ⎤
C= ⎢ Ei ⎜ − Ei ⎜ ⎥, (9.19)
method. When using a single-needle sensor, temperature with 4παΔTm ⎟
⎢⎣ ⎝ 4α(t m − t 0 ) ⎠ ⎝ 4αt m ⎟⎠ ⎥⎦
time data are obtained during and just after the needle is heated.
The thermal conductivity can be calculated from the tempera-
ture data (Jackson and Taylor, 1965; Horton and Wierenga, 1984; λ = αC, (9.20)
Shiozawa and Campbell, 1990).
de Vries and Peck (1958) reported that it may be possible to where
determine λ and α simultaneously with a single-needle sensor. tm is the time (s) at which the temperature maximum occurred
The unknown contact resistance between the line-source sensor ΔTm is the maximum temperature change (°C)
9-10 Properties and Processes

Top view (cutaway)

Heater probe

Heater wires
6 mm 16 mm
Thermistor
wires
Temperature
probe
Thermistor PVC block

Side view (cutaway)

28 mm 26 mm

Epoxy-filled cavity 6 mm

FIGURE 9.7  Diagram of a dual-probe HP sensor. (Reprinted from Kluitenberg, G.J. 2002. Heat capacity and specific heat, p. 1201–1208. In J.H.
Dane and G.C. Topp (eds.) Methods of soil analysis. Part 4. Physical methods. SSSA, Madison, WI. With permission. Soil Science Society of America.)

2.5 ΔTm = 1.87°C r = 0.006 m Heitman et al., 2003; Ochsner et al., 2003). Soil water content can be
t0 = 8 s estimated with the HP method by utilizing the linear dependence
2.0 q = 97.8 W m–1 of C on the soil water content (Equation 9.16).
Temperature (°C)

1.5
9.5  Modeling the Soil Thermal Regime
1.0
Heat transfer modeling offers the following contributions: (1) it
0.5 tm = 32 s describes energy partitioning at the soil surface; (2) it describes
soil heat flux within the soil profile; and (3) it describes soil
0.0 temperature distribution. The surface-energy partitioning and
0 20 40 60 80 100
Time (s) resulting soil temperature distribution directly and indirectly
affect plant growth and development, and many biological,
FIGURE 9.8  Typical temperature versus time curve for a dual-probe
chemical, and physical processes in the soil.
HP measurement. The maximum temperature rise (ΔTm) and time of
the maximum temperature rise (tm) are indicated.

A more recent simplification of Equation 9.19 was developed by

9.5.1  Conduction Models
Knight and Kluitenberg (2004): Analytical and numerical solutions to the following 1D, transient
conduction equation for various initial and boundary conditions
q ʹt 0 ⎛ ε 2 ⎪⎧ 1 ⎡ 1 ε ⎛ 5 7 ε ⎞ ⎤ ⎪⎫⎞ have been presented in the literature:
C= 2 ⎜ 1 − ⎨ + ε ⎢ + ⎜ + ⎟ ⎥ ⎬⎟ , (9.21)
eπr ΔTm ⎝ 8 ⎩⎪ 3 ⎣ 3 8 ⎝ 2 3 ⎠ ⎦ ⎭⎪⎠
∂T ∂ ⎛ ∂T ⎞
C = λ . (9.22)
∂t ∂z ⎜⎝ ∂z ⎟⎠

where
ε = t0/tm In many cases, heat transfer by radiation, convection, and conduc-
e is the base of the natural logarithm tion is modeled by the conduction equation alone (Wierenga and
de Wit, 1970; Hanks et al., 1971; Gupta et al., 1981, 1983; Horton
Equation 9.21 employs a telescoped polynomial rather than the et al., 1984a, 1984b; Parton, 1984; Persaud and Chang, 1984).
exponential integral and is thus easier to use in spreadsheets and Apparent thermal properties rather than real thermal properties
on-board dataloggers. Further details regarding the application of (Jackson and Kirkham, 1958) are assumed to account for both con-
the HP method are given by Kluitenberg (2002) and Bristow (2002). ductive and nonconductive heat flow. Several investigators have
One important application of the HP method is in monitoring also modeled soil heat transfer in two dimensions (Takakura et al.,
soil water content (Tarara and Ham, 1997; Campbell et al., 2002; 1971; Jury and Bellantuoni, 1976a, 1976b; Mahrer and Katan, 1981;
Soil Thermal Regime 9-11

Mahrer, 1982; Horton et al., 1984a, 1984b; Chung and Horton, Wierenga et al. (1969) presented two methods of determining
1987; Horton, 1989; Benjamin et al., 1990; Kluitenberg and Horton, α based upon Equation 9.25. The first is called the amplitude
1990; Novak, 1993). Two-dimensional models have been used to method. Note that Equation 9.25 indicates that temperature
analyze soil heat transfer beneath row crops, in ridged surfaces, amplitude should decrease exponentially with depth. Wierenga
and beneath partial mulch covers. Some of the models include con- et al. (1969) used the following equation to calculate the appar-
duction heat transfer alone, and some consider soil water impacts ent thermal diffusivity from the amplitude of the soil tempera-
on thermal properties and/or soil water movement (Wierenga and ture wave at two depths:
de Wit, 1970; van Bavel and Hillel, 1975, 1976; Sophocleous, 1979;
Milly, 1982; Campbell, 1985; Ross et al., 1985; Bristow et al., 1986; 2
ω ⎡ z 2 − z1 ⎤
Lascano et al., 1987; Pruess and Wang, 1987; Bear and Bensabat, α= ⎢ ⎥ . (9.26)
2 ⎢⎣ ln( A1/A2 ) ⎥⎦
1989; Nassar and Horton, 1989b, 1989c, 1992; Horton and Chung,
1991; Hares and Novak, 1992a, 1992b; Nassar et al., 1992a, 1992b;
Olivella et al., 1994; Scanlan and Milly, 1994; Bear and Gilman, The second approach is the phase method. Note that Equation
1995; Gawin et al., 1995; Bristow and Horton, 1996; Noborio et al., 9.25 indicates a phase shift as a function of depth. Wierenga et al.
1996a, 1996b; Saito et al., 2006). (1969) used the following equation to analyze the phase shift of
For homogeneous, isotropic conditions, the transient conduc- their observations:
tion equation is as follows:
2
1 ⎡ z 2 − z1 ⎤
∂T ∂2T α= , (9.27)
=α 2. (9.23) 2ω ⎢⎣ δt ⎥⎦
∂t ∂z

Analytical solutions to Equation 9.23 exist for certain initial and where δt is the time interval between occurrence of maximum
boundary conditions. Carslaw and Jaeger (1959) have compiled soil temperatures at depths z1 and z2 . Equations 9.26 and 9.27
a number of solutions to Equation 9.23 for heat transfer in solids. have been used to give first-order approximations of α. These
Although soil does not consist of solids alone, with the assump- methods work well for data obtained below a depth of 10 cm
tions of uniform, constant thermal properties and heat conduc- (Wierenga et al., 1969). Near the soil surface, Equations 9.26
tion processes dominating, conduction heat transfer theory for and 9.27 provide less accurate estimates of α because the soil
solids can be used to approximate heat transfer in soil. water content is not uniform and the soil temperature fluc-
van Wijk and de Vries (1963) present an analytical solution tuations are not sinusoidal. Effective use of these equations
to Equation 9.23 for periodic surface temperature variation for a requires soil temperature measurements at two or more depths
homogeneous soil. For initial conditions that result from infinite at frequent times. The observation period should include two
periodic surface temperature variation, semi-infinite space, and or more sunny days before the days for which soil temperature
surface boundary as will be analyzed. The sunny days will allow the soil temper-
ature initial condition to more closely match the theoretical
T (0, t ) = T + A sin(ωt + φ), (9.24)
requirements.
As an alternative to Equation 9.24, Horton et al. (1983) used
where
− the following general surface boundary condition:
T is the average temperature
A is the amplitude of the surface temperature wave
ϕ is the phase constant M

ω is the angular frequency (2π/period, e.g., 2π day−1 for diurnal T (0, t ) = T + ∑ A sin(nωt + φ ),
n n (9.28)
variation) n =1

and the analytical solution is and the method of superposition to obtain the following general
analytical solution to Equation 9.23:
⎛ ω ⎞ ⎛ ω ⎞
T (z, t ) = T + A exp ⎜ − z ⎟ sin ⎜ ωt + φ − z . (9.25)
⎝ 2α ⎠ ⎝ 2α ⎟⎠ M
⎛ nω ⎞ ⎛ nω ⎞
T (z , t ) = T + ∑ A exp ⎜⎝ −z
n ⎟ sin ⎜ nωt + φn − z
2α ⎠ ⎝ 2α ⎟⎠
,
9.5.1.1  Apparent Thermal Diffusivity n =1
Equation 9.25 provides a basis for estimating the apparent soil (9.29)
thermal diffusivity using measured soil temperature time series.
Soil temperature measurements at two or more depths are where
required. Temperature observations from the shallowest depth M is the number of harmonics
are used to establish the upper boundary condition, and the An and ϕn are the amplitude and phase constant, respectively,
lower depth(s) observations are used to determine α. of the nth harmonic for the upper boundary temperature
9-12 Properties and Processes

−
The coefficients An, ϕn, and T can be determined by least squares Horton and Wierenga (1983) used this analytical solution to
fitting of Equation 9.28 to the observed upper boundary soil tem- estimate heat flux for a bare soil and grass-covered field. The
perature data. Using these coefficients in Equation 9.29 leaves analytical solution worked well for both sunny and cloudy days.
only α as an unknown value. The value of α can be determined
by fitting Equation 9.29 to a set of soil temperature observations
9.5.2  Conduction–Convection Models
measured at a depth below the upper boundary depth. The value
of α is selected to minimize the sum of squares of the differences A few efforts have been made to measure or describe convective
between the measured and calculated temperatures. heat transfer under field conditions. Convective energy transfer
It is important to note that when α is determined from inverse in soil is associated with a net flux of fluids. Some observations of
fitting of conductive heat transfer theory to observed tempera- thermal effects on soil water infiltration have been made (Jaynes,
ture, it is not strictly correct to assume that the fitted α = λ/C. In 1990). Increases in seepage or infiltration rate were observed in
moist soil, conduction is not the only mechanism of heat trans- response to temperature increases (Constantz et al., 2003). Gao et al.
fer. All of the nonconductive heat transfer (sensible and latent (2003) presented an analytical model of transient conduction and
convective heat transfer) influences the parameter α. It is more steady convection heat transfer. Jaynes (1990) presented a numeri-
correct to call this α the apparent thermal diffusivity instead of cal model of heat and water transfer in soil during ponded irriga-
the true or real thermal diffusivity (Jackson and Kirkham, 1958). tion. Shao et al. (1998) developed an analytical solution describing
The real thermal diffusivity involves conduction heat transfer coupled conduction and convection heat transfer during ponded
alone, while the apparent thermal diffusivity includes convec- infiltration. Shao et al. (1998) reported periodic diurnal fluctuations
tion heat transfer in addition to conduction heat transfer. The in ponded infiltration rate. This infiltration rate was correlated with
apparent thermal diffusivity is a lumped parameter developed the water temperature. As water temperature oscillated, the infil-
for a practical reason, and while useful for predicting soil tem- tration rate oscillated. During infiltration, convection heat transfer
perature, it oversimplifies the many mechanisms of heat transfer had significant effects on soil temperature. Convection is especially
within porous media. We should not permit its use to become a important for heat transfer deeper in the soil profile. At a depth of
hindrance to our basic understanding of the numerous mecha- 0.6 m, diurnal temperature variation due to conduction was negli-
nisms of heat and water transfer in soil. gible; however, convection heat transfer caused noticeable diurnal
Not all approaches assume that the apparent thermal diffu- variation in soil temperature. Wierenga et al. (1970) observed irriga-
sivity is constant with depth. Nassar and Horton (1989a, 1990) tion water temperature impacting soil temperature, and Ren et al.
presented methods for determining apparent thermal diffusivity (2000), Wang et al. (2002), Hopmans et al. (2002), and Ochsner et al.
as a function of depth. Again, in these cases, the apparent ther- (2005) have presented conduction–convection models to determine
mal diffusivity lumps together conductive and convective heat water velocity based upon upstream and downstream temperature
transfer processes. Wiltshire (1982, 1983) and Massman (1993a) measurements in response to an application of a heat pulse.
presented analytical solutions to describe temperature distribu-
tions in nonuniform soil.
9.5.3  Coupled Heat and Water Transfer Models
9.5.1.2  Soil Heat Flux Models Coupled transfer of heat and water occurs in soil. For example,
Transient soil heat flux (G) has also been estimated by analytical near the surface of cropland soil, weather fluctuations often
solutions to Equation 9.23. The theory assumes that only con- cause simultaneous heat and water flow to occur. Buried radio-
duction heat transfer is occurring, so all of the actual convection active material, underground energy storage, and buried electric
heat transfer must be accounted for by apparent thermal prop- cables produce heat that causes temperature gradients, which
erties. Conduction heat transfer theory is utilized in a manner cause water to move. Temperature gradients can cause water to
to approximate both conduction and convection heat transfer move in the vapor phase from a hot site and to condense at a cold
conditions. Horton and Wierenga (1983) presented the following site. After vapor condensation, a total pressure head gradient can
equation for soil heat flux: drive water from the cold site to the warm site. Example profiles
showing the redistribution of soil moisture under imposed tem-
M
⎛ nω ⎞ perature gradients are plotted in Figure 9.9.
G(z,t ) = ∑A C
n =1
n nωα exp ⎜ − z
⎝ 2α ⎟⎠ Coupling of soil heat and water transfer has long been rec-
ognized (e.g., Bouyoucos, 1915). Thus, many studies have
⎛ nω ⎞
× sin ⎜ nωt + φn + π /4 − z . (9.30) attempted to address coupled soil heat and water transfer and
⎝ 2α ⎟⎠
provide theoretical description of the dominant transfer mech-
anisms (e.g., Philip and de Vries, 1957; Jury and Letey, 1979;
Equation 9.30 reduces to the following for surface heat flux: Sophocleous, 1979; Milly and Eagleson, 1980; Milly, 1982;
Nassar and Horton, 1997). Several studies have been performed
M
⎡ ⎛ π⎞⎤ to investigate interactions between heat and water (Philip and
G(0 , t ) = ∑A C n nωα sin ⎢nωt + φn + ⎜ ⎟ ⎥
⎣ ⎝ 4⎠⎦ (9.31) de Vries, 1957; Cary, 1966; Globus, 1983). Milly and Eagleson
n =1 (1980) and Milly (1982) described simultaneous heat and water
Soil Thermal Regime 9-13

40 Values for hydraulic conductivity and isothermal and thermal

θo = 0.10 m3 m–3 0.30 vapor diffusivities as functions of soil water content and tem-
perature were reported by Scanlon and Milly (1994). Hydraulic
35 T 0.25
θ conductivity increased with increasing soil water content and
temperature. Also, the isothermal and thermal vapor diffusivities

θ (m3 m–3)
0.20
30 increased with increasing temperature whereas they increased
T (°C)

0.15 with increasing soil water content to certain values then decreased
with further increases in the soil water content. Nassar and
25
0.10 Horton (1997) describe how to determine experimentally and/or
theoretically derived values of the transport coefficients of heat,
0.05
(a) 20 water, and solute in soils. They present coefficient values as func-
40 0.30 tions of temperature, water content, and solute concentration.
θo = 0.20 m3 m–3 There are limitations in the models used to predict coupled
0.25 heat and water transfer in soil (e.g., Philip and de Vries, 1957;
35 Cary and Taylor, 1962; Milly, 1982; Nassar and Horton, 1997;
0.20 Cahill and Parlange, 1998). Cahill and Parlange (1998) and
θ (m3 m–3) Parlange et al. (1998) report that existing diffusion-based the-
30
T (°C)

0.15 ory could not explain the large vapor fluxes and evaporation
rates measured in their field study. They proposed that diurnal
25 0.10 heating of the soil causes convective transport of soil air due to
temperature-driven expansion of the air, and this convective
0.05 enhancement (soil breathing) drives the large unexplained water
20
0 2 4 6 8 10 vapor fluxes observed in field studies. This concept has not yet
(b) Distance from warm end (cm) been confirmed. Philip and de Vries (1957) introduced a ther-
mal vapor enhancement factor to account for pore-scale features
FIGURE 9.9  Comparison of paired temperature (T) and water content
(θ) distributions for silt loam. Plots (a) and (b) show conditions after 96 h (e.g., unequal thermal gradients in various phases and nongas
for 150°C m−1 temperature gradient at 30°C mean temperature. The dot- phase diffusive pathways in the pores). Using Philip and de Vries
ted line in (b) represents a linear temperature distribution. (Reprinted theory to describe nonisothermal evaporation, Bachmann et al.
from Heitman, J.L., R. Horton, T. Ren, and T.E. Ochsner. 2007. An (2001) found a thermal vapor enhancement factor of 3.5 (mean-
improved approach for measurement of coupled heat and water trans- ing that thermal vapor transport was about 3.5 times larger than
fer in soil cells. Soil Sci. Soc. Am. J. 71:872–880. With permission. Soil expected) in a wettable soil, but only 0.35 in a hydrophobic soil.
Science Society of America.) In other words, soil columns that differed only in wettability
showed very different water evaporation rates and water distri-
transfer in terms of matric pressure head and temperature gradi- bution. No existing model can describe the pore-scale behaviors
ents. Their formulation accounted for inhomogeneous soil and that led to these greatly different thermal vapor enhancement
hysteresis of the moisture retention process. factors. There is growing appreciation for the utility of pore-
Nassar and Horton (1989c) introduced a theory describing scale models (e.g., Ewing and Horton, 2007) for gaining insight
water redistribution for conditions involving temperature, water, into the relative importance of coupled transport processes.
and solute concentration gradients. This theory was expanded Hopefully, in the near future, pore-scale models will become
by Nassar and Horton (1992) to include heat, water, and solute further developed, tested, and used to improve understanding
movement under soil water content, temperature, and solute con- and description of coupled heat and water processes in soil.
centration gradients. The theory includes several heat and mass Diffusion-based theory first introduced by Philip and de
transfer coefficients. The water, heat, and solute transport coef- Vries (1957) has long been used to describe coupled soil heat
ficients are usually affected by the water content, temperature, and water transfer. Discrepancies between measurements and
and solute concentration. theory point to the need for more careful evaluation of the the-
There are currently only a limited number of published ory. Heitman et al. (2008a) used data obtained from laboratory
reports that include values of these coefficients, especially under experiments with transient boundary conditions in an attempt
the combined effect of water content, temperature, and solute to both calibrate and test calculations of coupled heat and
concentration (e.g., Nassar and Horton, 1997). Effects of a wide water transfer. Simple calibration for a single boundary and
range of soil temperatures, 5°C–55°C, on water redistribu- initial condition through adjustment of saturated hydraulic
tion in solute-free soil columns were reported by Nassar et al. conductivity and thermal vapor enhancement factors provided
(1992a). A net water transfer was found toward the cold ends of a reasonable match for transient boundary conditions with
the soil columns with increasing mean soil temperature. It was gradual changes and at additional initial conditions. The find-
concluded that the temperature dependence of several soil water ings of Heitman et al. (2008a) indicate that after soil-specific
transfer coefficients affected the water transfer rates. calibration to one coupled heat and water transfer condition,
9-14 Properties and Processes

the Philip and de Vries theory can be used to predict coupled accounts for 20% of the heat budget in the Negev during the dry
heat and water transfer under other soil conditions. season (Agam et al., 2004). Despite this importance, evaporation is
often erroneously described as occurring at the soil surface rather
9.6  Measuring Soil Temperature than within the soil. The surface soil heat flux is generally assumed
only to account for conductive heat transfer into the soil. This is
Soil temperature is commonly measured using nonelectric ther- a restrictive assumption, because as a soil dries from the surface
mometers, thermocouples, or thermistors. Nonelectric thermom- downward, an increasing fraction of the soil-water evaporation
eters operate based on thermal expansion of liquids or solids. occurs below the surface (Mayocchi and Bristow, 1995; Yamanaka
These simple devices are appropriate when high accuracy or pre- et al., 1998). The assumption that all evaporation occurs at the soil
cision is not required. A thermocouple produces a small voltage surface does not account for the evaporation zone that propagates
(via the Seebeck effect) proportional to the temperature difference downward into the soil.
between its measuring junction and its reference junction. A sen- The Community Land Model (CLM3.5; Oleson et al., 2007), per-
sitive measuring device can be used to measure and record the haps the most detailed of the third-generation land surface mod-
voltage and corresponding temperature at the measuring junc- els, assumes that evaporation occurs at the soil surface. As a result,
tion if the temperature of the reference junction is known by some soil evaporation estimates are likely to be systematically incorrect
other means. Thermistors are ceramic semiconductors whose (Mahfouf and Noilhan, 1991; Milly, 1992; Guo and Dirmeyer,
resistance is strongly temperature dependent. By measuring the 2006). The current deficient treatment of the near-surface land/
resistance, one can infer the temperature. Thermistors are gener- atmosphere coupling is largely due to a lack of appropriate mea-
ally more sensitive than either nonelectric thermometers or ther- surement techniques. Aboveground techniques such as eddy cova-
mocouples. The World Meteorological Organization recommends riance (McInnes and Heilman, 2005) and Bowen ratio (Fritschen
routine soil temperature measurement depths of 5, 10, 20, 50, and and Fritschen, 2005) provide useful approaches to estimate evapo-
100 cm (WMO, 2006). A measurement frequency of once every 2 h transpiration. However, the inability to measure near-surface
is often sufficient to describe the diurnal soil temperature cycle. movement of heat and water has prohibited an accurate assessment
Measurement objectives, available equipment, and site charac- of the near-surface water evaporation and heat balance (de Silans
teristics may dictate different depth and measurement frequency et al., 1997). Recent advances in using the HP method for measur-
choices. For additional information on soil temperature measure- ing soil thermal properties, heat flux, and heat storage (e.g., Ochsner
ment, consult the chapters by McInnes (2002) and Ochsner (2008). et al., 2006, 2007) provide a new opportunity to investigate time
A significant recent development is the application of distrib- and depth patterns of heat transfer and evaporation within soil.
uted temperature sensing in soils. A distributed temperature
sensing instrument can be used to determine the temperature
9.7.1  Measuring Soil Heat Fluxes
at each location along a fiber-optic cable. Temperatures can be
measured with a precision of 0.1°C and spatial resolution of Soil heat flux measurements are most frequently obtained with
1 m along a cable, which is several kilometers long (Selker et al., the use of soil heat flux plates (Sauer, 2002). These small rigid
2006). With the aid of a special plow, the cables can be installed plates contain a thermopile whose voltage output is proportional
at shallow depths below the soil surface and used to measure the to the temperature difference between the upper and lower faces
spatial distribution of soil temperature over large areas (Steele- of the plate. The relationship between that temperature difference
Dunne et al., 2010). and the conductive heat flux through the plate is calibrated in a
laboratory setting. In the field, the assumption is made that the
heat flux through the plate is the same as that through the sur-
9.7  Measuring and Interpreting rounding soil at the same depth; thus, the voltage output from the
Soil Heat Fluxes plate (mV) is divided by an empirical constant (mV m2 W−1) to
estimate the soil heat flux (W m−2). Several criteria must be met for
Researchers have noted the strong connection between soil-water heat flux plates to produce accurate data: (1) there must be negli-
evaporation and soil heat flux (e.g., Gardner and Hanks, 1966; gible thermal contact resistance between the plate and the soil,
Mayocchi and Bristow, 1995). Unfortunately, an inability to mea- (2) the thermal properties of the plate must be the same as those
sure heat transfer at the fine scale necessary to observe evapora- of the surrounding soil, and (3) heat transfer through the soil
tive processes has limited investigations. Soil heat flux is typically must be by conduction alone. These criteria are rarely, if ever,
measured below the soil surface, and a correction is made for the satisfied in the field; thus, significant errors may be unavoid-
change in sensible heat storage above the flux measurement depth able. The typical result of violations of the three criteria above
(e.g., Fuchs and Tanner, 1968; Massman, 1993b). This approach is an underestimation of G. Recent studies have found that com-
ignores the transient, depth-dependence of the evaporation front mercially available heat flux plates underestimate G from 2% to
below the soil surface (de Vries and Philip, 1986). 73% in the laboratory (Sauer et al., 2003, 2007) and from 18% to
Evaporation plays a central role in the movement of heat and 66% in the field (Ochsner et al., 2006). The data in Figure 9.10a
water within the soil (Yamanaka et al., 1998; Wythers et al., illustrate the underestimation, which is typical of soil heat flux
1999) and the atmosphere. For example, evaporation of soil water plates. These data show that the magnitude of G at a 5 cm depth
Soil Thermal Regime 9-15

80 The self-calibrating plate method uses a soil heat flux plate to

Corn site
which a film heater is added on the upper face. The plate violates the
HFT1.1 plate Gr (W m–2) 60 three criteria identified in the first paragraph of this section; how-
ever, by introducing a known heat flux via the heater at predeter-
40
mined intervals (e.g., 3 h), an in situ calibration constant is obtained
20 that varies with the soil conditions. The procedure results in more
accurate soil heat flux data than the traditional plate method
0 (Ochsner et al., 2006). Increased adoption of the three-needle gra-
dient method and the self-calibrating plate method should lead to
–20
more accurate soil heat flux and surface energy balance data.
–40 Slope 0.737
r2 0.960
(a) 9.7.2  Interpreting Soil Heat Fluxes
80
It has been suggested that a sensible heat balance offers a means
60
Single probe gradient Gr (W m–2)

to track the soil evaporation front within the soil (Gardner and
Hanks, 1966; Mayocchi and Bristow, 1995). Evaporation of soil
40
water represents a large heat sink. A sensible heat balance is used
20 to determine the amount of latent heat involved with vaporiza-
tion of soil water following Gardner and Hanks (1966):
0

(H 0 − H1 ) − ΔS = LE (9.32)
–20

–40 Slope 0.935 where

r2 0.972 H0 and H1 are soil heat fluxes (W m−2) at depths 0 and 1,
–60 respectively
–60 –40 –20 0 20 40 60 80
ΔS (W m−2) is the change in soil sensible heat storage between
(b) –2
Three needle gradient Gr (W m ) depths 0 and 1
FIGURE 9.10  Soil heat flux at 5 cm (Gr) under corn as measured by L (J m−3) is the latent heat of vaporization
heat flux plates (REBS HFT1.1) shown in (a) and the single-probe gra- E is evaporation (m s−1)
dient method (b) versus the three-needle gradient method. The solid
lines are the regression lines, and the dashed lines are the one-to-one Using measurements of soil thermal conductivity (λ, W m−1 °C−1)
lines. (Reprinted from Ochsner, T.E., T.J. Sauer, and R. Horton. 2006. and the temperature gradient (dT/dz, °C m−1), values for H can
Field tests of the soil heat flux plate method and some alternatives. Agron. be determined from Fourier’s law (Ochsner et al., 2006). Ochsner
J. 98:1005–1014. With permission. American Society of Agronomy.) et al. (2007) provide several approximations for determining
ΔS from measured temperature (T, °C) and soil volumetric heat
was underestimated by ~26% using some of the best available capacity (C, J m−3 °C−1). One approximation is
soil heat flux plates. Some other commercially available plates
exhibit significantly worse performance (Ochsner et al., 2006). N
Ti , j − Ti , j −1
Two primary alternatives to the traditional soil heat flux
plate method are the three-needle gradient method and the self-­
ΔS = ∑C i , j −1
t j − t j −1
(zi − zi −1 ), (9.33)
i =1
calibrating plate method. The gradient method typically employs
a three-needle HP sensor capable of measuring the ambient soil where
temperature gradient and soil thermal conductivity (Cobos and z (m) is depth
Baker, 2003; Ochsner et al., 2006). Soil heat flux is then calcu- the subscripts i and j are index variables for depth layers and
lated directly from Equation 9.7. This three-needle gradient time steps, respectively
method has produced excellent results in field tests (Cobos and
Baker, 2003; Ochsner et al., 2006). Figure 9.10b illustrates the The residual from the energy balance provided by the left side
performance of the three-needle gradient method by comparing of Equation 9.32 is attributed to LE, which cannot be measured
it to an independent single-probe gradient method. The mag- directly. Values for L can be calculated from Equation 9.4 using
nitude of G at 5 cm measured by these two methods agrees to the soil temperature at the depth of interest. Having values for H,
within ~6%. The three-needle gradient method offers additional ΔS, and L, it is possible to calculate E from Equation 9.32.
benefits in that soil temperature, thermal properties, and water Heitman et al. (2008b, 2008c) placed several three-needle
content can be obtained simultaneously with the same sensor. HP sensors at shallow depths in a soil. The central needles
The method has been recently extended to measuring G under of the sensors were positioned at 6, 12, 18, 24, 45, and 60 mm
freezing and thawing conditions (Ochsner and Baker, 2008). below the soil surface. The plane formed by the three needles
9-16 Properties and Processes

of each sensor was oriented perpendicular to the soil surface. 0.8

(a) The sensors were connected to a data acquisition system, 3–9 mm
and HP measurements and soil temperature measurements 0.6 9–15 mm
15–21 mm

Evaporation (mm h–1)

were obtained each 4 and 0.5 h, respectively. They were able
21–27 mm
to use their measurements to estimate sensible and latent 0.4
heat fluxes with depth and time. The latent heat flux estimates
allowed them to estimate soil water evaporation as a function 0.2
of depth and time, thus revealing the temporal patterns of in
situ evaporation and condensation. This approach is measure-
0
ment driven, so it does not require determination of coupled
heat and water transfer coefficients (e.g., Nassar and Horton,
–0.2
1997) or soil-specific hydraulic properties. 174 175 176 177 178 179 180
Results for a 6 day period are presented in Figures 9.11 and
9.12. Data for the uppermost HP sensor (centered at 6 mm) are
FIGURE 9.12  Evaporation determined by heat balance using HP
sensors. Data were collected in 2007 from a bare field in Iowa follow-
60
ing rainfall on DOY 172. (Reprinted from Heitman, J.L., X. Xiao, R.
0 mm
45 6 mm Horton, and T.J. Sauer. 2008c. Sensible heat measurements indicating depth
12 mm and magnitude of subsurface soil water evaporation. Water Resour. Res.
T (°C )

30 44:W00D05. With permission.)

15 shown in Figure 9.10. During this time period, daily maximum

ambient T generally increases after rainfall through day of year
0
1.2 (DOY) 178 at the 0, 6, and 12 mm depths (Figure 9.11). Drying
2.5 1.0 in the upper portion of the soil profile also produces decreases
C (MJ m–3 °C–1)

λ (W m–1 °C –1)

2.0 0.8
in both C and λ (Figure 9.11). Accompanying these changes
1.5
are shifts in the magnitude of dT/dz at the 3 and 9 mm depths.
0.6
c The magnitude of dT/dz is similar with depth through DOY
1.0 0.4
C (0–12 mm) 175 (Figure 9.11). On DOY 176, the peak magnitude of dT/dz at
0.5 λ (0–12 mm) 0.2 3 mm begins to increase and thereafter remains relatively large.
0.0 0.0 A shift also occurs at 9 mm on DOY 176, but peak magnitudes
remain well below those at 3 mm until DOY 178 when the gradi-
200 ents begin to converge. This indicates that the zone of evapora-
dT/dz (°C m–1)

–200
tion has moved below 9 mm. Driven by dT/dz, heat flux density
demonstrates a similar pattern (Figure 9.11). The 3 and 9 mm
–600 deep heat flux densities are nearly identical through DOY 175.
–1000 3 mm However, beginning on DOY 176, divergence in the heat flux
9 mm density with depth indicates significant heat loss (>150 W m−2)
–1400 as heat is transferred through the soil. The amount of heat par-
titioned to ΔS can be quantified and remains consistently small
700 throughout this period (<25 W m−2). The difference between heat
G and ∆S (W m–2)

G1 (3 mm)
500 G2 (9 mm) flux density at 3 and 9 mm (i.e., G1 and G 2) appreciably exceeds
∆S (3–9 mm) ΔS through DOY 178 and thereby allows determination of LE
300 with Equation 9.33.
100 Results for sensors measuring the 3–9, 9–15, 15–21, and
21–27 mm depth increments are shown in Figure 9.12. Note
–100
174 175 176 177 178 179 180 that data are presented as evaporation rate, E (mm h−1), rather
Day of year 2007 than LE. The evaporation rate remains near 0 for all mea-
sured depth increments through DOY 175, which indicates
FIGURE 9.11  Measurements obtained with HP sensors: T is soil tem- that the evaporation zone has not passed below the 3 mm soil
perature, C is volumetric heat capacity and λ is thermal conductivity,
depth. All sensible heat transferred through the 3 mm depth is
dT/dz is temperature gradient, and G and ΔS are heat flux densities and
accounted for through ΔS or heat flux density at lower depths.
change in sensible heat storage. Data were collected in 2007 from a bare
field in Iowa following rainfall on DOY 172. (Reprinted from Heitman,
On DOY 176, the peak magnitude of E increases to 0.3 and
J.L., X. Xiao, R. Horton, and T.J. Sauer. 2008c. Sensible heat measurements 0.15 mm h−1 during the afternoon at the 3–9 and 9–15 mm
indicating depth and magnitude of subsurface soil water evaporation. depth increments, respectively. The peak magnitude of E
Water Resour. Res. 44:W00D05. With permission.) continues to increase for both depth increments on DOY 177
Soil Thermal Regime 9-17

before declining on subsequent days. Net evaporation rates have implications for the surface energy balance and evaporation.
are generally highest immediately following rainfall, assum- Horton et al. (1996) provide a review of crop residue effects on
ing that atmospheric demand is not limiting (Lemon, 1956). surface radiation and energy balances.
Thus, the relatively lower E on DOY 176 than 177 does not Plastic “mulches” (i.e., plastic film) placed on the soil surface
necessarily suggest less total evaporation. Rather, it indicates are another method often used to manage the soil thermal regime.
that evaporation is still occurring in the soil layer above the Plastic mulches modify the soil thermal regime by changing the
3 mm depth on DOY 176. Transition to evaporation at deeper radiation budget of the surface and by suppressing evaporation
soil depths is beginning to occur on DOY 176 as soil water (Ham et al., 1993). Plastic mulches usually result in higher soil tem-
stored above the 3 mm depth is depleted and cannot meet peratures, but the effects of plastic mulch depend on the optical
atmospheric demand. After DOY 177, measurements of the properties of the mulch and on thermal contact resistance between
3 mm heat flux density (Figure 9.11) suggest that nearly all the plastic and the soil surface (Ham and Kluitenberg, 1994).
evaporation occurs below the 3 mm soil depth. The shifting
pattern of evaporation continues on subsequent days as soil 9.9  Soil Temperature and Global
water storage is further depleted near the surface and peak E Climate Change
at 9–15 mm begins to exceed E at 3–9 mm (Figure 9.12). The
declining peak magnitudes of E for all depth increments after Soil temperature and temperature of underlying geologic for-
DOY 177 are indicative of decreased total evaporation as soil mations are strongly linked with global climate. The heat capac-
water becomes limiting. ity of soil and rock is much larger than that of air; thus, if heat
is accumulating on earth, we should expect more heat storage
9.8  Managing the Soil Thermal Regime in the soil and rock than in the atmosphere. Baker and Baker
(2002) examined a long-term data set of subsurface tempera-
Agricultural management practices, including irrigation, drain- ture measurements to quantify subsurface heat accumulation.
age, tillage, and crop residue management, have the potential to They found an average annual downward flux of 1.1 MJ m−2 at
affect the thermal properties of soils and therefore soil thermal the 1.6 m depth over a 37-year period. At the 12.8 m depth, the
regime. In particular, the effect of tillage and crop residue man- average annual downward heat flux was 0.22 MJ m−2. Similarly,
agement on soil heat flux has been the subject of several studies Beltrami et al. (2002) found a net downward long-term heat flux
(Allmaras et al., 1977; Pikul et al., 1985; Enz et al., 1988; Azooz at the land surface with a global average of 1.2 MJ m−2 annu-
et al., 1997; Richard and Cellier, 1998; Sauer et al., 1998). Tillage ally in the period from 1950 to 2000. Total heat accumulation
loosens the surface soil, although some local compaction may in the continental lithosphere from 1950 to 2000 (9.1 × 1021 J)
also occur. Lower soil bulk density generally translates to exceeded heat accumulation in the atmosphere (6.6 × 1021 J)
lower λ; thus, lower G has been observed in tilled soil as com- and was second only to heat accumulation in the world’s oceans
pared to untilled or compacted soil (Azooz et al., 1997; Richard (182 × 1021 J).
and Cellier, 1998). Tillage can also influence surface energy There is evidence that subsurface heat storage is not ade-
partitioning through its effects on albedo, emissivity, and near- quately simulated in general circulation models (GCMs), which
surface water content. are used for climate change projections. Current GCMs have 0
Crop residues can strongly influence the soil thermal regime. heat flux bottom boundary conditions at depths of between 1.5
They can shade the soil, increase the shortwave albedo, and and 10 m below the land surface (Smerdon and Stieglitz, 2006).
change the longwave emissivity of the land surface. Crop resi- The results of Baker and Baker (2002) indicate that >20% of sub-
dues slow the rate of soil water evaporation and can result in surface heat storage occurs below the 10 m depth; thus, even
higher soil water content. Water content, in turn, influences soil the GCM with the deepest bottom boundary (ECHO-G, 10 m)
physical properties and surface energy partitioning. Compared may contain significant errors. In a simulation study, a land
to bare soil, crop residues can reduce extremes of heat and mass model with a 600 m deep bottom boundary stored 6.2 times
fluxes at the soil surface. Managing crop residues can result in more heat than ECHO-G under Intergovernmental Panel on
more favorable agronomic soil conditions. The quantity, qual- Climate Change (IPCC) emission scenario A2 (MacDougall et
ity, architecture, and surface distribution of crop residues affect al., 2008). To put this result in perspective, the difference in pre-
soil surface radiation and energy balances, soil water content, dicted continental heat storage between the models with shallow
and soil temperature (e.g., Bristow, 1988). Crop residue has a low and deep bottom boundaries was 8.2 × 1022 J over the period
thermal conductivity and, whether lying on the soil surface or from 1991 to 2100, while the estimated heat accumulation in the
incorporated into the soil by tillage, inhibits heat transfer into atmosphere from 1955 to 2003 was only 0.5 × 1022 J. Neglecting
the soil. Residue layers also have a shortwave reflectivity that deep-subsurface heat storage in GCMs may lead to overpre-
is higher than most soils and provide a barrier to vapor flow dicting soil temperature changes, overpredicting ocean- and
(Gausman et al., 1975; Horton et al., 1996; Sauer et al., 1997). atmosphere-­temperature changes, and misrepresenting a host
Thus, soils with a large proportion of the surface covered by crop of atmosphere–land surface feedbacks and linkages. Clearly, a
residue tend to have higher water contents, lower temperatures, better understanding of the soil thermal regime and its connec-
and lower G. Such changes in soil thermal regime, of course, tion with global climate is needed.
9-18 Properties and Processes

9.10  Concluding Remarks Bouyoucos, G.T. 1915. Effect of temperature on the movement of water
vapor and capillary moisture in soils. J. Agric. Res. 5:141–172.
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Ohmura, A., and H. Gilgen. 1993. Re-evaluation of the global Sauer, T.J., J.L. Hatfield, J.H. Prueger, and J.M. Norman. 1998.
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 10
Soil Spatial Variability
10.1 Sampling a Soil Process.........................................................................................................10-1
10.2 Autocorrelation.......................................................................................................................10-2
10.3 Cross-Correlation...................................................................................................................10-3
10.4 Semivariogram........................................................................................................................10-5
10.5 Kriging......................................................................................................................................10-8
10.6 Cokriging...............................................................................................................................10-10
Ole Wendroth
University of Kentucky
10.7 Autoregressive State-Space Modeling...............................................................................10-13
10.8 Spectral Analysis...................................................................................................................10-15
Sylvia Koszinski 10.9 Cospectral Analysis..............................................................................................................10-18
Leibniz Centre for Agricultural 10.10 Wavelet Analysis...................................................................................................................10-19
Landscape Research (ZALF)
Appendix...........................................................................................................................................10-22
Vicente Vasquez Acknowledgments............................................................................................................................10-22
University of Kentucky References..........................................................................................................................................10-22

10.1  Sampling a Soil Process assures that the status of this plot is different from the one that
received a different treatment. Investigating a spatial or tem-
One of the parameters of soil ecosystems are soil processes poral process does not require the a priori installation of two
(Gregorich et al., 2001). Process is based on the Latin word or more treatments but is rather focused on measuring grad-
“procedere—to proceed, to advance, to go on.” Each individual ual changes with a series of observations of a state variable or
stage of a process depends on the previous stage in either a causal an ensemble of state variables, called state vector. Monitoring
(deterministic) manner or a probabilistic (stochastic) manner. gradual changes implies that changes in the observed variable
A soil process can be considered in space and time. A spatial soil are smaller between subsequent and neighboring observations
process is the change of a variable or a state vector consisting than over a long spatial distance or time interval. If changes over
of several variables across a spatial domain caused by underly- short distances or time intervals are indeed smaller than changes
ing effects. The spatial process of soil water content considered occurring over long intervals, the variation is called structured,
across a landscape can be influenced by spatial changes in soil and a range of representativity pertaining to an individual mea-
type, topography, vegetation, rainfall, evapotranspiration, man- surement can be derived. In this case, we can interpolate a value
agement, etc. Similarly, a temporal process is the change of a located between two measured points at an unobserved point. If
soil variable or state vector observed at the same location over on the other hand the variance observed over the shortest sam-
time caused by underlying effects. The temporal process of soil pling interval is in the magnitude of the population variance,
water content is influenced by temporal occurrences of precipi- this variation is called random, and any interpolation between
tation, evapotranspiration, drainage, capillary rise, etc. Hence, two points would not be justifiable. In this chapter, consider-
subsequent stages in either space or time do not vary randomly ations are given to the sampling of a spatial or temporal process,
but depend on each other. If in fact subsequent stages of a pro- to derive spatial or temporal relationships between different
cess do not depend on each other but rather vary randomly, the variables, apply coregionalization, develop simple spatial or
monitoring of a sequence of stages would not allow us to derive temporal time series models, and quantify cyclic variation com-
any causal or statistical relationships between various ongoing ponents or fluctuation patterns within data series. Appropriate
changes. In other words, the spacing or time increments between soil sampling schemes in which investigators aimed to detect
observations would be inappropriate to identify the process. variability structure have been widely discussed in the literature.
Sampling a soil process in either the spatial or the tempo- Burgess and Webster (1980), Warrick and Myers (1987), Brus
ral domain is different from what soil scientists usually try to and de Gruijter (1997), Boyer et al. (1996), Buscaglia and Varco
achieve when they aspire a “good” average, or a representative (2003) are a few examples from different ecological disciplines.
mean value for a plot that received a specific treatment, which When applied to soil, agronomic and ecological investigations,

10-1
10-2 Properties and Processes

none of the analytical approaches presented here requires an (Warrick et al., 1986). This condition underlies all randomized
experiment with treatments, but on the other hand, does not sampling designs and associated statistical analyses. Regardless
exclude treatment experiments. A wide variety of geostatisti- whether a data set manifests structured or random variation, at
cal applications in treatment experiments exists in the litera- zero lag, r(h) = 1, because an observation is perfectly related with
ture (e.g., Bhatti et al., 1991a; Mulla et al., 1992; Ball et al., 1993; itself. Nielsen and Wendroth (2003) illustrated the calculation
Mulla, 1993; Bishop and Lark, 2006). Some of these are focused scheme for the autocorrelation function in detail. Nielsen and
on the removal of underlying spatial soil trends whose impact Alemi (1989) determined the autocorrelation function not only for
was large enough to obscure treatment effects (e.g., Wilkinson static variables but also for a rate variable, that is, water flow rate.
et al., 1983; Mulla et al., 1990; Bhatti et al., 1991b). And among In view of sampling a spatial soil process, the purpose of this
many others, Raftery (1993) and Van Es and Van Es (1993) have paragraph is to apply autocorrelation analysis for the evalua-
demonstrated the application of state-space models and semi- tion of soil water content measurements along a 440 m transect
variography, respectively, in experiments with treatments. On in a northeast German moraine catena. Gravimetric soil water
the other hand, beneficial experiments in agriculturally related content was measured at 40–60 cm soil depth based on auger
disciplines, especially soil science, do not have to depend on rep- samples (Wendroth et al., 2006; Robinson et al., 2008). The spa-
licated randomized treatments. As pointed out by Collis-George tial resolution of measurements is varied in the analysis of mea-
and Davey (1960), though argued in some respects by Barley surements. First, samples taken at 40 m distances equally spaced
(1964), plant–soil interactions may be understood better in a few along the transect are considered (Figure 10.1a). No obvious
experiments focused on understanding the biogeochemical and trend exists in the data. In some cases, fluctuations in soil water
environmental controls on biological response. With the study content from one location to the next are small—about 0.01 g g−1
of landscape processes and the application of statistical analyses and in other cases, they are large—greater than 0.03 g g−1.
that do not depend on spatial or temporal independence, alter- The resulting autocorrelation function is depicted in Figure 10.1b.
native management practices can well be identified even without The immediate drop of r(h) at h > 0 reflects the random or unstruc-
treatment experiments (Nielsen, 1987). Inherent variations of tured variation of soil water content measurements. Regardless of
data series can be analyzed regardless of the size or extent of the the length of the transect over which we examine spatial differences
spatial or temporal domain. For example, techniques are appli- in soil water content, these differences remain random. Because the
cable to large scale investigations such as remote sensing or data autocorrelation coefficients are nil, a spatial range of representativ-
observed over a decade as well as to the small scale of an x-ray ity does not exist for this sampling scenario. This result implies that
image of a soil thin section or the change of soil water storage soil water content sampled at 40 m distances cannot be spatially
over time increments in the order of seconds or less. interpolated because no structured variation exists. Moreover, soil
water content measurements cannot be applied to explain the vari-
10.2  Autocorrelation ation of any other variable, since the spatial domain represented by
an individual water content measurement is unknown.
The autocorrelation function is a special expression of autoco- If the samples taken at 40 m intervals along this 440 m tran-
variance. The latter describes the average product of differences sect become part of a longer series of soil water content measure-
of two observations, Ai(xi) and Ai(xi + h), respectively, from the ments, that is, over several kilometers or a hundred kilometer or
−
mean of a series A, while the two observations are separated by a any distance over which large scale influences on soil water con-
distance, the so-called lag h (Salas et al., 1988): tent, such as varying soil type etc., become dominant, a struc-
tured variation of soil water content may perhaps be identified
1
N −h (Wendroth and Robinson, 2008). In such a case, the autocorrela-
cov[ Ai (x ), Ai (x + h)] =
N ∑[A (x ) − A][A (x + h) − A]. (10.1)
i i i i tion length of water content observations would be a multiple of
i =1 the 40 m lag interval. However, to quantify a correlation length
within the domain of the 440 m transect, samples need to be
Normalizing the autocovariance function yields the autocorre-
taken at distances closer than 40 m, or the volume of an indi-
lation function (Shumway, 1988):
vidual sample would have to be increased substantially or both.
Reducing the sampling distance to one half, that is, 20 m,
cov[ Ai (x ), Ai (x + h)] results in the water content data shown in Figure 10.1c exhibiting
r (h) = , (10.2)
var[ Ai (x )] var[ Ai (x + h)] a magnitude of local fluctuations close to the magnitude of the
average difference between neighboring observations. The corre-
where the two variance terms in the denominator describe the sponding autocorrelation behavior is illustrated in Figure 10.1d.
variance of both arrays of data Ai(xi) and Ai(xi + h). For large time Still, the spatial variation remains random. Hence, even over
series, the product in the denominator equals the variance s A2 . distances of 20 m, sampling was not close enough to allow spa-
For a data set with structured variation, the autocorrelation coef- tial interpolation. When the distance between samples was fur-
ficient r(h) decreases with increasing separation distance between ther reduced to 10 m, a more continuous picture of fluctuations
observations until it reaches zero. A data set without any vari- in soil water content can be observed (Figure 10.1e). The former
ability structure exhibits zero autocorrelation for all lag intervals peak water content at ∼160 m distance in Figure 10.1a is now
Soil Spatial Variability 10-3

0.20
40 m Distance (a) 1.0 (b)

0.6 r = exp(–h/0.8)
0.15
0.2

0.10 –0.2
0 100 200 300 400 500 0 40 80 120 160 200
0.20 1.0
20 m Distance (c) (d)

0.6 r = exp(–h/7.97)
0.15

Autocorrelation coefficient r(h)

0.2
Soil water content (g g–1)

0.10 –0.2
0 100 200 300 400 500 0 40 80 120 160 200
0.20 1.0
10 m Distance (e) (f)
0.6 r = exp(–h/9.70)
0.15
0.2

0.10 –0.2
0 100 200 300 400 500 0 40 80 120 160 200
0.20 1.0
5 m Distance (g) (h)
0.6 r = exp(–h/9.96)
0.15
0.2

0.10 –0.2
0 100 200 300 400 500 0 40 80 120 160 200
Distance (m) Lag distance (m)

FIGURE 10.1  Soil water content measured at the 40–60 cm soil depth across a moraine agricultural landscape in northeast Germany.
Measurements are shown for 40 m (a), 20 m (c), 10 m (e), and 5 m (g) sampling intervals. Respective autocorrelation functions r(h) are displayed in
(b), (d), (f), and (h).

supported by several values increasing toward that peak value measurement that was generally pointed out by McBratney and
and others decreasing when that peak location is passed (Figure Webster (1983), but spatial structure indicated in the autocor-
10.1e). From Figure 10.1a, the investigator could not tell whether relation function (Figure 10.1f and h) also qualifies a soil water
this large value at a distance of 160 m was a measurement error, content observation as a covariate for another state variable. This
or in fact, a large value belonging to the continuity of the spatial statement is explained in the following paragraph.
water content process shown in Figure 10.1e. This locally large
value gains reliability and represents the process in the context 10.3  Cross-Correlation
of previous and subsequent observations. The corresponding
autocorrelation function depicted in Figure 10.1f manifests the Once the spatial or temporal variation structure and a range of
structure of observed variations to a neighboring distance of representativity of a variable are identified, its spatial relation-
1 lag (10 m). By reducing the sampling distance still further to 5 m, ship or cross-correlation behavior to another variable can be
the spatial process of soil water content becomes even more obvi- quantified. This is accomplished through the cross-correlation
ous (Figure 10.1g), and the autocorrelation function manifests an function rc(h), which quantifies the relationship between two
obvious variance structure. The autocorrelation functions variables sampled at the same location or time and at different
depicted in Figure 10.1f and h imply that samples taken every locations with increasing separation distances. Knowing the
10 or 5 m would clearly support spatial interpolation through spatial or temporal variation of two sets of measurements, we
kriging or other techniques. Samples taken at intervals greater can determine from the cross-correlation function how far apart
than 10 m would not allow regionalization, at least not in the from each other samples can be taken to yield values that remain
limited size of this specifically sampled domain. related with each other (Cassel et al., 2000). This information
This brief introduction to the impact of sampling distance is especially important in situations where we cannot place two
on the identifiability of a spatial process is not only relevant for sensors or take soil samples at exactly the same location. The
obtaining insight into the representativity of a soil water content cross-correlation function is also relevant in situations where
10-4 Properties and Processes

two variables cover different spheres of influence, for example, In the same field where soil water content samples had been
the investigator wants to know whether a point measurement taken, soil clay content and geoelectrical resistivity ρ were
of soil texture is related to an average crop yield measurement measured at the same 40–60 cm soil depth. Data are presented
taken over an area of 10 m by 10 m. in Figure 10.2a for a sampling distance of 40 m. From the spa-
The cross-correlation function is defined as the covariance tial process of both data series, an inverse linear relationship
of variable Ai sampled at location xi and variable Bi sampled at is derived with a correlation coefficient of r = −0.505, given in
a lag interval apart, that is, at (xi + h), divided by the square Table 10.1. Progressively reducing the spatial sampling distances
root of the product of the variances of both variables (Shumway, along the 440 m transect from 40 to 20 m, to 10 m, and to 5 m
1988): (Figure 10.2a and b, showing only the 40 and 5 m data) not only
changes the correlation coefficient between clay content and ρ
cov[ Ai (xi ), Bi (xi + h)]
rc (h) = . (10.3) (Table 10.1), it also has a strong effect on the intercept and the
var[ Ai (xi )] var[Bi (xi + h)] slope of the linear regression (Table 10.1).

0.4 200
40 m distance
0.3 ρ 150

0.2 100

0.1 50
Clay
Clay content (g g–1)

Resistivity ρ (Ω m)
0.0 0
(a) 0 100 200 300 400

0.4 200
5 m distance
0.3 150

0.2 100

0.1 50

0.0 0
0 100 200 300 400
(b) Distance (m)

0.8
Clay vs. Resistivity
0.4
40 m distance
0.0
Crosscorrelation coefficient rc(h)

?
–0.4

–0.8
–80 –40 0 40 80
(c)

0.8

0.4 5 m distance

0.0

–0.4

–0.8
–80 –40 0 40 80
(d) Lag distance h (m)

FIGURE 10.2  Soil clay content and geoelectrical resistivity ρ measured in a moraine agricultural landscape in northeast Germany at 40 m (a) and
5 m (b) sampling intervals. The cross-correlation functions rc(h) corresponding to the two sampling scenarios are shown in (c) and (d), respectively,
where the question mark in (c) manifests the unknown cross-correlation length.
Soil Spatial Variability 10-5

TABLE 10.1  Linear Regression Equation Coefficients 10.4  Semivariogram

for the Soil Clay Content—Geoelectrical Resistivity ρ
Relationship at 40–60 cm Soil Depth and for Different The discussion in this section is focused on 1D soil water content
Spatial Resolutions (Sampling Distances s) data measured along a transect. Indeed, semivariography is not
Sampling Correlation limited to one dimension. It can also be applied in two or three
Distance s (m) Intercept a Slope b Coefficient r dimensions with directional anisotropy being quantified and
40 0.183 −5.98 × 10−4 −0.505 included in the analysis and interpretation. What is being said
20 0.224 −9.14 × 10−4 −0.597 here is valid for studies and data sets that also extend over more
10 0.264 −1.318 × 10−3 −0.679 than one domain.
5 0.266 −1.223 × 10−3 −0.669 In this paragraph, the semivariogram γ(h) that is inversely
related to the autocovariance is introduced and discussed.
Similar to the autocorrelation function r(h), the relationship
The cross-correlation behavior between both data sets differs between observations taken at locations separated by a lag dis-
for different spatial sampling distances. For the scenario of 40 m tance h is quantified. Unlike r(h), the semivariogram is not a
sampling distance, observations of clay content and geoelectri- normalized form of covariance but is based on absolute differ-
cal resistivity sampled at 40 m are not spatially cross-correlated ences in the original units in which the variable was measured.
(Figure 10.2c, with its “?” manifesting the unknown cross-cor- The semivariogram is defined as (Vieira et al., 1983; Isaaks and
relation length) while those sampled every 5 m are clearly cross- Srivastava, 1989; Journel and Huijbregts, 1991)
correlated (Figure 10.2d). The latter cross-correlation function
indicates that a clay content measurement is related to ρ over a N (h )
1
distance of 5 to 10 m but not beyond that distance (Figure 10.2d). γ(h) =
2N (h) ∑[A (x ) − A (x + h)] ,
i i i i
2
(10.4)
Notice that the results for different sampling distances are con- i =1

sidered over the same domain or extent. The left-hand side of

the cross-correlation function reflects clay content leading the ρ where the sum of squared differences between observations
series, and the right-hand side ρ leading the clay content series. separated by a common lag distance h is averaged and divided
Leading refers to the way in which both series are shifted against by the specific number of pairs of observations N(h) in each lag
each other for each lag in cross-correlation analysis (see scheme class and divided by 2. In other words, the semivariogram γ(h)
in Nielsen and Wendroth, 2003), that is, lag h = −1 refers to the manifests the average variance between pairs of observations
clay series being one position ahead of the ρ series. Before the within a given lag distance class.
spatial relationship between two series is examined in cross- At this point, we note that in the literature, the term semi-
correlation analysis, their individual autocorrelation structure variogram is frequently used interchangeably with variogram.
needs to be evident. If one or both series are not autocorrelated, Oftentimes, book indices refer to “see variogram” when the
their inclusion in a cross-correlation analysis is ineffective. reader looks for “semivariogram” (e.g., Isaaks and Srivastava,
Analyses obtained for the same pair of variables sampled at 1989; Deutsch and Journel, 1997) or vice versa (e.g., Nielsen and
different resolution manifests a classical problem in soil science: Wendroth, 2003). Others, such as Davis (1986) use “semivario-
When soil scientists obtain a regression relationship for two gram” exclusively. Cressie (1991) mentions the historical wording
variables over a large scale, such as a database for a pedotrans- and usages of the concept and provides a detailed analysis of vari-
fer function in order to derive soil hydraulic property param- ous equations used to estimate alternative formulations. Here, we
eters based on soil texture, the applicability of that information only point out a reason for the difference between the two terms
to estimate spatial processes at a smaller scale or resolution is that are related to variance and semivariance owing to the manner
flawed as long as the small scale spatial covariance and cross- in which they are calculated. The variance is the average squared
covariance remain unknown, ignored, or not even considered. deviation of individual observations from the mean, while the
In other words, because the regression relationships changed semivariance is calculated from Equation 10.4. The semivariance
from coarse to fine measurement resolution, applying the does not consider the deviation from the mean but is based on the
regression equation obtained from the 40 m scale to a smaller average of squared differences between observations that are sepa-
scale is invalid. Moreover, the lack of cross-correlation as obvi- rated by a given lag distance. When this average squared difference
ous from Figure 10.2c prohibits any coregionalization of these is divided by 2, it becomes comparable to the variance, since the
two variables. Only if the spatial range is known over which one deviation of either one of the two observations from the mean—as
variable is related with the other, a meaningful interpolation or typically calculated for the variance—is half as much as their dif-
estimation of one variable based on the other can be made for ference from each other (see Nielsen and Wendroth, 2003).
a smaller scale (Lascano and Hatfield, 1992). It is strongly sug- Hence, the magnitude of semivariance at unstructured varia-
gested here to include spatial covariance and cross-covariance tion is similar to the population variance. Although the mag-
in the concept of pedotransfer functions, to clearly define data nitudes of semivariance and variance may be compared with
requirements and identify their representativity, validity, and each other, they are nevertheless based on a different squared
limitation at various scales. deviation or difference. Probably for this reason, the y-axis of
10-6 Properties and Processes

a semivariogram is never named “variance” but always “semi- pairs of neighboring observations separated by lag distance h
variance” in order to avoid confusion and to refer to its specific decreases as shown with the open circles in Figure 10.4d.
manner of calculation. From here on, we shall use the terms Typically, we expect the semivariance to increase with increas-
semivariance and semivariogram. ing lag distance, and at some distance the semivariance reaches a
In cases where observations show structured variation, γ(h) plateau. Bell et al. (1993), who consider the semivariogram an eco-
increases with increasing lag distance until it reaches a pla- logically relevant measure of environmental structure, question
teau the so-called sill. The lag distance at which the plateau is this exception and state that environmental variance may further
reached is called the range. In Figure 10.3a, soil water content increase with distance so that environments can be regarded nei-
observations are shown based on gravimetric soil samples that ther as uniform at small scales nor as random at large spatial scales.
were taken along a 470 m transect every 5 m in the upper 10 cm Various types of semivariogram models, shown in detail in
of a farmer’s field soil in Kentucky. The resulting experimental Isaaks and Srivastava (1989), Deutsch and Journel (1997), and
semivariogram is depicted in Figure 10.4a. Notice, except for Nielsen and Wendroth (2003), can be fitted to experimental semi-
γ(h) at h = 5 m, the semivariance values increase with increasing variograms. Typically, a bounded semivariogram model (Nielsen
lag distance until the variance reaches a plateau somewhat above and Wendroth, 2003) consists of a nugget variance C0 that is the
70 m lag distance. With increasing lag distance, the number of theoretical intercept at h = 0, a structural component C, and the

0.35
5 m sampling distance

0.30

0.25

0.20
0 100 200 300 400 500
(a)

0.35
Nested sampling distances of 1 and 5 m
Soil water content (g g–1)

0.30

0.25

0.20
0 100 200 300 400 500
(b)

0.35
Individual subsamples at all locations

0.30

0.25

0.20
0 100 200 300 400 500
(c) Distance (m)

FIGURE 10.3  Soil water content sampled in the upper 10 cm of a silt loam farmer’s field soil in Kentucky. Data are shown sampled at every 5 m
(a), and in addition at 1 m before and behind the 5 m sampling locations at every 25 m (nested, b). Individual subsamples for all locations are shown
in (c) together with the average line from (b).
Soil Spatial Variability 10-7

3.5E–4 the opportunity to compare various data sets with respect to their
γˆ = 0.00015 + 0.00014 1.5 h – 0.5 h
3

3.0E–4
72 72 semivariance behavior, for example, based on the nugget–sill
ratio (Cambardella et al., 1994). Notice, when fitting a semivario-
2.5E–4 gram model to an experimental semivariogram for kriging pur-
2.0E–4 poses, it is important to obtain a good fit for those lags that carry
5 m sampling distance
a substantial weight in the kriging equations (Webster, 1985).
1.5E–4
(a)
0 30 60 90 120 Had the autocorrelation function been calculated for the series
of soil water content measurements shown in Figure 10.3a, it
Semivariance γ(h) (g2 g–2)

3.5E–4
would have approximated a vertical mirror image of the semivar-
3.0E–4 iogram shown in Figure 10.4a. Unlike the autocorrelation func-
2.5E–4 tion, the semivariogram displays the semivariance in terms of the
square of the original units of measurements. Hence, the investi-
2.0E–4
1 and 5 m sampling distance gator is enabled to quantify variance behavior for various sepa-
1.5E–4 ration distances, sampling domain sizes, and sample volumes as
(b) 0 30 60 90 120
well as to compare the semivariance of observations with the vari-
3.5E–4 ance or uncertainty associated with the measuring device.
Having noted the relatively large nugget semivariance shown
2.5E–4 in Figure 10.4a to be about 50% of the sill semivariance, the inves-
1 and 5 m sampling,
5 m lag interval tigator chose a narrower sampling distance to hopefully better
1.5E–4 define the variability structure at distances <5 m. But it is often-
Point variance
times not affordable to regularly sample a long transect at short,
5.0E–5
(c) 0 30 60 90 120 for example, 1 m intervals. In this case, every 25 m along the tran-
sect two additional soil samples were taken at 1 m distance away
240
from the sampling location within the regular 5 m scheme, as
c shown with the filled circles in Figure 10.3b. The resulting semi-
Lag pairs N(h)

160
variogram is shown in Figure 10.4b together with the same model
80 a
as in Figure 10.4a. Since sampling in the nested approach provides
1 m lag intervals in addition to the regular 5 m intervals, γ(h) can
b
0 be calculated for a finer spatial resolution and larger number of lag
0 30 60 90 120
classes at almost every 1 m interval. Except for multiples of 5 m lag
(d) Lag distance h (m)
intervals, the number of observed water content pairs present in
FIGURE 10.4  Spatial variability behavior quantified in semivario- each lag class is drastically reduced compared to the 5 m sampling
grams. Experimental semivariogram and semivariogram model for scheme to even no pairs of observations separated by specific lag
water content measurements taken at 5 m intervals depicted in Figure classes, for example, h = 3, 7, 8, 12, 13 m, etc. (Figure 10.4d, triangle
10.3a (a); associated numbers of semivariogram pairs N(h) are shown symbols). The semivariogram depicted in Figure 10.4b is noisier
with open circles in (d). Experimental semivariogram for water content
than the one in Figure 10.4a, and its general trend is similar to
measurements shown in Figure 10.3b at 5 m intervals and at 1 m intervals
the one calculated for the 5 m lag intervals. In this case, the nested
in nests for 1 m lag intervals (b); associated numbers of semivariogram
pairs N(h) are shown with triangles in (d). Experimental semivariogram sampling did not support a more precise quantification of the
for water content measurements shown in Figure 10.3b at 5 m intervals nugget variance, but confirmed the one obtained from sampling
and at 1 m intervals in nests but here for 5 m lag intervals (c); associated at 5 m distances. One useful conclusion would be that measure-
numbers of semivariogram pairs N(h) are shown with open squares in (d). ments obtained every 5 m could be spatially interpolated or down-
The filled diamond symbol in (c) refers to the average point variance scaled to 1 m sampling intervals.
between duplicate samples taken at each location. Notice the y-axis scale Thus, far in this analysis, lag classes were multiples of 1 or 5 m
in (c) differing from (a) and (b). because of either 1 or 5 m distances between sampling locations.
Alternatively, a range of lag distances can be included in the same
range a, which is the extension of spatial or temporal dependence lag class if an upper and a lower bound is defined accordingly.
of observations. The nugget variance represents short-scale varia- This procedure is especially helpful in designs with nonuniform
tion, sampling, and measurement errors (Isaaks and Srivastava, sampling intervals and for 2D or 3D data sets. Based on the data
1989; Mulla and McBratney, 1999). Nugget and structural semi- shown in Figure 10.3b, the semivariogram shown in Figure 10.4c
variance add up to the sill. A spherical semivariogram model was was recalculated for 5 m lag intervals while including all separa-
fitted to the experimental semivariogram in Figure 10.4a, where tion distances in-between the 5 m intervals. Hence, the first lag
the nugget and sill semivariances are 0.00015 and 0.00014 g2 g−2, class included all neighboring measurements separated by 1, 2,
respectively, and the range is 72 m. Most frequently, semivario- 4, and 5 m. Increasing the size of lag class intervals is associated
gram models are used for spatial interpolation using kriging or with a larger number of pairs of observations per lag class (Figure
cokriging. However, semivariogram model parameters provide 10.4d, open square symbols). Again, the same semivariogram
10-8 Properties and Processes

model as in Figure 10.4a and b represents the general trend of the unsampled point (Vieira et al., 1981; Trangmar et al., 1985).
the experimental semivariogram with the latter behaving much Based on the spatial relationship between neighboring observa-
smoother than in the former cases. tions and the distance of these neighboring locations relative to
In addition, the investigators evaluated the variance of soil the unsampled location, a weight λi is assigned to each of the
water content at an even smaller scale. Each of the individual neighboring observations to contribute to the estimate. The esti-
samples at every 5 or 1 m, respectively, was composed of two sub- mated value is the weighted sum of neighboring observations:
samples taken a few centimeters apart from each other. The values
of both individual subsamples of soil water content are shown in n

Figure 10.3c with the same line connecting average water contents A*0 (x0 ) = ∑ λ A (x ),
i i i (10.5)
at each location as shown in Figure 10.3b. The local point variance i =1

existing for a soil water content composed of the two subsamples where
is illustrated in the semivariogram plot in Figure 10.4c as the filled
diamond at h = 0. Indeed, this point variance between subsam- n
ples is much smaller than the nugget semivariance extrapolated
from γ(h) at lag distances >1 m. Notice the scale of the ordinate in
∑ λ = 1.
i =1
i (10.6)

Figure 10.4c is different than that in Figure 10.4a and b.

A decrease in local semivariance compared to the semivari- In the kriging algorithm, the weight coefficients are calculated
ance prevailing over short distances or from bulk samples is not while the difference between the estimated and the true value
always observed. Wendroth et al. (2001) and Giebel et al. (2006) is zero and the variance between both is at a minimum through
found scale-variant behavior of soil mineral nitrogen. Their
n
measurements based on individual small auger samples resulted
in a semivariance larger than the nugget semivariance, and only
∑ λ γ(x − x ) + μ = γ(x − x ),
j =1
j i j i 0 (10.7)

mixing four individual samples taken at the same point and

using this bulk sample in spatial analysis allowed identifying a where μ is the Lagrangian multiplier. The semivariance values
spatial structure of soil mineral nitrogen. for the respective distance between sampling locations xi and yi
In contrast to the above example, with the exception of taking and between sampling locations and the unsampled location xi
two or more individual samples at the local scale, had soil water and x0, respectively, are obtained from a semivariogram model,
content not been based on gravimetric samples but had been which is the line fitted to the experimental semivariogram. The
measured with a sensor, the same spatial design and concept to minimized kriging variance is calculated with
determine variance or error components could have been used.
n
With a sensor used in an access tube or being installed at a fixed
point in the soil, readings taken at the same location and depth
sk2 (x0 ) = ∑ λ γ(x − x ) + μ.
j =1
j j 0 (10.8)
within sufficiently short-time intervals to exclude temporal soil
water content changes could be used to derive the local spatial The set of equations in the kriging matrix is solved for obtaining
semivariance of soil water content. the weights λi and the Lagrangian multiplier μ. Kriging is called the
Studying the variance behavior of any state variable, not just best linear unbiased estimator. Illustrative examples for the setup
that of soil water content, over different distances in space or of the kriging matrix are given in Warrick et al. (1986), Yates and
time, determining the impact of data aggregation on the mean Warrick (2002), and Nielsen and Wendroth (2003).
value and its associated variance, and quantifying the instru- Kriging, generally used as an interpolation tool, effectively
mental contribution to variance in the way outlined in this smoothes the process between observed points based on the
example is in general a widely ignored or neglected concept for observed variability structure and its spatial extent. Hence, the
any type of measurement (Robinson et al., 2008). It is important, kriged distribution of a soil property or a univariate kriged map
however, to make these considerations part of the experimental can support visual assessment of spatial relationships between
protocol for determining a spatial or temporal process, for scale the variable of interest and any other underlying soil process. On
transfers of one or several variables, and for spatial or temporal the other hand, unlike other interpolation techniques, such as
relationships between different variables. inverse distances, kriging relies on a spatial variability structure
between observations. If that structure is not accurately derived
10.5  Kriging in the semivariogram, subsequent spatial interpolation cannot
be trusted. If the method of inverse distances being less rigid
As in the previous section, transect data are used to illustrate the than kriging is used in absence of spatial structure, it can lead
concepts of kriging and cokriging even though these interpola- to fallacious estimates and misleading maps of spatial distribu-
tion and coregionalization methods are more frequently applied tions (Gotway et al., 1996; Kravchenko, 2003) because of lack of
to 2D and 3D data sets. Kriging is a technique to estimate a value underlying variability structure.
of an observation A*0 (x0 ) at an unsampled location based on val- Yost et al. (1982a, 1982b) were among the first who derived spa-
ues of the same variable Ai(xi) observed in the neighborhood of tial variability structure of phosphate sorption distribution across
Soil Spatial Variability 10-9

0.4 6
Clay
ρ

Clay content (g g–1)

0.3

ln(ρ) (ln[Ω m])

5

0.2
4
0.1

0.0 3
0 100 200 300 400
Distance (m)

FIGURE 10.5  Soil clay content and geoelectrical resistivity ρ measured along a 440 m transect in a northeast German moraine catena at the
40–60 cm soil depth. Open square symbols depict clay content measured at every 5 m and closed square symbols measured clay content within four
nests at 1 m sampling distance. The measurements in the nests were disregarded for the kriging and cokriging estimation scenarios.

a large area and then interpolated unsampled locations based an attribute to be below a certain threshold value are interpolated
on spatial variability structure in a kriging procedure. Liebhold (e.g., Ritzi, 2000). In other applications of indicator kriging, Smith
et al. (1991) mapped moth insect populations based on kriging et al. (1993) and Halvorson et al. (1995) combined various indi-
estimates of spatial distributions. Goovaerts and Chiang (1993) ces to map soil quality. Recently, in several approaches, kriging
mapped field nitrogen status based on factorial kriging analy- was applied not only in a spatial domain but simultaneously in a
sis. In a similar fashion, Ghidey and Alberts (1999) mapped soil spatio-temporal extent (Jost et al., 2005; Cichota et al., 2006).
nitrate concentration based on topography, depth to claypan, and The soil clay content data considered above from a different
several other underlying variables. Sampling fields without ran- perspective (Figure 10.2) are used here again for spatial interpo-
domized treatments, Donald (1994) mapped weed distributions lation by kriging with a slight difference. Besides observations at
across landscapes using kriging and pointed out opportunities regular 5 m intervals (open square symbols in Figure 10.5), clay
for new research hypotheses on weed biology and control across content is known also at 1 m intervals within four nests (closed
landscapes. When applying geostatistical analysis and kriging to square symbols in Figure 10.5).
attributes that vary over orders of magnitude, indicator kriging In Figure 10.6a, the experimental semivariogram and the
can be applied in which spatial distributions of the probability of fitted model indicate a range of spatial dependence of 10 m.

0.008
3
h h
Semivariance γ (g2 g–2)

γˆ = 0.0008 + 0.0029 1.5 – 0.5

0.006 10 10

0.004

0.002

0.000
0 20 40 60 80 100
(a) Lag distance h (m)

0.4
Clay measured
Kriged and standard deviation-interval
Clay content (g g–1)

0.3

0.2

0.1

0.0
0 100 200 300 400
(b) Distance (m)

FIGURE 10.6  Kriging scenario: Experimental semivariogram and semivariogram model (nugget + spherical) for soil clay content at 40–60 cm
depth (a). Clay content measured at 5 m distances and kriged for 1 m distances (b) along a 440 m transect in a northeast German catena.
10-10 Properties and Processes

The sill proceeds in the order of magnitude of the total vari- N (h )

1
ance. It could be argued that the range should extend to a lag
distance h of ∼15 m, and the sill be somewhat higher. However,
γ AB (h) =
2N (h) ∑[A (x ) − A (x + h)][B (x ) − B (x + h)].
i i i i i i i i

i =1
in the kriging matrix, only the closest neighbors to the location (10.9)
of estimate are germane. Observations farther than 10 m away
from the location of interest do not make a sizeable contribu- In general, the same types of models usually fitted to semivario-
tion to the kriged estimate. grams can also be used for describing the cross-semivariogram.
The kriging result is depicted in Figure 10.6b. Clay content The cokriged estimate of a variable A*0 (x0 ) at an unsampled loca-
observations at 5 m intervals were the only information provided tion is obtained from observations at known locations of both
to estimate the clay content at 1 m intervals. The filled circles denote variables Ai(xi) and Bj(xj) by
the kriged estimates and the gray shaded area the ±1 standard
deviation interval around the kriged estimate. As expected, the n m
smooth process of kriged estimates between sampling locations
is noticeable. Moreover, because the kriging standard deviation
A*0 (x0 ) = ∑i =1
λ Ai Ai (xi ) + ∑λ
j =1
Bj B j (x j ). (10.10)

interval increases with increasing distances from sampling loca-

tions, it manifests relative maximum values midway between
two measured points. We learn from this example that krig- The weighting factors for both variables are determined to meet
ing merely interpolates values at unsampled locations based the conditions for Ai
on measurements at surrounding locations. Depending on the
change between the observed values—increase or decrease or no n
change—kriging estimates between two observed values either
consistently increase or decrease or do not change at all, respec-
∑λ
i =1
Ai =1 (10.11)

tively, but do not reveal fluctuations at unsampled locations that

might in fact exist at a scale smaller than the one chosen for the and for Bj
sampling. m
∑λ Bj = 0. (10.12)
10.6  Cokriging j =1

In many cases of soil surveys and environmental contamination

The cokriging matrix is designed as (Yates and Warrick, 2002)
studies, an attempt is made to estimate soil textural or contami-
nant distribution based on the distribution of another variable that
is expected to indirectly reflect the distribution of a particular tex- n m

tural fraction, but is easier and cheaper to monitor. In case of soil γ A (x Ai − x0 ) = ∑i =1

λ Ai γ A (x Ai − x A ) + ∑λ
j =1
γ (x Aj − x B ) + μ A
Bj AB

clay content, geoelectrical resistivity can be applied as a proxy vari-

able because both variables are spatially related. In spatial studies of n m

contaminants, the distribution of soil pH can help to estimate the γ AB (x Bi − x0 ) = ∑ λ Ai γ AB (x Bi − x A ) + ∑λ Bj BB γ (x Bj − x B ) + μ B .

distribution of heavy metals in an area (Van Groenigen et al., 1997). i =1 j =1

McBratney and Webster (1983) cokriged various soil textural parti- (10.13)
cle size fractions among different depths with each other. In various
other applications, existing soil landscape models were improved The cokriging variance is
based on using auxiliary variables especially in cases with limited
observations (e.g., Vauclin et al., 1983; Alemi et al., 1988; Ben-Jemaa n m
et al., 1994; Chaplot et al., 2000). In many cases of environmen-
tal studies in which a variable of interest is coregionalized using
σ2ck = γ A (0) + μ A − ∑i =1
λ Ai γ A (x Ai − x0 ) − ∑λ
j =1
γ (x Bj − x0 ).
Bj AB

cokriging, not all variables are collected at each location, causing (10.14)
only a limited number of common sampling locations contributing
to the cross-variogram. In this case, pseudo-cross-semivariograms When fitting semivariogram models with common covariance
are a compromise to overcome limited data support for variograms structure to the two experimental semivariograms γA and γB , and
(Zhang et al., 1992, 1999). the cross-semivariogram γAB ,
The theory and setup of the cokriging matrix are similar
to that of the kriging algorithm. Cokriging requires semivar-
iogram models for both individual variables involved in the ⎡ γ A,1(h) γ AB ,1(h)⎤ ⎡ c A,1 c AB ,1 ⎤ ⎡ γ 1(h) 0 ⎤
estimation and the cross-semivariogram γAB (h), which mani- ⎢ ⎥=⎢ ⎥⎢ ⎥
fests the variance behavior that both variables Ai and Bi have ⎣ γ BA,1(h) γ B ,1(h) ⎦ ⎣c BA,1 c B ,1 ⎦ ⎣ 0 γ 1(h)⎦

in common: (10.15a)
Soil Spatial Variability 10-11

⎡ γ A,2 (h) γ AB ,2 (h)⎤ ⎡ c A,2 c AB ,2 ⎤ ⎡ γ 2 (h) 0 ⎤ c Ai > 0 and c Bi > 0 for i = 1, 2,…, m (10.16a)
⎢ ⎥=⎢ ⎥⎢ ⎥
⎣ γ BA,2 (h) γ B ,2 (h) ⎦ ⎣c BA,2 c B,2 ⎦ ⎣ 0 γ 2 (h)⎦

c Aic Bi > c ABic BAi for i = 1,2,…, m. (10.16b)
(10.15b)

⎡ γ A,3 (h) γ AB ,3 (h)⎤ ⎡ c A,3 c AB ,3 ⎤ ⎡ γ 3 (h) 0 ⎤ In fact, this restriction causes simultaneous semivariogram and
⎢ ⎥=⎢ ⎥⎢ ⎥ cross-semivariogram model fitting to become a major challenge
⎣ γ BA,3 (h) γ B ,3 (h) ⎦ ⎣c BA,3 c B,3 ⎦ ⎣ 0 γ 3 (h)⎦
in the cokriging procedure. In Figure 10.7, the two experimen-
(10.15c) tal semivariograms and the common cross-semivariogram for
clay content and geoelectrical resistivity ln(ρ) are shown. Unlike
the following restrictions apply for the linear model of coregion- demonstrated in Figure 10.6, where a spherical semivariogram
alization remains positive definite (Isaaks and Srivastava, 1989): model for soil clay content was derived for kriging, a common

0.008
γˆ = 0.0010 + 0.0035[1.5(h/20) – 0.5(h/20)3]
+ 2.6e(–6)[1 – exp(–(h/32)2)]
Semivariance γ

0.006
(g2 g–2)

0.004

0.002

0.000
(a) 0 20 40 60 80 100

0.3
Semivariance γ
(ln[Ω m])2

0.2

0.1 γˆ = 0.0001 + 0.1269[1.5(h/20) – 0.5(h/20)3]

+ 0.0580[1 – exp(–(h/32)2)]
0.0
(b) 0 20 40 60 80 100

0.00
γˆ = –0.0004 – 0.0211[1.5(h/20) – 0.5(h/20)3]
Crossvariance Γ
(g g–1 ln[Ω m])

–0.01 + 0.0004[1 – exp(–(h/32)2)]

–0.02

–0.03
0 20 40 60 80 100
(c) Lag distance (m)

0.4
Clay content (g g–1)

0.3

0.2

0.1

0.0
0 100 200 300 400
(d) Distance (m)
Clay measured Cokriged and standard deviation-interval

FIGURE 10.7  Cokriging scenario: Experimental semivariogram and common linear model of coregionalization (nugget + spherical + Gaussian)
for soil clay content (a), geoelectrical resistivity (b) and cross-semivariogram of both variables (c) measured in a 440 m transect in a northeast
German catena. Measured (5 m) and cokriged (1 m) clay content (d).
10-12 Properties and Processes

spherical semivariogram model for clay content and ln(ρ) that and the common covariance behavior between both variables
would adequately represent the variability structure of both are taken into account in this coregionalization. In general,
variables at least for short lag intervals was not identifiable. the standard deviation of the estimated clay content is ∼25%
Instead, a combination of a spherical with a Gaussian semivar- smaller in the cokriging compared to the kriging scenario.
iogram model consisting of a nugget Unlike kriging, which mainly resulted in a smoothed process
of clay content between known locations, fluctuations over short
⎡ c A,1 c AB ,1 ⎤ ⎡ 0.00100 −0.00037 ⎤ distances become evident in the cokriging results based on the
⎢ ⎥=⎢ ⎥, (10.17a) second variable, ln(ρ), involved in the estimation (Figure 10.7d).
⎣c BA,1 c B ,1 ⎦ ⎣ −0.00037 0.00014 ⎦
Besides the general process of the series along the 440 m tran-
sect estimated with kriging or cokriging, the result is especially
a spherical component with a spatial range as = 20 m interesting with respect to the clay estimation within the four
nests, where clay content at every 1 m was known but not incor-
⎡ c A, 2 c AB ,2 ⎤ ⎡ 0.00351 −0.02110⎤ porated in the estimation procedure. How well did ln(ρ) capture
⎢ ⎥=⎢ ⎥ , (10.17b) the clay content process compared to actual measurements? This
⎣c BA,2 c B ,2 ⎦ ⎣ −0.02110 0.12687 ⎦
comparison is illustrated for the first nest, that is, a section of the
transect between 35 and 60 m in Figure 10.8.
and a Gaussian component with a range aG = 32 m
The smooth process of kriged clay content and the relatively
large kriging standard deviation are depicted in Figure 10.8a
⎡ c A, 3 c AB ,3 ⎤ ⎡ 2.6 e −6 0.00039 ⎤ together with measured clay content. On the other hand, cokrig-
⎢ ⎥=⎢ ⎥ (10.17c) ing resulted in pronounced fluctuations of estimated clay con-
⎣c BA,3 c B ,3 ⎦ ⎢⎣0.00039 0.05797 ⎥⎦
tent. This did not necessarily improve the agreement between
measured and estimated clay content from 35 to 39 m, but in
resulted in the best common fit of the experimental cova- most cases between 42 and 49 m, and definitely between 51
riance behavior. The complete set of semivariogram and and 59 m. In summary, ln(ρ) and its spatial relationship with
cross-semivariogram model equations is given in Figure 10.7a clay content helped to improve the clay estimation compared to
through c. These models were applied together with clay content univariate interpolation, that is, kriging. However, at the finest
measured at every 5 m (Figure 10.7d) and ln(ρ) at every 1 m to resolution of 1 m being investigated here, fluctuations in mea-
estimate clay content. Hence, with regard to clay content input sured clay content do not perfectly coincide with fluctuations of
data the estimation scenario is the same as in the above kriging ln(ρ). This result can be explained by the different domain of
procedure (Figure 10.6b), but in addition to clay content, ln(ρ) influence of an individual measurement of both variables. Clay

0.4
Clay measured
Clay content (g g–1)

0.3 Kriged and standard deviation-interval

0.2

0.1

0.0
35 40 45 50 55 60
(a) Distance (m)

0.4
Clay measured
Cokriged and standard deviation-interval 6
Clay content (g g–1)

0.3 ρ
ln(ρ) (ln[Ω m])

0.2 5

0.1
4

0.0
35 40 45 50 55 60
(b) Distance (m)

FIGURE 10.8  Detailed results of kriging and cokriging scenarios between 35 and 60 m distance depicted in Figures 10.6b and 10.7d.
Soil Spatial Variability 10-13

content samples were pulled with an auger 2 cm in diameter at a In the state equation, that is, in this case an autoregression
depth increment of 20 cm. A single value of geoelectrical resis- type model, the state vector at location i is related to the state
tivity results from the field measurement of apparent geoelectri- vector at i − 1 through the matrix of autoregression coefficients
cal resistivity undergoing a numerical inversion, and represents Φ and a model uncertainty ωi with
a horizontal domain of ∼50 cm, causing the smooth behavior of
the ln(ρ) series. Despite lack of sensitivity of clay content fluctua- Zi = ΦZi −1 + ωi . (10.19)
tions occurring over 1 m distance, clay content measurements
taken every 5 m were successfully downscaled in this coregion-
alization procedure based on small scale measurements of ln(ρ). The advantage of the state-space form of autoregressive models
compared to ordinary autoregressive models is the filtering of
observational noise, and the fact that the chosen model type
10.7  Autoregressive State- Space and order and the observation vector result in model uncer-
Modeling tainty. In other words, the model does not completely capture
the spatial or temporal process of the variable of interest. The
Requirements for identifying a spatial or temporal process were simultaneous optimization of autoregression coefficients, mea-
presented in the previous paragraphs. It became obvious that surement, and model variance used here is based on the Kalman
understanding the spatial process of an observed state variable filter (Kalman, 1960; Kalman and Bucy, 1961) and encoded
whose spatial covariance structure is successfully identified in the EM algorithm described by Shumway and Stoffer (1982).
strongly depends on its association with other spatial processes. In the filtering scheme, state estimations and state variance are
In other words, the question that needs to be addressed is: What updated whenever in the spatial or temporal series an obser-
other variables coincide with the process of interest across a spa- vation is available (Katul et al., 1993). This update depends on
tial or temporal domain and how can the association between the model and measurement error and is performed based on
the variables included in the state vector be described? a Kalman gain matrix and a recursive smoothing matrix. The
Coregionalization using cokriging is a method that is restricted filtering scheme is described in more detail in Shumway (1988),
to a common covariance model, that is, a set of semivariograms Shumway and Stoffer (2000), Katul et al. (1993), Nielsen and
with common covariance structure. Spatial association between Wendroth (2003), and in Webster and Heuvelink (2006). Not
soil variables observed along transects has been derived from only autoregressive but other kinds of equations can be imple-
autoregressive analysis (Morkoc et al., 1985; Shumway, 1985), a mented in state-space models. For example, Katul et al. (1993) and
technique that was adapted from time series analysis for spatial Wendroth et al. (1993) used a state-space scheme in connection
data series. Lebron et al. (2007) described the spatial process of with a physically based equation describing soil water transport,
soil hydraulic conductivity across a Pinyon-Juniper ecohydro- to estimate unsaturated hydraulic conductivity coefficients from
logical gradient. In autoregressive models, a variable at a location an internal drainage experiment. Parlange et al. (1993) applied
or a point in time is described based on antecedent observations a similar approach to estimate soil water diffusivity. Assouline
of the same variable and in case of multivariate autoregressive (1993) modeled the hydrologic budget of Lake Kinneret based
models on other related variables observed at the previous sam- on state-space analysis of individual water balance components,
pling location (e.g., Wendroth et al., 1992; Nielsen et al., 1994). Skaggs and Mohanty (1998) applied the Kalman filter scheme to
For a first-order autoregression model, each of the variables describe water table fluctuations, Cahill et al. (1999) estimated
measured at the previous location i − 1 is linked to the variable at field-effective soil hydraulic property coefficients using a physi-
location i through an autoregression coefficient φ or a matrix of cally based state-space model, and Wu et al. (2001) developed a
autoregression coefficients in case of several variables. A second- state-space scheme for modeling the water and salinity regime
order model utilizes antecedent measurements at locations i − 1 in a soil with a shallow groundwater table. Bierkens et al. (2001)
and i − 2, while an n-order model is based on measurements described the space-time development of water table depth based
at n previous locations. Coefficients of autoregression are usu- on a Kalman filter approach, and Walker et al. (2002) estimated
ally estimated in the same way as ordinary statistical regression 3D soil water storage based on surface soil water content measure-
coefficients. In the particular case of autoregressive state-space ments implemented in a state-space model. For further details on
models, however, autoregression coefficients are derived in a the state-space concept used in connection with physically based
different way including estimations of measurement and model models, the reader is referred to Nielsen and Wendroth (2003).
errors. The set of observations of one or several variables, that is, Autoregressive state-space analysis is used here to analyze
the observed vector Yi, does not have to be assumed absolutely measured solute concentration data in a field leaching experi-
correct but consists of the true status of observed variables Zi ment conducted in a Maury silt loam soil in Kentucky. Solute con-
and a measurement error υi in the observation equation centration was measured in two subsequent depths (20–30 and
30–40 cm) along a 16 m transect at 25 cm intervals. Logarithmic
Yi = Mi Zi + υi , (10.18) transforms of solute concentration measured in both depths are
shown in Figure 10.9a. Prior to autoregressive state-space analy-
where Mi is a measurement or design matrix. sis, spatial covariance structure of both variables was quantified
10-14 Properties and Processes

5
20–30 cm depth

ln(conc.)
ln(ppm)
1
30–40 cm depth
–1
0 4 8 12 16
(a) Distance (m)

1.0 1.0
30–40 cm depth
20–30 cm depth
Autocorr.

0.5 0.5
r(h)

0.0 0.0

–0.5 –0.5
0 1 2 3 4 5 0 1 2 3 4 5
(b) Lag distance h (m) (c) Lag distance h (m)

1.0
20–30 cm vs. 30–40 cm depth
Crosscorr.

0.5
rc(h)

0.0

–0.5
–5 –4 –3 –2 –1 0 1 2 3 4 5
(d) Lag distance h (m)
1.0 1.0
autocorr. (h)

20–30 cm depth 30–40 cm depth

0.5 0.5
Partial

0.0 0.0

–0.5 –0.5
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
(e) Lag distance h (m) (f) Lag distance h (m)

FIGURE 10.9  Ion concentration measured at 20–30 and 30–40 cm soil depth in a Kentuckian Maury silt loam (a), autocorrelation functions r(h)
at 20–30 cm (b) and 30–40 cm soil depth (c), cross-correlation function rc(h) between ion concentrations at both depths (d), and partial autocor-
relation functions φ(h) for the 20–30 cm (e), and the 30–40 cm depth (f).

via auto- and cross-correlation. With both series being spatially For i ≥ 2,
autocorrelated (Figure 10.9b and c) and cross-correlated (Figure
ϕij = ϕi −1, j − ϕii ϕi −1, i − j , j = 1, 2,…, n − 1. (10.22)
10.9d), measurements of solute concentration based on 10 cm
long soil samples, ∼2 cm in diameter taken every 25 cm provide The resulting partial autocorrelation functions φii where the order
ample opportunity to monitor the spatial process of solute con- is expressed as lag distance with φ(h) for the solute concentration
centration in both soil layers. data of both depths are depicted in Figure 10.9e and f. With the
In order to identify the model order of the autoregressive state- 95% significance level at 0.245, solute concentration data series
space model, the partial autocorrelation function φii of order p is can be described with a model of the order up to p = 2, that is,
calculated with the Durbin–Levinson algorithm (Shumway and solute concentration in both layers at location i can be described
Stoffer, 2000) as a function of solute concentration in both layers at preceding
locations i − 1 and i − 2.
i
For numerical stability, prior to state-space analysis, observa-
ϕii =
∑
r (i) −
j =1
ϕ pjr (i − j)
, i >1 (10.20)
tions yi are normalized (ysci) with (Nielsen and Wendroth, 2003)
i
1− ∑ ϕ pjr ( j)
j =1 yi − (μ y − 2σ y )
ysci = , (10.23)
4σ y
and
where μy and σy denote the mean and standard deviation, respec-
ϕ11 = r(1). (10.21) tively, of the particular series.
Soil Spatial Variability 10-15

1.5
nc(30)i = 0.0823 nc(30)i–1 + 0.8644 nc(20)i–1 + ωi
1.0

0.5

Normalized concentration nci

0.0 Measured
–2 ln(L) = –331.8 95% interval a
–0.5
0 4 8 12 16
1.5
nc(30)i = 1.0637 nc(30)i–1 – 0.0768 nc(20)i–1 + ωi
1.0

0.5
Measured
0.0 Not considered
–2 ln(L) = –423.6 95% interval b
–0.5
0 4 8 12 16
Distance (m)

FIGURE 10.10  First-order autoregressive state-space model of normalized ion concentration at the 30–40 cm soil depth nc(30)i along a 16 m tran-
sect in a Kentucky Maury silt loam soil. Ion concentrations are shown for the 30–40 cm depth [nc(30)i], and concentrations of ions in the 20–30 cm
depth [nc(20)i] are included in the estimation. A scenario where all observations are considered is shown in (a) and a scenario where all nc(20)i
observations are included but only every fourth nc(30)i observation is considered in (b).

Model equations and results for the process of normal- 10.8  Spectral Analysis
ized solute concentration at the 30–40 cm layer nc(30)i are pre-
sented in Figure 10.10a for a first-order model in a scenario, Managing soils and crops with machinery in spatially regular
where all normalized observations of nc(30) i and those paths may cause repetitive or cyclic patterns in the direction per-
in the 20–30 cm layer nc(20) i are included in the model pendicular to the management operation. Moreover, observing
calculations. ecologically relevant soil state variables over time often results
Notice that autoregressive models including state-space in sinusoidal patterns of variation, for example, the daily or the
models depend on equally spaced distances between obser- annual soil temperature cycle, the annual water cycle, and related
vations. On the other hand, samples do not need to be taken variables such as microbial respiration, crop water use, biomass
at each location. Scenarios where one or several variables are production, transpiration, drainage fluxes, etc. Such a cyclic fluc-
observed at each location and one or several other variables at a tuation of observations can be described with a sine or cosine
lower density at, for example, every other location or even less wave function or a combination of both. Each wave can be char-
frequent are common. For these missing locations, estimates acterized by its magnitude in signal, that is, the amplitude. The
are obtained in the state-space procedure as shown in the fol- amplitude is the distance between the baseline and the maximum
lowing example. of the wave, or it is half of the difference between maximum and
When only every fourth observation of nc(30)i is included in minimum of the wave. Furthermore, the length of the wave λ is an
the model calculations, the estimated series proceeds smoother important characteristic, which is the inverse of its frequency f.
(Figure 10.10b) and the 95% interval of estimation is larger The number of cycles or waves per basic time or spatial distance
than in the previous scenario. Although the value measured interval is another important measure to describe a cyclic-data
at a distance of 4.25 m was considered in the calculations, its series. Moreover, the start point of a wave is flexible relative to
extremely high fluctuation was not captured in the model. The another wave or another series. This shift of the starting point is
second-order model shown in Figure 10.11 results in a better called phase. Relative to each other, two series can be in phase or
representation of the point-to-point fluctuations than the first- out of phase. For further details, see Davis (1986).
order model. Additionally, the confidence interval of estima- From Jean Baptiste Fourier we learn that every continuous
tion remains narrower for the second-order model compared single-valued function can be represented by a series of sinusoids.
to that of the first order. For both second-order scenarios, the In other words, any observed series can be considered as a com-
coefficients in the autoregression equations clearly emphasize bination of many independent sinusoidal curves, all with differ-
the larger weight on i − 2 neighboring observations compared ent cyclic characteristics. Spectral analysis according to Fourier
to the i − 1 neighbors. In both scenarios, the log likelihood allows filtering the different waves and their characteristics that
[−2ln(L)] indicates a better model description for the models of contribute to the observed series, similar to a laboratory analyzer
second rather than of first order. that identifies the compounds of a mixed chemical. Similar to a
10-16 Properties and Processes

1.5
nc(30)i = 0.0568 nc(30)i–1 + 0.04574 nc(20)i–1
1.0 + 1.3809 nc(30)i–2 – 0.5051 nc(20)i–2 + ωi

0.5

Normalized concentration nci

Measured
0.0
–2 ln(L) = –342.0 95% interval a
–0.5
0 4 8 12 16

1.5 nc(30)i = –0.0334 nc(30)i–1 + 0.2253 nc(20)i–1

+ 1.3342 nc(30)i–2 – 0.5820 nc(20)i–2 + ωi
1.0

0.5
Measured
0.0 Not considered
–2 ln(L) = –433.3 95% interval b
–0.5
0 4 8 12 16
Distance (m)

FIGURE 10.11  Second-order autoregressive state-space model of normalized ion concentration at the 30–40 cm soil depth nc(30)i along a 16 m
transect in a Kentucky Maury silt loam soil. Ion concentrations are shown for the 30–40 cm depth [nc(30)i], and concentrations of ions in the
20–30 cm depth [nc(20)i] are included in the estimation. A scenario where all observations are considered is shown in (a) and a scenario where all
nc(20)i observations are included but only every fourth nc(30)i observation is considered in (b).

chromatogram that is obtained from such an analysis in the so- farmer’s field grown to corn. Wendroth and Nielsen (2002) found
called power spectrum, the individual variance components of frequency-based variations of soil water content and concomitant
the observed series are depicted. Unlike an ANOVA where the leaching of a chloride tracer associated with soil tillage operations.
statistical influences and significance of different factors and their The effect of tillage- and traffic-induced changes in soil structure
interactions are separated, spectral analysis decomposes the indi- was investigated by Roseberg and McCoy (1992) using spectral
vidual cyclical variance components of a series, their wavelength techniques. Domsch and Wendroth (1997) discovered cyclic vari-
or frequency, and their contribution to the overall variance. The ation of soil structure and penetrometer resistance caused by the
power spectrum S(f) is defined as management effect of soil tillage with varying intensity.
In Figure 10.12a and b, two cyclic series are given, both based
∞ on sine or cosine waves. Series x1 (Figure 10.12a) is a wavelet con-

∫
S( f ) = 2 r (h)cos(2π fh) dh,
0
(10.24) sisting of waves of different length and amplitudes, which will be
explained in the next paragraph. Series x2 (Figure 10.12b) con-
sists of 3.5 sine waves, each being 64 observations long. The sum
which is an integrated form of the autocorrelation function. of both series results is series x3, shown in Figure 10.12c.
Hence, in a power spectrum, the presence of a cyclic component The power spectrum of series x3 as a function of frequency f is
is manifested by a peak corresponding to its specific wavelength shown in Figure 10.13. Inasmuch as frequency is inversely related
or frequency. The lag distance corresponding to the full length to wavelength or lag distance of a particular cycle, as the posi-
of its cycle is the corresponding wavelength in the power spec- tion of a peak in the graph moves from left to right, it represents
trum. For more details, see Bazza et al. (1988), Shumway (1988), a variance component based on a cycle of decreasing wavelength
and Nielsen and Wendroth (2003). Sisson and Wierenga (1981) or lag distance. Hence, the peak observed at a frequency f = 0.016
decomposed the spatial variance of steady-state infiltration rates corresponds to a wavelength of 64, which reflects the sine wave of
into cyclic components. Folorunso and Rolston (1985) analyzed series x2 shown in Figure 10.12b whose length is 64 observation
cyclic relationships between soil properties and denitrification points. The other three peaks corresponding to a wavelength of
gas fluxes using spectral analysis. Kachanoski et al. (1985a, 1985b) 6.7, 5.5, and 4.5, respectively, are caused by the cyclic compo-
identified frequency dependence of soil microtopography and nents of series x1. Notice that none of the peaks based on series x1
thickness of A and B horizons. Nielsen et al. (1983) derived how approach the magnitude of the peak based on series x2. The sine
different micrometeorological impacts that would inhibit a uni- wave is the dominating process, whereas the cyclic components
form interpretation of plant canopy temperature and soil water of process x1 cause fluctuations smaller in magnitude. During
content measurements can be decomposed by cospectral analysis. spectral analysis, the resolution of the power spectrum, that is,
Böttcher et al. (1997) showed in a German pine stand that the spa- the number of wavelengths for which the power spectrum is cal-
tial variability of groundwater chemistry was related to a cyclic culated has to be determined. Depending on the resolution of
solute input pattern at the surface. Timlin et al. (1998) identified the frequency range, the number of spectral estimates must be
similar frequencies for curvature and grain yield spectra in a chosen as a power of 2. The statistical significance of a peak in
Soil Spatial Variability 10-17

0.8
7 5 4
0.4

Wavelet x1
0.0

–0.4

–0.8
(a) 0 50 100 150 200

0.8
64
0.4
Sine wave x2

0.0

–0.4

–0.8
(b) 0 50 100 150 200

0.8

0.4
Process x3

0.0

–0.4

–0.8
0 50 100 150 200
(c) Distance

FIGURE 10.12  Series of Morlet wavelets x1 (a), of sine waves x2 (b), and the sum of both denoted as process x3 (c).

2.0
64
Power spectrum of x3

1.5
5.5

1.0
6.7

0.5
4.5

0.0
0.0 0.1 0.2 0.3 0.4 0.5
Frequency f

FIGURE 10.13  Power spectrum for process x3 depicted in Figure 10.12, which is the sum of a set of Morlet wavelets and a sine wave.

the power spectrum can be quantified based on the F-statistics sensor, known as Greenseeker. Both data series were measured
of the spectral variance decomposition, which is not described along a transect, and sensor data aggregated over a width of 10 m
here. For further details see Bazza et al. (1988), Shumway (1988), and a length of 5 m. The most pronounced cyclic variation com-
and Wendroth and Nielsen (2002). ponents underlying the wheat yield and the NDVI data occur at
Two sets of data measured in a farmer’s wheat field in Kentucky a frequency f = 0.035, corresponding to a wavelength of 29 obser-
are shown in Figure 10.14. Wheat grain yield was obtained with vations. The distance of 29 observations taken at 5 m intervals
an automated combine harvester yield mapping system, and the matches almost perfectly to 150 m. This distance is the wave-
normalized difference vegetation index (NDVI) was measured length at which nitrogen fertilizer was applied at continuously
in spring time with an active laser-induced canopy reflectance varying rates between 0 and 168 kg ha−1—not randomized—in a
10-18 Properties and Processes

7 1.0

Yield

Wheat grain yield (t ha–1)

5 0.8

NDVI
3 0.6

NDVI

0.4
1
0 100 200 300 400 500 600
Distance (m)

FIGURE 10.14  Wheat grain yield and normalized difference vegetation index (NDVI) measured in a 650 m long strip in a farmer’s field in
Western Kentucky.

sinusoidal pattern in plots of 30 m width and 15 m length along variation component can be identified. Soil differences reaching
the farmer’s field, similar to a study of Shillito et al. (2009). At especially from 180 to 480 m along the transect coupled with
a band of smaller frequencies f = 0.016–0.023 or wavelengths long-term cropping history cause this long trend in variation.
between 43 and 64 observations, that is, 215–320 m whose center The peak at f = 0.0625, corresponding to a wavelength of 16
is depicted at f = 0.02 in Figure 10.15a, a less pronounced cyclic observations or 80 m is more pronounced in the NDVI (Figure
10.15b) than in the yield spectrum (Figure 10.15a).
10 In order to better understand and relate different spatial pro-
f = 0.02 = 1/50
8 cesses occurring in this field, spectral relationships between two
Wheat yield

f = 0.035 = 1/29
spectrum

6 different variables can be identified with joint analysis of both

4
f = 0.0625 = 1/16 data series using cospectral analysis.
2

(a)
0
0.0 0.1 0.2 0.3 0.4 0.5
10.9  Cospectral Analysis
0.03 As the spectrum is an integrated form of the autocorrelation
NDVI spectrum

function, the cross-spectrum Co(f ) is an integrated form of the

0.02 cross-correlation function rc(h):
0.01
∞

(b)
0.00
0.0 0.1 0.2 0.3 0.4 0.5

∫
Co( f ) = 2 rc (h)cos(2π fh)dh.
0
(10.25)
0.6
quad-spectrum

0.4 Cross-spectrum For cospectral analysis, the left- and the right-hand side of the
Cross- and

Quad-spectrum cross-correlation function needs to be averaged. In case of the

0.2 cross-spectrum, this average accomplished by
0.0
rc (h) = 0.5[rc (h < 0) + rc (h > 0)] (10.26)
(c) 0.0 0.1 0.2 0.3 0.4 0.5

1.0 yields an even function when both sides of the cross-correlation

Coherency

function are equal. The resulting cosine wave with a maximum

at 0, decreases to the minimum at a lag equal to half of the wave-
0.8
length and increases toward a lag corresponding to the full
length of the cosine wave. Hence, the cross-spectrum empha-
0.6 sizes cyclic variations described by a cosine wave. The second
0.0 0.1 0.2 0.3 0.4 0.5
(d) Frequency f component of cospectral analysis is the so-called quad-spectrum.
It is based on an averaging of positive and negative lags of the
FIGURE 10.15  Power spectra for wheat grain yield (a) and NDVI cross-correlation function with
(b) measured in a farmer’s field in Western Kentucky and presented in
Figure 10.14. Cross- and quad-spectra are shown in (c) and the coher-
rcʹ(h) = 0.5[rc (h < 0) − rc (h > 0)]. (10.27)
ency spectrum in (d).
Soil Spatial Variability 10-19

The quad-spectrum defined as component that is expected to cause variability in an experi-

ment, that is, at least four observations per cycle should be taken
∞ to avoid under sampling the spatial process.

∫
Q( f ) = 2 rcʹ(h)sin(2πfh)dh,
0
(10.28)

identifies those common cyclic variations between two series of

10.10  Wavelet Analysis
observations that are delayed or shifted against each other by As illustrated and discussed in the previous paragraph, spatial
a quarter of a wavelength. This odd function emphasizes cyclic and temporal data series can consist of fluctuations over short
variations that are described by a sine wave. or long distances and reflect trends, periodic fluctuations, etc.
For two series that yield a symmetric cross-correlation func- (Grinsted et al., 2004). Very often, different components of fluc-
tion at both sides of zero lag, that is, that are described by a cosine tuations underlie each other. In the previous paragraph, periodic
function, the cross-spectrum reflects common cyclic variations oscillations that can occur in a repetitive manner were identified
whereas the quad-spectrum is zero. On the other hand, com- for uni- and bivariate data sets using spectral and cospectral anal-
mon cyclic variation components of two series that are delayed ysis, that is, frequency domain-based techniques. Another analyt-
against each other by a quarter period or 90° can be described ical technique that decomposes cyclic variations of a data series is
by a sine function, and the quad-spectrum shows their common wavelet analysis. Unlike spectral analysis, wavelet analysis detects
frequency components while the cross-spectrum is zero. segments within a data set that consist of cyclic fluctuations but
The extent of the delay against each other or the phase lag is that do not necessarily repeat regularly over the entire data set. A
quantified in the phase spectrum hφ ( f ) with wavelet spectrum therefore indicates where in the data set such a
fluctuation occurs and over what scale it extends.
1 ⎡ Q( f ) ⎤ Basic ideas and simple applications of wavelet analysis are dis-
hϕ ( f ) = tan −1 ⎢ ⎥. (10.29)
2πf ⎣ Co( f ) ⎦ cussed in this paragraph. The more interested reader is referred
to Torrence and Compo (1998), Grinsted et al. (2004), Lau and
The cross-spectrum shown in Figure 10.15c clearly identifies Weng (1995), and especially the work of Shu et al. (2008), Si
the two strongly pronounced frequencies that the wheat yield (2003), and Si and Farrell (2004) who applied uni- and bivariate
and NDVI data have in common. Their physical interpretations wavelet analysis to identify spatial relationships between soil tex-
have been given above. For the same pair of variables, the quad- tural and soil hydraulic property information. Wavelet analysis
spectrum is merely different from zero for all frequencies as both was applied by Lark and Webster (1999) to detect spatial changes
series move along with any lag relative to each other. Hence, no in soil type. In this analysis, the continuous wavelet transform
matter what the shift between two series is against each other, is used. Alternatively, the discrete wavelet transform may be
the cross- or the quad-spectrum identifies common cyclic vari- applied, which can be considered as a subsampling version of
ance components. The shift against each other is quantified in the continuous wavelet transform (Shu et al., 2008). To be appli-
the phase spectrum. cable in wavelet analysis, the data set needs to consist of equally
Similar to the coefficient of determination in regression spaced observations in space or time. Prior to wavelet analysis,
analysis of two variables, the value of the coherency spectrum a basic or “mother” wavelet shape is chosen, for example, Haar
Coh(f ) is close to 1 for every frequency at which the two vari- or Daubechies (Nievergelt, 1999; Walker, 1999; Boggess and
ables Ai(xi) and Bi(xi) have common cyclic variation compo- Narcowich, 2001), Morlet, Paul, or Derivative of Gaussian
nents, regardless of any shift between them. The coherency (DOG) (Torrence and Compo, 1998), and Mexican Hat (Lark
spectrum is based on the cross- and quad-spectrum and the and Webster, 1999). The choice of the basic wavelet depends on
two univariate spectra: the nature of the data and the kind of information expected to
be extracted or filtered by the analysis. In the wavelet estimation
algorithm, this basic shape of the wavelet is moved across the
Co2 ( f ) + Q 2 ( f )
Coh( f ) = . (10.30) data series and fitted to individual segments of the series, while
SA ( f )SB ( f ) it is “stretched” in length and amplitude to fit the subset of data
as close as possible. Hence, the amplitude or magnitude of the
The coherency spectrum for yield and NDVI series is presented signal and the length scale over which a given wavelet fits a sec-
in Figure 10.15d and clearly reflects the common cyclic variance tion of a data series are both flexible. Unlike spectral analysis,
behavior of wheat yield and NDVI over the entire range of fre- the result of wavelet analysis is not a periodogram that manifests
quencies. Since both NDVI and wheat yield evidently show com- repetitive patterns of the data in one peak at a given frequency or
mon covariance and coherence, their statistical relationship can frequency band. A wavelet spectrum displays the segment of the
be used to predict yield based on NDVI measurements. data series exhibiting wavelet-like fluctuation. It shows where
It is important to notice that for spectral analysis, sampling within the data series the fluctuation occurs, over what length
distances need to be uniform. The sampling frequency needs to scale it extends, and how much it contributes to the overall vari-
be designed large enough to sufficiently cover the shortest wave ance. Hence, the x-axis of the wavelet spectrum is the same as
10-20 Properties and Processes

the x-axis of the data series, that is, distance in time or space. The N
δx δx
y-axis represents the scale given in the original sampling units
over which the fluctuation expands.
Wi (s) =
s ∑ X ψ ⎡⎢⎣( j − 1) s ⎤⎥⎦,
j =1
i (10.33)

From the various wavelet shapes, a Morlet wavelet is chosen
here, which is a plane wave modulated by a Gaussian (Torrence where the wavelet scale s denotes a complex conjugate. At each
and Compo, 1998) because it allows a good balance between scale, the wavelet is normalized in order to be comparable to
space and frequency localization (Shu et al., 2008) wavelets at other scales and in other series. Further details on the
normalization of wavelet functions are explained in Torrence and
2
ψ 0 (η) = π−1/ 4 eiω0 η e − η /2 , (10.31) Compo (1998). With increasing scale the length of the base wave-
let increases. Hence, the wavelet coefficient, that is, the weight over
where a wavelet domain depends on the location and the length of the
η is the dimensionless time parameter wavelet. Since the sum of these weights over the wavelet domain
ω0 the frequency, here equal to 6 always adds up to unity, the wavelet coefficients reflect the vari-
ation of samples. The larger the scale of a wavelet becomes, the
Expressing the complex exponential term containing the imagi- higher is the edge artifact. For this reason, the cone of influence
nary number i = −1 as (COI) is introduced (Grinsted et al., 2004).
Similar to cospectral analysis, the cross-wavelet spectrum
eiω0 η = cos(ω0η) + i sin(ω0η) (10.32) reflects areas of high common fluctuations at the same location
and across the same scale. The cross-wavelet spectrum is defined as

the Morlet wavelet is the sum of a cosine curve (its real part) and
a sine curve (its imaginary part). Wi XY (s) = WiY Wi X (s) , (10.34)
In Figure 10.16a, a series x4 consisting of five wavelets is given.
Each of the first four wavelets is extended over a length of 27 with
points. The fifth wavelet reaches from 109 to 216 distance, and its Wi X being the complex conjugate of Wi X
maxima and minima are reduced by a factor of 3 compared to Wi XY the local relative phase between Xi and Yi
the first four wavelets.
Here, only the continuous wavelet transform Wn(s) is pre- The normalized form of the cross-wavelet spectrum is the wave-
sented. Based on the inverted discrete Fourier transform, the let coherence, indicating the measure of correlation of two
wavelet transform of a series Xi (i = 1, …, N) with uniform sam- series at different resolutions. In its squared form and applying
pling distance δx is defined as the convolution of Xi as (Torrence a smoothing operator S, the wavelet coherence is defined as (Shu
and Compo, 1998; Grinsted et al., 2004; Shu et al., 2008) et al., 2008)

0.5
Wavelet x4

0.0

–0.5
(a) 0 50 100 150 200

16
4 8
4
8 2
Scale

1
16 1/2
32 1/4
COI 1/8
64 1/16
50 100 150 200
(b) Distance

FIGURE 10.16  Series x 4 consisting of four short Morlet wavelets between distances of 0 and 115, and one stretched Morlet wavelet reaching from
120–210 distance with a smaller amplitude (a). The corresponding wavelet spectrum is presented in (b) with contours reflecting data fluctuations,
their scale (period), and their location along the series. The COI is depicted.
Soil Spatial Variability 10-21

32
4 16
8
8 4
2

Scale (m)
16 1
1/2
1/4
32 1/8
1/16
64 1/32
50 100 150 200
Distance (m)

FIGURE 10.17  Wavelet spectrum for process x3, shown in Figure 10.12c.

16 8
2 4
S(Wi XY (s)s −1 ) 32 2
Ri2 (s) = 2 2
. (10.35) 1
S ⎛ Wi X (s) s −1 ⎞ S ⎛ WiY (s) s −1 ⎞ 64 1/2
⎝ ⎠ ⎝ ⎠ 1/4
128
1/8
(a) 100 200 300 400 500 600
The smoothing operator depends on the base form of the wave- 8
let. For further details see Torrence and Webster (1999) and Si 16 4
and Zeleke (2005). 32 2
The continuous wavelet transform of the process x4 is shown 1
64 1/2
in Figure 10.16b. As expected for this illustrative example, in the
128 1/4
six-point wavelength band, the four basic wavelets cause pro-
Scale (m)

1/8
nounced signal contours between distances of 0 and 110. At a (b) 100 200 300 400 500 600
different wave band reaching over an extent between 16 and 32 8
points, a less pronounced peak or signal contour manifests the 16
smaller variance of the individual longer wavelet. The contour of 4
the signal is stretched according to the more extended range of the
32 2
basic Morlet wavelet in the observed series. The area covered with
intensive colors marks the above-mentioned COI (Figure 10.16b). 1
Outside this cone, the detection of variance components may be 64
affected by edge artifacts. 1/2
The wavelet transform of process x3 (Figure 10.12c), empha-
128 1/4
sizes the diagnostic capabilities of wavelet transform analysis
as shown in Figure 10.17. At the six-point wavelength band, the 1/8
eight base wavelets contribute to the variation at their respective 100 200 300 400 500 600
locations. At the 64-point band, another pronounced variation (c) Distance (m)
component is reflected in the wavelet spectrum. The variation at
FIGURE 10.18  Wavelet spectrum for wheat yield (a) and NDVI (b)
this band clearly identifies the sine waves, whose wavelength was
data, both shown in Figure 10.14. The cross-wavelet spectrum is pre-
given with 64 points (Figure 10.12b). sented in (c).
The wavelet spectra for both wheat yield and NDVI data
(Figure 10.14) exhibit some common variability features at the
30 m band, at approximately 330 m distance in the transect spectrum, arrows to the right indicate in-phase behavior, and
referring to the transition zone between soil types and cropping arrows to the left out-of-phase behavior between the wavelet
history (Figure 10.18a and b). For the 150 m wavelength of nitro- spectra. In Figure 10.19, the coherency wavelet spectrum reflects
gen fertilizer application pattern, a strong variability influence is the strong association between both variables at the 16–30 m
evident from the wavelet spectra of both, wheat yield and NDVI. band between 300 and 360 m. Moreover, the common varia-
This feature is more pronounced for the NDVI spectrum (Figure tion pattern is present along the entire transect at the 150 m
10.18b) than for the yield spectrum (Figure 10.18a), as obvious band, manifesting the impact of cyclically varying nitrogen
from the original data. application.
The cross-wavelet spectrum (Figure 10.18c) emphasizes the Notice that the wavelet spectrum indicates the local pres-
common locations of fluctuations especially at the 30–60 m band ence of individual variation components, their wavelength
at ∼300–360 m along the transect, the zone where a transition band or scale, and their contribution to the variance at that
from higher to lower soil quality occurs. In this cross-wavelet scale. If the base wavelet shape is chosen appropriately, the
 10-22 Properties and Processes

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Monograph No. 9. ASA and SSSA, Madison, WI. Yates, S.R., and A.W. Warrick. 2002. Geostatistics, p. 81–118. In
Webster, R. 1985. Quantitative spatial analysis of soil in the field. J.H. Dane and G.C. Topp (eds.) Methods of soil analysis.
Adv. Soil Sci. 3:1–70. Part 4. 3rd edn., Chapter 1, Soil sampling and statistical
Webster, R., and G.B.M. Heuvelink. 2006. The Kalman filter for procedures. Soil Science Society of America Book Series
the pedologist’s tool kit. Eur. J. Soil Sci. 57:758–773. No. 5. Soil Science Society of America Inc., Madison, WI.
Wendroth, O., A.M. Al-Omran, C. Kirda, K. Reichardt, and D.R. Yost, R.S., G. Uehara, and R.L. Fox. 1982a. Geostatistical analy-
Nielsen. 1992. State-space approach to spatial variability of sis of soil chemical properties of large land areas. 1. Semi-
crop yield. Soil Sci. Soc. Am. J. 56:801–807. variograms. Soil Sci. Soc. Am. J. 46:1028–1032.
Wendroth, O., P. Jürschik, K.C. Kersebaum, H. Reuter, C. Yost, R.S., G. Uehara, and R.L. Fox. 1982b. Geostatistical analysis
van Kessel, and D.R. Nielsen. 2001. Identifying, under- of soil chemical properties of large land areas. II. Kriging.
standing, and describing spatial processes in agricul- Soil Sci. Soc. Am. J. 46:1033–1037.
tural landscapes—Four case studies. Soil Tillage Res. Zhang, R., D.E. Myers, and A.W. Warrick. 1992. Estimation of the
58:113–128. spatial distribution of soil chemicals using pseudo-cross-
Wendroth, O., G.G. Katul, M.B. Parlange, C.E. Puente, and D.R. variograms. Soil Sci. Soc. Am. J. 56:1444–1452.
Nielsen. 1993. A nonlinear filtering approach for determin- Zhang, R., P. Shouse, and S. Yates. 1999. Estimates of soil nitrate
ing hydraulic conductivity functions in field soils. Soil Sci. distributions using cokriging with pseudo-crossvariograms.
156:293–301. J. Environ. Qual. 28:424–428.
 II
Soil Chemistry
Donald L. Sparks
University of Delaware

11 Soil Organic Matter  Jeffrey A. Baldock and Kris Broos.......................................................................................................11-1

Introduction  •  Composition of Soil Organic Matter  •  Quantifying Soil Organic Matter Content and Allocation
to Fractions  •  Functions of Organic Matter in Soil  •  Factors Determining the Content of Organic Matter in
Soil  •  Contribution of Soil Organic Matter to the Global Carbon Cycle  •  Summary  •  Acknowledgments  •  References
12 Soil Solution  Paul Schwab....................................................................................................................................................... 12-1
Basic Concepts  •  Sampling the Soil Solution  •  Thermodynamics of the Soil Solution  •  Interactions of Gases
with the Soil Solution  •  Acid–Base Reactions in the Soil Solution  •  Formation of Soluble Complexes  •  Application
of Thermodynamic and Equilibrium Concepts to Soil Solutions  •  Current Status and Future Research
Directions  •  References
13 Kinetics and Mechanisms of Soil Chemical Reactions  Donald L. Sparks..................................................................... 13-1
Introduction  •  Timescales of Soil Chemical Processes  •  Application of Chemical Kinetics to
Heterogeneous Surfaces  •  Kinetic Models  •  Kinetics of Important Reactions on Soils and Soil
Components  •  Conclusions  •  References
14 Oxidation–Reduction Phenomena  Bruce R. James and Dominic A. Brose.................................................................... 14-1
Concepts, Principles, and Theories  •  Methods and Procedures  •  Applications of Redox Methods and Concepts to
Ecological, Engineered, and Agricultural Soil Systems  •  Earlier Reviews and Prescient Work on Oxidation–Reduction
Processes in Soils  •  References
15 Soil Colloidal Behavior  Sabine Goldberg, Inmaculada Lebron, John C. Seaman, and Donald L. Suarez.................. 15-1
Nature of Soil Colloids  •  Interparticle Forces  •  Colloidal Stability  •  Colloid Transport  •  References
16 Ion Exchange Phenomena  Ian C. Bourg and Garrison Sposito......................................................................................... 16-1
Introduction  •  Surface Charge and Ion Exchange Capacities  •  Ion Exchange Thermodynamics  •  Trends in
VK and ex K  •  Ion Exchange and Chemical Speciation Models  •  Micro- and Nanoscale Perspectives on Ion

Exchange Selectivity  •  References
17 Chemisorption and Precipitation Reactions  Robert G. Ford............................................................................................17-1
Introduction  •  Conceptual Distinctions in Chemisorption and Precipitation  •  Influence of Abiotic and Biotic
Processes  •  Quantitative Descriptions of Chemisorption and Precipitation Reactions  •  Observations of Cation
and Anion Solid-Phase Partitioning in Soils  •  References
18 Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids,
and Other Inorganics  Pan Ming Huang (Deceased) and A.G. Hardie............................................................................. 18-1
Introduction  •  Fundamentals of Catalysis  •  Abiotic Catalysis of Natural and Anthropogenic Organic
Compounds  •  Abiotic Catalysis in the Transformation of Metals, Metalloids, and Other Inorganics  • 
Role of Nanoparticles in Abiotic Catalysis  •  Conclusions  •  Acknowledgment  •  References
19 Soil pH and pH Buffering  Paul R. Bloom and Ulf Skyllberg.............................................................................................. 19-1
Introduction  •  Definition and Determination of Soil pH  •  Acids and Bases in Soil Solutions  •  Overview of
Reactions Controlling pH and pH Buffering  •  Buffering by Soil Organic Matter  •  Proton and Al Exchange in Silicate
Clays  •  pH-Dependent Charge Buffering by Mineral Components  •  Buffering by Dissolution and Precipitation
of Carbonates  •  H+ Consumption by Irreversible Weathering of Aluminous Minerals  •  Determination of Buffer
Capacities  •  Soil Acidification  •  References

II-1
II-2 Soil Chemistry

S
INCE THE FIRST EDITION of the Handbook of Soil development of advanced speciation and computational models
Science was published in 2000, many changes have taken have provided soil chemists with tools that are indispensable in
place in the area of soil chemistry. Global environmen- understanding soil chemical reactions and processes at mul-
tal challenges such as climate change, water quality, nutrient tiple scales. Accordingly, significant advances have been made
management, soil contamination, ecosystem health, and energy in understanding, as never before, the chemistry of soil organic
sustainability have brought soil chemistry research to the matter, soil solution and solid phase speciation, the kinetics and
forefront. Because these are complex challenges, they must be mechanisms of soil chemical reactions, soil colloidal chemistry,
tackled in a highly interdisciplinary/multidisciplinary manner oxidation–reduction, ion exchange, adsorption and precipita-
over a range of spatial and temporal scales. Thus, soil chemists tion processes and complexes, abiotic catalysis, and soil acidity.
are increasingly interacting with a wide array of scientists and Advances in these topics are comprehensively covered in the fol-
engineers in multiple fields such as chemistry, biology, physics, lowing chapters.
geochemistry, engineering, economics, ecology, and environ- I am extremely grateful to the authors for their excellent con-
mental policy. The use of highly sophisticated analytical tools, tributions and to the referees who made many helpful sugges-
particularly those that are in situ and synchrotron-based, and tions for improvement.
 11
Soil Organic Matter
11.1 Introduction............................................................................................................................ 11-1
11.2 Composition of Soil Organic Matter................................................................................... 11-3
Elemental Composition  •  Chemical/Molecular Composition  •  Physical
Composition  •  Biological Composition  •  Defining Biologically Relevant Soil
Organic Matter Fractions  •  Consistency between Biologically Relevant Soil Organic
Matter Fractions and Pools of Carbon in Simulation Models
11.3 Quantifying Soil Organic Matter Content and Allocation to Fractions..................... 11-18
Direct Measurement of Soil Organic Content and Component Fractions  • 
Proximate Analyses
11.4 Functions of Organic Matter in Soil.................................................................................. 11-19
Biochemical Functions  •  Physical Functions  •  Chemical Functions  • 
Complexation of Inorganic Cations
11.5 Factors Determining the Content of Organic Matter in Soil........................................ 11-25
Jeffrey A. Baldock Climate  •  Soil Mineral Parent Materials and Products of Pedogenesis  • 
Commonwealth Scientific and Biota: Vegetation and Soil Organisms  •  Topography  •  Land Management Practices
Industrial Research Organisation 11.6 Contribution of Soil Organic Matter to the Global Carbon Cycle............................... 11-36
Kris Broos 11.7 Summary................................................................................................................................ 11-37
Flemish Institute for Acknowledgments............................................................................................................................ 11-37
Technological Research References.......................................................................................................................................... 11-37

11.1  Introduction selective probing of SOM chemistry within samples of whole soil.
Application of these technologies avoids problems of incomplete
Research pertaining to the organic fraction of soils can be traced extraction, artifact synthesis, and lack of biological significance
back in excess of 200 years. Achard (1786) isolated a dark amor- often ascribed to alkaline extraction procedures. The combina-
phous precipitate upon acidification of an alkaline extract from tion of these techniques with SOM fractionation approaches that
peat. The effect of organic matter on soil N fertility (von Liebig, are capable of identifying biologically important SOM compo-
1840), studies on the use of animal manures for maintaining soil nents has significantly advanced our knowledge of the organic
fertility (Lawes, 1861), and the influence of soil and tree species fraction of soils and its dynamics over the last 30 years.
on the development of humus form (Muller, 1887) all demon- Despite such a long history of research and new methodologi-
strated the importance of organic matter in soil processes. The cal and technological advancements, many questions related to
advancement of organic chemical methodologies and confirma- the genesis and chemical composition of SOM and its impacts
tion of the presence of various chemical structures in soil organic on soil fertility, soil pedogenesis, and soil physical and chemical
matter (SOM) lead to the development of theories that SOM was properties persist today. Many excellent texts and review papers
composed of a heterogeneous mixture of dominantly colloidal have been written on the topic of SOM. Some of the more recent
organic substances containing acidic functional groups and N. of these are given in Table 11.1. Table 11.1 is not comprehensive,
More recently, the polyphenol theory was proposed in which but rather attempts to provide a starting point for anyone inter-
quinone structures of lignin and microbial origin polymerize in ested in understanding the nature and roles of organic matter
the presence of N-containing groups (amino acids, peptides, and in soils.
proteins) to produce nitrogenous polymers (Flaig et al., 1975). An examination of terms used to describe SOM and its com-
Early research pertaining to SOM has been reviewed by ponents in the literature revealed a lack of precise and consistent
Stevenson (1994). While alkaline extraction of SOM is still prac- definitions of what SOM is and what its various component frac-
ticed, modern analytical techniques, including solid-state 13C tions represent. Such a problem exists because of the heteroge-
nuclear magnetic resonance (13C NMR) spectroscopy, infrared neity of SOM with respect to its source, chemical and physical
(IR) spectroscopy, pyrolysis gas chromatography/mass spec- composition, diversity of function, and its dynamic character.
troscopy (Py-GC/MS), and x-ray adsorption (XAFS), allow As a result, the term SOM has been used to describe all organic

11-1
11-2 Properties and Processes

TABLE 11.1  List of Some of the Texts and Review Articles Pertaining to the Study of SOM Released Since 1995
Texts
SOM management for sustainable agriculture (Lefroy et al., 1995)
Humic substances of soils and general theory of humification (Orlov, 1995)
Carbon forms and functions in forest soils (McFee and Kelly, 1995)
The role of nonliving organic matter in the earth’s carbon cycle (Zepp and Sonntag, 1995)
Driven by nature: Plant litter quality and decomposition (Cadisch and Giller, 1997)
Soil carbon management: Economic, environmental, and societal benefits (Kimble et al., 2007)
Soil carbon sequestration under organic farming in the Mediterranean environment (Mainari and Caporali, 2008)
Review articles
The chemical composition of SOM in classical humic compound fractions and in bulk samples—A review (Beyer, 1996)
Carbon in primary and secondary organo-mineral complexes (Christensen, 1996a)
Applications of NMR to SOM analysis—History and prospects (Preston, 1996)
Analytical pyrolysis and computer modeling of humic and soil particles (Schulten et al., 1998)
Life after death—Lignin–humic relationships reexamined (Shevchenko and Bailey, 1996)
Stabilization and destabilization of SOM—Mechanisms and controls (Sollins et al., 1996)
Soil organic carbon/SOM (Baldock and Skjemstad, 1999)
Role of the soil matrix and minerals in protecting natural organic materials against biological attack (Baldock and Skjemstad, 2000)
The supramolecular structure of humic substances: A novel understanding of humus chemistry and implications in soil science (Piccolo, 2002)
Indications for SOM quality in soils under different managements (von Lützow et al., 2002)
Importance of mechanisms and processes of the stabilization of SOM for modeling carbon turnover (Krull et al., 2003)
Cycling and composition of organic matter in terrestrial and marine ecosystems (Baldock et al., 2004)
Soil mineral–organic matter–microorganism interactions: Fundamentals and impacts (Huang, 2004)
The depth distribution of soil organic carbon in relation to land use and management and the potential of carbon sequestration in subsoil horizons
(Lorenz and Lal, 2005)
Root effects on SOM decomposition (Cheng and Kuzyakov, 2005)
Mechanisms and regulation of organic matter stabilization in soils (Kögel-Knabner et al., 2005)
Labile organic matter fractions as central components of the quality of agricultural soils: An overview (Haynes, 2005)
Soil minerals and organic components: Impact on biological processes, human welfare, and nutrition (Haider and Guggenberger, 2005)
The soil carbon dioxide sink (Smith and Ineson, 2007)
Impacts of climate change on forest soil carbon: Principles, factors, models, uncertainties (Reichstein, 2007)
Composition and cycling of organic carbon in soils (Baldock, 2007)
An integrative approach of organic matter stabilization in temperate soils: Linking chemistry, physics, and biology (Kogel-Knabner et al., 2008a)
Physical carbon-sequestration mechanisms under special consideration of soil wettability (Bachmann et al., 2008)
Soil-carbon preservation through habitat constraints and biological limitations on decomposer activity (Ekschmitt et al., 2008)
Storage and stability of organic matter and fossil carbon in a luvisol and phaeozem with continuous maize cropping: A synthesis (Flessa et al., 2008)
Contribution of dissolved organic matter to carbon storage in forest mineral soils (Kalbitz and Kaiser, 2008)
Organo-mineral associations in temperate soils: Integrating biology, mineralogy, and organic matter chemistry (Kogel-Knabner et al., 2008b)
Comparison of two quantitative soil organic carbon models with a conceptual model using data from an agricultural long-term experiment
(Ludwig et al., 2008)
How relevant is recalcitrance for the stabilization of organic matter in soils? (Marschner et al., 2008)
Stabilization mechanisms of organic matter in four temperate soils: Development and application of a conceptual model (von Lützow et al., 2008)
For additional earlier references consult Hedges and Oades (1997) and Baldock and Nelson (2000).

materials found in soil (Stevenson, 1994), all organic materi- Baldock and Nelson, 2000). The term SOM is used in this work
als excluding charcoal (Oades, 1988), or all organic materials to refer to the sum of all naturally derived organic materials
excluding nondecayed plant and animal tissues, their partial present, and a series of further terms are proposed to define spe-
decomposition products, and the living soil biomass (MacCarthy cific components of SOM (Table 11.2).
et al., 1990). As suggested by MacCarthy et al. (1990), it is most With the advent of modern elemental analyzers, quantification
important that readers establish how particular authors apply of the organic fraction of a soil is now often completed by measur-
the various terms to fully understand and assess the implica- ing the amount of organic carbon present in a soil. Although this
tions of research findings. The definitions of SOM and its com- chapter is devoted to the composition, chemistry, and functions
ponents to be used in this chapter have been derived from several of SOM as well as the factors that define SOM content, where
sources (Oades, 1988; MacCarthy et al., 1990; Stevenson, 1994; particular research studies have focused on the measurement of
Soil Organic Matter 11-3

TABLE 11.2  Definitions of SOM and Its Components

Component Definition
SOM The sum of all natural and thermally altered biologically derived organic materials found in the soil or on the soil
surface irrespective of its source, whether it is living or dead, or stage of decomposition, but excluding the
aboveground portion of living plants
Living components
Phytomass Living tissues of plant origin. Standing plant components, which are dead (e.g., standing dead trees), are included
in phytomass
Microbial biomass Organic matter associated with cells of living soil microorganisms
Faunal biomass Organic matter associated with living soil fauna
Nonliving components
Surface plant residues Organic debris located on the soil surface typically dominated by pieces of plant residues (also referred to as litter)
Buried plant residues Pieces of organic debris >2 mm found in the soil matrix collected by sieving
DOM Water soluble organic compounds found in the soil solution, which are <0.45 μm by definition
POM Pieces of organic debris 53–2000 μm in size with a recognizable cellular structure that are collected on a 53 μm
sieve after complete dispersion of a soil (typically dominated by plant residues)
HUM Organic materials <53 μm remaining after removal of POM and DOM
Resistant organic matter Highly carbonized organic materials including charcoal, charred plant materials, graphite, and coal with long
turnover times
Additional fractions of organic matter
Macroorganic matter Fragments of organic matter >20 μm or >50 μm contained within the soil matrix and typically isolated by sieving
a dispersed soil
Light fraction Organic materials isolated from soils by flotation of dispersed suspensions on water or heavy liquids of densities
1.5–2.0 Mg m−3
Nonhumic biomolecules Organic biopolymers including polysaccharides and sugars, proteins and amino acids, fats, waxes and other
lipids, and lignin
Humic substances Organic molecules with chemical structures, which do not allow them to be placed into the category of nonhumic
biomolecules
Humic acid Organic molecules soluble in alkaline solution but precipitate on acidification of the alkaline extracts
Fulvic acid Organic molecules soluble in alkaline solution and remain soluble on acidification of the alkaline extracts
Humin Organic materials that are insoluble in alkaline solution

soil organic carbon (SOC), the discussion will refer to the results buried within aggregations of mineral particles. Such diversity
obtained in terms of SOC and not SOM. In most instances, in physical and chemical properties when combined with the
SOC and SOM can be used interchangeably; however, in some spatial heterogeneity of its distribution within the soil matrix at
instances, it is more appropriate to refer to the organic fraction size scales ranging from micrometer to meter makes studies of
of soils as SOM rather than SOC. For example, when referring to SOM composition and function challenging.
the nutrient content of the soil organic fraction, it would be most Often analytical techniques are applied to the whole organic
appropriate to use SOM since, by definition, SOC in itself only component of soils resulting in the acquisition of weighted aver-
refers to the carbon present and not the associated nutrients. age compositional or behavioral data. Such data may or may not
provide an adequate assessment of the potential involvement of
organic matter in soil processes. For example, the presence of a
11.2  Composition of Soil small amount of biologically labile organic matter could signifi-
Organic Matter cantly alter short-term measurements of soil carbon mineraliza-
tion but not be related to a measure of the total amount of organic
Soil organic matter is composed of a vast array of different carbon present. To better understand the nature of SOM and its
organic residues ranging in size from simple monomeric mol- roles in soil processes, various schemes have been developed to
ecules through complex polymeric compounds to pieces of plant divide SOM into more homogeneous components and to subse-
residue >1 cm in size in agricultural systems and potentially quently conduct separate analyses on the isolated fractions.
>1 m in forests. Independent of size, individual components of
SOM can exist at any point along a decomposition continuum
11.2.1  Elemental Composition
ranging from fresh unaltered materials to highly altered materi-
als bearing little chemical or physical similarity to their original Carbon accounts for the majority of the mass of SOM; however,
source. Additionally, SOM can exist in a free state or be asso- oxygen, hydrogen, nitrogen, phosphorus, and sulfur can also
ciated to varying degrees with surfaces of mineral particles or make significant contributions. Contents of organic matter in
11-4 Properties and Processes

soils are typically quantified by measuring the gravimetric con- different components of SOM (e.g., pieces of plant-residue and
tents of organic carbon and/or total nitrogen. The traditional well-decomposed materials—see Section 11.1) and particular
factor used to convert gravimetric contents of SOC into SOM is combinations of soil type and land use will aid the development
1.72 (Equation 11.1), which assumes a carbon content of approxi- of more accurate predictions of nutrient cycling and potential
mately 58% by weight. To obtain estimates of SOM content based responses to alterations in management. In particular, improved
on the gravimetric content of nitrogen requires the use of a C:N definition of the net mineralization of nutrients (i.e., the balance
ratio expressed on a mass basis and typically assigned a value between rates of gross mineralization and immobilization) and
of 12 for agricultural soils (Equation 11.2). Spain et  al. (1983) release into plant-available pools should be obtained.
summarized the C:N ratios across 3652 surface horizons from Molar ratios of carbon, oxygen, and hydrogen can also pro-
Australian soils and obtained ratios ranging from 5 to 35 across vide useful information pertaining to chemical changes that
all soil types under a variety of management strategies. Snowdon occur during decomposition, heating, or other processes where
et al. (2005) obtained values ranging from 6 to 51 for Australian transformations of SOM take place. One useful representation
forest soils. Higher C:N ratios would be expected where the of C:O:H ratios that appears underutilized in SOM studies is a
organic matter in a soil is dominated by less decomposed pieces van Krevelen plot (van Krevelen, 1950) in which molar H:C is
of plant debris rather than well-­decomposed organic matter. plotted against molar O:C. Where the elemental composition of
Conversely, where well-decomposed materials dominate, lower SOM components (biomolecules) can be defined, van Krevelen
C:N ratios would be expected. In a review of global C:N ratios plots can be used to define the possible compositional space in
for SOM, Cleveland and Liptzin (2007) obtained values ranging which a sample must reside and whether there is a prevalence of
from 1.7 to 25.7 when expressed on a gravimetric basis. Average one component over another. Additionally, the trajectory on a
gravimetric C:N ratios for the entire data set (n = 146), grass- van Krevelen plot associated with changes induced by a process
lands (n = 75), and forests (n  =  55) were 12.2, 11.8, and 12.4, of alteration can give an indication of the associated chemical
respectively, consistent with the typically assigned gravimetric changes (e.g., dehydration, loss of CO2, or oxidation, which are
C:N ratio of 12: all associated with different trajectories). Baldock and Smernik
(2002) used a van Krevelen plot to define the extent of alteration of
SOM (g kg −1 soil) = 1.72 × SOC (g C kg −1 soil), (11.1) natural organic materials during a heating process. When using
van Krevelen plots, it is essential that reliable values are obtained
for the molar concentrations of O and H. For soils, the presence
SOM (g kg −1 soil) = 1.72 × C : Nratio of hygroscopic water and alterations to soil mineral components
during the heating phase of C, O, and H determinations may
× soil organicnitrogen (g N kg −1 soil). (11.2) introduce errors in measurements of O and H concentrations.
Another useful property of SOM that can be calculated from
Although C:N ratios have typically been expressed on a gravi- its molar elemental composition is its oxidation state (Cox). The
metric basis for soils and plant materials, in aquatic and geo- value of Cox for a given organic molecule of the form CxHyOzNw
chemical sciences, elemental ratios have tended to be expressed can be calculated according to Equation 11.3 in which x, y, z,
on a molar basis. Redfield (1958) recognized that marine plank- and w represent the molar percentages of C, H, O, and N, respec-
ton maintained an average molar C:N:P ratio of 106:16:1 similar tively, in the molecule or weighted average molecule in the case
to that in marine water. The presence of such a defined relation- of SOM. The values for Cox can vary from −4 to +4 but typically
ship for marine systems has been used to constrain marine net vary between −2.2 and +3 in organic molecules. For example, lip-
primary productivity (NPP) (e.g., Hecky and Kilham, 1988; ids, carbohydrates, and organic acids have Cox values of −2 to −1,
Turner et  al., 2003), and the recognition of defined elemental 0, and 0 to +3, respectively (Masiello et al., 2008). Cox values of
ratios in components of terrestrial systems is used to constrain SOM and its components therefore contain information pertain-
nutrient dynamics within carbon and nutrient simulation mod- ing to molecular composition, biochemical synthesis pathway,
els (e.g., the Century model; Parton et  al., 1987, 1988). Such extent of decomposition, and diagenetic history. For example, if
relationships have led to the development of the concept of eco- Cox values <−1 are obtained, then there is likely to be a preponder-
logical stoichiometry in which it is recognized that variations ance of lipid/aliphatic structures present. Alternatively, if values
in molar elemental ratios fluctuate within defined boundaries >1 are obtained, then a high content of carboxylic acids is likely.
based on environmental conditions and biochemical require- Cox values between −1 and +1 are less informative as a large range
ments of organisms. A trend toward expressing elemental of combinations of different compounds could provide such val-
ratios on a molar basis is emerging for SOM. Stevenson (1986) ues. However, Cox values may still be used to constrain predic-
provided an estimate of the molar C:N:P:S ratio of SOM as tions of molecular composition of SOM and its components.
107:7.7:1:1. Cleveland and Liptzin (2007) defined average C:N:P Cox is mathematically related to the oxidative ratio (OR),
ratios of soils obtaining values of 186:13:1 for SOM and 60:7:1 which defines the molar ratio of O2 consumption to CO2 emis-
for soil microbial biomass with a tendency for grassland soils sion during decomposition. Organic molecules having positive
to be more nutrient rich and forest soils to be more carbon Cox values do not need as much oxygen for complete mineraliza-
rich. Further quantification of the variance of these ratios for tion as those with negative Cox values. Based on the assumption
Soil Organic Matter 11-5

that net photosynthesis occurs via Equation 11.4 with all N precipitation to separate soil organic and mineral components
being obtained as ammonia, the OR can be calculated from Cox include the following:
according to Equation 11.5. If the required N is obtained as
1. Questions related to the ability of alkaline extractable
nitrate or through biological fixation of N2, Equations 11.6
material to be representative of the composition of the
or  11.7, respectively, should be used to calculate OR (Masiello
unextracted and entire SOM fraction
et al., 2008). Quantification of the OR (and thus Cox) of terres-
2. The apparent lack of a relationship between the biological
trial forms of organic matter, including that found in soils, can
functioning of SOM and its alkaline extractability based
be used to define the fate of CO2 emitted to the atmosphere by
on C and N isotopic tracer studies (Oades, 1995)
fossil fuel burning (Randerson et al., 2006):
3. Incomplete segregation and probable mixing of SOM with
different molecular compositions and susceptibilities to
2z − y + 3w
C ox = , (11.3) decomposition
x 4. Creation of artifacts (alteration of molecular structure)
during the extraction and precipitation procedures
1
xCO2 + (y − 3w)H2O + wNH3 It is acknowledged that in early studies of SOM, separation of
2
soil organic and mineral components was essential to allow
⎛ 1 z⎞ selective characterization of the SOM, and that alkaline extrac-
→ C x H y Oz N w + ⎜ x + (y − 3w) − ⎟ O2 , (11.4)

⎝ 4 2⎠ tion provided such a capability. However, with the advent of
more selective degradation procedures and modern analytical
C OX instrumentation that can use intact soil samples, it is suggested
OR = 1 − , (11.5)
4 that the use of alkaline extractants as a means of characterizing
SOM should be avoided where possible.
C OX 2w Many additional methods have been developed based on vari-
OR = 1 − + , (11.6)
4 x ous extraction or degradative methods considered to be “selec-
tive” for particular molecular components of SOM. Hydrolysis
C ox 3w with 6 M HCl or methane sulfonic acid has been used to quantify
OR = 1 − + . (11.7)
4 4x the proportion of SOM associated with proteins, amino acids,
and amino sugars (e.g., Friedel and Scheller, 2002; Martens and
11.2.2  Chemical/Molecular Composition Loeffelmann, 2003; Appuhn et  al., 2004). Hydrolysis reactions
with sulfuric acid have been used to quantify the allocation of
A heterogeneous chemical structure and an ability to form strong SOM to carbohydrate structures (e.g., Rovira and Vallejo, 2000;
associations with soil minerals make the chemical characteriza- Martens and Loeffelmann, 2002). The proportion of lignin in
tion of SOM difficult. Two approaches to define the chemical/ SOM has been quantified using methods that attempt to either
molecular composition of SOM have been used: (1) chemical isolate the intact lignin molecule (e.g., Tuomela et  al., 2000)
extraction or degradative methodologies and (2) modern spec- or quantify the monomeric species released by breaking the
troscopic techniques capable of analyzing SOM in situ. With macromolecular structure into its component monomeric spe-
both approaches, it is essential to gain a full understanding of cies (e.g., Baldock et al., 1997b; Chefetz et al., 2002; Leifeld and
the methodology being used and possible deficiencies in order to Kögel-Knabner, 2005). Various solvent-based procedures have
assess how selective and quantitative the applied procedures are been developed and used to quantify the presence of lipids and
and whether there is a potential for creating artifacts. Without lipid-like organic materials in soils (e.g., Poulenard et al., 2004;
such an understanding, it is not possible to make appropriate Rumpel et al., 2004).
interpretations of the SOM compositional data obtained. Although more specific than alkaline extraction procedures,
results derived from these more specific degradation proce-
11.2.2.1  Chemical Extraction dures should be considered as approximate due to the potential
and Degradative Methods for incomplete extraction and/or nonselective action. Using a
Chemical extraction and degradative methods for characteriz- combination of extraction techniques in a “proximate analy-
ing SOM use aqueous solutions and organic solvents to liberate sis approach” designed to isolate and quantify klason lignin,
SOM components with particular chemical characteristics. One Preston et  al. (1997) demonstrated the presence of a range of
of the most common approaches uses an alkaline extraction fol- nonlignin forms of carbon. Additionally, the use of degradation
lowed by acidification (Schnitzer, 2000) of the extract to isolate procedures to quantify SOM components involved in biologi-
humic acid, fulvic acid, and humin (see Table 11.2 for defini- cal processes within the soil matrix may be questionable. As an
tions). These three fractions should not be considered as dis- example, consider a polysaccharide molecule located in a pore
crete compounds, as each will contain a multitude of different on the external surface of an aggregate versus the same molecule
chemical structures that can be further fractionated and puri- buried within a matrix of clay particles. Both polysaccharides
fied. Criticisms pertaining to the use of alkaline extraction/acid may be broken down by a sulfuric acid digestion procedure and
11-6 Properties and Processes

detected by subsequent analyses, but the availability of these two units of parts per million of the applied magnetic field). Duncan
molecules to microbial oxidation as well as their relative contri- (1987) has presented a comprehensive review of the chemical
bution to soil function would be expected to vary significantly. shift values associated with different types of carbon. Solid-state
Attempts to use chemical fractionation procedures to allocate 13C NMR spectra acquired for SOM are typically divided into

SOM to labile and recalcitrant fractions without defined molec- chemical shift regions indicative of the major chemical forms
ular composition have also been made. Hydrolysis with HCl and that individual carbon atoms can take Figure 11.1a. Integration
permanganate oxidation procedures have been proposed to offer of the signal intensity within each region provides a quantitative
such capabilities. With HCl hydrolysis, the proportion of car- indication of the amount of each form of carbon present in a
bon or nitrogen entering the hydrolysates has been considered sample, provided signal acquisition from all forms of carbon in
to be indicative of the biologically labile component of SOM. a sample is quantitative. Methods now exist to define the level
Both Leavitt et al. (1996) and Paul et al. (2001) found that car- of quantitative detection of carbon within solid-state 13C NMR
bon remaining in the nonhydrolysable fraction of soil subjected analyses of SOM (Smernik and Oades, 2000a, 2000b); however,
to HCl hydrolysis was older than that found in the total SOC adoption has been limited. 13C NMR detection efficiencies can be
fraction prior to hydrolysis. Quantifying the proportion of SOC improved by the application of hydrofluoric acid (HF) pretreat-
oxidized in permanganate solutions of increasing concentra- ments to concentrate carbon and remove paramagnetic species
tions has also been used to define SOC fractions with different (Skjemstad et al., 1994; Schmidt and Gleixner, 2005).
biological liabilities (Blair et  al., 1995). However, the existence Although the distribution of 13C NMR signal intensity within
of strong correlations between the amounts of SOC oxidized at various chemical shift regions has been used to infer the molecular
each permanganate concentration and total SOC (Lefroy et al., composition of organic matter in a sample, 13C NMR gives no direct
1993) question the selectivity of this approach toward identi- information pertaining how the different types of carbon present in
fying differentially labile SOC components (Blair et  al., 1995; a sample are arranged into molecules. For example, the presence of
Mendham et  al., 2002). Furthermore, Mendham et  al. (2002) signal intensity in the O-alkyl region (65–105 ppm) is often ascribed
showed that permanganate oxidizable SOC had little relation to to carbohydrates. However, three of the 11–12 carbons found in lig-
the labile pool of SOC respired over a 96 day incubation period, nin monomers will also resonate within the O-alkyl chemical shift
again questioning the existence of a link between chemical and region as will some carbon associated with proteins and lipid/wax
biological reactivities. The absence of a strong linkage between materials. To extend the level of molecular information obtained
chemical and biological reactivities and the lack of a clear defi- from the application of NMR to natural organic materials, molec-
nition of the chemical nature of the SOC components attacked ular mixing models have been defined (e.g., Hedges et  al., 2002;
by each permanganate solution can limit the ability of chemical Baldock et al., 2004; Nelson and Baldock, 2005). In this approach,
fractionation techniques to be used as proxies for biologically it is assumed that the organic carbon present in a sample can be
meaningful fractions of SOC (Baldock, 2007). described as a mixture of biomolecules (endmembers) with defined
representative chemical structures. The molecular composition of
11.2.2.2  Chemical Characterization 13C NMR observable organic carbon is then estimated by defining
with Analytical Instrumentation the mixture of endmembers that minimizes the sum of squares of
A variety of analytical techniques exist that can be used to char- differences between predicted and measured distributions of 13C
acterize the chemical composition of SOM. In this chapter, four NMR signal intensity. Baldock et al. (2004) and Nelson and Baldock
techniques that can be used to quantify the chemical nature of (2005) have used this approach to estimate the molecular composi-
SOM in situ will be examined: 13C NMR spectroscopy, analyti- tion and elemental stoichiometry of organic materials found in a
cal pyrolysis, Fourier transform infrared spectroscopy (FTIR), range of terrestrial and aquatic systems.
and x-ray spectroscopy. Examples of the chemical information Solid-state NMR has also been used to characterize the chemi-
obtained by applying these analytical techniques to SOM are cal composition of organic N in soils (Knicker et al., 1993; Clinton
given in Figures 11.1 and 11.2. The forms of analytical instru- et al., 1995; Knicker and Skjemstad, 2000); however, the low NMR
mentation to be discussed are all complementary and, where sensitivity and natural abundance of the 15N nucleus make the
possible, efforts should be made to utilize combinations of these acquisition of spectra with adequate signal-to-noise ratios diffi-
methods to confirm and provide additional insight into the cult. The majority of organic N present in soils is thought to reside
chemical composition of SOM. in protein (amide) or heterocyclic compounds. In most 15N NMR
studies, signals originating from amide structures dominate the
11.2.2.2.1  Solid-State Nuclear Magnetic Resonance Spectroscopy acquired spectra, with heterocyclic N structures being detected as
Solid-state 13C NMR spectroscopy can be used to define the a small shoulder on the amide resonance (Mahieu et al., 2000). To
chemical environment around individual carbon atoms in an improve spectral quality, 15N-labeled plant materials have been
intact soil sample. The only pretreatments required are dry- used in decomposition and composting experiments (e.g., Knicker
ing and then grinding to ensure homogeneity. A typical cross and Lüdemann, 1995) with the majority of N again being allo-
polarization 13C NMR spectrum for a soil is presented in Figure cated to amide structures. However, the typical use of short con-
11.1a. Organic carbon found in different chemical environments tact times (≤1 ms) and high-field spectrometers (≥300 MHz) have
can be differentiated on the basis of chemical shift (expressed in been found to discriminate against nonprotonated heterocyclic N
Soil Organic Matter 11-7

H H
C OH O C H
H
H C OH H H
C N
H
N H
C O C H
C H C
O

Signal intensity
C O H
H
O
O C C H
O
H

C O

250 200 150 100 50 0 –50 –100

(a) Carbonyl Aromatic O-alkyl Alkyl
Chemical shift (ppm)
100

80 2.0
Relative abundance

60
1.0
40

20
0.0

0
50 100 150 200 250 300 350 400
(b) m/z
1716 Carboxyl
1659 Amide

1391 Carboxylate
1556 Amide
3200 Hydroxyl

1453 Alkyl
1516 Lignin
2925 Alkyl
Absorbance

2854 Alkyl

3500 3000 2500 2000 1500

(c) Wavelength (cm–1)

FIGURE 11.1  Examples of the data obtained from (a) a solid-state 13C NMR analysis of soil humus, (b) a pyrolysis-field ionization mass spectrum
of a humic acid (Schulten, 1987), and (c) a diffuse reflectance FTIR spectrum acquired for the 0–2.5 cm layer of a mineral soil (52 g C kg−1) after
subtraction of mineral-derived signals.

(Keleman et  al., 2002). Smernik and Baldock (2005) applied a The 31P nucleus is well suited to NMR due to its high natural
spin counting technique to 15N NMR analyses of clay-associated abundance and relative NMR sensitivity. 31P NMR analyses have
organic matter and found that although the major form of N pres- been performed on solutions extracted from soils and on solid
ent was amide, up to half or more of the organic N present must whole soils (see Toor et al., 2006). Solution-state 31P NMR offers
have resided in a form that was insensitive to 15N NMR, poten- improved resolution and thus identification and quantification
tially heterocyclic N. Careful consideration of 15N pulse programs of P species; however, it suffers from the requirement to extract
and the use of spin counting techniques are required to obtain 15N P-containing materials into solution and thus may not allow
NMR results that are indicative of all N present in a sample of soil. characterization of all P in a sample. Solid-state 31P NMR can be
11-8 Properties and Processes

288.6
286.7 287.3

406.2
402.5
289.3

403.5
401.2
Alkaline

285.0
extract

400.0
398.7
Whole
soil

280 285 290 295 300 395 400 405 410 415
(a) Energy (eV) (b) Energy (eV)

2482
2473
2140 2160 2180 2460 2470 2480 2490 2500 2510
(c) Energy (eV) (d) Energy (eV)

FIGURE 11.2  (a) Carbon K-edge XANES spectra acquired for the alkaline extractable organic carbon from a forest soil in western Kenya
(Lehmann et al., 2008) and a whole soil from Elstow (Gillespie et al., 2009). (b) Nitrogen K-edge XANES spectrum acquired for a whole soil from
Elstow (Gillespie et al., 2009). (c) Phosphorus K-edge XANES spectrum for topsoil from a German peat (Kruse and Leinweber, 2008). (d) Sulfur
K-edge XANES spectrum acquired for whole soil taken from a podzol O horizon (Prietzel et al., 2007).

used to analyze a whole undisturbed sample without extraction; the pyrolysis products released during a rapid (Curie-point) or
however, the association of soil P with Fe or Mn can render it controlled heating of a sample. Several methods of ionization
invisible to 31P NMR. Organic phosphates tend to remain unre- are available to promote the movement of pyrolysis products
solved and appear as a broad resonance between +1 and −1 ppm through the mass spectrometer: field ionization (FI), chemi-
due to the wide variety of organic phosphate forms (e.g., phos- cal ionization (CI), fast atom bombardment (FAB), and laser
pholipids, nucleic acids, metabolic products) and their limited ionization (LI). Irrespective of the method of ionization used,
mobility. In solution-state 31P NMR, rapid tumbling of extracted distinctive patterns of pyrolysis products are produced (Figure
organic P-containing molecules leads to sharper signals. Toor 11.1b). After normalization of the m/z peak intensities, a qualita-
et al. (2006) concluded that solution-state 31P NMR is useful for tive assessment of the chemical nature of the organic C in a soil
characterizing the chemical composition of soil organic P, while sample can be obtained. Incorporation of a gas chromatograph
solid-state 13P NMR is more suited to the study of inorganic P between the pyrolysis chamber and the mass spectrometer can
components of soils. further aid in the separation of similar pyrolysis fragments prior
to detection and analysis by the mass spectrometer.
11.2.2.2.2  Analytical Pyrolysis Mass Spectrometry A cautionary note regarding the comparison of different m/z
Analytical pyrolysis characterizes the chemical composition signal intensities is required. First, the intensities observed at
of products of controlled pyrolysis of a sample to obtain infor- any single m/z value may result from multiple pyrolysate frag-
mation pertaining to the nature of the organic matter present ments if they have the same m/z ratio. Second, the volatilization
in the sample. The application of this technique to the analysis of different types of pyrolysis fragments varies (e.g., in pyrolysis
of organic matter in whole soils and soil extracts is given by FI MS, volatilization decreases with increasing polarity of the
Schnitzer and Schulten (1995). Several different approaches to fragments). As a result, differences in signal intensities at various
using analytical pyrolysis exist including off-line pyrolysis, pyrol- m/z values do not necessarily correlate with contents of the par-
ysis mass spectrometry, derivatization pyrolysis mass spectrom- ent molecules present in the original soil samples. It is appropri-
etry, and Py-GC/MS. A detailed description of each technique is ate, however, to utilize variations in a given m/z signal intensity
presented by Schulten and Leinweber (1996). In pyrolysis mass between samples run under a constant set of analytical condi-
spectrometry, the mass/charge ratio (m/z) is used to differentiate tions to infer compositional differences.
Soil Organic Matter 11-9

11.2.2.2.3  Fourier Transform Infrared Spectroscopy additional resonances and used XANES to quantify differences
FTIR can be used to determine the type of the atoms to which C between bulk and rhizosphere soil. The C K-edge XANES spectra
is bound as well as the nature of the bond. Detailed identification acquired by Gillespie et al. (2009) were complicated by the pres-
of chemical structure is therefore possible. However, the applica- ence of residual C in the beamline and second-order O K-edge
tion of FTIR to characterize the composition of SOM in whole features that are typically absent from spectra acquired for pure
soils is limited by two factors: the low organic matter content of organic compounds or samples with high (>50 mg C g−1 sample)
most mineral soils and the presence of significant signals from soil carbon contents. XANES has also been combined with scanning
mineral components. The use of “difference spectra” (spectrum of transmission x-ray microscopy (STXM) to define spatial changes
an untreated sample minus that of a pretreated sample) may pro- in carbon composition across microaggregates (Kinyangi
vide more useful data. Subtraction of an FTIR spectrum obtained et  al., 2006; Lehmann et  al., 2008) and black carbon particles
for a sample heated to 350°C to remove all organic matter from (Lehmann et al., 2005; Liang et al., 2006, 2008). Solomon et al.
the FTIR spectrum obtained for the original soil can provide an (2009) concluded that C K-edge XANES may provide a means
indication of the nature of the organic components removed, of fingerprinting complex organic C compounds of ecological
provided no significant alteration to soil mineral components importance; however, due to the broad spectral features found for
occurred during the heating process. Where significant altera- organic carbon in soils (e.g., Lehmann et al., 2008), it is unlikely
tions to soil mineralogy also occur on heating these changes will that XANES can be used on its own to provide an unambiguous
also be included in the difference spectrum. Figure 11.1c provides chemical characterization of SOC.
an example of a difference spectrum obtained for a soil. Gillespie et al. (2009) performed N K-edge XANES on whole
soils (Figure 11.2b) and attributed the following resonances
to organic N structures: aromatic N in six-membered rings
11.2.2.2.4  X-Ray Absorption Spectroscopy (398.7 eV), nitrilic and pyrazolic N (400.0 eV), amide (protein)
X-ray absorption spectroscopy (XAS) allows collection of atomic N (401.2 eV), pyrrollic N (402.5 eV), nitroaromatic N (403.5 eV),
scale chemical information. A summary of the fundamentals of and alkyl N (406.2 eV). Leinweber et  al. (2007) presented a
XAS techniques is given by Schulze and Bertsch (1995). In XAS, detailed systematic analysis of N K-edge XANES resonances
x-rays are absorbed by an atom at defined energies. In response, obtained for a range of known organic N structures likely to
a higher-energy electron replaces the ejected electron, and occur in soils and concluded that N K-edge XANES can be used
excess energy is released in the form of fluorescence. The energy to reliably distinguish pyridinic and nitrile N (≤400 eV) from
at which fluorescence occurs is characteristic for each electron amide, nitro, and pyrrollic N (>400 eV). Jokic et al. (2004) used
within an atom and can be used to provide chemical informa- N K-edge XANES to detect the presence of heterocyclic N com-
tion about a given type of atom (C, N, P, or S). XAS spectra are pounds in chemically unaltered whole soil samples.
typically divided into two regions: the near-edge and extended Most applications of P XANES spectroscopy have focused
region. X-ray absorption near-edge structure (XANES) spec- on the K-edge; however, the speciation of P forms, particularly
troscopy examines the region before the absorption edge to organic P, can be difficult or even impossible at the P K-edge. Kruse
around 100 eV past the edge. XANES spectra can also be referred and Leinweber (2008) determined the nature of the P present in a
to as near-edge x-ray absorption fine structure (NEXAFS) spec- series of inorganic and organic standard compounds as well as the
tra. XANES spectra are sensitive to the oxidation state of the topsoil (Figure 11.2c) and subsoil of a German peat using P K-edge
atom being examined. Resonances are identified by comparison XANES. The spectra obtained for the inorganic and organic stan-
with spectra acquired for standard compounds. In the extended dards showed only slight variations in the energy position of the
region of x-ray absorption spectra, NEXAFS spectra provide main resonance and thereby offered little potential to distinguish
information on coordination number, identity of nearest neigh- inorganic from organic P. Additionally, little distinction was noted
bors, and bond distances for the element being examined. XAS between the three organic P compounds (asolectin, ATP, and
has been used to examine the chemical nature of organic C, N, P, phytic acid). P XANES spectra collected at the L2,3-edge instead
and S found in soils (Figure 11.2). of the K-edge contain more distinguishable features. Kruse et al.
Solomon et  al. (2009) performed C K-edge XANES analysis (2009) present a detailed analysis of the P L2,3-edge XANES spec-
of a suit of known organic C compounds indicative of those tra obtained for a range of inorganic and organic forms of P. The P
found in soil (carbohydrates, amino sugars, amino acids, phe- L2,3-edge XANES spectra contained more spectral features than P
nols, quinine, benzenepolycarboxylic acid, and markers for black K-edge spectra, particularly for the organic P compounds, leading
C). The acquired spectra showed distinct features and resonance Kruse et al. (2009) to suggest that quantitative differentiation of
positions for each form of carbon in the known compounds. different types of P may be possible by applying linear combina-
Lehmann et  al. (2008) provided the following broad classifica- tion fitting to P L2,3-edge XANES spectra.
tions for XANES C resonances for alkaline extractable SOC: aro- K-edge XANES can also be used to examine S speciation in
matic carbon ring structures (284–286 eV), phenolic/pyrimidine soils (Prietzel et  al., 2003; Solomon et  al., 2005) (Figure 11.2d).
or imidazole carbon (286.4–287.4 eV), aliphatic carbon (287.3– S K-edge XANES resonances have been defined as 2472.6–
287.8 eV), and carboxylic/amide carbon (288–289 eV). Working 2473.4 eV (reduced S in organic polysulfide, disulfide, mono-
with whole soils (Figure 11.2a), Gillespie et al. (2009) identified sulfide, and thiol structures), 2475.8–2481.3 eV (intermediate S
11-10 Properties and Processes

in sulfoxide, sulfone, and sulfonate structures), and 2482.5 eV DOM enters the soil as soluble material in water passing
(oxidized S in ester sulfate structures). Prietzel et al. (2007) used through vegetation, litter layers, or organic-rich soil surface hori-
S K-edge XANES spectra to characterize the differences between zons. It can also be generated in situ by adsorption/desorption
S in whole soils with their corresponding humic extracts. In all reactions occurring on mineral surfaces, excretion of organic
soils examined by Prietzel et al. (2007), S was mainly present as compounds from plant roots, excretion of metabolic waste prod-
organic mono- and disulfide (27%–52%), ester sulfate (14%–39%), ucts from soil organisms, and excretion and action of extracel-
and sulfone (15%–27%) with sulfoxide and sulfite having more lular enzymes. DOM is lost through uptake and mineralization
minor contributes and an absence of sulfonate and inorganic sul- by soil organisms, sorption reactions with soil particles, precipi-
fide. However, inorganic SO2− 4 cannot be differentiated from ester tation reactions, and in leachate exiting the soil profile. The con-
sulfate because both species have an equivalent oxidation state centration of DOM in soil is governed by all these processes, and
of +6. Prietzel et al. (2007) noted that the contribution of reduced when expressed in terms of dissolved organic carbon (DOC),
forms of organic S (organic mono- and disulfides) increases and values typically range from 5 to 50 mg L−1 in surface and litter
the contribution of ester sulfate and SO2− 4 decreases with increas- horizons, and from 0.5 to 5 mg L−1 or less in B and C horizons.
ing OC content and decreasing O2 availability. When expressed on as annual fluxes, Michalzik et  al. (2001)
presented values of 10–40 g DOC m−2 year−1 for surface organic
horizons of temperate forest soils with an attenuation to 1–10 g
11.2.3  Physical Composition
DOC m−2 year−1 through soil C horizons. Hope et al. (1994) sug-
The major input of organic carbon into soils results from the depo- gested that DOC fluxes from terrestrial ecosystems should range
sition of carbon captured by photosynthesis. Deposition within from 1 to 10 g DOC m−2 year−1 based on river DOC fluxes.
the soil matrix occurs in the form of root residues and the organic Reductions in DOC flux on passage through mineral soils
materials exuded during root growth. Shoot residues are first are typically attributed to the processes of biologically mediated
deposited onto the soil surface and enter the soil via leaching, in mineralization and adsorption to soil minerals. In a review of lab-
the case of dissolved organic materials (DOM), or through some oratory incubation studies, Kalbitz and Kaiser (2008) indicated
form of mixing process that can be biotic (bioturbation), abiotic that between 5% and 93% of the DOM present in soil solutions
(opening of crack as swelling soils dry), or anthropogenic (cultiva- can be biologically mineralized. Kalbitz et al. (2003) concluded
tion). Approaches used to characterize the physical composition that the susceptibility to biological mineralization of DOM
of SOM have been based on solubility, particle size, and density. derived from forest floors, peats, and A horizons decreased with
increasing degree of decomposition of the materials from which
11.2.3.1  Dissolved Organic Materials it was derived. Aromatic compounds potentially derived from
Dissolved organic materials represents a small proportion of the lignin appeared to be the most biologically stable form of DOM
total organic material present in a soil. However, owing to its (Kalbitz et al., 2003). Other important chemical characteristics
mobility and chemical properties, it can contribute significantly of DOM that influence its reactivity, sorption behavior, and sus-
to soil processes through the provision of energy to microor- ceptibility to decomposition include its molecular size (102 to
ganisms, complexation and transport of elements within the >105 g mol−1 [Homann and Grigal, 1992]), acidity (6–15 mol C
soil profile, and dissolution of soil minerals. DOM refers to kg−1 [Herbert and Bertsch, 1995]), and degree of hydrophobicity.
the organic materials that do not settle out of the soil solution Differential adsorption of DOC onto soil minerals in two adja-
phase under the influence of gravity. It is operationally defined cent catchments with similar vegetation but different geological
as the organic matter that passes through a 0.45 μm filter. At the origins was proposed to account for the large differences in DOC
upper limit of the DOM size, the distinction between DOM and concentration in catchment drainage water (Nelson et al., 1993).
particulate forms of SOM becomes ambiguous. DOM must be DOC sorption capacity was shown to vary significantly with soil
extracted from soils to allow quantitative and qualitative analy- depth, mineralogy, and organic C content (Guggenberger and
sis. In the laboratory, DOM has been extracted in leachate col- Kaiser, 2003). Guggenberger and Kaiser (2003) found that sur-
lected at the base of undisturbed or disturbed soil columns or face-mineral horizons rich in organic carbon had little capac-
by suspension of soil in water or dilute salt solutions and collec- ity to adsorb additional DOC (1–2 g DOC m−2) compared to
tion of the <0.45 μm fraction (e.g., Dunnivant et al., 1992; Nelson iron- and aluminum-rich B horizons (often >150 g DOC m−2).
et al., 1993). In the field, DOM can be collected using a variety of Such measurements suggest that attenuation of DOC flux with
in situ devices, such as zero-tension or tension lysimeters using increasing depth is most likely dominated by mineralization in
porous cups or plates (e.g., Weihermuller et al., 2007; Sanderman the organic-rich surface horizons and then by adsorption reac-
et  al., 2008). It is important that the methods used to collect tions in iron- and/or aluminum-rich B horizons.
and isolate DOM are clearly specified and to assess the poten-
tial impacts that adsorption processes and filtering procedures 11.2.3.2  Particulate- and Mineral- Associated
could have on both the nature and amount of DOM isolated. Organic Materials
Reviews pertaining to the collection, analysis, and fate of DOM Other than the organic matter that enters as individual molecules
in soils include Herbert and Bertsch (1995), Kalbitz et al. (2000), (DOM and root exudates), organic matter enters soil as particles
Neff and Asner (2001), and Kalbitz and Kaiser (2008). that can vary significantly in size and chemical composition.
Soil Organic Matter 11-11

Particulate organic matter (POM) is composed of a variety of Additional approaches to disrupt soils and perform particle-size
molecular components (e.g., cellulose, lignin, lipids, proteins) and density fractionations have used a combination of sodium
that have different availabilities to processes of decomposition. saturation and physical dispersion methods (e.g., Skjemstad
As POM is decomposed and mixed into the mineral soil, particle et  al., 2004) or have applied a more complex combination of
size is reduced and the potential for interacting with soil miner- particle-size and density fractionation steps with increasing
als and entering the mineral-associated organic matter fraction amounts of disruption and/or increasing density fractionation
increases. A variety of names have been applied to the mineral- steps. These latter approaches have been designed to progres-
associated organic matter. In this work, we will use the abbrevia- sively isolate SOM materials from free through occluded to
tion of mSOM to denote mineral-associated SOM. Interactions various fractions associated to different extents with min-
between minerals and decomposing SOM will result in SOM/ eral components (e.g., Six et  al., 2001; John et  al., 2005; Sohi
mineral particle associations that increase in density as the et al., 2005; Swanston et al., 2005).
extent of association increases. The density will be greatest for Once isolated from bulk soil, a variety of methodologies can
individual organic molecules adsorbed onto the surfaces of soil be applied to particle-size and density fractions to quantify rates
minerals (mSOM). Density will be lowest for large POM par- of turnover and chemical composition. Acquiring Δ14C mea-
ticles with only a small mass of mineral particles bound to their surements for the organic carbon found in 2000-63, 63-2, and
surfaces. As a result, methods for extracting, quantifying, and <2 μm fractions of soils allowed Trumbore and Zheng (1996) to
characterizing the POM in soils are based on selective collection estimate turnover rates. After normalization of the Δ14C values
of materials with different particle sizes, densities, or a combina- to those measured for the 2000-63 μm fraction, both depletions
tion of both (Christensen, 1996a, 2001). and enrichment of 14C were found with decreases in particle size,
A prerequisite to quantifying the allocation of SOM to dif- indicating a respective increase or decrease in age of the carbon
ferent particle-size or density fractions is the use of disruptive with decreasing particle size. Schöning et  al. (2005) measured
techniques that separate the soil into primary particles or aggre- the percentage of modern carbon in the Ah horizons of luvi-
gations of particles. It is essential that any chemically or biologi- sols, leptosols, and phaeozems under a European beech (Fagus
cally induced alteration of the SOM or redistribution of SOM in sylvatica L.) forest and found a consistent trend of decreasing
response to soil structural degradation and exposure of mineral amounts of modern SOC with decreasing particle size.
surfaces previously inaccessible mineral surfaces be minimized. The extent of decomposition and turnover times of organic
Thus, the use of strong acids, alkalis, or chemical oxidation pre- carbon found in fine (<0.2 μm) and coarse (0.2–2.0 μm) mSOM
treatments and the exposure of disrupted suspensions to high fractions was assessed by Kahle et al. (2003) using δ13C and Δ14C
temperatures for prolonged periods should be avoided. measurements. Organic carbon found in the fine-clay fraction
Early approaches to SOM fractionation used a strong initial was more enriched with 13C and 14C, suggesting a greater extent of
ultrasonic disruption to disperse soil in an attempt to destroy microbial processing but a shorter turnover time than coarse-clay
all aggregation and obtain a suspension of primary particles organic carbon. Enrichments in 13C and a decrease in C/N ratio
after which particle-size and density fractionation procedures with decreasing particle size were also observed by Amelung et al.
were initiated (e.g., Baldock et  al., 1992). However, Golchin (1999). The general lack of consistency with respect to changes in
et al. (1994a) and Amelung and Zech (1999) showed that recov- 13C and 14C enrichment with decreasing particle size suggests that

ery of coarse POM decreased with increasing sonification time different processes of SOC stabilization operate in different soils
or energy resulting in a decrease in the physical size of POM and that relatively young and potentially labile SOC may be stabi-
and a redistribution of carbon into finer particle-size classes. lized against mineralization, particularly through the formation
Development of a two-step disruption process was demon- of mSOM via interactions with mineral surfaces.
strated to minimize these problems (Amelung and Zech, 1999). The application of density fractionation, either independently or
Free POM not associated with mineral materials was removed combined with particle-size fractionation methods, has also been
subsequent to an initial minimal disruption process in which used to isolate and characterize SOC fractions with different lia-
the integrity of soil aggregates was maintained. A more vigor- bilities. Trumbore and Zheng (1996) found that SOC in dense soil
ous second step achieving complete aggregate disruption and fractions (>2.0 g cm−3) was more depleted in 14C than that found
dispersion was then applied to release pieces of SOM that were in less-dense fractions (<2.0 g cm−3). John et al. (2005) determined
occluded within soil aggregates and allow the separation of this the δ13C of the following four density fractions isolated from a silty
material from mSOM. In its simplest form, this approach results soil that had undergone a C3/C4 plant species transition:
in the isolation of three SOM fractions:
• Free-POM <1.6 g cm−3 (fPOM<1.6)
• Light-occluded POM <1.6 g cm−3 (oPOM<1.6)
• fPOM—free pieces of organic residue found between soil
• Dense-occluded POM 1.6–2.0 g cm−3 (mSOM1.6–2.0)
particles
• Mineral-associated SOM >2 g cm−3 (mSOM>2.0)
• oPOM—occluded pieces of organic residue found within
aggregations of soil particles The δ13C data were used to calculate a mean age of the C in each
• mSOM—organic matter strongly bound to mineral par- pool. Elemental analyses showed a decreasing trend in C:N ratio in
ticle surfaces progressing from the fSOM<1.6 through to the mSOM>2.0 fractions
11-12 Properties and Processes

that were suggested to indicate an increase in the degree of degra- supported by the lack of a difference in rate of carbon respiration
dation and humification. The mean age of SOC in these fractions from free particulate and dense mineral-associated SOM over
and the values obtained for percent modern carbon (Rethemeyer the first 120 days of an incubation study (Swanston et al., 2002).
et  al., 2005) did not follow the same trend, suggesting that the Although it is challenging to apply all the methods of analysis
oldest carbon in a soil may not be the most decomposed. Such a described to a soil sample (i.e., elemental contents and ratios, iso-
situation can only arise when organic materials having a chemi- topic measurements for establishing turnover rates, and NMR to
cal composition that renders them biologically labile are stabi- define chemical composition), doing so allows a more complete
lized against biological attack within the soil matrix. picture of the nature and dynamics of SOM fractions.
A simpler density fractionation scheme using a density solu-
tion of 1.7 g cm−3 was used by Swanston et  al. (2005) to iso-
11.2.4  Biological Composition
late three fractions (fSOM<1.7, oSOM<1.7, and mSOM>1.7) from
14 C-labeled and unlabeled forest soils. The fSOM
<1.7 was found Research aimed at examining SOM in a biological context have
to be the most active fraction based on the measurement of SOC attempted to differentiate organic matter on the basis of its sus-
content, C/N ratio, and Δ14C. The oSOM<1.7 fraction appeared to ceptibility to decomposition and mineralization. Schemes devel-
be less dynamic with a minimal entry of 14C since the labeling oped to quantify the amount of biologically labile carbon have
event. Based on 13C NMR analyses (Golchin et al., 1994a; Sohi taken two general approaches: (1) quantification of the amount
et al., 2001, 2005; Poirier et al., 2005), oPOM is more degraded of carbon or nitrogen associated with the living soil microbial
compared to fPOM; however, this is not consistent with the biomass or (2) quantification of a product of a biological process
higher C/N ratios measured by Swanston et al. (2005). Such high (e.g., CO2–C mineralized over a defined time interval).
C/N ratios would be consistent with the presence of a signifi- Measurements of soil microbial biomass are assumed to be
cant amount of charcoal C, which could mask the entry of new representative of the total mass of living microorganisms present
labeled 14C into this pool based on Δ14C measurements alone. in a soil. The importance of microorganisms to soil functioning
13C NMR analyses of oPOM fractions shown in Figure 11.3 (Sohi is well recognized (Dalal, 1998; Stockdale and Brookes, 2006).
et al., 2001; Poirier et al., 2005) do indeed suggest the presence The soil microbial biomass regulates most transformations of
of charcoal-like carbon given the significant resonances in the SOM, responds rapidly to variations in climate or management,
vicinity of 130 mg kg−1. A significant movement of new labeled and has been defined as the eye of the needle through which all
14 C into the dense mineral-associated SOC fraction was also soil carbon passes (Jenkinson, 1977; Smith and Paul, 1990). Soil
measured by Swanston et al. (2005). The depleted 14C signature microbial biomass is routinely measured using a variety of direct
of this dense fraction at the near-background control site sug- and indirect techniques based on either carbon or nitrogen
gested that at the 14C-labeled site, the dense fraction consisted dynamics. Direct techniques attempt to quantify the amount
of at least two different pools of SOM: a fast-cycling pool and of carbon released to the soil after a fumigation event designed
an older more stable pool. The presence of a labile pool of car- to lyse living microbial cells. The carbon released is measured
bon within the dense mineral-associated SOM fraction was by an extraction or incubation technique (Jenkinson, 1976;

Hertfordshire Broadbalk plot 16,

Silty clay loam Continuous agriculture
(Sohi et al., 2001) (Poirier et al., 2005)

fPOM
ρ < 1.8 g cm–3

oPOM
ρ < 1.8 g cm–3

mSOM
ρ > 1.8 g cm–3

200 100 0 200 100 0

Chemical shift (ppm) Chemical shift (ppm)

FIGURE 11.3  Solid-state 13C NMR spectra obtained for fPOM, oPOM, and mSOM collected by Sohi et al. (2001) and Poirier et al. (2005) showing
strong unsaturated carbon resonances, particularly in the oPOM fraction, consistent with the presence of charcoal and other forms of thermally
altered organic matter.
Soil Organic Matter 11-13

Vance et al., 1987a, 1987b). Indirect techniques involve quanti- amount of organic carbon mineralized to carbon dioxide over a
fication of the respiration response on addition of a degradable given time period. Haynes (2005) has reviewed the use of poten-
substrate (Anderson and Domsch, 1978). Although the preced- tially mineralizable carbon and nitrogen to assess the biological
ing comments have focused on the use of carbon to quantify soil lability of SOM. In this approach, the amount of organic carbon
microbial biomass, equivalent approaches exist based on the or nutrient (typically nitrogen) that can be converted into an
measurements of nitrogen (Brookes et al., 1985), sulfur (Saggar inorganic from over a defined time interval is quantified (e.g.,
et al., 1981), and phosphorus (Brookes et al., 1982). Campbell et al., 1991; Franzluebbers et al., 1994). It is important
Once the measurements of extracted or mineralized carbon, to note that the mineralization of carbon and nitrogen are not
nitrogen, phosphorus, or sulfur are obtained, conversion factors analogous. Mineralization of organic carbon results in a gaseous
are applied to account for a lack of complete cell lysis and non- product that, for the most part, cannot be used by soil micro-
quantitative detection. For example, conversion factors of 0.45, organisms and can be quantitatively recovered in an adequate
0.45, and 0.40 have been suggested to convert measurements of experimental apparatus. Alternatively, organic nitrogen that has
extracted carbon, nitrogen, and phosphorus, respectively, into been mineralized to ammonium can be reused (immobilized)
their equivalent values within soil microbial biomass (Brookes by soil organisms, volatilized as ammonia under certain soil pH
et al., 1982, 1984, 1985; Jenkinson et al., 2004). Although these conditions, nitrified to nitrate, and subsequently denitrified or
conversion factors have been shown to be adequate for micro- leached if open incubation systems are used. Estimates of gross
organisms in cultures, they may vary across the diverse com- nitrogen mineralization are required to obtain data analogous
munity of microorganisms found in soils and between different to carbon mineralization (Bengtsson et al., 2003; Murphy et al.,
soils. Furthermore, the calculation of the size of the microbial 2003; Flavel and Murphy, 2006).
biomass from CO2 production requires a reliable estimate of the Mineralization of carbon and nutrients results from a com-
proportion of C that is assimilated and retained by the cell, that plex set of biochemical processes conducted by a wide range of
is, the microbial efficiency. This microbial efficiency, is not easily organisms and thus provides a measure of soil functional capac-
quantified, differs for different species within the soil microbial ity. Organic C mineralization is often called “soil respiration,”
community (Anderson and Domsch, 1973) and varies on the “basal respiration,” or “microbial respiration.” The amount or
basis of soil properties (Schimel, 1988) and the quality of the rate of C mineralization measured over periods from a few days
decomposing residue (Hart et al., 1994). to a few weeks is commonly used as an indicator of biological
Carbon associated with the soil microbial biomass can activity, whereas the total amount of CO2–C released on a lon-
account for 0.3%–7% of the total SOC (Wardle, 1992). Due to ger time frame (>3 months) is considered to provide information
its short turnover time of <1 year (Jenkinson and Rayner, 1977; about the fraction of SOC that is readily available to decomposer
Jenkinson and Ladd, 1981; Ladd et al., 1981; Jenkinson and Parry, organisms. Mineralized C can be expressed either per unit mass
1989; Wardle, 1992), the carbon associated with soil microbial of soil (mg CO2–C g−1 soil) or as a proportion of the original SOC
biomass is considered to be a component of the active or labile present (mg CO2–C g−1 SOC). When expressed per unit mass of
pool of SOM. Measurements of soil microbial biomass are con- soil, information regarding the size of the mineralizable C frac-
sidered to provide a sensitive indicator of potential direction and tion is obtained; whereas, when expressed per unit mass of SOC,
relative magnitude of management-induced changes in SOM an indication of the degradability of the organic carbon present
(Powlson and Jenkinson, 1976). However, the high spatial and in a soil is obtained.
temporal variability in the measurements of the soil microbial Although measurements of mineralizable nitrogen require
biomass and its dependence on soil water content, temperature, careful interpretation, the measure of net nitrogen mineraliza-
and substrate availability in the field will limit the usefulness tion (change in inorganic nitrogen status through time) can pro-
of single point in time measures as a robust indictor of changes vide a measure of the contribution that decomposition processes
in SOC status. This was shown in an assessment of several can make to the supply of plant-available N. Mineralizable soil
Australian field trials, which indicated that very high numbers organic N (SON) is composed of various organic substrates,
of field replicates (up to 93) were needed to significantly detect including microbial biomass, residues of recent crops (mainly
a 20% difference in soil microbial biomass carbon from control POM), and humus (HUM). The mineralizable SON can be mea-
treatments (Broos et al., 2007). sured as potentially mineralizable N using an aerobic incuba-
There is no doubt that measures of soil microbial biomass pro- tion under optimum moisture and temperature conditions
vide an assessment of the potential rate of soil biological processes. (Franzluebbers et  al., 1994; Chan et  al., 2002) or under field
However, such measures may or may not be related to actual bio- conditions (Dalal et  al., 2005) using the method developed by
logical process rates. Strong relationships will not exist where only Raison et  al. (1987). Attempts to correlate mineralizable SON
a certain component of the entire microbial community involved with measures of total SON or SOC have not been very success-
in the process being quantified or where all individuals capable of ful. It is suspected that one of the major reasons for this lack of
contributing are doing so at different rates. success is related to differences in the allocation of SON and SOC
Quantification of process rates provides an alternative to to different forms of SOM, the variability of C:N ratio of these
define the functional capability a soil microbial population. An materials and the impact this would have on the ­mineralization/
example of quantifying a process rate is the measurement of the immobilization balance.
11-14 Properties and Processes

11.2.5  Defining Biologically Relevant Soil other elements in an organic material to create new biochemicals
Organic Matter Fractions required for maintenance and growth of the decomposer com-
munity. As some of the assimilated carbon and nutrients may
Variability in elemental, chemical, physical, and biological com- be excreted in an organic form as metabolic waste products, net
position provides the different components of SOM with an abil- assimilation should be used to refer to the amount of carbon and
ity to contribute to a range of soil properties and processes (see nutrients taken up and retained within the decomposer commu-
Section 11.4). This variability also leads to differences in rates of nity. Additionally, since organic materials in soils are acted on
turnover as demonstrated using 14C measurements (e.g., Ladd by extracellular enzymes, it is possible that substrate alteration
et al., 1981; Anderson and Paul, 1984; Swanston et al., 2005). In can occur without subsequent assimilation or mineralization.
the context of SOM turnover studies, one objective of fractionat- Possible examples of this include the adsorption of products
ing SOM is to quantify the allocation of SOM to materials that of extracellular enzyme activity on soil mineral surfaces or the
are differentially available to decomposition. In this section, a leaching of these products through the soil profile before they
conceptual model of SOM decomposition will be presented and can be used. In both instances, the original organic material
used to identify biologically relevant SOM fractions that can be is altered but not accompanied by either a mineralization or
quantified through measurement. assimilation. In the context of these definitions, decomposition
Prior to the presentation of the model, decomposition and is taken to represent the total of the individual processes of min-
its component processes will be defined to ensure no ambi- eralization, assimilation, and alteration.
guity exists pertaining to the processes being referred to. In the decomposition model (Figure 11.4), all processes occur
Decomposition is used to define the alteration of the original in the aqueous phase of the soil and the behavior of simple
form of an organic material. Mineralization is used to define and complex substrates is differentiated. Simple substrates are
the conversion of an organic form of an element into an inor- defined as soluble molecules that can cross cell membranes
ganic from (e.g., organic carbon to CO2 or organic N to NH3). without further alteration. Once inside a cell, simple substrates
Mineralization of carbon and nutrients is thought to dominantly can be mineralized, assimilated, or transformed into products
occur within cells in response to respiration and other meta- of metabolic activity that are excreted back into the soil solution.
bolic processes. The extent to which mineralization, particularly Excreted metabolic products may be further transformed in the
nutrient mineralization, can occur external to cells remains soil solution and/or reused by individuals within the decom-
unquantified. However, if mineralization external to the cell poser community. Complex substrates consist of polymeric or
is a dominant process, then the concept of ecological stoichi- multicomponent mixtures that are not soluble and cannot pass
ometry would be flawed and constraining carbon and nutrient through a cell membrane in their original state.
cycling simulation models with carbon to nutrient ratios would Additional processes are required for decomposer organisms
be unsuccessful. Assimilation is defined as the use of carbon and to use complex substrates including excretion of extracellular

Enzymes find Extracellular

target molecules enzymes
and react released
Complex organic substrates

Decomposer community

Metabolic
Soil products Soil
particle particle

Simple
substrates

Products of
Uptake of enzyme
enzyme activity
products and
released to soil
simple substrates

Water filed soil pore

FIGURE 11.4  Schematic model of the decomposition of organic materials in soil. Substrates may exist as simple soluble molecules or in par-
ticulate form requiring enzymes to liberate molecules capable of passing cell membranes. Products of metabolic activity may or may not serve as
subsequent sources of either energy or nutrients.
Soil Organic Matter 11-15

enzymes, diffusion of the enzymes to their target sites, release refers to processes that affect the rate of decomposition but not
of the products of enzyme activity, diffusion of the products whether a given molecule is decomposable. Biological capacity is
back to the decomposers, and uptake of the products. For both defined by a series of factors governing the rate of biological pro-
simple and complex substrates, diffusion of soluble materials cesses (e.g., soil temperature and water content) and the duration
is required, and thus, the relative position of the substrate and of exposure to favorable conditions.
the organism is important. Minimizing the path lengths of dif- Combining the model of decomposition processes (Figure
fusion of both enzymes and products will enhance the rates of 11.4) with the concepts of biological stability (Figure 11.5) pro-
substrate decomposition and assimilation. Although each of the vides a means to identify biologically relevant fractions of SOM
various organic components identified in Figure 11.4 (extracel- that decompose at different rates. DOM contains a variety of
lular enzymes, products of enzyme activity, simple substrates, molecular structures with different chemical recalcitrance
and metabolic products) is grouped together in the figure, this that are free to diffuse throughout the soil solution. Given the
is only to illustrate the components involved in the process of requirement for all substrates to pass through an aqueous phase
decomposition. In reality, all these components will diffuse prior to uptake and utilization by the soil decomposer com-
throughout the soil solution. munity, DOM is likely to be the best indicator of the instanta-
Baldock (2007) indicated that two types of controls oper- neous availability of organic material at any given point in time.
ate to determine the biological stability of organic materials However, quantitative estimates of DOM content are unlikely to
in soils (Figure 11.5). Biological capability controls whether or provide a good indication of the longer-term biological availabil-
not a particular form of organic matter can decompose, while ity of SOM.
biological capacity controls the rate at which decomposition One of the most important forms of SOM, from the point
will proceed. Controls over the biological capability were sug- of view of provision of a longer-term supply of energy to soil
gested to include three factors: chemical recalcitrance, decom- organisms, is the POM fraction with its high content of more
poser capability, and protection by the soil matrix. Chemical easily degradable material (e.g., cellulose). POM may or may
recalcitrance describes the type and arrangement of atoms and not provide nutrients depending on its elemental ratios. POM
bonds within an organic substrate. Some organic material in soil with high C:nutrient ratios (e.g., C/N ratio >40) will tend to
offers little chemical recalcitrance to decomposition (e.g., cel- immobilize nutrients as its carbon is mineralized. This may
lulose and proteins) while others contain components that are reduce the availability of nutrients to plants, but also enhance
highly resistant at least on a timescale of decades (e.g., charcoal). nutrient retention within surface soil layers by limiting losses
Decomposer capability refers to the presence of the appropri- due to leaching. The mSOM fraction tends to have a chemical
ate DNA sequences required to construct the enzymes needed composition more indicative of decomposed materials [lower
to attack and decompose the molecular components within the C:nutrient ratios and higher ratio of alkyl:O-alkyl carbon
organic materials present. The third factor is protection by the (Baldock et al., 1997a)]. When considered in conjunction with
soil matrix, which describes whether a molecule is in a position its high level of interaction with mineral surfaces, the mSOM
in the soil where it is accessible to enzymes. Biological capacity fraction is more resistant to decomposition than the POM frac-
tion. The low C:nutrient ratios of mSOM suggest that it can
Biological capability contribute significantly to the provision of nutrients to plants
and decomposer organisms. An additional fraction of SOM
Biological that is important to consider and monitor is charcoal or black
stability of a = f Biochemical Decomposer Protection by carbon. This material has been found to account for up to 60%
, ,
particular form recalcitrance capability soil matrix
of the carbon in a soil (Skjemstad et al., 1996, 1998, 1999, 2002;
of SOM
Schmidt et  al., 1999; Skjemstad and Taylor, 1999). Although
Rate Duration of a fraction of newly created charcoal may be decomposable
,
modifiers exposure
× (Hamer et al., 2004; Marschner et al., 2008), a high recalcitrance
of charcoal C to biological mineralization in laboratory-based
Biological capacity incubation has also been demonstrated (Baldock and Smernik,
2002). Long-residence times measured for charcoal in soil also
FIGURE 11.5  Factors important to defining the biological stability suggest that a significant proportion is resistant to decomposi-
of organic materials in soil. Factors describing biological capability tion (Pressenda et al., 1996; Skjemstad et al., 1998; Swift, 2001;
define whether a particular form of SOM can be decomposed or not. Krull et al., 2003, 2006).
Factors describing biological capacity define the rate at which decom-
Given the more recalcitrant behavior of charcoal carbon than
position occurs rather than whether it will or will not occur. Rate modi-
the other forms of soil carbon, it is important to be able to selec-
fiers include properties such as temperature and water content, which
need to be combined with the duration of exposure to favorable con- tively quantify the amount of charcoal carbon. In Figure 11.6, the
ditions to define the biological capacity. (Modified from Baldock, J.A. impact that the presence of increasing proportions of charcoal
2007. Composition and cycling of organic carbon in soil, p. 1–35. In P. carbon can have on SOC dynamics is shown using a modeling
Marschner and Z. Rengel (eds.) Soil biology. Vol. 10. Nutrient cycling in exercise completed with a modified RothC soil carbon model. In
terrestrial ecosystems. Springer-Verlag, Berlin, Germany.) this modified model, the original resistant plant material (RPM)
11-16 Properties and Processes

0% Charcoal 10% Charcoal 25% Charcoal 50% Charcoal

140 140 140 140

Amount of soil organic carbon

(Mg C/ha for 0–30 cm layer)
120 120 120 120

100 100 100 100

80 80 80 80

60 60 60 60

40 40 40 40

20 20 20 20

0 0 0 0
0 25 50 0 25 50 0 25 50 0 25 50
Years since start of simulation

TOC RPM HUM IOM

Proportion of SOC allocated to charcoal

0.00 0.10 0.25 0.50
Total organic carbon 55.3 62.6 73.5 91.6
Non-charcoal organic carbon 55.3 49.8 41.5 27.7

FIGURE 11.6  Changes in total organic carbon (TOC), 2.0–0.053 mm POC, carbon associated with the <0.053 mm fraction (HUM), and charcoal
carbon (Char-C) estimated from the RothC soil carbon model with different initial contents of charcoal carbon. For this modeling exercise, the
total organic carbon at the start of the simulation was kept constant, the fraction of noncharcoal carbon allocated to the POC and HUM frac-
tions was kept constant, and carbon inputs over the simulation period were set to zero. The DPM and two biomass pools in the RothC model were
included in the modeling exercise but are omitted from the figure. The 1970–2005 average climate data for Beverly, WA, Australia were used. The
table at the bottom of the figure gives the final values obtained after 50 years of simulation for total organic carbon and the noncharcoal organic
carbon (POC + HUM) in units of Mg C ha−1 for the 0–30 cm soil layer.

and HUM fractions are equated to the POM and mSOM frac- potential broadscale application of quantifying the implications
tions described above. For all four modeling scenarios, the same of land use and land-use change on SOM cycling. Baldock and
starting level of SOC was used (127 Mg C ha−1), and the alloca- Skjemstad (1999) proposed a three-component fractionation
tion of carbon to each of the noncharcoal fractions was fixed at scheme to identify measurable SOM fractions for soil samples
a given percentage of the total noncharcoal C components (27% sieved to <2 mm: POC (organic carbon associated with 2000-
for POC and 69% for mSOM). Over the 50-year period, inputs 53 μm particles), HUM (organic carbon associated with <53 μm
of carbon were set to 0. With increasing initial allocation of SOC particles), and ROC (resistant organic carbon associated with
to the charcoal fraction, the decline in TOC over the simula- <53 μm particles after removal of nonresistant materials with
tion period was reduced. However, when the dynamics of the UV photo-oxidation and correction with 13C NMR analyses).
POC and mSOM fractions are examined, despite there being Recently, modifications have been made to the Baldock and
more total carbon where charcoal accounted for 50% of the ini- Skjemstad (1999) fractionation scheme to cover all forms of
tial SOC, the amount of noncharcoal C remaining after 50 years SOM at a given location and to account for recent analyses that
was largest in the soil with no charcoal. If soil productivity was have indicated the presence of significant quantities of charcoal
related more to the amount of mSOM carbon than charcoal car- in the POM fraction (Figure 11.7).
bon present, despite the greater loss of carbon from the soil with
no charcoal, a higher level of productivity would be retained in
11.2.6  Consistency between Biologically
this soil due to the higher amounts of mSOM maintained.
Relevant Soil Organic Matter
As a result of the preceding discussion, selective quantifica-
Fractions and Pools of Carbon
tion of biologically relevant fractions of SOM requires an allo-
in Simulation Models
cation of SOM across POM, mSOM, and charcoal fractions for
longer-term studies (weeks to years) and an additional inclu- Simulation models of SOC cycling (e.g., Rothamsted [Jenkinson
sion of DOM for short-term studies (hours to days). Although et al., 1987], Century [Parton et al., 1987], and APSIM [McCown
many approaches varying in number of fractions isolated and et al., 1996]) are often based on conceptual pools of carbon that
complexity of the fractionation process exist, it is suggested that are not measured directly. The construct of most SOC models
the most simple fractionation system capable of allocating SOM is similar and includes fractions of SOC with a rapid turnover
to the POM, mSOM, charcoal fractions, and possibly DOM, (annual), moderate turnover (decadal), and slow turnover (mil-
depending on the application, would be most practical for the lennial) as well as a passive or inert component. It has been
Soil Organic Matter 11-17

Organic carbon present at a sampling site

Organic Organic carbon in plant

Organic carbon in
carbon in residues on the soil surface
the soil
vegetation SPR-C

Pass through 2 mm sieve

>2 mm fraction <2 mm fraction
Buried plant residue C SOC fractions <2 mm
BPR-C SOC

Disperse soil with SHMP and pass through a 53 μm sieve

53–2000 μm fraction <53 μm fraction

Particulate organic C >53 μm including Humus organic C including <53 μm
charcoal (ROCPOC) if present charcoal (ROCHUM) if present

Quantify and subtract Quantify and subtract

ROCPOC as defined by ROCHUM as defined by
13C NMR 13C NMR

Particulate organic carbon ROCPOC + ROCHUM Humus carbon

(53–2000 μm) POC (<2 mm) ROC (<53 μm) HUM

FIGURE 11.7  Schematic presentation of the proposed methodology for defining the allocation of total SOC to its ecologically significant compo-
nent fractions. SPR-C is the organic carbon associated with plant residues on the soil surface collected on an area basis. BPR-C is the organic carbon
in buried plant residues having a size >2 mm. SOC is the total amount of organic carbon found in the <2 mm fraction of the soil. POC is the organic
carbon found in the noncharcoal component of particles 53–2000 μm in size. HUM is the organic carbon found in the noncharcoal component of
particles <53 μm. ROC is the resistant organic carbon obtained by adding together the charcoal C found in particles <2 mm (the sum of charcoal C
found in the 53–2000 μm and the <53 μm fractions). SHMP is sodium hexametaphosphate.

recognized that developing a capability to replace these con- could be used to replace the RPM, HUM, and inert organic
ceptual pools of SOC with measurable pools would offer several matter (IOM) pools of the RothC model, respectively. This was
advantages: (1) internal verification of appropriate allocations an important step forward in simulating SOC dynamics and
of SOC to pools, (2) greater mechanistic understanding of the demonstrated the potential for “modeling the measurable”
implication of management and environment on the components (Christensen, 1996b; Magid et al., 1996; Baldock, 2007).
of SOC most affected, and (3) improved confidence in simulation It must be noted that the soil microbial biomass (BIOf and
outcomes. A suitable fractionation procedure should be capable BIOs in the RothC model) and decomposable plant materials
of isolating and quantifying the allocation of SOC to pools that (DPM in the RothC model) were not included in the fraction-
differ significantly in their biological availability (Baldock, 2007). ation scheme described by Baldock and Skjemstad (1999) or used
Several methods have been proposed to link measurable frac- in the RothC calibration by Skjemstad et  al. (2004). The main
tions of SOC to the conceptual pools contained within models reasons for this were as follows:
using density fractionation techniques (Christensen, 1996b;
Poirier et  al., 2005; Sohi et  al., 2005). However, the biological 1. Difficulties associated with quantitatively separating the
availability of the carbon in each fraction of these studies was microbial biomass from the other forms of SOC
never measured, and no attempt was made to substitute the mea- 2. The questionable link between measures of microbial bio-
surable pools of SOC into a working carbon simulation model to mass carbon and rates of mineralization of SOC
demonstrate the utility of this proposal. Skjemstad et al. (2004) 3. The contributions made by the DPM, BIOf, and BIOs
showed that the pool structure of the RothC model could be fractions to the total SOC are small and within the errors
approximated using a three-component fractionation scheme associated with measurement of the other larger fractions
as described by Baldock and Skjemstad (1999). Skjemstad et al. 4. These fractions equilibrate quickly in SOC simulation
(2004) demonstrated that the POC, HUM, and ROC fractions models
11-18 Properties and Processes

11.3  Quantifying Soil Organic Matter soil and its fractions), requires the use of expensive analytical
instrumentation (e.g., a 13C NMR spectrometer and a UV photo-
Content and Allocation oxidizer system), and involves the use of hazardous chemicals
to Fractions (e.g., HF). It would therefore be unlikely that this SOM fraction-
ation process would move beyond a research implementation
Soil organic matter content, as indicated in Section 11.2, is typi-
and become a routine measure available to land managers inter-
cally quantified by measuring the content of organic carbon.
ested in understanding the impact of management practices.
Initially, measurements of SOM or SOC were completed to inves-
Provision of a more cost-effective and rapid means of quanti-
tigate pedogenic processes and, given its diverse and important
fying SOC content and its allocation to component fractions is
functions in soils (Section 11.1), to provide a measure of soil
required. The development of such a capability would also be
productivity. However, being able to accurately define the con-
very useful to support the carbon cycling work and scenario
tent of organic carbon in soil has become important because of
predictions by providing appropriate data for initializing soil
the potential for soils to sequester atmospheric CO2–C (Section
carbon models.
11.1). An additional requirement to move beyond the measure-
Diffuse reflectance mid-infrared spectroscopy (MIR) offers
ments of total organic carbon content and define the allocation
a simple, rapid, and low-cost methodology that is sensitive to
of organic carbon to its ecologically significant fractions has
both mineral and organic materials present in soils. In MIR, the
emerged to support and improve predictions related to the influ-
chemical bonds associated with a variety of organic functional
ence of land use and management on soil carbon dynamics.
groups (alkyl, carbohydrate, carboxyl, amide, amine, aryl) can
be identified (Janik et al., 2007). The problem is that signals from
11.3.1  Direct Measurement of Soil Organic these components are often hidden within soil MIR spectra by
Content and Component Fractions signals derived from soil mineral components. The develop-
Methods to measure the content of SOC have been assembled ment of partial least squares (PLS) regression approaches and
recently by Skjemstad and Baldock (2008) and previously by their application to spectroscopic data has allowed the signals
Nelson and Sommers (1996) and include dry and wet combus- obtained throughout the entire MIR spectrum to be examined
tion methods. Total C analyses involve the complete conversion for correlation to a set of analytical values derived from tradi-
of all C (organic and inorganic) in a soil to CO2 and quantifica- tional laboratory procedures. The ability of MIR/PLS to predict
tion of the evolved CO2 by various means (e.g., infrared detec- total organic carbon was demonstrated by Janik and Skjemstad
tion, increased mass of an ascarite trap, or others). Corrections (1995) and Janik et  al. (1998). Using the PLS process detailed
for the presence of inorganic C must be performed when using by Haaland and Thomas (1988), Janik et al. (2007) applied the
total C methods to quantify SOC contents. Of the methodolo- MIR/PLS approach to the data collected for total organic car-
gies currently available, a dry combustion-automated analyzer bon content and its allocation to the POC and ROC (charcoal C)
that measures CO2 evolution with an infrared detector is the fractions. Successful calibration was achieved and used to
preferred methodology for determining SOC, provided accu- compare laboratory-derived analytical data with correspond-
rate estimates of inorganic C contents can be obtained where ing data derived from the MIR/PLS predictions (Figure 11.8).
required or samples can be pretreated to remove all inorganic C The predictive capability for total organic carbon was excellent
(Baldock and Skjemstad, 1999). and that for ROC (charcoal C) was good. Agreement between
The successful calibration of the RothC model using measur- predicted and measured values for POC was not as good but
able fractions of SOC has led to the development of the proto- remained acceptable. Given the stronger dependence of POC
col described in Figure 11.7. This methodology differs slightly on the nature of the vegetation from which it was derived, it is
from that presented by Baldock and Skjemstad (1999) in that perhaps not surprising that predictability of this fraction was
the resistant fraction (charcoal) is quantified in both the 2000- lower. With time and the development of additional calibra-
53 μm particulate and <53 μm HUM fractions rather than just tion data, it may be possible to define more specific calibrations
the HUM fraction. Once isolated and dried, the carbon content for POC derived from soils under different vegetation types.
of the various fractions (SPR-C, BPR-C, SOC, 53–2000, and The current approach defined by Janik et  al. (2007) calculates
<53 μm) is quantified using the dry combustion technique. The the allocation of carbon to the HUM fraction by difference
amounts of carbon associated with the POC, ROC, and HUM (HUM = total − particulate − resistant).
fractions are then defined after using 13C NMR to quantify the It should be recognized that the MIR/PLS process is completely
allocation of carbon to the ROC fractions in the 53–2000 and empirical and may be based as much on positive correlation with
<53 μm materials (ROCPOC and ROCHUM, respectively). MIR signals from organic materials as positive or negative sig-
nals derived from particular soil minerals. Subsequent unpub-
lished MIR/PLS work completed in the same laboratory has
11.3.2  Proximate Analyses
indicated that although the calibrations presented by Janik et al.
The SOM fractionation process described in Section 11.1 is time- (2007) provided adequate estimates of soil carbon fractions,
consuming to complete (3–6 weeks to progress a sample from improved predictions could be obtained by performing sample
start to finish depending on the contents of carbon present in the set–specific calibrations. To perform these sample set–specific
Soil Organic Matter 11-19

Total organic Particulate organic Resistant organic

carbon (mg C/g soil) carbon (mg C/g soil) carbon (mg C/g soil)
70 20 12
18
60 10
16
50 14 8
MIR predicted

MIR predicted

MIR predicted
40 12
10 6
30 8
4
20 6
4
10 2
2
0 0 0
0 10 20 30 40 50 60 70 0 5 10 15 20 0 2 4 6 8 10 12
Measured Measured Measured
n = 177 n = 141 n = 121
Range: 0.8–62.0 g C/kg Range: 0.2–16.8 g C/kg Range: 0.0–11.3 g C/kg
(a) R2 = 0.94 (b) R2 = 0.71 (c) R2 = 0.86

FIGURE 11.8  Relationship between measured and MIR/PLS predicted contents of (a) total organic carbon, (b) POC (53–2000 μm), and (c) ROC
(dominated by charcoal). (Adapted from Janik, L.J., J.O. Skjemstad, K.D. Shepherd, and L.R. Spouncer. 2007. The prediction of soil carbon fractions using
mid-infrared-partial least square analysis. Aust. J. Soil Res. 45:73–81.)

calibrations, a subset of 10%–20% of the samples were selected 11.4  Functions of Organic Matter in Soil
to span the range of predicted values, analyzed using the labora-
tory procedure and used to recalibrate the MIR/PLS estimation Despite its often minor contribution to the total mass of mineral
procedure. soils, SOM can influence a variety of soil properties, ecosystem
The MIR/PLS procedure appears to offer a robust, rapid, and functioning, and the magnitude of various obligatory ecosys-
cost-effective way to predict the total amount of organic carbon tem processes (Table 11.3). The properties influenced by SOM
in soils as well as its allocation to fractions. With further testing have been classified into three groups: biological, chemical, and
and development of calibration data sets, this methodology may physical. It should be noted that strong interactions and interde-
be able to underpin soil carbon modeling activities and provide pendencies exist between these groups. For example, the ability
useful data to land managers. of SOM to chelate multivalent cations can affect its potential to

TABLE 11.3  Properties and Functions of Organic Matter in Soil

Property Function
Biological properties
Reservoir of metabolic energy Organic matter provides the metabolic energy, which drives soil biological processes
Source of macronutrients The mineralization of SOM can significantly influence (positively or negatively) the size of the plant-available
macronutrient (N, P, and S) pools
Ecosystem resilience The buildup of significant pools of organic matter and associated nutrients can enhance the ability of an
ecosystem to recover after imposed natural or anthropogenic perturbations
Physical properties
Stabilization of soil structure Through the formation of bonds with the reactive surfaces of soil mineral particles, organic matter is capable
of binding individual particles and aggregations of soil particles into water-stable aggregates at scales ranging
from <2 μm for organic molecules through to mm for plant roots and fungal hyphae
Water retention Organic matter can directly affect water retention because of its ability to absorb up to 20 times its mass of water
and indirectly through its impact on soil structure and pore geometry
Thermal properties The dark color that SOM imparts on a soil may alter soil thermal properties
Chemical properties
CEC The high-charge characteristics of SOM enhance retention of cations (e.g., Al3+, Fe3+, Ca2+, Mg2+, NH4+, and
transition metal micronutrients)
Buffering capacity and pH effects In slightly acidic to alkaline soils, organic matter can act as a buffer and aids in the maintenance of acceptable
soil pH conditions
Chelation of metals Stable complexes formed with metals and trace elements enhance the dissolution of soil minerals, reduce losses
of soil micronutrients, reduce the potential toxicity of metals, and enhance the availability of phosphorus
Interactions with xenobiotics Organic matter can alter the biodegradability, activity, and persistence of pesticides in soils
11-20 Properties and Processes

100 through fertile grassland where primary production via photosyn-

Soluble
Particulate
thesis was 10 Mg C ha−1 year−1. Of the 3 Mg C ha−1 year−1 that was
80 added to the SOC fraction, the soil fauna were estimated to utilize
Humus
Clay content (%)

Resistant 0.3–0.45 Mg C ha−1 year−1, while the soil microbial biomass was
60
estimated to utilize 2.4 Mg C ha−1 year−1. The majority of SOM pro-
cessing is thought to be completed by the soil microbial biomass.
40
However, other activities of the soil fauna enhance the ability of soil
20 microbial decomposers to utilize organic residues added to soil.
These include (1) fragmentation of plant debris, which enhances
0 the surface area per unit weight of plant residue available to micro-
Cation Stability Energy for Provision Water bial attack and (2) distributing organic materials throughout the
exchange of soil biological of holding
capacity structure processes nutrients capacity soil matrix, which provides an avenue for greater contact between
decomposer microorganisms and substrates. Of the various SOM
FIGURE 11.9  Conceptual representation of the contribution that fractions, the POC fraction is suspected to play the biggest role in
SOM and its component fractions make to some of the soil properties the provision of metabolic energy to decomposer populations.
to which organic matter makes a positive contribution. Changes in the
width of the overall shape with changing clay content define the relative 11.4.1.2  Source of Macronutrients
contribution made by organic matter to the function defined. Within
A result of SOM decomposition is the conversion of macronutri-
each shape, the width of the various shadings defines the importance
ents (N, P, and S) locked within organic chemical structures into
of each type of organic matter to the function defined. (Adapted
from Krull, E.S., J.O. Skjemstad, and J.A. Baldock. 2005. Functions of inorganic forms, which are either immobilized and used in the
soil organic matter and effects on soil properties, p. 107. Cooperative synthesis of new tissues within soil organisms or mineralized and
Research Centre for Greenhouse Accounting, Canberra, Australia.) released into the soil mineral nutrient pool. With the exception
of intensively managed soil receiving significant fertilizer inputs,
stabilize soil structure and also its biodegradability. In addition, organic matter provides the largest pool of macronutrients in the
the effects of SOM on soil properties often involve interactions soil, with HUM being clearly the dominant fraction holding most
with the soil mineral fraction. Thus, variations in SOM function macronutrients. McGill and Cole (1981) proposed that the miner-
across different soils may not be solely a consequence of qualita- alization of C, N, P, and S followed a dichotomous system involv-
tive or quantitative variations in the soil organic component but ing both biological and biochemical mineralization. Biological
may also arise in response to changes in soil clay content. In Figure mineralization is driven by the need of decomposer organisms
11.9, an attempt has been made to conceptualize this idea using a for C as an energy source and accounts for the mineralization
series of shapes to illustrate the selective importance of SOM frac- of N- and C-bonded S. Biochemical mineralization refers to the
tions in performing specific functions. In Figure 11.9, the width of release of phosphate and sulfate from the P and S ester pool via
the overall shape and that of the SOM components are meant to enzymatic hydrolysis outside of the cell membrane. As a result and
provide an indication of the relative importance to the function in contrast to organic N, organic P and S accumulation and min-
identified at the base of the figure. As the shapes widen, the rela- eralization in soils can occur independently of C and N dynamics.
tive importance increases and vice versa. Shapes have been used
in this conceptual framework due to the absence of strong quanti- 11.4.1.2.1  Nitrogen
tative relationships linking SOM content and composition to the The soil N pool is dominated by N found in organic structures.
functions identified. The generation of quantitative relationships In soils with significant contents of K+-containing clay minerals
linking SOM content and composition to functions performed in (e.g., illite) capable of fixing NH +4 , approximately 90% of the soil
soil should form the basis for future research projects. N is contained in organic structures, 8% exists as fixed NH +4 , and
1%–3% can be found in the inorganic plant-available pool (NO3−
11.4.1  Biochemical Functions and NH +4 ). In soils with little capacity to fix NH +4 in clay miner-
als, the proportion of organic N is >97% and the inorganic frac-
11.4.1.1  Reservoir of Metabolic Energy tion is 1%–3%. On a global scale, Söderlund and Svensson (1976)
The most fundamental function of SOM is the provision of meta- estimated that the organic N fraction of soils accounted for 95%
bolic energy, which drives soil biological processes and the direct of the total soil N pool, which is equivalent to the average value
and indirect effects, which this has on other soil properties and presented by Bremner (1968).
processes. Photosynthesis fixes CO2 into glucose, which is then SON has been traditionally divided into the following five
converted into a wide range of organic compounds (e.g., cellulose, fractions based on a variety of acid hydrolysis procedures: (1)
hemicellulose, lignin, lipids, and proteins) by various enzymatic acid-insoluble N, (2) ammonia N recovered after hydrolysis, (3)
processes. The C fixed into such compounds is deposited in or on amino acid N, (4) amino sugar N, and (5) hydrolyzable uniden-
the soil during plant growth and as the plant or a portion of its tified  N. Data summarized by Stevenson (1994) for 11 studies
tissues senesce, thereby providing C substrates for soil decom- where acid hydrolysis procedures were applied to different soil
poser organisms. Oades (1989) presented an estimate of the C flow types showed that there was as much variation in the contents
Soil Organic Matter 11-21

of each form of N within similar soils as between different soil 11.4.1.2.3  Sulfur
types. The proportions of each form of organic N were 7%–44% Reviews of the cycling and chemical composition of soil organic
acid-insoluble N, 9%–37% ammonia N, 13%–50% amino acid N, S include Stevenson (1986, 1994) and Nguyen and Goh (1994).
1%–14% amino sugar N, and 4%–40% hydrolyzable unidentified Sulfur-containing organic compounds found in soils are gener-
N. Although methodological differences may account for a por- ally grouped into two pools: compounds in which the S can be
tion of the large variations noted in the composition of SON, reduced to H2S by hydroiodic acid (HI) and compounds in which
it is evident that approximately 50% of the total soil N cannot the S is directly bound to C. The HI-reducible fraction consists
be identified by acid hydrolysis procedures (acid-insoluble N + mainly of ester sulfates (C–O–S bonds) and some ester sulfa-
hydrolyzable unidentified N). mates (C–N–S bonds). The C-bonded S fraction contains amino
Initial attempts to identify the chemical composition of acid S (C–S bonds) or sulfonates (C–SO3 bonds). The ester sul-
unidentifiable organic N utilized gel filtration followed by acety- fates and sulfamates are typically associated with aliphatic side
lation and GC/MS (Schnitzer, 1985; Schnitzer and Spiteller, 1986). chains of soil organic compounds (Bettany et al., 1979), while the
Schulten et  al. (1995, 1997) used Curie-point—Py-GC/MS with C-bonded S is incorporated along with C and N into the core of
N-selective detection of the pyrolysis products. These studies sug- soil organic compounds and is generally less biologically acces-
gested that heterocyclic N compounds represented an important sible (McGill and Cole, 1981; Stewart and Cole, 1989). Organic S
component of unidentified SON (see Schulten et  al., 1997, for typically accounts for >90% of the total S found in nonsaline and
examples of the chemical structure of the heterocyclic N com- nontidal soils (Nguyen and Goh, 1994; Stevenson, 1994).
pounds). The formation of heterocyclic N compounds via non-
biological fixation of 15NH3 by humic substances (IHSS Suwannee
River fulvic acid and peat and leonardite humic acids) and by 11.4.1.3  Ecosystem Resilience
reacting 15N-labeled aniline with humic materials was noted by The resilience of an ecosystem can be defined as its capacity to
Thorn and Mikita (1992) and by Thorn et al. (1996), respectively. return to its initial state after being subjected to some form of dis-
In contrast to these results, studies utilizing solid-state 15N NMR turbance or stress (e.g., Webster et al., 1975; DeAngelis, 1980). The
spectroscopy have failed to observe substantial contributions important role played by SOM in determining the resilience of an
from heterocyclic N, and spectra tend to be dominated by signals ecosystem can be exemplified by a comparison of the contents of
arising from amides and terminal amino groups (Clinton et al., chemical energy and nutrients stored within the soil organic frac-
1995; Knicker and Lüdemann, 1995; Knicker et al., 1995). Further tions in several ecosystems. In temperate grasslands, high SOM
effort is required to address these inconsistencies and to quanti- contents result from large belowground additions of photosynthate,
tatively characterize the composition of the fraction of N, which limited leaching, and slow decomposition rates. Storage of C in such
cannot be identified by conventional acid hydrolysis procedures. ecosystems is greater in the soil than in vegetation (Szabolcs, 1994).
The large store of chemical energy and nutrients contained in SOM
11.4.1.2.2  Phosphorus offers resistance to the loss of soil fertility induced by natural or
The composition and cycling of soil organic P have been reviewed agricultural disturbance. Temperate grassland soils (e.g., mollisols)
by Stevenson (1986, 1994) and Sanyal and Datta (1991). As a result will remain agriculturally productive with limited inputs for many
of potential adsorption and inorganic precipitation reactions years, despite the mining of energy and nutrient reserves contained
capable of reducing the availability of P in soils, mineralization within SOM (Janzen, 1987; Tiessen et al., 1994). Such systems can
of organic P is important to soil fertility (Tiessen et  al., 1984; be considered resilient, at least initially, but one must question how
Beck and Sanchez, 1994). The relative importance of organic long such systems can be sustained. Tiessen et  al. (1983) showed
P as a nutrient source tends to be greater on highly weathered that rates of organic P mineralization in a grassland soil were in
soils (Duxbury et al., 1989). The principal organic P-containing excess of crop requirements over the first 60 years of agricultural
compounds in soils and their approximate proportions include production. Subsequent to the first 60 years, only the less labile, low-
inositol phosphates (2%–50%), phospholipids (1%–5%), nucleic energy-providing forms of organic matter remained, and organic P
acids (0.2%–2.5%), trace amounts of phosphoproteins, and met- mineralization rates decreased below crop demand.
abolic phosphates (Stevenson, 1994). Soil organic P accounts for In temperate forests, SOM contents are less than that of
a variable proportion of the total soil P. Halstead and McKercher temperate grasslands and more C and nutrients are stored
(1975) and Uriyo and Kesseba (1975) presented soil organic P in aboveground vegetation than in the readily available soil
values ranging from 4 to 1400 μg g−1 soil, which accounted for organic materials (Szabolcs, 1994). As a result, the impact of a
3%–90% of the total soil P. Uriyo and Kesseba (1975) derived the natural disturbance such as fire can significantly deplete eco-
relationship between organic P and organic C given in Equation system stores of energy and nutrients, and ecosystem recover-
11.8, which produces an organic C:P ratio of 115 and is consis- ies (resilience) are slow due to low residual contents of SOC and
tent with the average value of 117 proposed by Stevenson (1994): associated nutrients. Where temperate forests are cleared and
agricultural production is initiated, SOM losses must be mini-
Organic C (mg g −1 soil) mized; however, production systems that increase SOM and
nutrient reserves (e.g., crop rotations including legume pastures)
= 4.9 + 0.059 organic P (mg g −1 soil) (R2 = 0.49). (11.8) can lead to highly productive and sustainable agriculture.
11-22 Properties and Processes

In tropical forest ecosystems, the storage of energy and nutri- enhanced root growth (length or density). Da Rosa et al. (2009)
ents in vegetation dominates, and the rapid utilization of plant observed enhanced growth and K uptake by common beans
residues by decomposer organisms and cycling of nutrients when exposed to humic substances extracted from charcoal.
maintain ecosystem stability. This, when coupled with the low Vaccaro et al. (2009) noted positive effects on growth and enzy-
stores of energy and nutrients in organic matter of tropical soils, matic activity of maize seedlings when exposed to the hydro-
indicates a reduced importance of SOM in ecosystem resilience philic component or the entire soluble component extracted
(Anderson, 1995). A comparison of a temperate grassland mol- from a compost. Verlinden et al. (2009) noted an overall positive
lisol with a tropical oxisol (Tiessen et al., 1994) demonstrated the effect on dry matter yield and N uptake for a variety of plants
important contribution of SOM to the resilience of the grassland (permanent grassland, maize, potato, and spinach) due to the
soil and its reduced significance in the tropical soil. application of humic substances originating from leonardite for-
mations. Such positive effects on plant growth have been postu-
11.4.1.4  Stimulation and Inhibition of Enzyme lated to result from increased permeability of cell membranes,
Activities and Plant and Microbial Growth increased chlorophyll content, increased rates of photosynthesis
Research pertaining to the impacts of SOM on plants, microor- and respiration, enhanced protein synthesis resulting from a
ganisms, and enzyme activities has typically used humic sub- stimulation of ribonucleic acid synthesis, and enhanced enzyme
stances (e.g., humic and fulvic acids) as surrogates for SOM. The activity (Vaughan and Malcolm, 1985).
influence of humic and fulvic acids, tannins, and melanins on Addition of humic substances to soil can also influence the
the activity of various enzymes was summarized by Ladd and activity of soil microorganisms through the provision of a
Butler (1975), Müller-Wegener (1988), and Gianfreda and Bollag metabolizable source of carbon, increased nutrient supply, and
(1996). Based on earlier studies, Ladd and Butler (1975) con- enhanced permeability of cell membranes toward required
cluded that the effect of humic acids on the activity of proteolytic solutes (Valdrighi et  al., 1996). Addition of humic substances
enzymes varied and that the mechanism of humic acid–enzyme at concentrations ≤30 mg L−1 to a nutrient solution increased
interaction involved primarily the carboxyl groups of humic growth rates in microbial cultures (Visser, 1985). Humic acid
acids. Inhibition of nonproteolytic enzyme activities by humic addition was also found to stimulate in vitro growth and activity
acids has also been demonstrated (Sarkar and Bollag, 1987). of aerobic nitrifying bacteria, but not actinomycetes or filamen-
Müller-Wegener (1988) indicated that possible humic acid– tous fungi (Vallini et al., 1993, 1997; Valdrighi et al., 1995, 1996).
enzyme interactions, which could impact on enzyme activity, A greater promotion of microbial growth has been noted as
included the following: (1) a direct interaction of the humic acid the molecular weight of the added humic substances decreased
with the enzyme resulting in a modification of enzyme struc- (Garcia et al., 1991; Valdrighi et al., 1995). It has been suggested
ture or changes in the functioning of active sites, (2) interference that interactions between added humic materials and micro-
in the equilibrium of the enzyme reaction via the humic sub- bial cell surfaces (Stehlickova et  al., 2009) or humic materials
stances acting as analogue substrates, and/or (3) a reduction in and hydrophobic pollutants (Vacca et al., 2005) may be respon-
the availability of cations, which often act as cofactors required sible for enhanced rates of decomposition and mineralization.
for enzyme catalysis or structural stabilization of the protein Enhanced microbial activity due to the addition of humic sub-
molecule, by fixation on the humic acid molecule. stances is not always noted, particularly where the added humic
The influence of soil humic substances on plant growth and substances form the sole source of available carbon (Filip and
cellular activity have been reviewed (Chen and Aviad, 1990; Tesarova, 2004). Whiteley and Pettit (1994) noted a decreased
Clapp et al., 2001; Varanini and Pinton, 2001; Nardi et al., 2002) ability to decompose wheat straw in the presence of humic acid
and are generally attributed to direct (e.g., enhanced biochemi- derived from lignite, and Yasmeen et  al. (2009) observed that
cal activity of plants) and indirect (e.g., increased efficiency humic acids isolated from oil palm compost inhibited the myce-
of nutrient uptake) effects typically involve the absorption or lial growth indicating the presence of a fungicidal activity.
adsorption of humic substances and the impact of these pro-
cesses on biochemical properties at cell walls, cell membranes,
and/or in the cytoplasm. Information on the impacts of humic 11.4.2  Physical Functions
materials in field studies is scarce and often confounded with
other impacts of humic materials on soil properties (e.g., cat- 11.4.2.1  Stabilization of Soil Aggregates
ion exchange capacity [CEC], nutrient status). Favorable effects Organic matter is considered important to the maintenance of
on plants grown in defined media have included the following: the structural stability of a wide range of soil types including
(1) increased uptake of water and germination rate of seeds, (2) mollisols, alfisols, ultisols, and inceptisols. Its importance tends
enhanced growth of shoots and roots as assessed by measure- to be less in oxisols and andisols, where hydrous oxides play an
ments of length and fresh and/or dry mass, and (3) increased root important stabilizing role, and in self-mulching soils (e.g., some
elongation, number of lateral roots, and root initiation (Nardi vertisols), which contain clays with a high shrink/swell poten-
et al., 1996, 2002). Canellas et al. (2009) found that exposure of tial. In soils where organic matter is an important agent bind-
maize seedlings to solutions with 20 mg of humic acid carbon ing mineral particles together, a hierarchical arrangement of soil
per liter for 7 days significantly altered metabolic activity and aggregates exists in which aggregates break down in a stepwise
Soil Organic Matter 11-23

manner as the magnitude of an applied disruptive force increases by 0.01 kg kg−1. Increases in AWHC of 0.039 and 0.020 (m3 m−3)
(Tisdall and Oades, 1982; Oades and Waters, 1991; Oades, 1993). were obtained for the soils with 7% and 35% clay, respectively,
Golchin et al. (1997a) and others have proposed the existence of at a relative bulk density of 0.75. Application of the same equa-
three levels of aggregation: (1) the binding together of clay plates tions to a data set acquired by Wegner et al. (1989) for 80 South
into packets <20 μm, (2) the binding of clay packets into stable Australian red brown earths (alfisols) showed that the increase in
microaggregates (20–250 μm), and (3) the binding of stable AWHC induced by increasing organic C content by 0.01 kg kg−1
microaggregates into macroaggregates (>250 μm). soil could be expressed by Equation 11.10. These results indicate
The importance and nature of the organic materials associ- that the presence of additional organic matter enhances AWHC
ated with each level of aggregation varies. At the scale of packets of soils. Although the magnitude of the increase decreases with
of clays, aggregation is primarily dictated by soil mineralogical increasing clay content, building SOC content would be expected
and chemical properties important in controlling the extent of to be more difficult on a sand than on a clay soil:
dispersion and is often a function of pedological processes. The
binding together of clay packets to form microaggregates occurs θv = aψ mb , (11.9)
via a range of mechanisms. The dominant mechanism is pro-
posed to involve polysaccharide-based glues (mucilages or muci- where
gels) produced by plant roots and soil microorganisms (Ladd
a = exp(−4.15 + 0.68 lnCL + 0.42 lnOC + 0.27 lnBD),
et al., 1996). Emerson et al. (1986) presented transmission elec-
tron micrographs showing mucilage located between packets b = −0.54 + 0.11 lnCL + 0.02 lnOC + 0.10 lnBD,
of clay plates. Small microaggregates (<53 μm) held together by
humified organic matter and biologically processed materials are
Change in AWHC = −0.0012 (%clay ) + 0.055 (R2 = 0.82). (11.10)
bound together around a particulate organic core (Oades, 1984;
Elliott, 1986; Beare et al., 1994a; Golchin et al., 1994b) to produce
larger microaggregates and small macroaggregates <2000 μm. 11.4.2.3  Soil Thermal Properties
Macroaggregates >2000 μm are stabilized by the presence of The typical dark color of SOM contributes to the dark color of
roots, fungal hyphae, and larger fragments of plant residues, surface-mineral soils and can enhance soil warming and pro-
which interconnect soil aggregates via bonding to aggregate sur- mote biological processes related to temperature in cooler cli-
faces, penetration into or through aggregates, and/or physical mates (e.g., plant growth and mineralization of C and nutrients
enmeshment (Tisdall and Oades, 1982; Churchman and Foster, contained in SOM). However, the presence of litter layers or
1994; Foster, 1994). organic horizons can insulate a soil against fluctuations in air
temperature and solar heating. On several Canadian forest soils
11.4.2.2  Water Retention subject to cold winters and cool springs, average soil tempera-
Organic materials can influence soil water retention directly tures and the growth of fertilized seedlings were greater where
and indirectly. SOM can absorb and hold substantial quantities the litter layers were removed compared to where they were left
of water, up to 20 times its mass (Stevenson, 1994). This direct intact (Burgess et al., 1995). Similar effects have been observed in
effect, however, depends on the morphological structure of the a comparison of cropping systems, which leave different amounts
organic materials and will not impart any beneficial effect to the of crop residue on the surface of the mineral soil (Fortin, 1993).
soil unless it serves to enhance the ability of soil to hold water at
potentials within the plant-available range. Organic matter in the 11.4.3  Chemical Functions
form of surface residues can also influence water retention directly
by reducing evaporation and increasing the infiltration of water. 11.4.3.1  Cation Exchange Capacity
The indirect effect of SOM on water retention arises from its Organic matter contributes 25%–90% of CEC of the surface lay-
impact on soil aggregation and pore-size distribution, and thus ers of mineral soils and practically all of the CEC of peats and
on plant-available water-holding capacity, AWHC, of the soil forest litter and humus layers (Stevenson, 1994). The percent
(the difference between volumetric water content at field capac- contribution is greatest for soils with low clay content or where
ity and permanent wilting point). This effect is best exemplified the clay fraction is dominated by minerals with a low-charge
by the inclusion of SOC content as a significant parameter in density, such as kaolinite, and is lowest for soils with high con-
pedotransfer functions, which predict pore-size distribution tents of highly charged minerals, such as vermiculite or smec-
(e.g., Vereecken et al., 1989; da Silva and Kay, 1997; Kay et al., tite. Organic matter will contribute most significantly to soil
1997). Equation 11.9 presents the pedotransfer function derived CEC in sandy soils.
by da Silva and Kay (1997) to describe the relationship between The contribution of organic matter to soil CEC is pH depen-
volumetric water content, θv (m3 m−3), and matric potential, dent. At typical soil pH values (>5), the CEC of organic matter
ψ (MPa), clay content, CL (%), organic C content, OC (%), and is derived principally from carboxyl functional groups, but phe-
bulk density, BD (Mg m−3). Using this equation, Kay et al. (1997) nol, enol, and imide groups may also contribute at higher pH
calculated predicted changes in AWHC for soils ranging in clay values. Given that an increase in degree of oxidation is typically
content from 7% to 35% when organic C content was increased associated with decomposition of organic materials in soil, more
11-24 Properties and Processes

highly degraded organic materials would be expected to have a exhibiting buffering capacities of 9.8–40.8 and 0.1–5.2 cmolc kg−1
higher CEC than their less decomposed analogues. An increase (pH unit)−1, respectively. For 59 agricultural soil samples taken
in CEC was noted by Roig et al. (1988) during the degradation from the 0–15 cm layer of cultivated fields, Curtin et  al. (1996)
of manure over time. Beldin et al. (2007) measured the CEC of noted that titratable acidity could be described by Equation 11.11
light and heavy soil fractions and found a positive correlation in which the terms OC and clay represent the soil organic C and
between CEC and %C for the light fractions but not for the heavy clay contents expressed in units of kg kg−1 soil and ΔpH is the
fractions, presumably due to the high content of mineral soil reference pH (e.g., 8) minus the initial pH. Assuming the organic
constituents that contribute to CEC in the heavy fractions (e.g., C content of SOM is 58%, Equation 11.11 indicates that the
clay). The result from Beldin et al. (2007) and results obtained buffering capacity offered by organic matter was approximately
for black carbon by Liang et al. (2006) indicate that the different 34 cmolc kg−1 (pH unit)−1 and was an order of magnitude greater
forms of SOM found in soil will contribute differently to CEC than that offered by clay (34 versus 3 cmolc kg−1 [pH unit]−1). The
and that significant contributions can be made by the nonhumi- average clay/organic C ratio for the soils studied by Curtin et al.
fied components of SOM. (1996) was 7.9/1, indicating that even though most soils con-
Beldin et al. (2007) also noted that predicted whole soil CEC tained much more clay than organic C, organic C accounted for
values obtained by mathematically combining the CEC values about two-thirds of the soil buffering capacity.
measured for the light and heavy fractions on a mass basis were
much greater than those measured for the whole unfractionated Titratable acidity to pH 8
soils. The potential for carboxylic acid groups to be involved in
organomineral interactions and the complexation of cations = 0.02 + 59OCΔ pH + 3.0 clay Δ pH (R2 = 0.95). (11.11)
may reduce their ability to contribute to soil CEC. CEC mea-
surements made on organic matter fractions isolated from soils Addition of organic matter to soil may result in increases or
must therefore be treated with caution, particularly where the decreases in soil pH, depending on the influence that the addi-
potential exists to break organomineral associations and dis- tion has on the balance of the various processes that consume
place complexed cations during the fractionation process. and release protons. A detailed presentation of these soil pro-
One approach used to assess the impact of SOM on soil CEC cesses and their ability to release or consume protons is given
has involved performing CEC measurements before and after by van Breemen et al. (1983). Factors that need to be considered
organic matter removal (Tan and Dowling, 1984; Thompson include the chemical nature of the soil and that of the organic
et al., 1989; Turnpault et al., 1996). However, this approach may materials added as well as environmental properties including
result in an underestimation of the CEC of SOM since organic water content and extent of leaching. The net effect of adding
matter removal may expose inorganic CEC sites that were previ- organic matter to acidic soils is generally an increase in pH values
ously involved in organomineral interactions and not capable of (e.g., Yan et al., 1996; Pocknee and Sumner, 1997) with the main
contributing to whole soil CEC. Derivation of regression rela- processes leading to the increase being (1) a decomplexation of
tionships between CEC and SOM/carbon has also been used to metal cations, (2) mineralization of organic N, and (3) denitrifi-
define the contribution of organic materials to soil CEC (Asadu cation. Pocknee and Sumner (1997) found that on the acid Cecil
et  al., 1997; Oorts et  al., 2003; Liang et  al., 2006; Rashidi and soil, the extent of the increase in pH was controlled by the N con-
Seilsepour, 2008; Seilsepour and Rashidi, 2008; Yimer et  al., tent to basic cation content ratio. The decarboxylation of organic
2008). CEC values generated for SOM have ranged from 15 to acids has also been shown to increase the pH of acid soils (Yan
>600 cmolc kg−1 C. As a general rule, each weight percentage of et al., 1996). Under alkaline soil conditions, however, these pro-
SOC contributes approximately 3 cmolc kg−1 soil (300 cmolc kg−1 cesses would be ineffective and would contribute to a reduction
SOC) to the CEC of neutral permanent charge soils (McBride, in soil pH as a result of their influence on soil CO2 concentra-
1994) and approximately 1 cmolc kg−1 soil (100 cmolc kg−1 SOC) tions. The addition of organic matter to alkaline soils tends to
to the CEC of variable charge soils (Oades, 1989). acidify them especially under waterlogged and leaching condi-
tions (Nelson and Oades, 1997). The main processes involved in
11.4.3.2  Buffering Capacity and Soil pH the acidification of alkaline soils on addition of organic materials
The presence of weakly acidic chemical functional groups on soil include (1) mineralization of organic S and P, (2) mineralization
organic molecules that can act as conjugate acid/base pairs makes followed by nitrification of N, (3) leaching of the mineralized
SOM an effective buffer. The diversity in chemical composition of and nitrified organic N, (4) dissociation of organic ligands, and
the functional groups (e.g., carboxylic, phenolic, acidic alcoholic, (5) dissociation of CO2 during decomposition.
amine, amide, and others) provides organic matter with the abil-
ity to act as a buffer over a wide range of soil pH. James and Riha
11.4.4  Complexation of Inorganic Cations
(1986) reported buffer capacities of 18–36 and 1.5–3.5 cmolc kg−1
(pH unit)−1 for the organic and mineral horizons, respectively, The presence of various functional groups on SOM provides
of forest soils. Starr et  al. (1996) obtained a good correlation the capacity for interaction with inorganic cations. Possible
between acid buffer capacity and organic matter content for interactions can take the form of simple cation exchange reac-
29 organic and 87 mineral soil horizons (E, B, and C horizons) tions, such as that between negatively charged carboxyl groups
Soil Organic Matter 11-25

and monovalent cations, or more complex interactions where associated elements. Processes that accelerate decomposition
coordinate linkages with organic ligands are formed, such as increase the rate of loss. Additionally, losses of organic matter
occurs between amino acids and Cu2+ (Harter and Naidu, 1995; can occur through erosion or leaching. Erosion losses are rapid
Baldock and Skjemstad, 2000). The influence that the complex- and event driven and may be catastrophic in localized areas.
ation of inorganic cations by SOM has on soil properties and Losses by leaching are typically small compared to mineraliza-
processes includes the following: tion losses, but over time can lead to a significant removal or
redistribution of organic matter within the soil profile.
1. Altered solubility and degradability of associated organic
During pedogenesis, organic matter accumulation in soil goes
materials (Skyllberg and Magnusson, 1995; Christl and
through a series of development phases. In the initial phase, a
Kretzschmar, 2007; Scheel et al., 2007)
slow colonization by photosynthetic organisms occurs. A lack
2. Increased availability of insoluble mineral P through
of available nutrients places a ceiling on the amount of CO2–C
complexation of Fe3+ and Al3+ in acid soil and Ca 2+ in
that can be fixed. Low rates of carbon capture and low nutri-
calcareous soil, competition for P adsorption sites, and
ent status limit both production and decomposition of SOM.
displacement of adsorbed P (Stevenson, 1994; Cajuste
Accumulation of SOM in this phase, expressed in units of g m−2,
et al., 1996)
proceeds slowly and can be aided by interactions with soil min-
3. The release of plant nutrients through the weathering of
eral components that are capable of biologically protecting SOM
rocks and soil parent materials by the removal of struc-
against decomposition. With continued soil development, SOM
tural cations from silicate minerals (Robert and Berthelin,
content and the activity of decomposer organisms increase to a
1986; Tan, 1986)
point where a continued supply of nutrients in a plant-available
4. Enhanced availability of trace elements in the upper por-
form is reached. At this point, the rate of CO2–C capture and
tion of the soil profile as a result of upward transloca-
organic matter deposition is greater than mineralization, and
tion by plant roots and subsequent deposition on the soil
SOM accumulates at an exponential rate. With increasing SOM
surface and complexation during residue decomposition
content, the ability of the soil to protect additional organic matter
(Stevenson, 1994)
declines and an increasing proportion of added organic matter
5. Facilitated adsorption of organic materials to soil miner-
remains accessible to decomposition. As a result, the increase in
als, which aids in the generation and/or stabilization of
organic matter content through time proceeds through an
soil structure (Oades, 1984; Emerson et al., 1986)
inflection point and then begins to decrease. Once the capac-
6. Buffering of excessive concentrations of otherwise toxic
ity for biological protection offered by soil mineral components
levels of metal cations (e.g., Al3+, Cd2+, and Pb2+; Anderson,
is approached, the rate of mineralization of SOM tends toward
1995)
the rate of deposition of fresh organic residues and SOM levels
7. Pedogenic translocation of metal cations to deeper soil
approach an equilibrium value. It is important to note that this
horizons (McKeague et  al., 1986) and the formation of
biological protection rarely equates to a permanent and complete
minerals (Huang and Violante, 1986)
removal of organic C from the decomposing pool, but rather
to a reduction in its rate of decomposition, when compared to
11.5  Factors Determining the Content similar materials existing in an unprotected state (Baldock and
of Organic Matter in Soil Skjemstad, 2000). As the older protected C is slowly mineralized,
its position in the biologically protected pool is replaced with
The amount of organic matter present in a soil is defined by the younger modern organic C.
balance between the competing rates of input and loss of organic The progression of SOM content with soil development and the
matter. Rates of input are typically defined by the amount of plant magnitude of the equilibrium level of SOM will also depend on
residue added to the soil. Any practice that enhances the amount interactions, which occur between the factors of soil formation.
of carbon captured by plants and the return of organic residues to Where cold and water-saturated soil conditions persist, decom-
the soil (above- and belowground) will increase inputs. For exam- position is confined to slow anaerobic processes and organic
ple, appropriate use of fertilizers to maximize productivity will matter contents expressed in units of gram per square meter may
also maximize returns of organic residues to the soil under any continue to increase leading to the formation of organic soils.
given management regime. Other factors such as the availability In sandy soils, the extent of biological protection offered by the
of water may place an upper limit on input rates by constraining soil mineral component will be lower than that offered by clay-
potential plant productivity and thereby placing an upper limit rich soils and large differences in SOM content can develop.
on input rates. Where organic wastes are available (e.g., munici- Therefore, with the exceptions of peatland and wetland soils,
pal green waste, residual materials derived from animal produc- which have been estimated to accumulate 0.1–0.3 Pg C year−1
tion, and biosolids), their application to soil can increase rates of globally (Post et al., 1990), organic matter levels in soil do not
input beyond that defined by environmental, soil, and manage- increase indefinitely but rather tend to equilibrium values dic-
ment factors that normally limit plant production. tated by the soil-forming factors of climate, biota (vegetation and
Losses of organic matter from soil result from decomposi- soil organisms), parent material, and topography (Baldock and
tion and subsequent mineralization of organic carbon and its Skjemstad, 1999; Six et al., 2002).
11-26 Properties and Processes

An additional factor that must be considered in an examina- correlated with precipitation and, at a given level of precipita-
tion of factors influencing organic matter contents in soils used tion, negatively correlated with temperature. Similar results
for agriculture and forestry is land management practice. Land were observed by Guo et al. (2006) in an analysis of factors con-
management can induce rapid and drastic changes to equilib- trolling SOC in the United States using maps generated from
rium contents of SOM attained under natural undisturbed the State Soil Geographical database (STATSGO). Guo et  al.
conditions and completely override the influence of soil-forming (2006) found that SOC content increased as the mean annual
factors. For example, the conversion of native ecosystems to precipitation (MAP) increased up to 700–850 m and then fluctu-
agriculture often, but not always (Skjemstad and Spouncer, ated as the MAP increased further. When other variables were
2003), results in a net loss of SOM (Mann, 1986; Davidson and highly restricted, there was a clear decline in SOC with increas-
Ackerman, 1993; Paustian et al., 1997b). ing temperature. In the Great Plains of North America, precipi-
When measurements of SOM are conducted on perturbed tation controls NPP and temperature is considered to exert its
systems, it must be acknowledged that they may still be in the strongest control over rates of SOC mineralization (Parton et al.,
process of attaining a new equilibrium content. When combined 1987; Sala et al., 1988; Burke et al., 1989). Ladd et al. (1985) com-
with the potential impacts that variations in climatic conditions pared the mean loss of 14C-labeled plant residues from four soils
can have, it can be difficult to detect the true direction of SOM in South Australia with that obtained by Jenkinson and Ayanaba
change induced by alterations to land use at timescales <10 years. (1977) for soils in England and Nigeria and observed a doubling
In fact, more than 50 years may be required to reestablish equi- of the rate of substrate C mineralization for an 8°C –9°C increase
librium conditions representative of a new land use (Baldock and in mean annual temperature. An influence of temperature on
Skjemstad, 1999). Combining this observation with early results decomposition can also be inferred from 14C content of SOC,
presented by Jenny (1930) suggests that the relative importance which showed a latitudinal gradient in the mean residence time
of the soil-forming factors on SOM content can be viewed as of SOC (Bird et al., 1996).
management > climate > biota (vegetation and soil organisms) > The observed trend of decreasing SOC content with increas-
topography = parent material (Baldock and Skjemstad, 1999). ing temperature implies that the relative temperature sensitiv-
An independent evaluation of the influence of any single factor ity of decomposition is greater than that of NPP. Because of the
on SOM contents is difficult because of the requirement that all strong interactions between temperature, water availability, and
other factors remain constant. Variations in the soil-forming fac- substrate quantity, it is difficult to assess the temperature depen-
tors experienced on a landscape scale and the interdependence dence of decomposition without confounding effects. In a com-
of these factors contribute to the large variability noted for SOM pilation of data extracted from controlled incubation studies
contents, even within localized areas. When trying to assess where water limitations were avoided and a common substrate
changes of SOM content in a soil, it must be noted that rates of was used at all temperatures, Kirschbaum (1995) showed that
change in SOM (typically less than 0.5 Mg C ha−1 year−1) are quite the Q10 value (rate of change of a process with a 10°C temper-
small compared to the large amounts of SOM often present (as ature increase) of C mineralization from soil was greater than
high as 100 Mg C ha−1, or more, in the top 60 cm soil layer; Ellert that for NPP developed by Lieth (1973), especially at tempera-
et al., 2008). Thus, changes in SOM can only be reliably measured tures <15°C. Increases in temperature, particularly when start-
over a period of years or even decades (Post et al., 2001). Since ing from temperatures <15°C, will enhance decomposition more
the distribution of SOM in space is inherently variable, tempo- than NPP. The greater sensitivity of carbon mineralization to cli-
ral changes (e.g., attributable to management practices, envi- matic variation was also observed at a regional (Goulden et al.,
ronmental shifts, successional change) must be distinguishable 1998; Saleska et al., 2003) and global scale (Hicke et al., 2002).
from spatial ones (e.g., attributable to landform, long-term geo- Hicke et al. (2002) showed that the variability in NPP was con-
morphic processes, nonuniform management) to assess whether siderably less than the variability in growth rate of atmospheric
SOM is either increasing or decreasing (Ellert et al., 2008). CO2 using inverse modeling, suggesting that the cause of the
Computer simulation models of SOM dynamics, as defined year-to-year variability in carbon fluxes is largely from varying
through changes in SOC (Jenkinson et  al., 1987; Parton et  al., rates of respiration rather than photosynthesis.
1987; McCown et  al., 1996), can be used to provide valuable Climate has also been shown to affect the chemical structure
information pertaining to the interaction of soil-forming factors of SOC. Using Py-GC to characterize the chemical structure of
on SOC levels and thus, ecosystem functioning, provided the SOC in a climosequence of nine New Zealand soils, Bracewell
models are structured appropriately. However, it is essential that et al. (1976) observed significant correlations between changes in
field data are available to validate predictions (Burke et al., 1989). the intensity of peaks in the chromatograms and MAP and tem-
perature. By including both temperature and precipitation in a
regression analysis, the resultant regression line explained 90% of
11.5.1  Climate
the variation in chromatogram peak intensities. Amelung et  al.
Climate impacts SOM content primarily through the effects (1997) used 10 grassland samples originating from different cli-
of temperature, moisture, and solar radiation on the array and matic zones of the North American Great Plains to investigate
growth rate of plant species and the rate of SOC mineralization. the impacts of mean annual temperature and precipitation on
Post et al. (1982) found that the amount of SOC was positively the chemical structure of SOC using a combination of chemical
Soil Organic Matter 11-27

methods and 13C NMR. MAP was capable of accounting for only The degree and amount of protection offered by each mecha-
10% of the variation in alkaline CuO oxidizable lignin. Higher nism depends on the chemical and physical properties of the
precipitation tended to favor an accumulation of polysaccharide mineral matrix and the morphology and chemical structure of
carbon; however, at a given MAP, polysaccharide carbon tended the organic matter. Furthermore, as with other aspects of SOC
to decrease with increasing temperature. Amelung et  al. (1997) dynamics, strong interactions can exist between these charac-
suggested that the increased content of polysaccharide carbon in teristics (e.g., the presence and type of multivalent cations will
more humid conditions may have resulted from (1) a positive feed- undoubtedly be related to the chemical nature of the minerals
back mechanism in which increased plant production enhanced present). Finally, each mineral matrix will have its unique and
microbial activity and soil structural conditions, thereby offer- finite capacity to protect organic matter. In the extreme case
ing the potential for protecting microbial polysaccharides within where mineral protection mechanisms are not present, such as
aggregates, and/or (2) an enhanced activity of earthworms that in well-aerated peat or forest litter layers, decomposability will
elevated polysaccharide content relative to the surrounding soils be controlled by the recalcitrance offered by the chemical struc-
(Guggenberger et  al., 1995) and offered organic carbon some ture of the SOM itself.
physical protection against mineralization (Lavelle and Martin,
1992). Accompanying the decrease in polysaccharide carbon 11.5.2.1  Chemical Nature of the Soil Mineral Fraction
noted with increasing temperature, Amelung et al. (1997) further An analysis of different soil types indicates that soils with high
noted an increase in aliphatic carbon content. This accumula- contents of calcium carbonate (CaCO3) and amorphous Al and
tion of alkyl carbon at high temperature may be explained by (1) Fe tend to have higher organic C contents compared to other soil
enhanced mineralization of carbohydrates and selective preserva- types (Spain et  al., 1983; Oades, 1988; Sombroek et  al., 1993).
tion of plant or microbially derived alkyl structures by adsorption In a study of the influence of soil properties on SOC genesis,
onto clay particles (Baldock et al., 1989, 1992) and/or (2) higher Duchaufour (1976) suggested that the presence of calcium car-
inputs of plant-derived alkyl carbon in plant residues due to the bonate in a rendzina could protect both particulate organic and
presence of thicker cuticles on plants growing in warmer climates. HUM carbon. Thin carbonate coatings visible under magnifica-
In a study using a soil sequence along an elevational gradi- tion and a precipitation of organic molecules induced by Ca 2+
ent ranging from subtropical to subalpine climate zones in the complexation were implicated in the protection of POM and
Etna region (Sicily, southern Italy), Egli et al. (2007) examined HUM, respectively, and helped to explain the observed imped-
changes in SOC and C:N ratios. Egli et al. (2007) showed that ance of mineralization. Protection of SOC in high-base-status
the concentration of SOC in the topsoil, the stocks of SOC in soil soils with less reactive or low contents of calcium carbonate
profile and the nature of the SOC were strongly related to eleva- results predominantly from the formation of Ca-organic link-
tion and, thus climate and vegetation. However, the C:N ratio ages. In such soils, the initial decomposition of plant residues
in the topsoil was more defined by the vegetation type. A better is rapid, but the subsequent utilization of initial decomposition
protection of SOC at lower altitude was found and suggested to products is slow leading to higher SOC contents, lower C:N
be an effect of the specific climate conditions with more pro- ratios, and longer retention times. Soils with high base status
nounced change in periods of humidity alternating with periods typically have higher clay contents, are more fertile, and have
of drought and resultant fire activity. Repeated bushfires had greater annual vegetative inputs than similar low-base-status
played a significant role in the soil formation as indicated by the soils. Establishment of causative relationships between base
presence of aromatic compounds and charcoal (Egli et al., 2007). status and SOC contents must therefore be examined carefully
because of the potential confounding effects of increased vegeta-
tive inputs and protection mechanisms involving clay minerals.
11.5.2  Soil Mineral Parent Materials Soils derived from volcanic ash (andisols) are typically char-
and Products of Pedogenesis acterized by large accumulations of SOC, high C:N ratios, and
high allophane contents. The formation of Al-organic complexes
The mineral phase of soils can exert a strong influence on SOM
is considered to be important to the biological protection of
contents as a result of mechanisms capable of protecting organic
organic C in andisols. Boudot et al. (1986, 1988) obtained a sig-
materials against biological attack (Baldock and Skjemstad,
nificant correlation between the amount of native C mineralized
2000). Each soil has a given capacity to protect SOC dictated by
from 10 French highland soils and the contents of amorphous
the following:
Al and allophane, without observing significant correlations
1. The chemical nature of soil minerals with clay content, exchangeable Al3+, or crystalline iron oxides.
2. The presence of multivalent cations and their ability to Decreased organic C mineralization rates from 14C-labeled
form complexes with organic molecules in soils organic substrates in allophanic soils and nonallophanic soils
3. The adsorptive capacity of soil minerals for organic mate- amended with allophane, relative to that noted in unamended
rials as governed by particle size and surface area nonallophanic soils, also demonstrated a protective effect of
4. Physical protection mechanisms, which restrict access of allophanic material on SOC (Zunino et al., 1982; Boudot et al.,
organic materials to biological attack, that is, the architec- 1988, 1989). Zunino et al. (1982) demonstrated that the influence
ture of the soil matrix of allophane on mineralization of C from an organic substrate
11-28 Properties and Processes

varied with the chemical structure of the substrate. The presence 11.5.2.3  Adsorption of Organic Materials
of amorphous Fe compounds and Fe3+ cations has been shown to onto Mineral Surfaces
have a similar effect to that of allophane and Al3+ cations on the Clay particles provide a reactive surface onto which organic
mineralization of C from organic materials; however, the mag- materials can be adsorbed, and it is generally accepted that such
nitude of the protective effect was reduced (Boudot et al., 1989).
adsorption reactions provide a mechanism of protecting SOC
11.5.2.2  Impacts of Multivalent Cations against microbial attack. The mineralogy, surface charge char-
acteristics, and precipitation of amorphous Fe and Al oxides on
The presence of multivalent cations in soil has important implica-
clay mineral surfaces give clay minerals the capacity to adsorb
tions on the behavior of clays and organic materials and the bio-
organic matter and protect it from biological degradation.
logical availability of organic C. When saturated with ­multivalent
Correlations between SOC and clay contents have been observed
cations, clays remain flocculated, which reduces exposure of
(Schimel et al., 1985a, 1985b; Spain, 1990; Feller et al., 1991), and
organic materials adsorbed onto their surfaces (Section 11.5.2.3)
the various interactions between soil clays and organic materials
and macromolecular organic materials bearing functional groups
have been summarized by Oades (1989). Such interactions are
become more condensed (altering their 3D structure) and thus
principally defined by the chemical nature of organic materials
less susceptible to the enzymatic attack.
(functional group content, molecular size, etc.) and the type of
The dominant multivalent cations present in soils include Ca 2+
clay mineral (kaolinite, illite, smectite, etc.). Numerous studies
and Mg2+ in neutral and alkaline soils and hydroxypolycations
utilizing isotopically labeled organic substrates have shown a
of Fe3+ and Al3+ in acidic, ferrallitic, and andic soils. A protecting
positive relationship between the contents of residual substrate
effect of Ca 2+, relative to Na+, on organic C mineralization was
C and soil clay content (Amato and Ladd, 1992). Clay particles
effectively demonstrated by Sokoloff (1938), where the extent
have also been observed to encapsulate particles or patches of
of mineralization and solubility of organic C in two soils was
SOM (Baldock, 2002).
reduced by the addition of Ca 2+ salts and enhanced by the addi-
Not only the amount of clay, but also the specific surface area
tion of Na+ salts. Other studies have also shown a decreased solu-
(SSA) of the clay and more generally the soil mineral particles is
bility of SOC in the presence of Ca 2+ (Muneer and Oades, 1989c)
of importance. For example, Ransom et al. (1998) showed that
and reduced mineralization of native organic materials and
adding even small amounts of high-SSA (100 m2 g−1) clay-size
organic substrates on the addition of Ca 2+ in incubation stud-
(<2 μm) material can have a significant effect on the total SSA
ies (Linhares, 1977; Muneer and Oades, 1989a, 1989b). In such
of mineral particle mixtures. It must be noted that the relative
studies, the question remained as to whether the effect of Ca 2+
magnitude of the effect of adding high-SSA clays to nonclay
addition on mineralizable C resulted from an indirect effect on
mineral particles decreases as the size of the nonclay mineral
colloidal dispersibility or from a direct effect of Ca 2+ complex-
ation on the biodegradability of the organic molecule. particles decreases (Baldock and Skjemstad, 2000).
A direct effect of multivalent cation complexation on biode- In a field experiment where 14C-labeled plant residues were
gradability in soil has been demonstrated by the following results: added to four cultivated soils varying in clay content (5%–42%)
but having similar clay mineralogy, climatic conditions, and no
1. A reduced oxygen absorption on incubation of humic other organic inputs, the amounts of residual 14C and total organic
acids saturated with Ca 2+, Al3+, or Fe3+ in the same soil, C in the topsoil (0–10 cm) remaining after 8 years of decompo-
relative to that noted for Na+-saturated humic acids (Juste sition were nearly proportional to soil clay content (Ladd et al.,
and Delas, 1970; Juste et al., 1975) 1985). Saggar et  al. (1996) completed a similar study in which
2. An increased protection of Al3+ and Fe3+ forms of plant the decomposition of 14C-labeled ryegrass was monitored over
and microbial polysaccharides (Martin et al., 1966, 1972) 6 years in four soils having variable clay content (16%–60%) and
3. A threefold increase in the amount of C mineralized from clay mineralogy. The mean residence time of the 14C-labeled
an organic soil after replacing Ca 2+ cations with K+ during ryegrass was not related to clay content but rather to the SSA as
a 25 week incubation (Gaiffe et al., 1984) measured by adsorption of p-nitrophenol. The increase in mean
Indirect evidence for the involvement of cations in the accu- residence time with increasing SSA, suggested that the protec-
mulation of SOC can also be obtained through a comparison tive capacity of the soils toward transformed metabolites derived
of the organic C contents of a variety of soil types. Using data from plant residues was principally controlled by adsorption
derived from Spain et al. (1983) for the organic C contents of 29 onto soil surfaces. Since the data presented by Ladd et al. (1985)
Australian great soil groups, Oades (1988) showed that, exclud- were derived from soils with a similar clay mineralogy, SSAs
ing soils subject to waterlogging, there was a positive correlation would have been well correlated with clay content. The impor-
between SOC contents and either high base status or the pres- tance of available surface area was also suggested by the results of
ence of substantial contents of Al and Fe oxides. Of interest was Sørensen (1972, 1975) where the addition of high-SSA montmo-
the comparison of siliceous and calcareous sands, which have rillonite to a soil/sand mixture protected microbial metabolites,
little or no clay, but indicate an increased SOC content in the but the addition of low-SSA kaolinite had little influence.
presence of Ca 2+-containing mineral fractions (<0.5% to 1.5% Hassink (1997) found a relationship between the silt- and
versus 1.5% to >4% organic C, respectively.) clay-associated C and soil texture, whereas this relationship
Soil Organic Matter 11-29

did not exist for the C in the sand-sized fraction (i.e., POM C) non-HF- and HF-treated soils provides an assessment of the rel-
suggesting that the capacity of soil to preserve C was linked to ative importance of mechanisms of mineral protection in defin-
silt and clay particles. Using data from Hassink (1997), Six et al. ing the biological stability of the SOC present.
(2002) were able to define significantly different relationships for
1:1 clays versus 2:1 clays, demonstrating the effect of clay type 11.5.2.4  Physical Protection within Soil Matrix
in C protection. Clearly, 1:1 and 2:1 clays have significant dif- Offered by Soil Architecture
ferences in CEC and SSA that may lead to a different capacity to The architecture or structural condition of a soil can exert sig-
adsorb organic materials. nificant control over processes of biological decomposition
SSA and mineralogy have been identified as key components through its effects on water and oxygen availability, dynamics
in the preservation of organic matter in marine sediments (Keil of soil aggregation, and by limiting the accessibility of SOC to
et  al., 1994; Mayer, 1994a, 1994b). Based on data generated in decomposer microorganisms and of microorganisms to their
these studies, Ransom et al. (1998) showed that total organic car- faunal predators. This limitation results from the ability of clays
bon in the marine sediments was linearly related to SSA as well to encapsulate organic materials (Tisdall and Oades, 1982), the
as to the content of high surface area minerals present. All these burial of SOC within aggregates (Golchin et al., 1997a, 1997b),
results suggest that the potential protective capacity of soil min- and the entrapment of SOC within small pores (Elliott and
eral particles, and more specifically that of the clay minerals, is Coleman, 1988; Strong et  al., 2004). As outlined by van Veen
more a function of the SSA available for adsorption of SOC than and Kuikman (1990) and Hassink (1992), evidence of the impor-
the absolute amount of clay. tance of these processes in the protection of SOC in soils can be
The protective effect of mineral surfaces can also be shown inferred from the following observations:
experimentally by removing the minerals associated with the
1. A faster turnover rate of organic substrates in liquid
various fractions as defined by Skjemstad et al. (1999) with HF,
microbial cultures relative to that of similar substrates in
since HF is known to dissolve soil minerals with little alteration
mineral soils
to the composition of organic matter. In a recent experiment
2. An enhanced mineralization of C and N when soils are
conducted by the authors, incubation studies were used to com-
disrupted prior to incubation
pare the mineralizability of HF- and non-HF-treated fractions
3. A more rapid mineralization of organic C and plant resi-
of SOM (unpublished data, Figure 11.10). Mineralizability was
dues in sandy soils than clay soils
defined as the cumulative amount of CO2–C emitted per gram of
organic C present in the sample being incubated. CO2–C emis- A continuum of pore sizes exists in soils, starting with large
sions were quantified by repeatedly sampling and then refresh- macropores (>20 μm) and decreasing to micropores (<0.1 μm).
ing the headspace of an incubator system for up to 70 days using Kilbertus (1980) suggested that bacteria can only enter pores
infrared detection of CO2–C. Comparison of the mineralizabil- >3 μm, which suggests that a significant proportion of the soil
ity of SOC with and without HF treatment revealed an increased pore space may not be accessible to microbial decomposers.
mineralizability with destruction of soil minerals consistent with Organic materials adsorbed onto clay particles contained in
the ability of minerals to stabilize a portion of the SOC against pores <3 μm would only be decomposed as a result of diffusion
biological attack. The magnitude of the difference between the of extracellular enzymes released by microorganisms followed

50 50
Soil 8 Soil 10
Cumulative carbon mineralization

40 40
(mg CO2-C g–1 added C)

30 30

20 20

10 10
<53 μm <53 μm
<53 μm HF treated <53 μm HF treated
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Incubation duration (days)

FIGURE 11.10  Change in mineralizability of <53 μm SOC fractionated from two different Australian soils induced by pretreatment with 2% HF
according to Skjemstad (1994).
11-30 Properties and Processes

by a diffusion of the products of enzyme reactions back to the and a model assuming an aggregate formation rate proportional
microorganisms (see Section 11.1). With increasing soil clay to the respiration rate. There was no evidence that aggregate for-
content, the proportion of the total soil pore space contained mation differed amongst the three soils examined, which all had
in micropores increases, and the potential for protection due to a different structure. A subsequent study (De Gryze et al., 2006)
the exclusion of soil microorganisms increases. This concept of confirmed this finding and showed that soil texture affected
exclusion can be extended to the predation of microorganisms aggregate stabilization rather than aggregate formation.
by soil fauna. van der Linden et  al. (1989) suggested that pro-
tozoa and nematodes are excluded from pores <5 and <30 μm, 11.5.3  Biota: Vegetation and Soil Organisms
respectively. Killham et al. (1993) showed that although placing
glucose into pores <6 or <30 μm did not impact the rate of glu- 11.5.3.1  Vegetative Inputs: Variations
cose decomposition, the turnover of glucose C incorporated into across and within Ecosystems
the microbial biomass was slower where glucose was only added Vegetation influences SOC content as a result of the amount,
to pores <6 μm. Strong et al. (2004) showed that decomposition placement, and biodegradability (chemical recalcitrance) of
occurs faster in soils with a large volume of pores with neck plant residues returned to the soil. Plant residues can be consid-
diameters of 15–60 μm. Their observations pointed to particularly ered the dominant input and thus the primary source of organic
rapid rates of decomposition near the air–water interface, most carbon into or onto soils (Kögel-Knabner, 2002). Organic mol-
likely because of the ideal conditions for the organisms’ mobil- ecules created by the soil fauna and microorganisms are the
ity, nutrient or toxin diffusion, and oxygen supply. Furthermore, secondary source of decomposable organic carbon in a soil. The
they suggested that on the one hand, SOC in large air-filled greatest effects of vegetation on SOC contents are confined to
pores decomposes more slowly than in intermediate-sized pores the A horizon. Concentrations of organic C detected below the
(most likely due to decreased organism mobility, diffusion of A horizon result from a combination of plant input through
solutes, and intimacy of contact between SOC and soil minerals) roots as well as pedogenic processes, which occur over longer
whereas on the other hand, the carbon trapped in the smallest timescales. Volkoff and Cerri (1988) showed that for Brazilian
pores was physically protected against decomposition. soil profiles, current vegetative cover was only in direct equilib-
The ability of clay particles to adsorb organic materials can rium with topsoil (A horizon) organic C, while that in subsoils
also contribute to a biological protection of SOC through encap- was largely unaffected by the nature of vegetative cover. Once the
sulation and the formation of stable aggregates. Encapsulation SOC moves to depth (e.g., argillic or spodic horizons), it becomes
of particulate organic residues in soils not only places a physi- less accessible to decomposer organisms, as exemplified by the
cal barrier between decomposer organisms indigenous to soils increased depletion of 14C with soil depth (Pressenda et al., 1996).
and potential substrates, but can also limit the movement of Scharpenseel et al. (1992) provided estimates of the amount
water and oxygen to sites of potentially active decomposition. A of organic C contained in the vegetation, soil, and annual litter-
similar situation develops within soil aggregates. Relative to the fall associated with various ecosystems (Figure 11.11). Across the
larger pores between aggregates, the smaller pores within aggre- tropical, temperate, and boreal forests, a continuous decrease in
gates are more likely to remain filled with water during drying the amount of plant biomass and litter C is noted, with little
events, and therefore restrict oxygen movement into the aggre- change in the amount of organic C stored in soils. The decrease
gate. The presence of organic cores in aggregates (Beare et  al., in the ratio of plant biomass C:SOC was associated with an
1994a, 1994b; Golchin et al., 1994a, 1997a) will serve to increase increase in turnover time from 18 to 60 years. Presumably, most
this effect by enhancing oxygen consumption within the aggre- of this variation was related to the effect of temperature on lit-
gate. It has been found that anaerobic conditions can exist in terfall decomposition; however, significant changes in litterfall
the core of moist aggregates even under well-aerated conditions quality and morphology are also evident. The amount of residue
(Sexstone et  al., 1985). Smaller decomposition rates of SOC returned to the soil under similar types of vegetation appears
enclosed within soil aggregates compared to SOC located out- to be a function of climatic factors, principally the amount of
side of soil aggregates have also been shown (Sollins et al., 1996; precipitation; however, this will depend on the nature of the fac-
Angers et  al., 1997). In native grasslands, Amelung and Zech tor most limiting plant growth. Where ample water is available,
(1996) demonstrated that the exterior 0.5 mm of >2 mm diam- the amount of residues returned to the soil may be a function of
eter peds contained less SOC and had a higher C:N ratio, less lig- some other factor such as nutrient supply. For example, it has
nin, and more microbial-derived saccharides than ped interiors. been shown that P fertilization of Australian pasture soils can
The SOC associated with ped surfaces, therefore, appeared to increase SOC by 150% or more relative to the native condition
turn over more rapidly and exhibited a greater degree of decom- (Russel, 1960; Barrow, 1969; Ridley et al., 1990).
position than that contained within peds. Where climatic and soil factors are constant, residue place-
Soil aggregation is a transient property and aggregates are ment may become important. A comparison of the amounts of
constantly being formed and destroyed. Quantitative data on soil organic C contained in the plant biomass and soils of temper-
structural dynamics are, however, lacking. Recently, De Gryze ate grassland and forest ecosystems reveals that despite a much
et al. (2005) were able to define a macroaggregate turnover time smaller amount of plant biomass in the grassland, annual litter
of 40–60 days using data from a 3 week incubation experiment C inputs, and SOC contents were approximately twice that of the
Soil Organic Matter 11-31

25,000 Soil carbon 800

Litter carbon input (g m–2 year–1)

Plant biomass 700

Soil organic or plant biomass

20,000 Litter input
600

carbon (g m–2)
15,000 500
400
10,000 300
200
5,000
100
0 0
Tropical Temperate Boreal Savana Temperate Tundra
forest forest forest grassland
Plant biomass C
1.38 1.56 0.60 0.33 0.06 0.01
Soil organic C
Turnover time 18 24 60 15 34 29.3
(year–1)

FIGURE 11.11  Variations in mean soil organic C contents, plant biomass C contents, and rate of litter deposition in various ecosystems. (From
Scharpenseel, H.W., H.U. Neue, and S. Singer. 1992. Biotransformations in different climatic belts: Source sink relationships, p. 91–105. In J. Kubat (ed.)
Humus, its structure and role in agriculture and environment. Elsevier Science Publishers, Amsterdam, the Netherlands.)

forests. The occurrence of deep organic-rich mineral horizons in altered by soil fauna and microorganisms, predominantly after
temperate grassland soils (e.g., mollisols), in comparison with deposition in or on the soil, resulting in changes in the origi-
the concentration of organic materials in litter layers in boreal nal chemical structure and in the synthesis of new compounds;
forest soil (e.g., spodosols), is an example of the influence that just as some soil minerals dissolve and others precipitate during
vegetation can have on SOC content and distribution within the pedogenesis. An understanding of the chemical nature of plant
soil profile. The apparent larger input of belowground residues in materials is therefore important to studies of SOC genesis and
grassland soils compared to forest soils places organic C in close composition. Kögel-Knabner (2002) provides a comprehensive
vicinity to the soil mineral components, thereby enhancing the review of the molecular composition of plant matter.
potential for biological protection via the mechanisms discussed Plant materials consist of a range of different compounds
in Section 11.1. varying in concentration across plant species, plant components
The fate of surface-deposited residues depends on the activity (e.g., conducting, supporting, or photosynthetic tissues), growth
of soil microorganisms and fauna and their ability to mix these stages, and space (distribution in the landscape). Plant cells can
residues into the surface-mineral horizons. In well-drained be divided up into three components, the cytoplasm, cell mem-
soils with high calcium status, the activity of earthworms and branes, and cell walls. The cytoplasm contains the simple sugars,
other soil fauna is high, leading to a mixing of organic residues organic acids, amino acids, and enzymes essential to maintain
through processes of particle-size diminution, ingestion and metabolic activity. Cell membranes consist of globular proteins
casting, and bioturbation. Under such conditions, a mull-type embedded within a lipid bilayer. Plant cell-wall components
HUM layer is formed and litter layers do not develop. Plant include hemicelluloses, celluloses, lignins, proteins, cuticular,
residues and their decomposition products are intimately mixed and root waxes. Oades (1989) presented the following average
with soil mineral particles, which facilitates potential biological contents for the major types of organic C in plant residues:
protection through the various organomineral interactions, as
1. Extractable materials including water extractables (simple
discussed in Section 11.5.2. Soils low in calcium do not support
sugars, amino acids, and organic acids) and organic sol-
as active soil faunal populations and plant residues tend to accu-
vent extractables (free and bound alkyl molecules includ-
mulate on the soil surface forming organic-rich, mor-type HUM
ing fats, oils, and waxes)—200 g kg−1
layers. Within mor-type HUM, little potential exists for biologi-
2. Hemicelluloses—200 g kg−1
cal protection other than that due to the chemical recalcitrance
3. Celluloses—300 g kg−1
of highly decomposed residues. The intermediate form of HUM
4. Lignins—200 g kg−1
is referred to as a moder.
5. Proteins—60 g kg−1
11.5.3.2  Composition of Plant Materials: The organic components of plant cell walls account for the
The Parent Material for Soil Organic C majority of the mass of plant residues deposited in soils.
Plant materials can be viewed as the parent material for SOC Carbohydrate structures consist mainly of the polysaccharides
in much the same manner as we view primary minerals as the cellulose and hemicellulose. Cellulose is the primary compo-
parent materials of soil mineral components. Plant materials are nent of cell walls with a dominant structure of d-glucopyranose
11-32 Properties and Processes

Cellulose Noncellulosic polysaccharides (hemicellullose) Chitin

D-glucopyranose residues linked by β-1,4-linkages Pectin with α-1,4-linkages N-acetylglucosamine with β-1,4-linkages

H OH CH2OH COOH COOH CH2OH CH2OH

O O O O O
OH H H H H H H H H H H
O O O O
O O O
O OH H O
H H H OH H H OH H OH H
H
OH H H
O
CH2OH H OH H OH H OH H NHCOCH3 H OH

Lignin precursors
Examples of β-O-4-linked lignins
Hydroxycinnamyl Coniferyl alcohol Sinapyl alcohol Guaiacyl Syringyl p-Hydroxyphenol
alcohol
CH2OH O CH2OH O CH2OH O
CH=CH-CH2OH CH=CH-CH2OH CH=CH-CH2OH
HC HC HC
CH2 CH2 CH2
OCH3 CH3O OCH3
OH OH OH
OCH3 CH3O OCH3
HOH2C CH2OH HOH2C
O O O
HC HC HC
CH2 CH2 CH2

Cutin and suberin monomers

18-hydroxy-9-octadecenoic acid 9,10,18-trihydroxyoctadecanoic acid
OH
HOCH2(CH2)7CH=CH(CH2)7COOH HOCH (CH ) CHCH(CH ) COOH
2 27 27
OH

FIGURE 11.12  Representative chemical structures of the organic macromolecules found in plant and microbial residues entering the soil.

residues linked into a polymer via β-1,4-linkages (Figure 11.12). guaiacyl-based lignin, hardwoods (angiosperms) contain a
Cellulose can exist in either a crystalline or amorphous state mixture of guaiacyl- and syringyl-based lignin, and grasses are
as indicated by x-ray diffraction (Atalla and Vanderhart, 1984) dominated by syringyl lignin. Results presented by Hedges et al.
and solid-state 13C NMR (Vanderhart and Atalla, 1984). The (1985) suggested that such changes in lignin composition can
crystalline state is more highly resistant to microbial and enzy- affect its biodegradability, with syringyl lignin being more sus-
matic degradation than the amorphous form (Ljungdahl and ceptible to decomposition than guaiacyl lignin.
Eriksson, 1985). Hemicellulose is defined as the polysaccharide The protein and water-soluble components of plant resi-
extractable in alkali solution. The hemicelluloses exist as linear dues, unless protected against biological attack, provide a read-
and branched polymers of d-xylose, l-arabinose, d-mannose, ily decomposable substrate capable of supplying the chemical
d-glucose, d-galactose, and d-glucuronic acid monomers, which energy and nutrients required to drive soil biological processes.
may be acetylated or methylated. Most hemicelluloses are com- Enzymatic cleavage of the peptide linkages to form amino
posed of 2–6 of these monomers linked together primarily via acids and mineralization of amino acid N to form NH +4 provide
a 1,4-β-linkage backbone as shown in Figure 11.12 for pectin, a sources of N for soil biological processes, and the abiotic chemi-
glucuronic acid polymer. cal processes, to be discussed subsequently.
Lignin represents the second most abundant organic com- Alkyl components of plant materials include free and bound
pound in plant residues and accounts for approximately 5% of lipids, polyesters, and nonsaponifiable alkyl C dominated bio-
the mass of grasses and up to 30% of the mass of hardwood for- polymers. Free and bound lipids represent a heterogeneous
est species (Haider, 1992). The basic building block of lignin, group of neutral and polar molecules, which are classified
coumaryl alcohol, can be substituted with none, one, or two together based on their solubility in organic solvents (Tegelaar
methoxyl groups at the C-3 and C-5 positions on the benzene et al., 1989). The neutral component consists of triacylglycerols
ring to produce the p-hydroxyphenol, guaiacyl, and syringyl lig- and waxes, which serve to protect external plant surfaces and to
nin monomeric units, respectively (Figure 11.12). The units are store energy. The polar component is dominated by the esteri-
then linked together by more than 12 possible interunit linkages fied fatty acids found in cell membranes. Insoluble polyesters,
based on C–O or C–C bonds (McDougall et al., 1993). The major derived from hydroxy fatty acids, are found in cutin in plant
interunit linkage, accounting for about 60% of the linkages, is cuticles and in suberin in roots. Cutin and suberin are composed
the β-O-4-linkage depicted in Figure 11.12 for the three lignin of various long-chain (C16 and C18), substituted fatty acids. The
monomeric units. The nature of the lignin molecule changes main substituent group is hydroxyl with lesser amounts of epoxy,
with plant type: softwoods (gymnosperms) are dominated by ketone, and carboxyl groups also present (Holloway,  1982).
Soil Organic Matter 11-33

Two examples of cutin and suberin monomers are presented in mineralization observed between the soils. Hassink et al. (1993)
Figure 11.12, and Tegelaar et  al. (1989) have presented figures concluded that soil protozoa and nematodes did not signifi-
showing additional monomeric chemical structures and a pro- cantly influence soil C mineralization despite a positive response
posed model of the structure of intact cutin and suberin. Plant of bacterivorous nematodes on the amount of N mineralized.
cuticles and roots have also been shown to contain nonsaponifi- Several other studies have shown that soil fauna enhanced nutri-
able aliphatic biopolymers, which have been labeled cutan and ent mineralization had both positive and negative effects on
suberan (Nip et al., 1986a, 1986b, 1987). Cutan and suberan are SOC mineralization (Griffiths, 1994; Kajak, 1995; Alphei et al.,
considered similar to cutin and suberin with the exception that 1996). In a study including protozoa, nematodes, and earth-
they are highly cross-linked by nonester bonds. worms, Alphei et al. (1996) noted that none of the fauna studied
In order to assess the influence of plant-residue composition significantly affected basal respiration. However, other studies
on decomposition and mineralization, it is essential to remove showed that earthworm invasion can have a marked potential to
other confounding effects such as climatic, soil, and biological alter (usually reduce) soil C storage on local and regional scales
parameters. In field studies, this can be accomplished by exam- (Alban and Berry, 1994; Bohlen et al., 2004).
ining decomposition of all residues of interest at a single site. The role of soil fauna in decomposition processes should not
Vedrova (1997) assessed the impact of forest species on litter be based only on their direct contribution to C mineralization.
decomposition rates by placing litter collected from each species Soil fauna also act to reduce the particle size of litter, distribute it
on small plots located within a single unforested site. Mean rates within the soil, transport otherwise immobile microorganisms
of mineralization measured for cedar, pine, larch, spruce, aspen, to new sites within the soil matrix, and prime microorganism
and birch litter over ≈2 years were 1.93, 1.57, 1.85, 2.20, 2.56, and activities by the production of readily available substrates (e.g.,
2.57 mg C g−1 litter C day−1, respectively. A limitation of such earthworm intestinal mucus). In so doing, soil fauna generally
studies is demonstrated, however, by the work of Elliott et  al. enhance microbial activity and rates of decomposition. Soil con-
(1993), in which the decomposition of four different forest litters ditions, which limit (e.g., water saturation and the development
(mixed hardwood, red pine, beech, and hemlock) was examined of anaerobic conditions) or enhance (e.g., tillage or installation
in each of the original four forest types. The rates of decom- of drains in imperfectly drained soils) the activity of soil micro-
position were principally a function of litter type, with mixed organisms or fauna, will also impact significantly SOC mineral-
hardwood litter decomposing the fastest and hemlock litter the ization rates and thus alter SOC levels.
slowest. However, with the exception of the mixed hardwood lit-
ter, decomposition rates of the individual litter types were high- 11.5.3.4  Composition of the Microbial Community
est when they were placed in the forest type from which they were The population of decomposer microorganisms in soil is exten-
derived (i.e., decomposition of the hemlock litter was greatest in sive; densities up to 1010 bacteria and several kilometers of
the hemlock forest). This interaction between litter type and for- fungal hyphae per gram of soil have been measured in a wide
est type suggests that decomposition pathways in any given eco- range of soils (Lavelle et al., 1993). As a result of the diversity
system may be tailored to the type of litter deposited. Thus, the of decomposer organisms, the existence of interactions between
results of decomposition studies where litters are removed from specific types of organic residue and species of decomposer
their ecosystem of origin, or where the community structure of the organisms can have pronounced effects on the chemical struc-
decomposer organisms is altered, may not accurately reflect the ture and biological availability of residual organic materials.
relative effects of residue composition on decomposability. The decomposition of woody materials provides an excellent
example of how the species composition of the decomposer
11.5.3.3  Relative Impacts of Soil Fauna population can influence the chemical nature of decomposition
and Microorganisms products. Laboratory incubations of Eucryphia cordifolia wood
The requirement of soil organisms for chemical energy and with a brown-rot fungus (unidentified species) and a white-rot
nutrients drives processes of heterotrophic decomposition in fungus (Ganoderma australe) showed a more selective utiliza-
soils, which account for the major pathways through which SOC tion of carbohydrate C by the brown-rot fungus and a delignifi-
is mineralized. Abiotic chemical oxidation is unlikely to account cation by the white-rot fungus (Martínez et al., 1991). Using the
for >20% of total C mineralization (Moorhead and Reynolds, same white-rot fungus in a solid-state fermentation procedure
1989) and more often accounts for <5% (Lavelle et  al., 1993). with beech wood, Martínez et al. (1991) noted little change in
Microorganisms are the major contributors to soil respiration the chemical composition of the wood, despite a 36% mass loss.
and are responsible for 80%–95% of the mineralization of C Barrasa et  al. (1992) obtained similar results in an ultrastruc-
(Brady, 1990; Hassink et al., 1994). Hassink et al. (1994) calcu- tural study. Selective delignification of Laurelia philippiana
lated that the contribution of the fauna to C mineralization in wood by the white-rot fungus Phlebia chrysocrea was noted,
two sandy and two loamy grassland soils to range from 5% to but decomposition of the same wood by G. australe resulted in
13% of the total C mineralization. The pattern of C mineraliza- increased lignin contents. The selective degradation of carbo-
tion by the soil fauna through time differed from that of total hydrates by brown-rot fungi appears to occur independently of
C mineralization, suggesting that the activity of the soil fauna the fungal or wood species involved. However, the presence of a
did not contribute substantially to the differences in total C selective or nonselective degradation process for white-rot fungi
11-34 Properties and Processes

appears to depend on interactions between the species of fungus units in polymers, and the content of aromatic and aliphatic
and wood. Under anaerobic conditions, the activity of obligate functional groups (Baldock et al., 1997a; Gleixner et al., 2001).
aerobes such as wood-degrading fungi is limited and bacterial Rates of decomposition of known organic substances in soils
decomposition processes dominate. In examinations of buried were reviewed by Paul and van Veen (1978). Although variations
woods, it has been found that decomposition processes invari- in decomposition rates for any single substrate were evident as
ably result in a preferential utilization of carbohydrates and a a result of differences in soils and incubation conditions, simple
concentration of lignin (e.g., Bates and Hatcher, 1989; Bates organic molecules and monomeric compounds decomposed
et al., 1991). Such data indicate that changes in species composi- most rapidly. Oades (1989) showed that the extent and rate of
tion of the decomposer community can significantly alter the mineralization of C for a series of polysaccharides (glucose,
decomposition processes and thus, rates of accumulation or loss dextran, cellulose, and a fungal polysaccharide) decreased with
of organic C from soils. increasing molecular complexity and branching. Similar results
Earlier in this chapter, a conceptual framework to describe were obtained by Martin and Haider (1975) for the mineraliza-
the controls over the decomposition process was presented tion of C from specifically 14C-labeled benzoic and caffeic acid
(Figure 11.5) that was built around the concepts of biological monomers and polymers. C mineralization was most extensive
capability and capacity. Various methods can provide informa- from carboxylic acid groups, less extensive from the aromatic
tion regarding the biological capability and capacity of decom- ring C of the monomers, and least extensive from the polymeric
poser communities and the way these properties can be affected aromatic ring C. Of the polymeric materials contained in plant
by environmental parameters and management practices. For residues, lignin and other polyphenolic C and aliphatic C appear
example, the potential degradative capabilities of decomposer to be the most recalcitrant, but, as discussed in the previous sec-
communities can be measured using substrate utilization pro- tion, the stability of lignin C will be also related to the species
files based on Biolog plates (e.g., Bochner, 1989; Bucher and composition of the decomposer community.
Lanyon, 2005) or microrespirometry like the MicroResp• Many studies have demonstrated a relationship between
method (e.g., Campbell et al., 2003; Wakelin et al., 2008), which decomposition and plant-residue characteristics thought to
is a relatively recent method of community level physiological be indicative of residue quality (e.g., Edmonds and Thomas,
profiling (CLPP) and uses whole soil samples rather than soil 1995; Ågren and Bosatta, 1996; Cortez et  al., 1996; Hobbie,
extracts thereby eliminating extraction bias. Furthermore, the 1996). Included in these residue characteristics are N concen-
extraction and analysis of DNA and RNA (e.g., PCR-DGGE) tration, C:N ratios, lignin and/or polyphenol concentration,
from soils as well as phospholipid fatty acids (PLFA) can pro- lignin:nitrogen ratios, and acid-soluble carbohydrates (Heal
vide an indication of the genetic diversity and structure of soil et  al., 1997). Ågren and Bosatta (1996) found that the propor-
microbial communities (Muyzer et  al., 1993; Widmer et  al., tions of extractable, acid-soluble, and acid-insoluble C obtained
2001; Crecchio et al., 2004; Wakelin et al., 2008). Several indi- from a conventional chemical fractionation could be used to
ces and multivariate statistical analyses can be used with these assess the quality of forest litter, particularly when the acid-
techniques to determine the influence of soil and environmen- insoluble fraction did not dominate.
tal properties on the capability and capacity of the microbial During the decomposition of plant residues, significant
community. Several factors have already been investigated like changes in chemical composition of residual C are evident
the influence of soil type (Schutter and Dick, 2000; Banu et al., (Baldock et  al., 1997a). In response to such changes, Berg and
2004; Wakelin et al., 2008), crop rotation (Bending et al., 2004; Staaf (1980) proposed a model of litter decay in which decomposi-
Crecchio et al., 2004), application of various fertilizers (Bucher tion was controlled initially by N content but subsequently by lig-
and Lanyon, 2005), vegetation (De Fede et al., 2001), and agri- nin concentration. This was supported by the results of Edmonds
cultural management practice (Wakelin et al., 2008). Although and Thomas (1995), which showed that organic C mineralization
the methods have proven to be reproducible, different results rates from green needles of western hemlock and pacific silver fir
between the different methods have been identified (Widmer were initially similar, but became more a function of litter chem-
et al., 2001). Therefore, it is recommended not to use these meth- istry (e.g., lignin:N ratio) as decomposition progressed.
ods in isolation if a representative assessment of the composition
of the microbial community is desired.
11.5.4  Topography
11.5.3.5  Relationship between Organic Residue Topography exerts its major control over SOC contents through
Composition and Biochemical Recalcitrance a modification of climate and soil textural factors and through
All organic C in soils can serve as a substrate. In addition to the its impacts on the redistribution of water within a landscape.
potential mechanisms of biological protection of organic materi- Soils in downslope positions are often wetter and have finer
als offered by the soil mineral fraction, the chemical structure of textures than soils in upslope positions or at the top of knolls.
the organic residue itself can also impart a degree of biochemi- Topographic-induced changes in the soil microenvironment
cal recalcitrance. This biochemical recalcitrance of the potential often lead to changes in plant communities (Sebastia, 2004),
substrate is defined by the strength of intra- and intermolecular which in turn can influence the magnitude and quality of resi-
bonds, the degree of polymerization and regularity of structural due returns. Burke et  al. (1995) examined the extent to which
Soil Organic Matter 11-35

SOC content varied at a landscape scale at two sites differing in The most dramatic influence of agricultural practices occurs
soil texture but having similar climatic characteristics. Burke when soils are first brought into production. Typically, SOC lev-
et  al. (1995) noted increased organic C contents (and clay and els decrease for the first few decades after cultivation and then
silt contents) in downslope positions relative to the summits at stabilize at a new equilibrium level, which is dictated principally
both sites. Such a finding has been attributed to the downslope by the ability of the soil to protect organic C and the amount,
movement of organic C and organic-rich clay (Reiners, 1983). quality, and distribution of plant-residue inputs. For example,
However, additional gradients in available water along slopes, Haas et al. (1957) observed a loss of 28%–59% of the SOC fol-
especially in water-limited systems, influence plant production lowing 30–43 years of cropping at 11 sites within the North
(Peterson et al., 1988), with greater biomass inputs and greater American prairies. David et al. (2009) also measured reductions
potential biological protection of organic C via higher clay con- SOC (30%–50%) due to the conversion of prairies to annual
tents at the base of slopes. Where excessive water exists, drain- cultivation and artificial drainage using archived samples and
age of depressions in the landscape can be restricted, leading to long-term resampling of soils.
the development of anaerobic conditions and a preservation of The following characteristics of crop production systems, in
organic C relative to the better-drained higher landscape ele- comparison with those of native grasslands, help to explain the
ments during wetter times of the year. observed losses of SOC induced by cultivation:
Guo et al. (2006) showed that the SOC decreases as elevation
1. 80% lower allocation of organic C to soils (Buyanovsky
increases and that level topography had twice the SOC content
et al., 1987)
of other slope classes. Particularly, in mountain areas that are by
2. Reduced belowground allocation of photosynthate
nature highly heterogeneous, taking topography into account is
(Anderson and Coleman, 1985)
required to predict SOC stocks across the landscape. In a study
3. Enhanced aggregate disruption and exposure of physi-
investigating the SOC storage in mountain grasslands of the
cally protected organic C due to cultivation
Pyrenees, Garcia-Pausas et al. (2007) found that the SOC stocks
4. Enhanced rates of decomposition of available organic C
were particularly low at high altitudes probably as a result of
substrates due to more favorable abiotic conditions (e.g.,
an overall temperature limitation of NPP. Climatic and topo-
aeration, temperature, and water content)
graphic variables were able to predict a significant part of the
C storage variability in the mountain grasslands examined by In practice, continuous alteration of land management and crop-
Garcia-Pausas et al. (2007). The microclimate conditions related ping practices (e.g., adoption of reduced tillage, the inclusion,
to topographic position (aspect and slope) were identified as or removal of pasture) will lead to a system where SOC levels
important factors for predicting C storage in soils of the high- are always in a state of flux, increasing with some practices and
altitude grasslands and should be taken into account to achieve decreasing with others (Baldock and Skjemstad, 1999). Only if
accurate estimations of C stocks in mountain ecosystems. management practices are left in place long enough, it is possible
As a consequence of all the possible confounding factors, it to gain an indication of what the new equilibrium SOC value
is difficult to study the sole effects of topography. For example, would be for any given land management system.
the interactive effects of topography (depositional and erodible Field trials set up to examine the impact of fertilizer additions
zones) and tillage (conventional versus minimum tillage [MT]) on SOC content, have revealed that the addition of N fertiliz-
on the redistribution of C, N, and P within an agricultural ers typically enhances SOC contents. This is particularly true
landscape were examined by De Gryze et al. (2008). In general, in temperate-zone ecosystems where N availability is thought
organic matter content and moisture content were greater in to limit NPP (Peterson and Melillo, 1985; Schimel et al., 1996;
lower, depositional areas compared to erodible areas, and the Holland et  al., 1997). Explanatory mechanisms suggest that
impact of topography on the stabilization and redistribution N-fertilizer additions result in a greater return of plant residues
processes of nutrients was more pronounced in conventional to soils due to enhanced production, a reduction in decomposi-
tillage (CT) than MT. This last finding clearly demonstrates that tion rates due to enhanced soil drying (Andrén, 1987), a promo-
interactions between topographic characteristics and land man- tion of soil acidification (Thurston et al., 1976), a repression of
agement practices should be considered in regional inventory lignolytic enzymes, and a formation of recalcitrant humic mate-
assessments of SOC (De Gryze et al., 2008). rials through the reaction of amino acids with humic precursors
(Fog, 1988).
In tropical systems, the establishment of pastures after clear-
11.5.5  Land Management Practices
ing of forests is widespread (Sombroek et al., 1993). Pasture estab-
Paustian et  al. (1997b) reviewed the influence of agricultural lishment immediately after deforestation, using species with high
management practices on SOC levels. Hutchinson et al. (2007) proportions of belowground biomass, may increase SOC contents
summarized the relative rates of SOC change for a range of as demonstrated in the Brazilian Amazon (Serrâo et  al., 1979),
“carbon friendly” agricultural management treatments and Latin America (Ligel, 1992), and East Africa (Boonman, 1993).
found that most changes were <0.6 Mg C ha−1 year−1. The influ- The intensity with which a soil is cultivated can impact both
ence of forestry management practices has also been reviewed the total amount of SOC and its distribution with soil depth.
(Johnson, 1992; Johnson and Curtis, 2001; Johnson et al., 2002). No-till systems tend to concentrate residue inputs at the soil
11-36 Properties and Processes

surface and generally enhance soil organic C and N contents in resultant balance between losses and inputs. The net change in
soil surface layers (Angers and Eriksen-Hamel, 2008). To accu- inputs and losses will be defined by the soil and environmental
rately evaluate the influence of tillage practices on SOC stocks, properties and land management practices discussed previously.
it is important to collect soil samples beyond the depth of tillage Sequestration of organic carbon in soil is a slow process typically
and to account for variations in soil bulk density. Paustian et al. requiring decades, but is suggested to offer the most efficient nat-
(1997b) presented data from a number of long-term field trials ural strategy for offsetting increased atmospheric CO2–C con-
indicating that SOC retention is typically enhanced under no- centrations (Metting et al., 1999; Post et al., 1999; Lal, 2004b).
till relative to more intensive CT systems. However, in a review Over the next century, improved land management strategies
of Australian publications, Valzano et  al. (2005) found that a may have the capacity to sequester up to 150 Pg of CO2–C (Lal
positive effect of no-till or reduced till on SOC in the 0–30-cm et al., 1998; Lal, 2004a). Considerable uncertainty exists in such
soil layer could only be demonstrated at high annual rainfalls estimates because of an inability to accurately predict the poten-
(>660 mm). Valzano et al. (2005) also noted that the separation tial sequestration of carbon that is possible in soil. Improving
of residue handling from the physical effect of passing an imple- our understanding of SOC cycling processes and how these are
ment through the soil was difficult to separate given the wide affected by environment and land management practices will be
range of residue handling practices associated with the different vital to identify opportunities for building SOM and sequester-
tillage systems. ing carbon in soils.
Estimates of the potential to sequester carbon in agricultural
soils have been made for the United States (Lal et  al., 1998),
11.6  Contribution of Soil Organic Matter Canada (Bolinder et al., 2008), China (Han et al., 2005, 2006),
to the Global Carbon Cycle the European Union (Freibauer et al., 2004; Janssens et al., 2005;
Romanenkov et al., 2007), and South America (Cerri et al., 2004,
The organic carbon contained within SOM represents a significant 2006). Such estimates are typically based on the use of long-term
reservoir of carbon within this global carbon cycle (Figure 11.13). field experiments or simulation modeling. Where estimates are
SOC has been estimated to account for 1200–1550 Pg of C (1 Pg = based on field experiments, it is important to ensure that the
1015 g) to a depth of 1 m and for 2300–2450 Pg of C to a depth potential for saturation of the soils capacity to protect carbon
of 2 or 3 m (Eswaran et  al., 1995; Jobbagy and Jackson, 2000; from decomposition is acknowledged and that measured car-
Lal, 2004a; Houghton, 2005). Comparative estimates of organic bon sequestration rates are not projected unimpeded into the
C contained in living biomass (550–560 Pg) and the atmosphere future. A similar consideration must be applied to soil carbon
CO2–C (760–780 Pg; Lal, 2004a; Houghton, 2005) indicate that simulation modeling activities. Most soil carbon models apply
variations in the size of the SOC store could significantly alter first-order kinetics to the decomposition of component carbon
atmospheric CO2–C concentrations. For example, a 5% shift in pools (Paustian, 1994). Therefore, predicted equilibrium car-
the amount of SOC stored in the 0–2 m soil profile has the poten- bon stocks are linearly proportional to carbon inputs (Paustian
tial to alter atmospheric CO2–C by up to 16%. et  al., 1997a, 1997b; Six et  al., 2002), and modeling activities
Land-use changes can induce either a net emission or a predict that unlimited increases in soil carbon stocks can occur
net sequestration of organic carbon in soil depending on the provided inputs of carbon to the soil can continue to increase.

Decomposition
Atmosphere
~58
780
(annual increase 3.2)
Respiration Photosynthesis
59 120 6.3 90 ~92
Land
Vegetation use
550 change Ocean
(annual increase 0.7) 2.2 Surface biota 3
Dissolved inorganic 37,000
60 Dissolved organic 1,000
(annual increase ~1.8)
Soil
1500
(annual increase ~0.1)

Fossil fuels
5,000–10,000

FIGURE 11.13  The global carbon cycle. All pool sizes are in units of Pg C and all fluxes are given in units of Pg C year−1. (Adapted from
Houghton, R.A. 2005. The contemporary carbon cycle, p. 473–513. In W.H. Schlesinger (ed.) Biogeochemistry. Elsevier Science, Amsterdam,
the Netherlands.)
Soil Organic Matter 11-37

Since carbon inputs to soil will be limited by constraints placed SOM contributes and an assessment of any soil type speci-
on photosynthesis (e.g., availability of water, nutrients, heat, and ficity that may exist
ultimately light) and current soil carbon simulation models do 3. Parameterization of carbon cycling models build on mea-
not define a maximum soil carbon protective capacity, modeled surable components and inclusion of the quantitative rela-
estimates of potential carbon sequestration in soils need to be tionships between SOM composition and soil properties
carefully scrutinized. (functions) to allow the prediction of both SOM dynamics
The concept of soil carbon saturation suggests that each soil and the subsequent impacts on soil properties
has a unique carbon saturation level dictated by soil properties
With the potential for large-scale introduction of carbon trad-
including texture, mineralogy, bulk density, and depth (Ingram
ing schemes and a requirement to reduce the emission of green-
and Fernandes, 2001; Six et  al., 2002; Stewart et  al., 2008a,
house gases, a more complete understanding of SOM dynamics
2008b). Soil carbon sequestration potential should therefore be
and how altering SOM will alter soil properties will be essential.
estimated as the difference between the current and saturated
Such understanding is required to develop viable land manage-
soil carbon content. Defining soil carbon saturation values has
ment practices that accommodate the potentially conflicting
proven difficult, although Hassink (1992) suggested that the
issues of maintaining food security for an increasing global pop-
amount of carbon obtained under long-term pastures may pro-
ulation, ensuring profitability of individual farming enterprises,
vide an indication. Furthermore, true soil carbon saturation
and enhancing the capture of atmospheric CO2 as organic mat-
values may be of limited importance if the inputs of organic car-
ter in soils while reducing emissions of other greenhouse gases
bon required to attain and maintain such levels are beyond the
(nitrous oxide and methane).
capture of carbon by photosynthesis and deposition within soil.
Of more practical interest would be the behavior of soils as they
approach their carbon saturation capacity as well as the influ- Acknowledgments
ence of soil carbon saturation deficit on the efficiency of the SOC
accumulation in saturated soils. Contributions from the Australian Department of Climate
Although soil carbon does offer the possibility for sequester- Change and the Grains Research and Development Corporation
ing atmospheric CO2–C, the potential for soil carbon seques- of Australia to research projects of the Carbon and Nutrient
tration in soil is small compared to projected emission of CO2 Cycling Group within CSIRO Land and Water as well as the
form current energy practices (about 150 Pg versus 600 Pg over many interactions that the authors have had with research scien-
the next 100 years). Soil carbon sequestration is also finite, an tists globally are gratefully acknowledged.
upper limit exists, and as soils move toward the upper limit,
the rate of soil carbon sequestration will diminish. Enhancing References
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Macromolecules 17:1465–1472. Wegner, P.F., C.J. McDowall, and A.B. Frensham. 1989. Monitoring
Varanini, Z., and R. Pinton. 2001. Direct versus indirect effects farming systems. Effects of cropping practices. Limitations
of soil humic substances on plant growth and nutrition, p. to wheat yields. Technical Paper 23. Department of
141–158. In R. Pinton et al. (eds.) The rhizosphere. Marcel Agriculture of South Australia.
Dekker, Basel, Switzerland. Weihermuller, L., J. Siemens, M. Deurer, S. Knoblauch, H. Rupp,
Vaughan, D., and R.E. Malcolm. 1985. Soil organic matter and A. Gottlein, and I. Putz. 2007. In situ soil water extraction:
biological activity. Martinus Nijhoff/Dr. W. Junk Publishers, A review. J. Environ. Qual. 36:1735–1748.
Dordrecht, the Netherlands. Whiteley, G.M., and C. Pettit. 1994. Effect of lignite humic acid
Vedrova, E.F. 1997. Organic matter decomposition in forest lit- treatment on the rate of decomposition of wheat straw. Biol.
ters. Eurasian Soil Sci. 30:181–188. Fertil. Soils 17:18–20.
Vereecken, H., J. Maes, J. Feyen, and P. Darius. 1989. Estimating Widmer, F., A. Fließbach, E. Laczkó, J. Schulze-Aurich, and
the soil moisture retention characteristic from texture, bulk J.  Zeyer. 2001. Assessing soil biological characteristics: A
density and carbon content. Soil Sci. 148:389–403. comparison of bulk soil community DNA-, PLFA-, and
Verlinden, G., B. Pycke, J. Mertens, F. Debersaques, K. Verheyen, Biolog-analyses. Soil Biol. Biochem. 33:1029–1036.
G. Baert, J. Bries, and G. Haesaert. 2009. Application of Yan, F., S. Schubert, and K. Mengel. 1996. Soil pH increase due
humic substances results in consistent increases in crop to biological decarboxylation of organic anions. Soil Biol.
yield and nutrient uptake. J. Plant Nutr. 32:1407–1426. Biochem. 28:617–624.
Visser, S.A. 1985. Physiological action of humic substances on Yasmeen, S., M. Sariah, I. Razi, R. Mawardi, and A. Asgar. 2009.
microbial cells. Soil Biol. Biochem. 17:457–462. In vitro fungicidal activity of humic acid fraction from oil
Volkoff, B., and C.C. Cerri. 1988. Humus of Brazilian soils. Nature palm compost. Int. J. Agric. Biol. 11:448–452.
and relationship with the environment. Cahiers ORSTOM Yimer, F., S. Ledin, and A. Abdelkadir. 2008. Concentrations of
24:83–95. exchangeable bases and cation exchange capacity in soils
von Liebig, J. 1840. Die Chemie in ihrer Anwendung auf of cropland, grazing and forest in the Bale Mountains,
Agrikultur and Physiologie Braunschweig. Vieweg. As cited Ethiopia. For. Ecol. Manage. 256:1298–1302.
by Hedges and Oades (1997). Zepp, R.G., and C. Sonntag. 1995. The role of nonliving organic
von Lützow, M., I. Kogel-Knabner, B. Ludwig, E. Matzner, H. Flessa, matter in the earth’s carbon cycle. Wiley, New York, 342 pp.
K. Ekschmitt, G. Guggenberger, B. Marschner, and K. Kalbitz. Zunino, H., F. Borie, S. Aguilera, J.P. Martin, and K. Haider. 1982.
2008. Stabilization mechanisms of organic matter in four tem- Decomposition of 14C-labeled glucose, plant and microbial
perate soils: Development and application of a conceptual products and phenols in volcanic ash-derived soils of Chile.
model. J. Plant Nutr. Soil Sci. 171:111–124. Soil Biol. Biochem. 14:37–43.
 12
Soil Solution
12.1 Basic Concepts........................................................................................................................12-1
Definitions  •  Composition
12.2 Sampling the Soil Solution....................................................................................................12-3
Laboratory Methods  •  Field Methods
12.3 Thermodynamics of the Soil Solution.................................................................................12-5
Fundamentals, Units, and Variables  •  First and Second Laws of Thermodynamics   • 
Associated Thermodynamic Relationships  •  Chemical Potential and Free Energy  • 
Chemical Potential and Activities in Ideal Solutions   •  Activities and Activity Coefficients:
Nonideal Solutions  •  Equilibrium Constants  •  Effects of Temperature and Pressure  • 
Single-Ion Activity Coefficients  •  Electrochemical Potential  •  Heat of Hydration of Ions
12.4 Interactions of Gases with the Soil Solution....................................................................12-10
Henry’s Law  •  Volatile Organic Compounds  •  Rates of Dissolution of Gases in Water
12.5 Acid–Base Reactions in the Soil Solution.........................................................................12-12
Fundamentals of Acid–Base Chemistry in Soil Solution  •  Calculations for Acid–Base
Equilibria  •  Buffering Capacity of Soil Solutions  •  Soluble Organic Acids
12.6 Formation of Soluble Complexes....................................................................................... 12-14
Types of Complexes  •  Hard and Soft Acid–Base Rules  •  Rates of Formation
of Solution Complexes
12.7 Application of Thermodynamic and Equilibrium Concepts to Soil Solutions...........12-16
Speciation and Single-Ion Activity Determinations  •  Geochemical Models  • 
Oxidation/ Reduction Reactions  •  Successful Applications of Geochemical Modeling
to Soil Solutions  •  Limitations to Applying Geochemical Models to Soil Solutions
Paul Schwab 12.8 Current Status and Future Research Directions..............................................................12-21
Purdue University References..........................................................................................................................................12-21

The soil solution is the hub of chemical and biological activity seemingly does not participate in some important phenomena.
in the soil. Most reactions are slow in the absence of water: Soil Many examples exist in different disciplines of soil science that
organisms become dormant or die, mineral transformations illustrate this point. In soil physics, the concepts of “mobile” and
become imperceptibly slow, and soil chemical weathering and “immobile” water have been introduced to explain why water is
formation processes become greatly impeded. Addition of mois- often observed to move more rapidly through soil than would be
ture to previously dry systems reinitiates these reactions. predicted assuming that water participates in the transport pro-
cess. Higher plants and microorganisms undergo serious mois-
ture deficit even when measurable water still exists in the soil.
12.1  Basic Concepts The composition and kinetics of reaction of water very near solid
surfaces in the soil are significantly different than in the bulk
12.1.1  Definitions
solution. Therefore, a more functional definition of soil solution
The simplest definition of the soil solution is “aqueous liquid goes beyond simply the “aqueous liquid phase” and reflects that
phase of the soil and its solutes” (SSSA, 2009). A broader defini- the soil solution may be dependent upon the application and, in
tion describes the soil solution as a natural system that is both some instances, the methodology used to obtain this solution
open and dynamic. Its composition is the result of the concur- from the soil.
rent reactions of the labile soil minerals, organic materials, and From the viewpoint of a soil chemist, the soil solution may be
biological metabolism. Any discussion of the soil solution, how- defined as “the aqueous liquid phase in soil with a composition
ever, must take into account that from physical, chemical, and that is influenced by exchanges of matter and energy with soil
biological perspectives, a significant fraction of the soil solution air, soil solid phases, the biota, and the gravitational field of the

12-1
12-2 Properties and Processes

earth” (Sposito, 2008). By defining it as a phase, Sposito implic- 2−

contain elevated concentrations of Ca 2+, Mg2+, Cl−, SO4 , and
itly requires that the soil solution has uniform bulk properties sometimes Na , depending upon pH and the source of the salts.
+

(such as composition and temperature) and can be isolated from Concentrations of inorganic constituents in the soil solution
the soil. The requirement of uniformity can be met only on small are controlled by many factors, including pH, redox potential, and
scales of time and space because of the dynamic and spatially solid-phase composition. These considerations will be addressed
variable nature of soils. later in this chapter and elsewhere in Chapters 15 through 18.
The soil solution viewed on a molecular level would reveal
that it is not a distinct entity but a part of the 12.1.2.2  Organic Constituents
The composition of the soluble organic compounds in the soil
continuum of phases exhibiting indistinct interfaces at solution is not as complex as that in the organic solid phase (see
the molecular level. Solutes in the aqueous phase may be Chapter 11) but is a reflection of the organic components of the
associated with bound water at the surfaces of soil colloids, solid phase. Soluble organics also originate from the organisms
free water percolating through soil macropores, water in in the soil including exudates from plant roots and soil microbes.
the free space of plant roots, or immobile water in soil Because these compounds are generated and degraded by micro-
micropores. bial activity, the concentrations of these compounds in the soil
solution can be more transient and more variable than soluble
(Wolt, 1994) inorganic constituents.
As with soluble inorganic species, the organic constituents
12.1.2  Composition can be positively charged, negatively charged, or neutral. The
chemical reactions of these compounds will be influenced by
Because soil solutions are highly variable over space and time, their electronic charge, but hydrophobic and hydrophilic ten-
their composition can be discussed only in general terms. Trends dencies are critical as well. For example, positively charged
in relative concentrations of soluble inorganic and organic con- compounds that are water soluble can be adsorbed by cation
stituents (see Chapter 11) are similar for most soils, but natural exchange sites, negatively charged organics may form strong
and anthropogenic factors influence some or all components. complexes with iron or aluminum oxides, and uncharged com-
pounds may adsorb onto hydrophobic sites of soil minerals and
12.1.2.1  I norganic Constituents
organic matter.
The most common inorganic cations in the soil solution (Table The low-molecular-weight carboxylic acids typify soluble
12.1) usually are Ca 2+, Mg2+, and K+ (in that order) with a large organics (Table 12.2). They are continually exuded by plant
number of minor cations, including various forms of Na+, Fe2+, roots and soil microorganisms and are readily degraded with a
Cu2+, and Zn2+. The most prevalent anions are HCO3 −, Cl−, and half-life of hours. Carboxylic acids have the COOH functional
SO4 2− . Soils that become flooded are strongly influenced by group. The proton usually is dissociated in soil solutions, and
reducing conditions and microbial activities, and Fe2+, HS−, and the resulting negatively charged ligand often can act as a com-
SO4 2− can take on greater importance. In contaminated environ- plexing agent for metals. Formic and tartaric acids are exuded
ments, the entire composition of the soil solution will change to by grass roots, acetic acid is generated under anaerobic condi-
reflect the most soluble components of the contaminants. tions, oxalic acid is often associated with ectomycorrhizae, and
The sum of soluble cations and anions usually is less than 10−2 citric acid is excreted by fungi and plant roots (Sposito, 2008).
mol L−1. Among the cations, Ca 2+ will comprise at least half of Typical concentrations for these acids range from 10−5 to 10−3
this total; for the anions, the division among HCO3 − , Cl−, and mol L−1. Stevenson (1967) published an extensive review of these
SO4 2− will be dependent upon soil pH and composition of the soil and other organic constituents in the soil solution.
solids. Naturally, saline soils (see Chapter 17 of Handbook of Soil
Sciences: Resource Management and Environmental Impacts) will
TABLE 12.2  Organic Components Found in Typical Soil Solutions
TABLE 12.1  Inorganic Components Found in Soil Solutions Major Components Minor Components
Major Components Minor Components Category (10−4–10−2 mol L−1) (10−6– 10−4 mol L−1)
Category (10−4–10−2 mol L−1) (10−6–10−4 mol L−1) Othersa Naturally Formate, acetate, Citrate, phenolics, siderophores,
Cations Ca2+, Mg2+, Na+, K+ Fe2+, Mn2+, Zn2+, Cr3+, Ni2+, Cd2+, occurring oxalate, amino proteins, alcohols, sulfhydryls
Cu2+, NH 4 +, Al3+ Pb2+ acids, simple sugars
Anions HCO3 −, Cl−, SO4 2− H2 PO4 −, F−, HS− CrO4 2− , HMoO4 − Anthropogenic a Herbicides, fungicides,
insecticides, PCBs, petroleum
o o
Neutral Si(OH) 4 B(OH) 3 hydrocarbons, surfactants,
solvents, antibiotics, hormones
Concentration ranges are estimates and could change depending upon spe-
cific environments. The components listed are not necessarily the dominant Concentration ranges are estimates and are subject to variability depending
solution species. upon specific environmental conditions.
a Components normally found in concentrations <10−6 mol L−1 unless in a a Organic contaminants are present in low concentrations except in the case

contaminated environment. of spills, leaks, and accidental releases.

Soil Solution 12-3

Organic pollutants include those compounds that have 7

been introduced artificially into the soil, whether by design or
accident. Most organic pesticides are applied at very low con-
centrations (0.1–10 kg ha−1). Organics that have been spilled
or accidentally leaked onto the soil can be present at many
orders of magnitude higher. The resulting concentration in the 6
soil solution will be dependent upon the total concentration
in the soil, water solubility, strength of adsorption, volatility,
and degradability of the compound in question. For example,

pH
the triazine herbicide, atrazine, normally is applied at a rate of
approximately 2 kg ha−1, has a water solubility of 35 mg L−1, is
weakly adsorbed by the soil, has a half-life of approximately 5
Sandy loam
30 days, and has limited volatility. In contrast, glyphosate is
Silty clay
applied at about the same rate as atrazine but is 1000 times more
Ap horizon
soluble, very strongly adsorbed, and not volatile. Immediately
after application, atrazine concentrations in the soil solution Waterlogged
can exceed 5 mg L−1 and represent an environmental threat 4
1:1 1:2 1:5 1:10
to surface and groundwater. In contrast, aqueous glyphosate Dilution ratio
concentrations are nearly always <1 μg L−1, and glyphosate is
seldom detected in drinking water. (McBride, 1994, provides FIGURE 12.1  The impact of soil:solution ratio on the measured pH of
an excellent overview of the chemical behavior of pesticides two soils. Data for sandy loam and silty clay soils from Schwab (1992);
surface horizon and waterlogged soil from Elberling and Matthiesen
in soil.) Organic solvents and petroleum hydrocarbons tend to
(2007). (Data from Schwab, A.P. 1992. Chemical and physical charac-
have very low water solubilities (<1 μg L−1), but their potential
terization of soils. In L.E. Erickson, S.C. Grant, and J.P. McDonald (eds.)
toxicity is high, and even trace concentrations in the soil solu- Conf. Proc. Hazard. Subst. Res. University of Colorado, Boulder, Co.,
tion may be environmentally significant. p. 326–344; Elberling, B., and H. Matthiesen. 2007. Methodologically
controlled variations in laboratory and field pH measurements in water-
logged soils. Eur. J. Soil Sci. 58:207–214.)
12.2  Sampling the Soil Solution water increased, the pH increased significantly. These obser-
vations lead to the following inescapable conclusion:
The definition of the soil solution given in Section 12.1.1 is ideal-
ized and serves as a point from which the soil solution may be
Consideration of soil at field moisture contents is necessi-
conceptualized. At the experimental level, the “soil solution” is
tated by the inability to predict consistently the effects of
defined by the method used to separate the aqueous phase from
variation in soil to water ratios across broad ranges of soil
the rest of the soil. As discussed later, sampling methodology has
solution composition; neither variation in total electrolyte
a profound influence on the composition of the soluble constitu-
concentrations or the activity ratios of specific ion compo-
ents. Thus, consistent with the Heisenberg uncertainty principle
nents of the soil solution can be adequately resolved when
for the study of subatomic particles, one cannot sample and
water to soil ratios vary from field moisture contents to
examine the soil solution without altering it.
ratios >1. This is the main limitation to the use of water
For both laboratory and field studies of the soil solution, one
extracts as models of soil solution.
of the major problems associated with obtaining an unaltered
soil solution is that the moisture content of field soils can rap- (Wolt, 1994)
idly change from air dry to saturated, and the moisture con-
tent influences the chemical and microbiological dynamics in
12.2.1  Laboratory Methods
the aqueous phase. Most techniques for obtaining samples of
the soil solution function poorly when the moisture content Many laboratory methods have been developed for sampling the
is below saturation, and very few function at all moisture ten- soil solution; only a few will be summarized here. The methods
sions of ≤33 kPa (1/3 bar). The choice of method and moisture may be broadly categorized as aqueous extracts, column dis-
content for obtaining a sample of the soil solution must be placement, and pressure extraction. Each technique has advan-
made to minimize the impact on solution composition while tages and limitations. (One must also consider proper sampling
realizing that the act of sampling necessarily changes it. and handling techniques for the samples. For example, the
An example of the influence of moisture content on soil simple act of air-drying the soil can have a profound effect on
chemical properties is the often-observed change in pH at dif- the soil chemical and microbiological properties [Bartlett and
ferent soil:solution ratios (Figure 12.1). Soil pH was measured James, 1980; West et al., 1992].)
for four soils with moisture contents ranging from 1:1 to a ratio The steps to obtaining aqueous extracts include adding water
of 10:1 water:soil (on a volume/mass basis). As the amount of to the soil to the point of saturation or beyond, equilibrating, and
12-4 Properties and Processes

removing solution. Equilibration times and separation techniques from the outlet. The centrifugation method, similarly, requires
will depend upon the method used and desired application. If a sat- specialized equipment. The apparatus usually consists of a cen-
urated paste is prepared (United States Salinity Laboratory Staff, trifuge tube to contain the moist soil; a permeable frit, filter, or
1954) for the assessment of soil salinity, the paste is equilibrated ceramic beneath the soil; and a small volume at the bottom of the
for 16 h followed by vacuum removal of the soil solution. If equilib- apparatus for collection of the extruded solution (Elkhatib et al.,
rium with soil solid phases is desired, equilibrations of hundreds to 1986). Large samples (up to 1 kg) usually are centrifuged at low
thousands of hours may be required (Kittrick, 1977; Schwab, 1989; speed, but smaller samples can be subjected to much greater speed
Evans and Banwart, 2006; Sposito, 2008). The advantages of these and result in a greater fraction of the soil water being collected. An
techniques include ease of preparation, simple separation of soil and immiscible liquid also may be placed on the top of a small sample
solution, and the ability to control many experimental parameters prior to centrifugation, a modification of immiscible displacement.
such as aeration and shaking. Limitations are unrealistic moisture The pressure-membrane approach has not been used as widely
contents, abrasion of soil surfaces during shaking, and uncertain as the centrifuge method because of lower yields, requirement
impacts of wide soil:solution ratios on solution composition. This for large samples, and specialty apparatus. The high-speed cen-
method has been applied with success in many instances (Lindsay, trifuge method is an excellent choice because it uses equipment
1979; Berggren and Mulder, 1995). that is normally available in a soil chemistry laboratory, yields a
Column displacement consists of forcing a fraction of the soil sample very quickly (<1 h), and is amenable to a large number of
solution from the soil by leaching the soil with an aqueous solu- samples. The disadvantages are similar to other displacement-
tion (miscible displacement) or a water-insoluble organic solvent type methods: short incubation times, an unknown fraction
(immiscible displacement). These techniques have a long his- of the “true” soil solution that is sampled, uncertain impact of
tory, perhaps beginning with Thompson (1850) and Way (1850) organic solvents (if used), and potential changes in the dissolved
leaching ammonium sulfate solutions through columns of soil gas composition. The centrifugation method was used by van
and finding that the ammonium had been replaced by calcium. Hees et al. (2001) to infer the importance of organic matter and
Schloesing (1866) used miscible displacement to obtain a sam- exchange reactions in the chemistry of Al in soils.
ple of the soil solution; this method is quite similar to modern
miscible displacement techniques (Adams, 1974). In all column
12.2.2  Field Methods
displacement procedures, moist soil is packed into columns to
a desired bulk density, sealing the surface by mechanically dis- As is often the case in soil science, field methods of sampling
persing the clays, and leaching with the displacing liquid. The the soil solution are more challenging than laboratory methods,
soil solution is collected in fractions until the displacing liquid particularly when one is interested in obtaining samples that are
appears in the leachate. This system may be modified to include truly representative. Field methods cover a wide range of con-
pressure from the top (Ross and Bartlett, 1990) or vacuum figurations: block or monolithic lysimeters; zero-tension or pan
applied to the bottom of the column (Wolt and Graveel, 1986). lysimeters; and porous-cup vacuum samplers.
The advantages of column displacement methods are obtaining Monolithic lysimeters are large blocks of soil (undisturbed or
soil solution from a soil at field moisture conditions, no require- refilled) contained in a structure that has some means of collect-
ment for grinding or shaking, and maintaining the dissolved ing leachates. The apparatus are labor intensive and expensive to
gas content (except in the vacuum modification). Disadvantages construct but are generally placed in a typical field setting to allow
include (1) generally short incubation times to prevent unusual growth of vegetation while measuring a variety of soil parameters.
microbial growth or changes in moisture content; (2) lack of The leachate collection system may be free drainage (i.e., zero-
knowledge of the fraction of the “true” soil solution that is tension or air-entry potential) or use a vacuum system to impose
obtained because of chemical and physical heterogeneity of the a moderate moisture tension. Soil in contact with a free-drainage
columns and because a large fraction of the water-filled pore space collection system must be very near saturation to allow water to
being occupied by the diffuse double layer; and (3) (in the case of move from the column to the collection area. The thickness of the
immiscible displacement) an unknown influence of organic sol- near-saturated zone above the collection area will be dependent
vents on the displacement of ions. upon the texture of the soil, and the saturated condition will impact
Pressure extraction is the use of positive pressure, vacuum the chemistry, microbiology, and physics of the soil. Addition of a
(negative pressure), or force applied by a centrifuge to remove the vacuum system, while adding to the complexity and cost of con-
soil solution. For soils with moisture contents below saturation, the struction, will overcome the saturation problem. Unfortunately,
centrifuge method is more efficient than the positive pressure or the vacuum will at least partially “degas” the collected leachates.
vacuum methods. The efficiency of the latter two methods can be Water flow through large lysimeters will affect directly the chem-
increased by employing a displacing solution, similar to some of the ical composition of the leachates. In refilled versions, the original
techniques described immediately above. Positive pressure meth- structure is destroyed, and, in the absence of plants, preferential
ods generally refer to the use of a pressure membrane (Richards, flow within the soil is eliminated. However, this is unrepresentative
1941). A cylinder, equipped with small-pore filters on the inlet and of natural conditions. Block-type “undisturbed” lysimeters pre-
outlet, is packed with the moist soil. Pressure of approximately serve much of the original soil structure, and water movement will
2 MPa (20 bar) is applied to the inlet, and the solution is collected be similar to the original field condition. In both block and refilled
Soil Solution 12-5

A B
Pressure or Sample retrieval line
vacuum line

Rubber stopper

PVC pipe

Drain
tube Collection pan

Porous ceramic

Sample collection vessel

FIGURE 12.3  Design of a typical porous-cup vacuum lysimeter.

FIGURE 12.2  A zero-tension, pan lysimeter in a typical field context. cup. (A continuous vacuum may be applied, or the vacuum may
The collection vessel and drain tube are located in an excavated trench be applied intermittently.) The second air line extends to the
cut into the soil along the side of the sample area. bottom of the cup and is used for retrieving the collected sample
either by drawing a vacuum on the retrieval line (marked B in
lysimeters, wall flow (movement of water in the spaces between the Figure 12.3) or by applying pressure on the other line (A).
lysimeter walls and the soil) can be an important form of preferen- Porous-cup lysimeters have been criticized as field samplers
tial transport of water and solutes (Till and McCabe, 1976). Wall of the soil solution (Caron et al., 1999). The ceramic cup has the
flow can be minimized through careful design and construction, potential to retain analytes or to contaminate the sample (Wood,
and its relative impact is lessened as the ratio of surface area of the 1973), particularly for inorganic species. Likewise, the PVC tube
side walls to the total volume of soil increases. can retain organic compounds of interest. The area of soil that is
Zero-tension lysimeters include any device installed in the soil sampled is not known (Warrick and Amoozegar, 1977), but will
that collects water by free drainage of the soil above including pans, be influenced by the vacuum applied (Morrison and Lowry, 1990),
troughs, funnels, and plates. These lysimeters usually are installed the texture of the soil, the method of installation, and soil mois-
from a trench. A slot is excavated from the trench into the soil that ture content. Unlike the other field methods described above,
allows installation of the lysimeters (Figure 12.2). Leachate collects vacuum pore water samplers will operate only when the operator
in the lysimeter, and the sample is removed by means of a hose engages them. Unless the porous cup is in saturated soil, the soil
or tube leading to the trench or to the soil surface. This lysimeter solution will not flow into it until vacuum is applied.
design is useful for monitoring the solutes that move with water. Each field method has positive and negative aspects. The
The assumption is made that the soil disturbance from digging the monolithic lysimeters are, in essence, a field laboratory with all
trench and installing the pan will have little impact on water flow parameters either controllable or measurable. However, they
and solute composition. However, water will not flow into the pan are difficult and expensive to construct and maintain, and wall
until the soil is nearly saturated. Water can accumulate above the effects can be dominant. Zero-tension lysimeters are less expen-
interface between the soil and lysimeter and cause incoming water sive but require significant disturbance to the soil adjacent to
to move laterally away from the lysimeter. Modifications to this the site, and water flow patterns may be altered immediately
procedure such as putting the lysimeter under tension (Cole et al., above the interface between soil and lysimeter. Vacuum pore
1961) can overcome this problem in part. water samplers are the least expensive of all field methods but
Porous-cup vacuum lysimeters (Figure 12.3) are widely used collect the smallest fraction of the soil solution. In all cases, the
in sampling the soil solution. Their design is simple, and they are soil solution will be defined by the specifics of the method used.
easily installed using standard soil sampling equipment. Entire
assemblies are readily built or available commercially. A length
of PVC pipe is fitted with and glued to a ceramic cup. A rubber 12.3  Thermodynamics
stopper with two air lines is placed in the opposite end of the of the Soil Solution
pipe. The lysimeter is buried in the soil with the ceramic cup
facing down and the air lines extending to the soil surface. One In discussing the thermodynamics of aqueous systems, strong
air line is used for drawing a vacuum, either with a hand pump distinctions are made between chemical equilibrium and
or with a portable electric pump. The lines are sealed, and the nonequilibrium (kinetic) systems. Overlap exists between
lysimeter is allowed to draw the soil solution into the ceramic the statics and dynamics of solutions both on theoretical and
12-6 Properties and Processes

practical basis. In this section, only equilibrium thermodynam- Important variables and functions and associated units are
ics will be addressed. Kinetics are addressed in Chapter 13. The given in Table 12.3. Nearly all thermodynamic equations rela-
assumption of equilibrium may be applied safely to only a frac- tive to soil solutions are derived from the four principles of ther-
tion of the reactions occurring in soils; many reactions do not modynamics and the first and second laws of thermodynamics
achieve equilibrium before new perturbations are imposed. (Stumm and Morgan, 1996). The four principles of thermody-
Despite serious practical limitations, equilibrium models are namics establish an absolute temperature scale, define the inter-
important because “they are simpler in that they require less nal energy of a system, and describe the relationship between
information, but they are nevertheless powerful when applied entropy and temperature.
within their proper limits” (Stumm and Morgan, 1996).
Soil solutions are open systems in which energy and mat- 12.3.2  First and Second Laws
ter are exchanged readily with the surrounding environment. of Thermodynamics
Experimentalists often are more familiar with closed systems
The first law of thermodynamics for equilibrium systems of fixed
in which such exchanges do not occur and rigorous mass and
compositions,
energy balances can be applied. Thus, the study of soils in natu-
ral settings can require some adjustments in design, execution, dE = dq − dw, (12.1)
and interpretation. Open systems will be assumed in all deriva-
tions discussed later unless otherwise noted. represents the changes in internal energy (E) as affected by heat
Chemical thermodynamics of aqueous solutions have been transferred to the system (q) and work done by the system (w).
developed to various degrees of depth and detail, depending upon For a reversible process, the second law is given by
the application. Stumm and Morgan (1996) provide an excellent,
in-depth discussion of equilibrium thermodynamics for aqueous dq
dSsys = (12.2)
systems. Wolt (1994) provided a discussion of similar depth but T
with the ultimate application to soil solutions. Sposito (1981) dedi- and relates the temperature and heat transferred to a system with
cated an entire textbook to the subject of the thermodynamics of entropy (S). Other forms of this equation exist for the system
soil solutions. The reader is referred to these references for a thor- plus its surroundings as well as irreversible changes in a system.
ough discussion of chemical thermodynamics applied to aqueous From the basic (not differentiated) equations H = E + PV and
solutions. In this chapter, important thermodynamic laws and G = E + PV – TS, one can obtain the important relationship,
equations will be stated and discussed; they will not be derived. G = H − TS, where G is the Gibbs free energy, H is enthalpy, P is
pressure, and V is volume. For a finite state change at constant
12.3.1  Fundamentals, Units, and Variables pressure and temperature,
As mentioned previously, true equilibrium is achieved in only ΔG = ΔH − T ΔS. (12.3)
a fraction of the reactions that occur in soil solutions but is a
powerful tool when properly applied. Some of the reasons for This equation, a restatement of the second law of thermodynamics
investigating the application of equilibrium thermodynamics to in terms of state functions of the system, is used in the application
systems that are frequently not in equilibrium include determin- of thermodynamics to numerical solutions of chemical problems.
ing whether some or all of the components of the solution are in
equilibrium; comparing the measured system with systems in 12.3.3  Associated Thermodynamic
equilibrium; quantifying the energy of disequilibrium (i.e., the Relationships
energy input necessary to achieve equilibrium); and calculating The development of theoretical thermodynamics can be quite
the effects of temperature on equilibria. The equations necessary detailed, but its utility can be realized only if expressed in mea-
to obtain these goals are presented in the following sections. surable variables. For example, enthalpy change (dH) in Table
12.3 can be described as dH = dq + V dP; if dP = 0 (constant
pressure process), then dH = dqP. This expression is particularly
TABLE 12.3  Variables, Thermodynamic Functions, useful in determining temperature effects because constant
and Equations of State
pressure heat capacity (CP) is measurable and is given by
Variable Units Function Equation of State
⎛ dq ⎞
Temperature (T) K Enthalpy (H) dH = T dS + V dP CP = ⎜ . (12.4)
⎝ dT ⎟⎠ P
Entropy (S) J deg−1 Helmholtz free dA = −S dT − P dV
energy (A)
In the absence of external work, qP = ΔH.
Pressure (P) kPa Gibbs free energy (G) dG = −S dT + V dP
Under conditions of constant pressure and constant
Volume (V) L Internal energy (E) dE = T dS − P dV
­temperature the state of a system is characterized by dG. For
Chemical J mol−1
irreversible changes in a system,
potential
Quantity mol dG − V dP + SdT < 0,
(12.5)
Soil Solution 12-7

and for reversible changes, The resulting relationships depend upon assumptions made dur-
ing the derivation. Equations for gases and electrolytes are
dG − V dP + SdT = 0. (12.6) summarized in Table 12.4. As an example derivation for an ideal
gas, consider the partial free energy of this gas with respect to P at
The above equations are applicable only for systems of constant
constant T and n:
chemical composition, dni = 0. When the composition of only
species i is allowed to change,
⎛ ∂G ⎞ (12.11)
⎜⎝ ∂P ⎟⎠ = V
T ,n
⎛ ∂G ⎞ ⎛ ∂G ⎞ ⎛ ∂G ⎞
dG = ⎜
⎝ ∂T ⎟⎠ P ,n j
dT + ⎜
⎝ ∂P ⎟⎠ T ,n j
dP + ∑ ⎜⎝ ∂n ⎟⎠
i i P ,T ,n j
dni .

(12.7) and, thus,

⎛ ∂G ⎞ nRT (12.12)
12.3.4  Chemical Potential and Free Energy ⎜⎝ ∂P ⎟⎠ = P .
T ,n

The chemical potential, μ, of a species i is defined as

If the second equation is rearranged and integrated from Go
⎛ ∂G ⎞ (standard free energy) to G and from Po (standard pressure) to
μi = ⎜ . (12.8)
⎝ ∂ni ⎟⎠ P ,T ,n j P, the result is

Employing the relationships (∂G/∂T)P,nj = −S and (∂G/∂P)T,nj = V ⎛ P⎞

G − G o = nRT ln ⎜ o ⎟ . (12.13)
yields the equation ⎝P ⎠

dG = −SdT + V dP + ∑ μ dn ,
i i (12.9) Differentiation with respect to n and recalling the definition for
chemical potential gives
and for a single-phase system at constant temperature and
pressure, ⎛P ⎞
μi = μio + RT ln ⎜ io ⎟ , (12.14)
⎝P ⎠
dG = ∑ μ dn .
i i (12.10)
where �io is the chemical potential for the ideal gas in its standard
state (e.g., as defined by the conditions given in Table 12.4) at
For a multiphase system, dG for the entire system is obtained by T  = 298.15 K and P = 101.33 kPa (1 atm). Similar derivations for
summing μi dni over all phases. When equilibrium is established real gases, condensed phases that obey Raoult’s law and condensed
for all reactions and phases, dG = 0. phases that obey Henry’s law, are summarized by Wolt (1994).
These basic equations can be manipulated further to yield equa- Sposito (1994) discussed the standard states for phases and
tions for chemical potentials of components in various phases. elements relevant to the study of soil solutions.

TABLE 12.4  Expressions for the Chemical Potential of Components in Gas and Condensed Phases as Influenced
by the Assumptions of the Behavior of the Component
Phase Chemical Potential Coefficients Standard State
Ideal gas μi = μ + RT ln(Pi/P )
o
i
o 298.15 K, 101.33 kPa; pure ideal gas at 101.33 kPa
Nonideal gas μi = μoi + RT ln(Piλi) λi ≡ fugacity coefficient 298.15 K, 101.33 kPa; pure nonideal gas at 101.33 kPa, λi = 1
Condensed phase: follows Henry’s law μi = μoi + RT ln(Ci) Ci ≡ Pi/KHi Pure condensed phase component, Cio = 1
Condensed phase: does not follow μi = μoi + RT ln(Ciλi) λi ≡ Henry’s law Pure condensed phase component, Cio = 1 and λi = 1
Henry’s law coefficient
Condensed phase: follows Raoult’s law μi = μoi + RT ln(χi) χi = Pi/Po Pure condensed phase component, χio = 1
Condensed phase: does not follow μi = μ + RT ln(χiλi)
o
i λi ≡ Raoult’s law Pure condensed phase component, χio = 1 and λi = 1
Raoult’s law coefficient
Solute in ideal, dilute solution μi = μoi + RT ln(Ci) Pure condensed phase component, Cio = 1
Solute in nonideal solution μi = μoi + μRT ln(Ciγi) γi ≡ single ion activity Pure condensed phase component, Cio = 1 and γi = 1
coefficient
Solute in nonideal solution μi = μ±o + νRT ln(C±γ±) γ± ≡ mean activity Pure condensed phase component, C± = 1 and γ± = 1
coefficient ν =
stoichiometric
coefficient

Sources: Wolt, J.D. 1994. Soil solution chemistry. Applications to environmental science and agriculture. John Wiley & Sons, New York; Stumm, W.,
and J.J. Morgan. 1996. Aquatic chemistry. Chemical equilibria and rates in natural waters. Wiley Interscience, New York.
12-8 Properties and Processes

12.3.5  Chemical Potential and Activities 1/ 2

to (γ Na + γ Cl − ) ; γ Na + γ Cl − can be determined experimentally by
in Ideal Solutions measuring water vapor pressures over NaCl solutions of varying
Perhaps the most important expressions for chemical potential concentrations.
in dealing with soil solutions are those for solutions of electro-
lytes. A classical case is that of NaCl dissolved in water. Sodium 12.3.7  Equilibrium Constants
chloride is a strong electrolyte, indicating that it is dissociated
fully with no NaCl complexes in the aqueous solution. The The Gibbs free energy of a reaction can be related to the system
chemical potential of this solution is the sum of the chemical composition through the expressions for chemical potential:
potentials for the Cl− and Na+ species:
μ I = μio + RT ln ai (12.23)
μ NaCl = μ Na + + μC l− . (12.15)
and ΔG
In an ideal, dilute solution, the equations for the chemical poten-
tials of the individual ions with concentrations CNa + and CCl −
would be
ΔG = ∑υ μ , i i (12.24)
i

μ Na + = μ oNa + + RT ln(CNa + ), (12.16) in which υi is the stoichiometric coefficient of a component i in

the reaction. Combining these equations gives
μ Cl − = μ oCl − + RT ln(CCl − ). (12.17)
ΔG = ∑υ μ i
o
i + RT ∑ υ ln(a ) i i (12.25)
The standard potential for an aqueous solution of NaCl (� o
NaCl(aq) ) i i
is defined as
or
μ o
NaCl(aq) ≡μ o
Na+
+μ o
Cl −
, (12.18)

and the total chemical potential is

ΔG = ΔG o + RT ln ∏(a ) i
ui
, (12.26)
i

μ NaCl(aq) = μ oNaCl(aq) + RT ln(CNa + CCl − ). (12.19) where

If the concentration of the salt is defined as CNaCl and realizing

that CNaCl = CNa + = CCl −, then
ΔG o = ∑υ μ ,
i
i
o
i (12.27)

μ NaCl = μoNaCl + RT ln(CNaCl )2 . (12.20) ΔGo is the standard Gibbs free energy change of the reaction
Πi is the quotient of concentrations of products over reactants

12.3.6  Activities and Activity Coefficients: Consider the reaction,

Nonideal Solutions
aA + bB ↔ cC + dD, (12.28)

For nonideal solutions, the concept of activity and activity coef-
ficient is introduced. A nonideal solution of NaCl would have a in which
chemical potential of a and b are the stoichiometric coefficients of reactants A
and B
μ NaCl(eq ) = μ oNaCl(aq ) + RT ln(aCl − aNa+ ) (12.21) c and d are the stoichiometric coefficients of products C
and D
or
The expression for Πi would be
μ NaCl(eq ) = μ oNaCl(aq ) + RT ln(CCl − γ Cl − CNa + γ Na+ ), (12.22)
⎡ aCc aDd ⎤
⎢ a b ⎥.
in which ai is the activity of component I and γI is the activity ⎣ a Aa B ⎦
coefficient of component i. The product aNa+ aCl − is designated by The expression often is given the symbol Q. Thus,
aNaCl, which is the activity of the aqueous solute, and its mean
activity is a± = (aNa+ aCl − )1/2, which can be determined experi-
ΔG = ΔG o + RT ln Q. (12.29)
mentally. Similarly, the mean activity coefficient, γ±, is equal
Soil Solution 12-9

At equilibrium, ΔG = 0, Q = K (the equilibrium constant), and and Morgan, 1996). The general expression, when ΔVo is inde-
pendent of pressure,
ΔG o = −RT ln K . (12.30)
⎛ KP ⎞ ΔV o (P − 1)
Both K and Q are written in terms of activities (ai), but activi- ⎜ ln K ⎟ = − RT
. (12.38)
⎝ 1 ⎠P
ties of individual species are not measurable. However, both
can be written in terms of concentrations using the relationship With specific reference to aqueous solutions,
between activity and concentration, ai = Ci γI:
μi = μio + RT ln γ iC, (12.39)
c d c d

a a
C (C γ ) (C γ )
D
K= a
= C C a D D b.
b (12.31)
a a (C A γ A ) (CB γ B )
A B
⎛ ∂ ln K ⎞ ΔV o
⎜⎝ ∂P ⎟⎠ =− , (12.40)
RT
T ,C

12.3.8  Effects of Temperature and Pressure
o
The general expression for the effect of temperature on the free ⎛ ∂ ln γ i ⎞ Vi − V i
energy of reaction is ⎜⎝ ∂P ⎟⎠ = − RT , (12.41)
T ,C
o
⎛ ∂ΔG /T ⎞ ΔH o

⎜ ∂T ⎟ = − T 2 , (12.32) where
⎝ ⎠P -
V i is the partial molar volume
o
V i is the standard partial molar volume of species i
and the van’t Hoff equation for the corresponding equilibrium
constant is
12.3.9  Single-Ion Activity Coefficients
d ln K ΔH o
The mean activity coefficient of a salt in solution, γ±, is measur-
= . (12.33)
dT RT 2 able by experimental methods. However, the activity coefficient
of a single ion, such as γ Na + or γ Cl −, is not measurable and must
The temperature dependence of enthalpy of reaction is
be estimated by theoretical models. Such a model was provided
T2
by the Debye–Huckel theory, which combined thermodynamic
and electrostatic expressions to describe the interaction between
∫
H 2 − H1 = C p dT . (12.34)
charged species in solution. In its first configuration, the theory
T1
was based upon the assumption that the ions act as point charges.
The resulting equation, the Debye–Huckel limiting law, was
If ΔHo is independent of temperature,
log γ i = − AZi2 (I 0.5 ), (12.42)
K ΔH o ⎛ 1 1 ⎞
ln 2 = − (12.35)
K1 R ⎜⎝ T1 T2 ⎟
⎠ where
Zi is the valence of the ion
or, when the heat capacity (�C op) is independent of temperature, I is the ionic strength of the solution ( I = 0.5 ∑ Ci Zi2 )
A is related to the dielectric constant for water and has a value
K 2 ΔH o ⎛ 1 1 ⎞ ΔCPo ⎛ T1 T⎞ of 0.509 at 298.15 K and 101.33 kPa
ln = ⎜ − ⎟ + ⎜ − 1 − ln 1 ⎟ (12.36)
K1 R ⎝ T1 T2 ⎠ R ⎝ T2 T2 ⎠
Activity coefficients calculated from this equation begin
or to deviate from measurements when I > 0.005 mol L−1. The
Debye–Huckel theory was extended to greater ionic strengths
⎛ ΔH o ⎞ ΔCPo (I  =  0.1 mol L−1) by adding terms that account for the spatial
ln K = B − ⎜ + ln T , (12.37)
⎝ RT ⎟⎠ R interaction of the ions:

where B and ΔHo are constants (Stumm and Morgan, 1996). − AZi2 I 0.5
log γ i = , (12.43)
When �C op is a function of temperature, the form of the final 1 + βaio I 0.5
equation will reflect the temperature-dependent expression for
the heat capacity. in which β is a constant that depends upon the nature of the
The effects of pressure on free energy and equilibrium con- solvent and temperature. For water, β is equal to 0.328 × 108 at
stants are handled in a fashion similar to temperature (Stumm 298.15 K and 101.33 kPa. The ion size parameter, aio, ranges from
12-10 Properties and Processes

(2.5 to 9) × 10−8 and must be obtained from a compilation of val- 0

ues (Kielland, 1937). The Davies equation is a further modifica-
tion of the Debye–Huckel and is applicable when I < 0.5 mol L−1:
–1000
⎛ I 0. 5
2 ⎞
log γ i = − AZ ⎜i 0. 5
− 0. 3 I ⎟ . (12.44)
⎝1+ I ⎠

ΔHhyd (kJ mol–1)

–2000
The advantages of the Davies over other equations are the appli-
cability to higher ionic strengths and the elimination of the
necessity of using β values. –3000

12.3.10  Electrochemical Potential Monovalent

–4000 Divalent
The standard electrochemical potential of a oxidation/reduction Trivalent
reaction, Eo, is the potential of the reaction relative to the oxida- Halide
tion of H2(g) to H+ in aqueous solution. The balanced chemi- –5000
cal reaction of such a cell involving the reduction of Cu2+ to the 0 0.05 0.10 0.15 0.20 0.25
Crystallographic radius (nm)
metal would be
FIGURE 12.4  Relationship between crystallographic radius and
Cu 2 + (aq) + H2 (g) ↔ 2 H + + Cu(s). (12.45) enthalpy of hydration of monovalent, divalent, and trivalent cations
and monovalent halide anions. The drawn lines represent linear regres-
The half-cell reactions are conveniently written as follows, with sions: R 2 = 0.98 for monovalent cations; R 2 = 0.90 for divalent cations;
the implicit understanding that the hydrogen half-cell is always R 2  =  0.99 for trivalent cations; and R 2 = 0.98 for monovalent anions.
present: (Data from Bohn, H., B. McNeal, and G. O’Connor. 1985. Soil chemis-
try. Wiley Interscience, New York; Morris, D.F.C. 1969. Ionic radii and
enthalpy of hydration of ions. Struct. Bond. 63:157–159.)
Cu 2 + (aq) + 2 e − ↔ Cu(s). (12.46)

For any given reaction, the Nernst equation may be derived: 12.3.11  Heat of Hydration of Ions
One of the most important reactions for ions in solution is hydra-
EH = EHo +
2.303RT
log
∏ i
{ox}ni
, (12.47)
tion, the electrostatic interaction between the polar water mol-
ecules and the charged ion. When an ion is released into aqueous

nF
∏ {red}
j
nj
solution, heat is released as water molecules form a somewhat
ordered structure around the ion. The water that surrounds
where the ion tends to insulate the charged species from other ions in
EH is the measured potential solution. In infinitely dilute solutions, this solvation effect com-
EHo is the standard potential of the cell pletely isolates the ions from interacting with each other.
R is the gas constant The heat released during solvation of an ion by water is the heat
T is temperature in degrees K of hydration, ΔHhydration. The strength of the water–ion interaction
n is the number of electrons involved in the reaction increases with increasing valence because higher charged ions have
F is the Faraday constant the capacity to react with more water molecules. Within a group of
Π designates the product of either the reactants or products ions of the same valence, ΔHhydration decreases (becomes more nega-
in the equation tive) linearly with decreasing crystallographic radius (Figure 12.4).
Thus, a small monovalent ion such as Li+ releases more heat upon
For any oxidation/reduction reaction, the relationship between hydration than the much larger Cs+ ion. A direct result of this is
the electrode potential and pe, negative logarithm of the electron that Li+ also has a greater hydrated radius than Cs+, which is partly
activity, −log(e−), may be derived as responsible for some of the differences in strength of retention of
F these ions by cation exchange sites in soil (see Chapter 17).
pe = EH , (12.48)
2.303RT
12.4  Interactions of Gases
or pe = EH/59.2 when EH is in mV and determined at 298.15 K. with the Soil Solution
As with H+, aqueous solutions do not contain free electrons,
and the concentration of solvated electrons is vanishingly small. Chemical reactions between gases and the liquid aqueous phase
Nevertheless, pe is a very convenient parameter in manipulating are important not only in the soil solution but also in biologi-
equilibrium equations and plotting data. cal systems, surface water, groundwater, and the atmosphere.
Soil Solution 12-11

For example, acid rain is a long-recognized problem that results TABLE 12.5  Henry’s Law Constants (KH) for Important
from the combustion of fossil fuels. The oxidation of C, S, and Gas–Water Reactions
N in the fuels generates several gaseous oxides including CO2, Gas KH,298.15K (mol L−1 atm−1) Gas KH,298.15K (mol L−1 atm−1)
NO2, NO, SO2, and SO3. When these oxides dissolve in water,
H2 7.78 × 10−4 O2 1.27 × 10−3
they generate acids: H2CO3, HNO3, HNO2, H2SO3, and H2SO4.
N2 6.53 × 10−4 N2O 2.42 × 10−2
The extent to which the gaseous oxides dissolve in the water can
NO 1.92 × 10−3 CO 9.77 × 10−4
be described by Henry’s law referenced in Section 12.3.4 and
CO2 3.39 × 10−2 H2S 1.02 × 10−1
given in Table 12.4.
SO2 1.36 Cl2 9.31 × 10−2
CH4 1.41 × 10−3 NH3 5.71 × 101
12.4.1  Henry’s Law O3 1.04 × 10−4

The equilibrium distribution of a species between the gas phase Constants were calculated from the data of Gevantman (2001) with
the exception of NH3 (Sposito, 2008).
and the aqueous is given by Henry’s law. The expression is based
upon the thermodynamic parameter, chemical potential, and
requires the determination of a partitioning coefficient for each controlling variable for the total dissolved component in aque-
gas. The thermodynamic expression is ous solution. Calculations also can be complicated by whether
the system contains an infinite sink of the gas (open system)
f A = KaA , (12.49) or if the gas is limited (closed system). These calculations are
handled in detail by Stumm and Morgan (1996).
where
K is a constant
12.4.2  Volatile Organic Compounds
fA is the fugacity of the gas
aA is the activity of the species in the aqueous phase Many organic compounds are subject to loss from solid, liquid,
or aqueous phases through volatilization. As with inorganic
The transition between the above thermodynamic equation gases, the tendency for volatile organic compounds to partition
and a usable expression with measurable terms is made simpler between the aqueous phase and the atmosphere can be described
if one first assumes the condition of dilute solutions and low by Henry’s law. Henry’s law constants can be calculated by mea-
concentrations in the gas phase. Under these circumstances, suring aqueous and gaseous phase concentrations in systems at
Henry’s law may be written in one of two ways, either of which equilibrium (Table 12.6).
is correct. In the first expression, the partitioning coefficient
(H) is dimensionless:
12.4.3  Rates of Dissolution of Gases in Water
[ A(aq)] = H . Quantification of equilibrium distributions of volatile com-
(12.50) pounds between the atmosphere and aqueous phase is more
[ A(g)]
powerful when accompanied by an understanding of the rates
The units of concentration for the gaseous and aqueous species of reactions. Transfer of a gas across the liquid/gas interface can
must be the same (e.g., mol L−1). In the second form of Henry’s be approximated by a diffusion model with two diffusion films
law, the partitioning coefficient is not dimensionless:
TABLE 12.6  Water Solubilities, Vapor Pressures, and Henry’s Law
[ A(aq)] = K Constants for Selected Organic Compounds
H . (12.51)
PA Water Solubility Vapor Pressure, KH (mol L−1
Compound (mol L−1) PA (atm) atm−1)
If the units of concentration for the aqueous component are mol Hexane 7.0 × 10−4 0.25 2.8 × 10−3
L−1 and the partial pressure is in atmospheres, then KH must have n-Octane 5.8 × 10−6 1.8 × 10−2 3.1 × 10−4
units of mol L−1 atm−1. The conversion between H and KH is Dieldrin 5.8 × 10−7 6.6 × 10−9 88
Lindane 2.6 × 10−5 8.3 × 10−8 313
H Naphthalene 2.6 × 10−4 1.0 × 10−4 2.6
KH = . (12.52)
RT Benzene 2.3 × 10−2 0.12 0.19
Toluene 5.6 × 10−3 3.7 × 10−2 0.15
Table 12.5 contains a compilation of KH values for important Biphenyl 4.9 × 10−5 7.5 × 10−5 0.65
gases in soils and other settings. Dimethyl sulfide 0.35 0.63 0.56
Although Henry’s law dictates that the solubility of gases in
Source: Stumm, W., and J.J. Morgan. 1996. Aquatic chemistry. Chemical
water is a linear function only of their partial pressures, many equilibria and rates in natural waters. Wiley Interscience, New York.
of the dissolved species react further with water to form acids A more comprehensive compilation is available in Staudinger and Roberts
that are subject to deprotonation. Thus, pH is an important (1996).
12-12 Properties and Processes

(liquid phase and gas phase) assuming that the bulk phases are dissolution, partitioning of some gases, and bioavailability of
well mixed (Stumm and Morgan, 1996). The diffusion films are critical nutrient elements. This section will address some of the
assumed to be within a very small distance of the interface. important acid–base concepts and discuss the numerical handling
The flux across the films of thickness z is expressed by Fick’s of related equilibria.
law:

dc 12.5.1  Fundamentals of Acid– Base Chemistry

F = −D . (12.53)
dz in Soil Solution
The central component of acid–base reactions is the proton or
The units for flux, F, will depend upon the units of concentration
hydrogen ion, H+. This ion does not actually exist as H+ in aque-
(c), diffusion coefficient (D), and thickness; assuming concen-
ous solutions but is hydrated to form H3O+, H7O3 + , H9O4 +, etc.
trations in mol m−3, D in m2 s−1, and distance in m, then F will
For the sake of simplicity in representing the equilibria involv-
have units of mol m−2 s−1. A steady state will have been achieved
ing the proton, the symbol H+ will be used.
when the flux across the two films is equal. The thickness of the
According to the Bronsted–Lowry concept, an acid is any
air diffusion film is assumed to be zair; the thickness of water
substance that donates a proton to another substance. Similarly,
diffusion film is zwater; the concentrations in the air and water
a Bronsted–Lowry base is any substance that accepts a proton
are cair and cwater; the concentrations in the air–water interface
from another substance. Using this definition, hundreds of
is ca−w; and the concentration in the water–air interface is cw−a .
reactions in soil solutions are examples of acids and bases. For
Therefore, at steady state,
example, bicarbonate ion dissociates readily to form carbonate
and H+:
Dw D
F =− (cw −a − cw ) = − a (ca − ca −w ). (12.54)
zw za
HCO3 − ↔ CO32 − + H + . (12.57)
Assuming that the transfer across the interfaces is much faster
than any ensuing chemical reactions that may occur, Henry’s In this case, bicarbonate is acting as an acid. Bicarbonate may
law may be applied to the concentrations in the interface regions also act as a base, accepting a proton to form carbonic acid:
(using the dimensionless constant from Section 12.4.1):
HCO3 − + H + ↔ H2COo3 . (12.58)
c
H = w −a = K H RT . (12.55) Although the discussions of Bronsted–Lowry theory for acids
ca − w
and bases presented here will be limited to aqueous systems,
Substituting into the steady-state equation, the theory is applicable to all solvents in which protons may be
exchanged, including ammonia, sulfuric acid, and ethanol.
Da ⎛ cw −a Metal ions in aqueous solutions are readily solvated and, as
⎞ D
F= ⎜ − ca ⎟ = w (cw − cw −a ). (12.56) such, exist as hydrates rather than bare ions. The number of
za ⎝ H ⎠ zw
water molecules surrounding a cation in the first hydration layer
will be dependent upon the ionic radius of the cation and its
Using data from Lovelock et al. (1993 in Stumm and Morgan,
charge. The water in the hydration sphere tends to act as a weak
1996), one can calculate that the flux of freon across the water–
acid, donating a proton to the solution and (in essence) contrib-
gas interface in marine environments is 1.5 × 10−9 g cm−2 year−1.
uting a hydroxyl ion to the metal:
Extended derivations and similar calculations can be made for
other chemical systems after making allowances for chemical
reactions. For example, the steady-state flux of CO2(g) from a [Fe(H2O)6 ]3+ ↔ [Fe(H2O)5 OH]2 + H+ . (12.59)
lake into the atmosphere is 6 × 10−9 mol cm−2 s−1 at pH 6.7, total
alkalinity of 3 × 10−3 mol L−1, and 298.15 K. The acidity of the water associated with the hydrolysis reaction
increases with increasing valence and decreasing ionic radius of
the central cation.
12.5  Acid–Base Reactions Another acid–base concept was formulated by G.N. Lewis
in the Soil Solution (Lewis and Randall, 1923). A Lewis acid accepts a pair of elec-
trons from a Lewis base. All Bronsted–Lowry acids and bases are
Acid and base reactions are the most fundamental and often also Lewis acids and bases, but the Lewis definition encompasses
the most important in soil solutions. The weathering of primary more reactions. In the neutralization reaction of H+ with OH− to
minerals often generates alkaline conditions, and natural and give water, a lone pair of electrons on the hydroxyl is donated to
anthropogenic activities can generate acidic conditions. The hydrogen; thus, this reaction fits both acid and base definitions.
rates and extents of many chemical reactions are dependent When an orthophosphate ion reacts with Fe(III) in the structure
upon soil solution pH including biological activity, mineral of goethite, the Fe(III) accepts an electron pair from the oxygen
Soil Solution 12-13

on the phosphate group to form the bond. This fits the Lewis 1.0
definition of an acid–base reaction but is clearly not a Bronsted– HCO3–
Lowry acid–base pair. 0.8
H2CO3o CO32–
12.5.2  Calculations for Acid–Base Equilibria

Mole fraction
0.6
Graphical representations of acid–base equilibria can take sev-
eral forms, but the underlying calculations are built on the same
0.4
theoretical foundation. Whether the system is simple or com-
plex, the approach is the same, although organizing and execut-
ing the computations can be challenging for large systems. The 0.2
first step is to identify the participating components, assemble
the pertinent equations, identify the master variables, and solve 0.0
the equations in terms of the master variables. A simple system, 4 5 6 7 8 9 10 11 12
pH
aqueous solution of carbonate, will be used as an example with
more complex systems developed later in this chapter. FIGURE 12.6  Mole fraction distribution of carbonate species as a
In this system, the species in solution would be OH−, H+, H2COo3 , function of pH. For all calculations, activity coefficients are assumed
HCO3 −, and CO32− with CO2(g) in the gas phase. The defining reac- to be unity (γi = 1.0).
tions and equilibrium constants are given in Table 12.7. The equi-
librium constants (Ko) are given at zero ionic strength, 298.15 K, and
101.33 kPa (1 atm) and are taken from Lindsay (1979). By defining and 10.36, the dominant carbonate species is HCO3 − with CO32−
the equilibrium constants at zero ionic strength, it is assumed that being present at the greatest activities above pH 10.36. However, the
all species are given in terms of activities. In Figure 12.5, activities total carbonate in solution approaches molar quantities near pH 10
of the three solution species in equilibrium with 0.0003 atm CO2(g) in equilibrium with carbon dioxide at this pressure, concentrations
are plotted as a function of pH. The predominant solution species rarely seen in natural solutions. Thus, the kinetics of CO2(g) disso-
below pH 6.33 is H2COo3 at an activity of 10−4.98. Between pH 6.33 lution probably predominate over equilibrium predictions at these
high pH values in open systems.
TABLE 12.7  Controlling Equations for Information similar to Figure 12.5 can be provided without
Equilibria Involving CO2(g) and H2O(l) the overlying assumption of an open system or predicting equi-
Equation log Ko librium activities. Figure 12.6 is a mole fraction distribution
CO2(g) + H2O(l) ↔ H2CO3o (aq) −1.46
diagram depicting the relative concentrations of the three car-
H2CO3o ↔ HCO3 − + H+ −6.36
bonate species as a function of pH. The mole fraction is defined
−16.69
as the ratio of the concentrations of a given species to the sum of
H2CO3o ↔ CO32− + 2H+
the concentrations of all the carbonate species. For CO32−,
Source: Lindsay, W.L., Chemical Equilibria in
Soils, Wiley Interscience, New York, 1979.
[CO32 − ]
0 Mole fraction(carbonate) = .
[H2COo2 ] + [HCO3− ] + [CO32 − ]
(12.60)
–2
The equilibrium expressions for these species in Table 12.4 are sub-
–
CO
3 stituted appropriately and solved across pH (Lindsay, 1979). The
–4 H resulting diagram (assuming that γi = 1) is applicable to either open
log (activity)

H2CO3o
or closed systems and requires equilibrium only among the solu-
tion species; equilibrium between the aqueous and gaseous phases
–6
is not required. As Figures 12.5 and 12.6 illustrates that bicarbon-
ate ion is dominant between pH 6.36 and 10.33 with carbonic acid
3 2–

dominant below pH 6.36 and carbonate above pH 10.33.

CO

–8
In the examples above, the simple system of carbon dioxide
in water was considered. Multiple component systems or other
–10 complexities can be handled in the same fashion.
3 4 5 6 7 8 9 10 11
pH 12.5.3  Buffering Capacity of Soil Solutions
FIGURE 12.5  Activities of carbonate species as affected by pH Because of the many acids and bases present in the soil and dis-
assuming equilibrium with PCO2 = 0.0003 atm. solved in the soil solution, the acid–base chemistry of soils is
12-14 Properties and Processes

11 the buffering can be shown to be represented as (Stumm and

Morgan, 1996)
Carbonate
10 ⎛ [HA][A − ] ⎞
0 Buffering = 2.3 ⎜[H + ] + [OH − ] + . (12.62)
0.001 mol L–1 ⎝ [HA] + [A − ] ⎟⎠
0.0003 atm CO2
This equation defines the buffering of the system at any point
pH

9
in the titration of the monoprotic acid, HA. Similar expressions
can be derived for mixtures of acids or for polyprotic acids.
8
12.5.4  Soluble Organic Acids
The chemistry of soluble organic acids in soil solutions has not
7 been studied to the extent of inorganic acids, although detailed
0 0.001 0.002 0.003
reviews exist (e.g., Stevenson, 1967). The relative lack of informa-
Base added (mol L–1) tion is not because of the lack of importance of soluble organic
FIGURE 12.7  Theoretical titration curves of an aqueous solution in soils but is a reflection of the difficulty in quantitatively char-
containing pure water (◻) in a closed system (no access to atmospheric acterizing the organic components in solution and the dynamic
CO2(g)), 0.001 M total carbonate in a closed system (Δ), or an open nature of soil organic molecules. Many simple organic acids have
system in equilibrium with atmospheric CO2(g) at 30 Pa (0.0003 atm) been identified in solution ranging from formic and acetic acids
•
(⚬ ). In all systems, the assumption is made that γi = 1 and the volume to more complex aromatic acids such as catechin (McKeague
remains constant. et  al., 1986). The aliphatic carboxylic acids are degraded very
rapidly, but the aromatic acids tend to be more persistent.
highly complicated. One of the results of this complex system is
For organic acids that can be identified, the theoretical
that the pH of soils and, to a smaller extent, soil solutions does
approach to defining their chemistry is identical to that of inor-
not change greatly in response to inputs of acid or base. The abil-
ganic acids. Extensive lists of acidity constants have been com-
ity of a system to resist pH changes is called the buffering capac-
piled (Martell and Smith, 2004), and these constants may be
ity or buffering intensity and can be determined experimentally
used to generate activity and mole fraction diagrams similar to
by titrating the solution and measuring the pH at each increment
Figures 12.5 and 12.6. The concepts of buffering intensity and
of acid or base addition. A simple, qualitative illustration of the
acid neutralizing capacity of organic acids are applied in identi-
buffering power of carbonate in water is illustrated in Figure
cal fashion as those of inorganic acids.
12.7 in which aqueous solutions are theoretically titrated with
Methods also exist for quantifying the acid–base behavior of
base from pH 7 to 11. In the first case, only pure water is titrated,
more complex organic mixtures. A direct approach is to titrate
and the solution shows little capacity to resist pH change; with
the soil solution or extract, plot the titration curve, and identify
each increment of base, a large pH change is noted. In the second
the characteristic buffering regions (Dudley and McNeal, 1987;
case, a solution containing 0.001 M total carbonate is initially
Sposito, 2008). The resulting curves can be modeled based on
adjusted to pH 7 and titrated with NaOH to pH 11. In this theo-
hypothetical mixtures of organic acid groups, or the acid neu-
retical titration, activity coefficients are ignored (γi = 1), but the
tralizing capacity and formation functions may be determined.
volume is assumed to remain constant. The carbonate solution
There is general agreement that complex organic matter in soil
has a significant resistance to pH change (buffering capacity)
and in soil solution is a broad mixture of carboxylic and benzoic
compared with the pure solution. The third case in Figure 12.7 is
acids with a wide range of acidity constants.
an open system in equilibrium with atmospheric CO2(g) assum-
ing 0.0003 atm (30 Pa). The buffering capacity of this solution is
low when pH < 8, but at greater pH values, the dissolution of CO2 12.6  Formation of Soluble Complexes
into the solution radically increases the buffering.
12.6.1  T ypes of Complexes
Buffering may be quantified mathematically by defining buff-
ering as the change in pH induced by the addition of acid or base A solution complex is the close association between a central
to a solution: molecular component (such as a cation) with other atoms or
molecules. Very often, metals or other positively charged spe-
ΔCbase ΔC cies act as the central component attracting neutral or negatively
Buffering = = − acid . (12.61)
Δ pH Δ pH charged ligands. In the hydrolysis of Fe3+ to form Fe(H2O)5OH2+,
the Fe3+ cation is acting as the central unit with water and
Thus, the buffering is mathematically defined as the change in hydroxyl acting as the ligands. This is a special case of com-
pH induced by an increment of acid or base (in mol L−1) added plex formation called a solvation complex. Two other categories
to the system. For a monoprotic acid (HA) dissolved in water, of complexes can be formed depending upon the strength of
Soil Solution 12-15

bonding between the central unit and the ligand. If the inter- Hydrolysis reactions generally are quite rapid for the monova-
action between the cation and ligand is strong enough that the lent and divalent cations but can proceed slowly for the higher
ligand displaces the solvation sphere, the resulting association charged cations. The rate of these reactions can be approximated
is termed an inner-sphere complex. Typical examples of inner- by examining the rate of water exchange from a hydrated cation,
y+
sphere complexes are AlFn3−n and Fe(III)citrate. If the attraction Me(H2O)x (Stumm and Morgan, 1996):
between the cation and ligands are not strong enough to dis-
place the hydration layer, an outer-sphere complex is formed or, Me(H2O)x y + + H2O* ↔ Me(H2O)x y + H2O* , (12.64)
sometimes, an ion pair. An inner-sphere complex can form if the
heat evolved during the association exceeds the energy needed where H2O* is the water being exchanged into the solvation
to displace the hydration sphere. If the heat evolved is less than complex. The forward rate constant in this expression is k1, and
the energy necessary to displace the water, then the hydration the rate constant for the reverse reaction is k−1. The exchange
sheath remains intact and an outer-sphere complex results. reaction is completed in this equation with a rate constant of k−w:
If a ligand occupies more than one coordination site in the
complex, the ligand is referred to as multidentate. For example, Me(H2O)x y + H2O* → Me(H2O)x −1(H2O* ) y + . (12.65)
two of the oxygens in oxalate can bond simultaneously with a
central Fe(III) ion. Such a complex is called a chelate, and the The rate of this reaction is
process is chelation. The multidentate nature of the interac-
tion can significantly increase the strength of the bond, and
d ⎡Me(H2O)x −1(H2O* ) y + ⎤
the resulting formation constant is much higher than ordinary ⎣ ⎦ = k ⎡Me(H O) y + (H O)* ⎤ . (12.66)
−w 2 x 2
complexes. dt ⎣ ⎦

At steady state,
12.6.2  Hard and Soft Acid–Base Rules
Other useful concepts in predicting the association between cat- d ⎡⎢Me(H2O)x y + (H2O* )⎤⎥
ions and ligands are the hard and soft acid–base rules (Pearson, ⎣ ⎦
1963). Hard acids and bases are those species that tend to have dt
smaller radii and are not readily deformable (Table 12.8). Soft = k [Me(H O) y + ][H O *]− (k + k ) ⎡Me(H O) y + H O* ⎤ = 0.
1 2 x 2 −1 −w ⎢ 2 x 2 ⎥⎦
acids and bases are often larger and more polarizable (have a ⎣
more easily deformed electron sheath). The tendency is that hard (12.67)
acids bond preferentially with hard bases, and soft acids bond After further manipulation and assuming that k−1 ≫ k−w ,
preferentially with soft bases. Thus, Ca 2+ would tend to bond
with phosphate and carbonate rather than chloride and sulfide.
d ⎡⎣Me(H2O)x −1(H2O *) y + ⎤⎦
= k− w K OS ⎡⎣Me(H2O)x y + ⎤⎦[H2O *],
12.6.3  Rates of Formation dt

(12.68)
of Solution Complexes
The rates of formation of solution complexes are often rapid, where KOS = k1/k−1 is the outer-sphere complex formation equilib-
establishing equilibrium very quickly. Certain reactions, how- rium constant. Thus, the rate constant for the exchange of water in
ever, proceed very slowly. For example, the reaction the hydration shell is estimated by k−wKOS. The same development
can be used to describe the kinetics of complex formation with a
Al 3 + + F− ↔ AlF2 + ligand, L, rather than H2O*. The resulting equation is
(12.63)

requires nearly 20 min to proceed half way to completion. This d ⎡⎣Me(H2O)x −1 Ly + ⎤⎦

is in contrast to the formation of MnSOo4, which requires 10−5 s. = k− w K OS ⎡⎣Me(H2O)x y + ⎤⎦[L]. (12.69)
dt
TABLE 12.8  Hard and Soft Acids and Bases
Hard Intermediate Soft Omitting the waters of hydration results in the standard
Bases notation:
F−, CO32−, Cl−, OH−, CH3COO−, SO32−, NO2 − , S2−, CN−, I−,
PO4 3− , SO4 2−, NH3, R–NH2, C6C5NH2, Br− R–SH, SCN−,
H2O, R–OH, NO3 − S2O32− d[Me L]
= k[Me][L], (12.70)
Acids H+, Li+, Na+, K+, Mg2+, Ca2+, Mn , Fe ,
2+ 2+ Ag+, Cu+, dt
Sr2+, Al3+, La3+, Si4+, Zr4+, Th4+, Cu2+, Zn2+, Cd2+, Hg2+,
Th4+, Cr3+, Mn3+, Fe3+ Pb2+, Bi3+, Cs+ where k = k−wKOS. This development illustrates the importance of
Ni2+, SO2 the equilibrium constant for the outer-sphere complex (i.e., the
Source: Pearson, R.G. 1963. Hard and soft acids and bases. J. Am. Chem. energetics of the reaction) as well as the kinetics of exchange of
Soc. 85:3533. waters of hydration surrounding the metal.
12-16 Properties and Processes

Stumm and Morgan (1996) compiled the values of k−w for 12.7  Application of Thermodynamic
water exchange reactions for several metals. For Pb2+, Hg2+, Cu2+,
Ca 2+, Cd2+, La3+, Zn2+, Mn2+, Co2+, Fe(OH)2 + , and Fe(OH)4 − , the
and Equilibrium Concepts
values were k−w ≥ 106 s−1. Values of k−w for other metals were 2 × to Soil Solutions
102 for Fe3+, 1.0 for Al3+, and 5 × 10−7 for Cr3+.
The chemical composition and dynamics of the soil solution are
Sequential reactions can be “coupled” and solved. Exact ana-
reflections of all the processes, which depend upon the aque-
lytical solutions to these models can be obtained (Sposito, 1994),
ous phase: biological activity, mineral dissolution/precipitation,
but it is typical to use experimental observations to help estab-
adsorption/desorption, physical transport, and anthropogenic
lish simplifying assumptions.
inputs. Wolt (1994) described the soil solution as “a window to
The formation of the solution complex CdCl+ in the presence
chemically reacting soil systems where the intensity and dis-
of 10−3 mol L−1 Cl can be used to illustrate the application of
tribution of chemicals in the soil aqueous phase represents the
these equations:
integration of multiple physical, chemical, and biological pro-
cesses occurring concurrently within the soil environment.” The
Cd(H2O)x 2 + + Cl − ↔ Cd(H2O)x −1 Cl + + H2O. (12.71) information provided by the chemical composition is further
enhanced by the knowledge of time trends and the application
The rate of reaction can be given by of kinetic and thermodynamic theories.

d ⎡⎣Cd(H2O)x −1 Cl + ⎤⎦ 12.7.1  Speciation and Single-Ion

= K OSk− w ⎡⎣Cd(H2O)x 2 + ⎤⎦[Cl − ] Activity Determinations
dt
The determination of free ion activities (or concentrations) for soil
d ⎡⎣Cd(H2O)x 2++ ⎤⎦ solution components provides a powerful interpretative tool for
=− , (12.72)
dt chemical reactions in soils. A limited number of ion activities can be
determined directly (such as the H+ activity using a glass electrode),
where but the rest must be approximated through rigorous calculations.
k−w = 108.48 (s−1) The steps in calculating ion activities and the distribution of
KOS = 101.98 (mol L)−1 solution species include obtaining and analyzing the soil solu-
(k−w)(KOS) = 1010.46 (L mol−1 s−1) tion, identifying the important solution species that can form,
assembling relevant equilibrium constants and reactions for the
Substituting these values into the above equation and simplify- formation of these species, obtaining an analytical or numerical
ing by not expressing the waters of hydration, solution for the series of equations, and calculating activity coef-
ficients. All the steps in the calculations can be handled by any
of the many geochemical models currently available (discussed
d[Cd 2 + ] later); however, understanding the chemical concepts behind the
− = (1010.46 )(10−3 )[Cd 2 + ] = 107.46[Cd 2 + ]. (12.73)
dt models and how the activities are determined will be helpful in
properly executing the computer models and obtaining the best
For a first-order reaction such as this, the half-life of the reac- possible data. The following sections provide a brief review of the
tion (i.e., the time required for the reaction to proceed half way important chemical reactions and activity calculations.
to completion) is equal to (ln 2) k−1. Thus, the half-life for this
reaction is 0.693/2.88 × 107 or 2.40 × 10−8 s. Sposito (1989) tabu- 12.7.1.1  Hydrolysis, Complexation,
lated the half-lives for several solution reactions, and the values and Oxidation/Reduction Reactions
ranged from 10−9 s for the formation of MnSOo4 to 103 s for the To help illustrate the steps involved in activity calculations, solu-
formation of AlF2+. ble Fe will be used as an example. The first step is to determine the
The relationships presented in this section demonstrate that important reactions in solution, and this can be done with the aid
most reactions in the soil solution are rapid enough that equi- of some of the compilations of thermodynamic data for aqueous
librium can be achieved during the course of most experiments. systems, such as Garrels and Christ (1965), Lindsay (1979), Sadiq
Even the slowest example given above, the formation of AlF2+ in and Lindsay (1979), and Martell and Smith (2004). Many of the
103 s, will be nearly complete in less than 1 h. However, the rate of metals undergo hydrolysis reactions, and Fe(III) and Fe(II) have
certain oxidation/reduction reactions can proceed very slowly, many important hydrolysis species as indicated in Table 12.9.
particularly reactions that involve oxyanions (such as arsenates The distribution of these Fe(III) and Fe(II) hydrolysis species as a
or chromate) or that are not microbially catalyzed. These reac- function of pH (Figure 12.8) shows that the predominant species
tions can take days to reach completion, if at all. Therefore, will be strongly dependent upon pH with mole fractions ranging
knowledge of equilibrium predictions alone may be of limited from 0.0 to over 0.9. Examination of Table 12.9 indicates that the
utility if the kinetics of reaction are unfavorable. complexes listed must be considered if (Cl−)  >  10−2, (F−)  >  10−7,
Soil Solution 12-17

TABLE 12.9  Reactions and Equilibrium Constants (SO42− ) > 10−5 mol L−1. The constants in Table 12.9 and their cor-
for Selected Solution Complexes of Iron
responding equations can be used to solve for ionic activities.
Reaction log Ko
Fe(III) hydrolysis 12.7.1.2  Solution Composition Example
Fe3+ + H2O ↔ FeOH2+ + H+ −2.19 Consider a soil solution with the following composition: 0.2 μmol
Fe3+ + 2H2O ↔ Fe(OH)2 + + 2H+ −5.69 L−1 total Fe, 20 mmol L−1 total Cl, 10 μmol L−1 total F, 1 mmol
Fe3+ + 3H2O ↔ Fe(OH)o3 + 3H+ −13.09 L−1 total sulfate, ionic strength 0.01 mol L−1, pH 6.5, and a redox
Fe3+ + 4H2O ↔ Fe(OH)4 − + 4H+ −21.59 potential of 600 mV. This is enough information to estimate the
Fe(II) hydrolysis Fe2+ and Fe3+ activities. The solution is fairly complex and requires
Fe2+ + H2O ↔ FeOH+ + H+ −6.74 a few assumptions to make it solvable. The first assumption will
Fe2+ + 2H2O ↔ Fe(OH)o2 + 2H+ −16.04 be that the ligands will not form complexes with any cations in
Redox solution of other Fe2+ and Fe3+. This is a poor assumption because
Fe3+ + e− ↔ Fe2+ 13.04 each ligand forms a number of complexes with other cations, par-
Complexation ticularly Al3+, Ca2+, and Mg2+. The second assumption is that the
Fe3+ + Cl− ↔ FeCl2+ 1.48 only species of Fe to be considered are those given in Table 12.9.
Fe3+ + F− ↔ FeF2+ 6.00 The approach given here is to identify all potential variables,
Fe3+ + SO4 2− ↔ FeSO4 2− 4.15 establish the same number of independent equations as the
Fe3+ + H2 PO4 − ↔ FeHPO4 − + H+ 3.71 number of variables, and solve the equations simultaneously.
Fe2+ + SO4 2− ↔ FeSO4o 2.20
The system variables are the activities of H+, OH−, e−, Fe3+, Fe2+,
2−
Cl−, SO4 , F−, FeOH2+, Fe(OH)2 + , Fe(OH)3o, Fe(OH)4 −, FeOH+,
Source: Lindsay, W.L. 1979. Chemical equilibria in
Fe(OH)2 , FeCl2+, FeF2+, FeSO4 +, and FeSO4 o, for a total of 18
o
soils. Wiley Interscience, New York.
variables. The relevant equations include 11 complexation equa-
tions from Table 12.9 (all equations except for the formation of
FeHPO4 +), Kw (water dissociation equation), pH = 6.5, Eh =
1.0 600 mV (pe = 10.1), and the four mass balance equations for the
Fe(OH2)+ Fe(OH4)– components:
0.8
Fe(OH)3o ∑ Fe = [Fe 3+
] + [Fe2 + ] + [FeOH2 + ] + [Fe(OH)2 + ] + [Fe(OH)3o ]
Mole fraction

0.6
+ [FeOH + ] + [Fe(OH)2o ] + [FeCl 2 + ]

0.4 + [FeF2 + ] + [FeSO4 + ] + [FeSO4 o ], (12.74)

0.2 FeOH2+
∑ SO 4
2−
= [SO4 2 − ] + [FeSO4 + ] + [FeSO4 o ],

(12.75)

0.0
4 5 6 7 8 9 10
pH
∑ Cl = [Cl ] + [FeCl
− 2+
],

(12.76)

1.0

Fe2+
FeOH+
∑ F = [F ] + [FeF
− 2+
].

(12.77)
0.8
In the mass balance expressions, brackets [x] represent concen-
trations of species x. Activity coefficients must be calculated for
Mole fraction

0.6
each species to tie together the mass balance equations with the
formation equations. Thus, there are a total of 18 equations for
0.4
Fe(OH2)o the 18 variables. Many methods exist for solving this system of
equations including back substitution and matrix algebra. These
0.2 systems can be solved by hand, but solutions are reached more
rapidly using computers.
0.0
4 5 6 7 8 9 10
pH 12.7.2  Geochemical Models
FIGURE 12.8  Distribution of Fe(III) and Fe(II) hydrolysis species in Over the past decades, scientists and research groups have
solution as a function of pH. recognized the need for computer programs to solve chemical
12-18 Properties and Processes

equilibrium systems, and several computer models have been The Pitzer equations require a relatively large number of
established. Models vary widely in their construction and com- parameters that are specific to the ions and systems under con-
position as well as their intended use (Baham, 1984; Melchior sideration. The number of required parameters increases rap-
and Bassett, 1990; van der Lee and de Windt, 2001; Hummel, idly as the systems become more complex. The Pitzer, Davies,
2005). Many of the models are based upon single-ion activities, and Debye–Huckel equations calculate single-ion activity
single-ion activity coefficients, and formation constants; Pitzer’s coefficients. Unfortunately, these activity coefficients cannot
equations for applications at high ionic strength; or a free energy be defined unambiguously because they are dependent upon a
minimization approach. clear, thermodynamic definition of single-ion concentrations.
As stated by Sposito (1994) when discussing the activity coeffi-
12.7.2.1  Formation Constant Approach cients for a metal ion, γM, and a ligand, γL , “For γM and γL to have
In Section 12.7.1.2, an example was given outlining the forma- chemical significance, the species molalities, mM and mL , must
tion constant approach to determine single-ion activities in have a well-defined operational meaning. Thus, the single-ion
soil solutions. Several series of published models take this same activity coefficient has no meaning apart from the set of opera-
approach. The WATEQ series (Truesdall and Jones, 1974; Ball tional procedures used to define ionic species and to determine
et al., 1979) was developed by the U.S. Geological Survey to com- their concentrations in an aqueous solution.” Although the
pute single-ion activities to predict the fate of critical elements determination of single-ion activities can provide useful infor-
in geochemical environments. Emphasis was placed on obtain- mation, single-ion activity coefficients cannot be experimentally
ing a well-documented thermodynamic database with the best determined and do not have a thermodynamic foundation.
available equilibrium constants; a reaction would be kept out of
the database if the constant was estimated or suspected to be of 12.7.2.3  Solving Example Problem
poor quality. The mathematical solution method was back sub- with Visual MINTEQ
stitution and required recompilation of the programming code The geochemical model, MINTEQ, and later MINTEQA2
if new reactions were added or if constants were changed. The (Allison et al., 1990), were developed by merging the mathemat-
MINEQL series (Westall et al., 1976) was developed using the ics and computer code from MINEQL with the database from
mathematical approach of REDEQL (Morel and Morgan, 1972) the WATEQ series. Although the MINTEQ database is not
to solve equilibrium problems and provide information about as extensive as SOILCHEM’s, all values were fully documented
trends in observed data. The mathematical solution method is as to their source and reason for selection. Visual MINTEQ was
rapid and efficient, but the thermodynamic database was not rig- developed to provide a graphic interface for MINTEQA2 version
orously reviewed. The model SOILCHEM (Sposito and Coves, 4 (Gustafsson, 2009) as well as expanding the database. Visual
1988) was an extension of the MINEQL model with emphasis on MINTEQ provides solution speciation, mass transfer through
expanding the database. Some smaller models have been devel- precipitation and dissolution of solid phases, ion adsorption,
oped, such as SOILSOLN (Wolt, 1989) and CALPHOS (Adams, ion exchange, redox, and humic complexation models, and gas
1971), for very specific (but limited) applications. SOILSOLN phase calculations.
was designed as a teaching tool with an easy-to-use interface and The hypothetical analytical data for the example problem in
embedded graphics. Section 12.7.1.2 were entered into a Visual MINTEQ input file,
and the program executed. The resulting activities (Table 12.10)
12.7.2.2  H igh Ionic Strength Models
The general approach in the models described in Section TABLE 12.10  Activities of Selected Aqueous Species
12.7.2.1 is the combination of equilibrium constant expressions Calculated Using Visual MINTEQ Version 2.61 for the
Example Solution Composition Given in Section 12.7.1.2
with mass balances. The impact of ionic strength (and activ-
ity coefficients) is disregarded or single-ion activity coefficients Species Log (Activity) Species Log (Activity)
are calculated. The single-ion activity coefficient is not rigor- Fe3+ −14.00 Fe2+ −11.11
ously defined in thermodynamic theory, and the equations Fe(OH)2+ −9.52 FeOH+ −14.00
used to approximate activity coefficients are subject to error, Fe(OH)2 + −6.75 Fe(OH)o2 −18.60
particularly at high ionic strength. A special approach must Fe(OH) o −9.50 FeSOo4 −11.89
3
be taken for aqueous solutions with high-salt concentrations
Fe(OH)4 −
−10.70 FeF+ −14.94
(ionic strength greater than 0.5 mol L−1). One such approach
FeF2+ −13.00 FeCl+ −13.05
is to use the Pitzer equations (Pitzer, 1979) for calculation of
FeF2+ −13.43 F− −5.05
single-ion activity coefficients, and at least two published mod-
els currently use this approach. Felmy and Weare (1995) dis- FeF3o −15.43 SO4 2− −3.18
cussed their model and experimental results of simple systems FeSO4 −12.92 Cl− −1.74
+

with high ionic strengths. The agreement between theory and FeCl 2+ −14.26
experimental determinations is promising. The C-SALT model Source: Gustafsson, J.P. 2009. Visual MINTEQ version
(Smith et al., 1995) also uses the Pitzer equations. The model 2.61. http://www.lwr.kth.se/English/OurSoftware/vminteq/,
has been tested against experimental data. accessed on May 16, 2011.
Soil Solution 12-19

show that the hydrolysis species of Fe(III) and Fe(II) are much A strongly reducing potential can generate hydrogen gas:
more important than the chloro, fluoro, and sulfate species. This
is because these ligands react only with the unhydrolyzed cat- H + + e − ↔ 0.5 H2 (g). (12.82)
ions, and, in the case of Fe(III), the activity of Fe3+ is very low. In
Again solving for pe,
the case of Fe(II), the ligand concentrations simply are not high
enough to become the predominant solution species. (It is to be
pe = −0.5 log ( H2 (g) ) − pH. (12.83)
noted that the program was executed with the specification that
supersaturated solid phases would not be allowed to precipitate.
At 1 atm H2(g), this reduces to pe = −pH. Again converting to the
Many solid phases were supersaturated, and allowing their pre-
combined parameter, pe + pH,
cipitation would have changed the results.)
The comparison of the Fe(III) and Fe(II) species also is worth
pe + pH = 0. (12.84)
noting. In Table 12.9, the constant for the equilibrium between
Fe3+ and Fe2+ suggests that Fe2+ will be present are higher activi-
In a plot of pe versus pH, the region between the lines pe =
ties than Fe3+ when the pe < 13 (770 mV). In this case, Fe2+ is
−pH and pe = 20.78 − pH represents the stability field for water.
nearly 1000 times greater than Fe3+, but the Fe(III) hydrolysis
Water is thermodynamically unstable at potentials outside this
species are by far the predominant Fe solution species. At this
region. Another important aspect of these equations is the equi-
pH, the oxidation/reduction potential would have to be pe < 6.0
librium partial pressures of H2(g) and O2(g) at typical redox
(355 mV) before the predominant Fe(II) species is present at a
potentials in soil solutions. For example, highly reduced soils
greater activity than the predominant Fe(III) species.
seldom have redox potentials below pe + pH = 4, correspond-
ing to P H2 = 10−8 atm. Measured redox potentials in fully oxi-
12.7.3  Oxidation/Reduction Reactions dized soils seldom exceed pe + pH 18, and equilibrium at this
potential would require 10−11.23 atm O2(g). If equilibrium were
Chemical reactions involving oxidation and reduction are rapidly established with these gases, then the partial pressures
important in all biological systems, and soils are no excep- of hydrogen and oxygen would be expected to be quite small in
tion. In all soils, localized areas can be found that are highly all situations. An equilibrium approach can be used to inves-
oxidized and highly reduced. Areas of reduction generally are tigate many redox reactions in soil solutions. The Fe(III)/Fe(II)
associated with small microsites that are saturated with water system was discussed in a prior section, and many other redox
and have restricted O2(g) diffusion. Microbial activity within active species exist in soil solutions including Cu 2+, Mn2+, and
these sites rapidly depletes the available oxygen, and the redox CrO4 2−. Chromium is an environmentally important metal and
potential of the soil solution decreases. The ability to predict has an interesting redox behavior. The Cr(III) species is consid-
the impact of changes in redox on soil solution composition is ered environmentally less hazardous than the Cr(VI), which is
a useful tool. closely regulated. Published equilibrium constants can be used
The first step in handling oxidation/reduction equilibria in to determine the redox potential at pH 7 at which the predomi-
soil solution is defining the limits of stability of aqueous sys- nant Cr(III) species, Cr(OH)2 + , converts to the predominant
tems. If a solution is subject to a high oxidizing potential, then Cr(VI) species, CrO4 2−. From the MINTEQ database, the fol-
the water spontaneously can be degraded into oxygen: lowing reaction and constant were obtained:

0.5 H2O(l) = H + + e − + 0.25 O2 (g) (12.78) CrO4 2 − + 6H + + 3e − ⇔ Cr(OH)2 + + 2H2O log K o = 67.38.
(12.85)
with an equilibrium constant expression:
The expression for the equilibrium constant, converted to loga-
0.25
(H + )(e − ) ( O2 (g) ) rithms, would be
Ko = = 10−20.78. (12.79)
(H2O)0.5

Substituting, rearranging, and solving for pe in terms of pH, log ⎢

(
⎡ Cr(OH)2 + ⎤ )
⎥ + 6 pH + 3 pe = 67.38. (12.86)
⎢ (CrO 4 2 − ) ⎥
⎣ ⎦
pe = 20.78 + 0.25 log(O2 ) − pH. (12.80)
The redox potential at which Cr(III) converts to Cr(VI) occurs
The pe at which water spontaneously decomposes to oxygen gas when the predominant species of each oxidation state of Cr have
would correspond to O2(g) pressure of 1 atm or pe = 20.78 − pH. equal activities, (Cr(OH)2 + ) = (CrO4 2 − ). The ratio of these activi-
Using the combined parameter, pe + pH, the upper oxidizing ties would equal unity, the logarithm of which is 0. Therefore,
limit of the stability field of water would be after dividing by 3,

pe + pH = 20.78. (12.81) 2pH + pe = 22.46 (12.87)

12-20 Properties and Processes

or, solving for pe + pH, 4

Davies
pe + pH = 22.46 − pH (12.88) HCl

3 NaCl

and, at pH = 7,

γ±
2
pe + pH = 15.46. (12.89)

This is a moderately reducing condition for soil solutions, 1

roughly the same redox potential at which denitrification occurs
(Lindsay, 1979).
0
0 1 2 3 4 5 6
Molality
12.7.4  Successful Applications of Geochemical
Modeling to Soil Solutions FIGURE 12.9  Changes in experimentally determined mean activity
coefficients (γ±) for various electrolytes compared with those generated
The application of equilibrium thermodynamics to soil solutions
by the Davies equation. Measured values are symbols, and predicted val-
will have several requirements for success, and the definition of ues are lines. (From Felmy, A.R., and J.H. Weare. 1995. The development
success will depend upon individual interpretations. The kinet- and application of aqueous thermodynamic models: The specific ion-
ics of some reactions in soil solutions were discussed in Section interaction approach. In R. Loeppert et al. (eds.) Chemical equilibrium
12.6.3; most reactions were found to proceed quickly, but others and reaction models. Soil Science Society of America Special Publications
are quite slow. Therefore, care must be taken to apply equilibrium No. 42. ASA, Madison, WI.)
thermodynamics only to the systems having enough time to
equilibrate, and this is dependent upon the method of sample col-
lection. For example, miscible displacement methods often have 6
equilibration periods of less than 24 h, which is not long enough Halite
for some solid-phase equilibria or redox reactions involving oxy- 5
anions. However, most of the field methods should be adequate. Teepleite
The success of applying a model to a chemical system will 4
NaCl (m)

increase as more information is known. One of the important

areas of progress in geochemical modeling in recent years has 3
been the addition of aluminum–phosphate speciation and empiri-
cal models for evaluating the impact of soluble organic matter. 2 Experimental data Sodium
A critical aspect of employing a geochemical model is exper- . metaborate
NaBO2 2H2O
imental validation. Models have been validated by published
1 NaCl . NaBO2 . 2H2O
laboratory tests followed by extending the model to similar
NaCl(c)
systems in natural settings. Felmy and Weare (1995) incor-
0
porated Pitzer’s equations into an ion-interaction model, the 0 1 2 3 4 5
purpose of which was to allow chemical speciation in high NaBO2 (m)
ionic strength solutions. The Davies equation for activity coef-
ficients was found to inadequately predict γ± for many salts at FIGURE 12.10  The system NaBO2–NaCl–H2O at 20°C. Experimental
ionic strengths as low as 0.2 mol L−1 for 1:1 electrolytes and data of Skvortsov et al. (1976) are shown as symbols, and the model pre-
0.05 mol L−1 for 2:1 electrolytes (Figure 12.9). The parameters dictions of Felmy and Weare (1995) are represented as lines.
for the ion-interaction model were obtained experimentally
and applied to several systems, including Na 2B 4O7–Na 2SO4 – more thorough studies involved the controlled reduction of fer-
H2O, Na 2B 4O7–Na 2CO3 –H 2O, and NaBO2–NaCl–H 2O systems. ric oxides (Brennan and Lindsay, 1998). Figure 12.11 is a redraft-
Salt concentrations were varied, and other activities measured. ing of the experimental data in conjunction with the solubility
The agreement between modeling predictions and experimen- constants of the solid phases from the Visual MINTEQ data-
tal results were ±10%, even in the NaBO2–NaCl–H 2O system base. The implications of the original publication are unchanged
(Figure 12.10) with very high borate concentrations and ionic despite some significant differences between the MINTEQ
strengths as high as 14 mol L−1. constants and those used by Brennan and Lindsay (1998). The
The effect of redox on the solubility of Fe in soil and aqueous observed solubilities of Fe2+ as a function of redox had a slope
systems has been a subject of study for decades. The presence of consistent with a solid phase with a stoichiometry of Fe(II)
mixed valence state oxides has been observed and implied, and Fe(III)2O4. Although the molecular structure and Fe valence
extensive equilibrium studies have been published. One of the states of the resultant precipitate were not verified, the authors
Soil Solution 12-21

20 and we have the least thermodynamic information about them.

Hematite These compounds can be very complex and contain a wide
Fer Ferrihydrite range of functional groups and molecular chemical environ-
15 r ihy
dri
te
Aged ments, making it difficult to approximate complexation con-
stants. Thus, a decision must be made either to ignore the effects
of soluble organics completely because their impact cannot be
log(Fe2+) + 2pH

10
Fe O quantified exactly or to apply estimates of the constants. The lat-
Hem 3
4 (am ter approach has been applied with some success, including the
atite or)
5 addition of an organic component to Visual MINTEQ.

Fe
3O
4 (m
12.8  Current Status and Future
0 agn
etit
e) Research Directions
–5
This review of the chemistry of the soil solution assumed a distinct
0 5 10 15 theoretical approach and did not focus on some of the excellent,
pe + pH recent advances in other aspects of the science. Topics not covered
FIGURE 12.11  Oxidation/reduction experiments under controlled include colloidal chemistry (both inorganic and organic), spectro-
conditions with different starting materials or different incubation peri- scopic approaches to identifying important complexes in the soil
ods. The open squares began with hematite, the open circles began with solution, salinity, xenobiotics in soil solutions, and heavy metals.
ferrihydrite, and the filled triangles were aged for 15 days. (From Brennan, Most of these topics are covered in other chapters.
E.W., and W.L. Lindsay. 1998. Reduction and oxidation effect on the solu- The study of the soil solution has its origins in agriculture,
bility and transformation of iron oxides. Soil Sci. Soc. Am. J. 62:930–937.) and a great portion of soil chemical research remains agricul-
turally oriented. Many challenges exist in which soil chemists
suggested that Fe solubility was being controlled by an amor- will play a pivotal role including managing soil acidity, grow-
phous form of magnetite, Fe3O4(amorphous). ing crops in arid regions with limited or poor quality irrigation
water, adapting to the inevitable trend toward lower quality fer-
12.7.5  Limitations to Applying Geochemical tilizers, and contributing to the development of truly sustainable
Models to Soil Solutions agricultural systems.
Although soil chemistry has its history and future firmly
Four major limitations exist in the application of equilibrium rooted in agriculture, soil chemists are increasingly finding a
geochemical models to soil solutions: the dynamic (nonequilib- niche in other, less traditional research areas. Geochemists,
rium) nature of soils, poorly defined equilibria, limitations in the environmental engineers, hydrologists, and chemical engi-
analytical chemistry, and lack of knowledge of how to accurately neers are finding that soil chemists make excellent research
handle soluble organic compounds. The ever-changing nature partners in solving environmental and production problems.
of soils naturally leads to nonequilibrium conditions. Although Working knowledge of and the ability to use new technologies
equilibrium within the soil solution may be attained quickly, have allowed soil chemists to explore new areas: molecular-level
solid and gas phases often establish equilibrium at a slow rate, if spectroscopy to quantify the chemistry of surfaces, complex-
at all. Unfortunately, these systems have a very strong impact on ation reactions in solution, and chemical associations in both
the composition of the soil solution. Understanding the degree the solid and solution phases; analytical instrumentation to
of nonequilibrium and the rate at which a steady state is being quantify ultratrace quantities of contaminants; and molecular
approached can be discerned by sampling the soil solution over genetics of microorganisms to help answer difficult ecological
time and monitoring the progress of the chemical reactions. and environmental questions.
Suarez (1995) discussed the merits of a nonequilibrium approach
to modeling the carbonate system.
The problem of poorly defined equilibria arises when informa- References
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 13
Kinetics and Mechanisms
of Soil Chemical Reactions
13.1 Introduction............................................................................................................................13-1
13.2 Timescales of Soil Chemical Processes...............................................................................13-1
13.3 Application of Chemical Kinetics to Heterogeneous Surfaces........................................13-2
Rate-Limiting Steps  •  Rate Laws  •  Determination of Reaction Order
and Rate Constants/ Coefficients
13.4 Kinetic Models........................................................................................................................13-5
Ordered Models  •  Elovich Equation  •  Parabolic Diffusion Equation  • 
Fractional Power or Power Function Equation  •  Z(t) and Diffusion Models  • 
Implications of Diffusion Models  •  Multiple Site Models
13.5 Kinetics of Important Reactions on Soils and Soil Components..................................13-11
Sorption/Desorption Reaction Rates  •  Kinetics of Mineral Dissolution  •  Redox Kinetics
Donald L. Sparks 13.6 Conclusions...........................................................................................................................13-25
University of Delaware References.........................................................................................................................................13-25

13.1  Introduction soil CRs. Arguably, this will be a major leitmotif in soil chemis-
try research for decades to come.
Since its inception in the mid-1850s, soil chemistry has focused In this review, the application of chemical kinetics to hetero-
on the macroscopic, equilibrium aspects of soil chemical reac- geneous systems, such as soils and soil components (clay miner-
tions (CRs) and processes. From these studies, much was als, organic matter, metal hydr(oxides), and humic substances),
learned about important soil chemical processes, including with emphasis on sorption/release processes will be discussed.
sorption, desorption, precipitation, complexation, dissolution, A critical review of kinetic models that can be used to describe
and ­oxidation/reduction. However, such investigations do not reaction rates on heterogeneous surfaces will be covered. The
convey information on reaction rates or reaction mechanisms. review will also present discussions on the rates of important
In the past three decades, as concerns and interests about soil soil CRs and processes including inorganic and organic sorp-
and water quality have increased, soil and environmental chem- tion/desorption, dissolution, and redox. For additional details
ists, environmental and chemical engineers, and geochemists on these topics and other aspects of kinetics of soil chemical and
have increasingly realized that reactions in subsurface environ- geochemical processes, the reader should consult a number of
ments are time dependent. Thus, to accurately predict the fate, recent books and monographs (Sparks, 1989, 1995, 2002, 2005;
mobility, speciation, and bioavailability of environmentally Sparks and Suarez, 1991; Stumm, 1992; Schwarzenbach et  al.,
important plant nutrients, trace elements, radionuclides, and 1993; Sposito, 1994; Grossl et al., 1997; Matocha et al., 2005;
organic chemicals in soils, one must understand the kinetics Borda and Sparks, 2008).
and mechanisms of the reactions.
While major progress has been made in better understand- 13.2  Timescales of Soil
ing the kinetics of soil chemical processes, much uncertainty Chemical Processes
remains. In part, this is due to the complex, heterogeneous nature
of natural materials such as soils. However, with the develop- A variety of CRs occur in soils and often in combination with
ment of kinetic techniques that can be used to measure a wide one another. Reaction timescales can vary from microseconds to
range of timescales, time-dependent models that can describe milliseconds for many ion association and some ion exchange,
both CR and mass transfer processes, and the employment of sorption, and redox reactions to years for many mineral solu-
state-of-the-art in situ spectroscopic and microscopic surface tion and mineral crystallization phenomena and for some sorp-
techniques in combination with rate studies, major advances are tion/release reactions (Figure 13.1). Ion association reactions
being made in understanding the kinetics and mechanisms of include ion pairing, inner- and outer-sphere complexation,

13-1
13-2 Properties and Processes

Ion association
studied, but the CR rate appears to be rapid. For example, CR
rates of metals and oxyanions on goethite occurred on millisec-
Multivalent ion hydrolysis ond timescales (Zhang and Sparks, 1989, 1990a, 1990b; Grossl
Gas–water et al., 1994, 1997). Reaction rates of redox processes can also be
very rapid. For example, Parikh et al. (2008) found that 50% of
Ion exchange
the initial reaction process for As(III) oxidation on Mn oxides
Sorption occurred in 1 min. Half-times for divalent Pb, Cu, and Zn sorp-
Mineral–solution
tion on peat ranged from 5 to 15 s (Bunzl et al., 1976). A num-
ber of studies have shown that heavy metal sorption on oxides
Mineral crystallization (Bruemmer et al., 1988; Ainsworth et al., 1994; Scheidegger
and Sparks, 1996a; Scheidegger et al., 1998) and clay minerals
(Lövgren et al., 1990) increases with longer residence times. The
us s min h day month year mil
mechanism for these lower reaction rates is not well understood
Timescale but has been ascribed to diffusion phenomena, sites of lower reac-
FIGURE 13.1  Time ranges required to attain equilibrium by differ- tivity, and surface nucleation/precipitation (Scheidegger and
ent types of reactions in soil environments. (Reprinted with permission Sparks, 1996b; Sparks, 1998, 1999a, 1999b). Recent findings on
from Amacher, M.C. 1991. Methods of obtaining and analyzing kinetic slow metal retention rates and mechanisms at the mineral/water
data, p. 19–59. In D.L. Sparks and D.L. Suarez (eds.) Rates of soil chemical interface will be discussed later.
processes. SSSA, Madison, WI.) Sorption/desorption of metals and organic chemicals on soils
is often very slow, which has been attributed to diffusion into
and chelation in solution. Gas–water reactions involve gaseous micropores of inorganic minerals and into humic substances,
exchange across the air–liquid interface. Ion exchange reac- retention on sites of varying reactivity, and surface nucleation/
tions occur when cations and anions are adsorbed (outer-sphere precipitation (Sparks 1989, 1999a, 1999b, 2002, 2005; Scheidegger
complexation) and desorbed from soil surfaces by electrostatic and Sparks, 1996b; Matocha et al., 2005; Borda and Sparks, 2008).
attractive forces. Ion exchange reactions are reversible and These reactions will be discussed in more detail later.
stoichiometric. Sorption reactions can involve adsorption pro-
cesses, including partitioning, outer-sphere and inner-sphere 13.3  Application of Chemical Kinetics
complexation, and multinuclear complexation (e.g., surface pre- to Heterogeneous Surfaces
cipitation). Mineral–solution reactions include precipitation/
dissolution of minerals and coprecipitation reactions in which The study of chemical kinetics, even in homogeneous systems,
small constituents become a part of mineral structures (Sparks, is complex and often arduous. When one attempts to study the
1989; Amacher, 1991). kinetics of reactions in heterogeneous systems such as soils, sedi-
The type of soil component can drastically affect the reac- ments, and even soil components, such as clay minerals, hydrous
tion rate. For example, sorption reactions are often more rapid oxides, and humic substances, the difficulties are greatly magni-
on clay minerals, such as kaolinite and smectites, than on ver- fied. This is largely due to the complexity of soils that are made
miculitic and micaceous minerals. This is in large part due to up of a mixture of inorganic and organic components. These
the availability of sites for sorption. For example, kaolinite has components often interact with each other and display different
readily available planar external sites, and smectites have pri- types of sites with various reactivities for inorganic and organic
marily internal sites that are also quite available for retention of sorptives. Moreover, the variety of particle sizes and porosities
sorbates. Thus, sorption reactions on these soil constituents are in soils and sediments further adds to their heterogeneity. In
often quite rapid, even occurring on timescales of seconds and most cases, both chemical kinetics and multiple transport pro-
milliseconds (Sparks, 1989, 2005). cesses are occurring simultaneously. Thus, the determination
On the other hand, vermiculite and micas have multiple sites of chemical kinetics, which can be defined as the investigation
for retention of metals and organics, including planar, edge, and of rates of CRs and of the molecular processes by which reac-
interlayer sites, with some of the latter sites being partially to tions occur where transport is not limiting (Gardiner, 1969), is
totally collapsed. Consequently, sorption and desorption reac- extremely difficult, if not impossible, in heterogeneous systems.
tions on these sites can be slow, tortuous, and mass transfer con- In these systems, one is studying kinetics, which is a generic
trolled. Often, an apparent equilibrium may not be reached even term referring to time-dependent or nonequilibrium processes.
after several days or weeks. Thus, with vermiculite and mica, Thus, apparent and nonmechanistic rate laws and rate param-
sorption can involve two to three different reaction rates: high eters are determined (Skopp, 1986; Sparks, 1989).
rates on external sites, intermediate rates on edge sites, and low
rates on interlayer sites (Jardine and Sparks, 1984; Comans and
13.3.1  Rate-Limiting Steps
Hockley, 1992).
Metal sorption reactions on oxides, hydroxides, and humic Both transport and CR processes can affect the reaction rates
substances depend on the type of surface and metal being in the subsurface environment. Transport processes include
Kinetics and Mechanisms of Soil Chemical Reactions 13-3

system, and a, b, y, and z are stoichiometric coefficients and are

assumed to be equal to 1 in the discussion that follows on rate
laws. The power to which the concentration is raised may equal
0 (i.e., the rate is independent of that concentration), even for
1 2 reactant A or B. Rates are expressed as a decrease in reactant
concentration or an increase in product concentration per unit
3 time. Thus, the rate of conversion of reactant A above, which
4 has a concentration [A] at any time t, is (−d[A]/(dt)) while the
6 5 rate with regard to product Y having a concentration [Y] at time
t is (d[Y]/(dt)).
The rate expression for Equation 13.1 is therefore as follows:

d[Y ] d[ A]
= [ A] [B] , (13.2)
α β
=−
dt dt
Liquid Film Solid

FIGURE 13.2  Transport processes in solid–liquid soil reactions— where

nonactivated processes: (1) transport in the soil solution, (2) transport k is the rate constant
across a liquid film at the solid–liquid interface, (3) transport in a liquid- α and β are the orders of the reaction with respect to reac-
filled macropore—activated processes, (4) diffusion of a sorbate at the tants A and B, respectively, and can be referred to as a par-
surface of the solid, (5) diffusion of a sorbate occluded in a micropore,
tial orders for the total reaction
(6) diffusion in the bulk of the solid. (Reprinted from Aharoni, C., and
D.L. Sparks. 1991. Kinetics of soil chemical reactions: A theoretical treat-
These orders are experimentally determined and not necessarily
ment, p. 1–18. In D.L. Sparks and D.L. Suarez (eds.) Rates of soil chemical
integral numbers. The sum of all the partial orders (α and β) is
processes. SSSA, Madison, WI.)
the overall order (n) of the total reaction and may be expressed
(Aharoni and Sparks, 1991) the following: (1) transport in the as follows:
solution phase; (2) transport across a liquid film at the particle/
n = α + β + (13.3)
liquid interface (film diffusion [FD]); (3) transport in liquid-
filled macropores (>2 nm), all of which are nonactivated diffu-
Once the values of α, β, etc., are determined experimentally,
sion processes and occur in mobile regions; (4) particle diffusion
the rate law is defined. Reaction order provides only informa-
(PD) processes, which include diffusion of sorbate occluded in
tion about the manner in which rate depends on concentration.
micropores (<2 nm, pore diffusion) and along pore wall surfaces
Order does not mean the same as molecularity, which concerns
(surface diffusion); and (5) diffusion processes in the bulk of
the number of reactant particles (atoms, molecules, free radicals,
the solid, all of which are activated diffusion processes (Figure
or ions) entering into an elementary reaction. One can define
13.2). Pore and surface diffusion within the immediate region
an elementary reaction as one in which no reaction intermedi-
can be referred to as interaggregate (interparticle) diffusion
ates have been detected or need to be postulated to describe the
while that in the solid is intraaggregate diffusion. The actual
CR on a molecular scale. An elementary reaction is assumed
CR at the surface, for example, adsorption, is usually instan-
to occur in a single step and to pass through a single transition
taneous. The slowest of the CR and transport processes is rate
state (Bunnett, 1986).
limiting.
To demonstrate that a reaction is elementary, one can use
experimental conditions that are different from those employed
13.3.2  Rate Laws in determining the reaction rate law. For example, if one con-
There are two important reasons for investigating the rates of ducted kinetic studies using a flow technique with set steady-
soil chemical processes (Sparks, 1989, 1995, 1998, 1999a, 1999b, state flow rates, one could see if reaction rate and rate constants
2002) (1) to determine how rapidly reactions attain equilibrium changed with flow rate. If they did, one would not be determin-
and (2) to infer information on reaction mechanisms. One of the ing mechanistic rate laws (see definition below).
most important aspects of chemical kinetics is the establishment Rate laws serve three purposes: (1) they assist one in predict-
of a rate equation or law. By definition, a rate law is a differen- ing the reaction rate, (2) mechanisms can be proposed, and
tial equation. For the following reaction (Bunnett, 1986; Sparks, (3) reaction orders can be ascertained. There are four types of
1989, 1995, 1998, 1999a, 1999b, 2002), rate laws that can be determined for soil chemical processes
(Skopp, 1986): mechanistic, apparent, transport with apparent,
aA + bB → yY + zZ , (13.1) and transport with mechanistic. Mechanistic rate laws assume
that only chemical kinetics are operational and transport phe-
the rate is proportional to some power of the concentrations nomena are not occurring. Consequently, it is difficult to deter-
of reactants A and B and/or other species (C, D, etc.) in the mine mechanistic rate laws for most soil chemical systems due
13-4 Properties and Processes

to the heterogeneity of the system caused by different particle Equations 13.5 and 13.6 are only applicable far from equilib-
sizes, porosities, and types of retention sites. There is evidence rium where back or reverse reactions are insignificant. If both
that with some kinetic studies, using chemical relaxation tech- forward and reverse reactions are occurring, Equations 13.5 and
niques (Sparks, 1989; Sparks and Zhang, 1991), that mechanis- 13.6 must be combined such that
tic rate laws are determined or closely approximated since the
agreement between equilibrium constants calculated from both d[ A]
= −k1[ A][B] + k−1[Y ]. (13.7)
kinetic and equilibrium studies are comparable (Hachiya et al., dt
1984; Tang and Sparks, 1993). Recent studies using molecular
scale in situ spectroscopic methods such as attenuated total Equation 13.7 applies the principle that the net reaction rate is
reflectance Fourier transform infrared (ATR–FTIR) and quick the difference between the sum of all reverse reaction rates and
x-ray absorption spectroscopy (QXAS; Parikh et al., 2008; the sum of all forward reaction rates.
Ginder-Vogel et al., 2009; Landrot et al., 2010) to measure rapid One way to ensure that back reactions are not important is to
initial reaction rates also show that chemical kinetics are being measure initial rates. The initial rate is the limit of the reaction
measured, and, thus, mechanistic rate laws can be proposed. rate as time reaches zero. With an initial rate method, one plots
Since natural materials are heterogeneous and transport pro- the concentration of a reactant or product over a short reaction
cesses often affect the reaction rate, apparent rate laws are usu- time period during which the concentrations of the reactants
ally determined for such systems. Apparent rate laws include change so little that the instantaneous rate is hardly affected.
both chemical kinetics and transport-controlled processes. Thus, by measuring initial rates, one could assume that only the
Thus, soil structure, stirring, mixing, and flow rate all would forward reaction in Equation 13.4 predominates. This would
affect the kinetics. Transport with apparent rate laws emphasizes simplify the rate law to that given in Equation 13.5, which, as
transport-limited phenomena. One often assumes first-order or written, would be a second-order reaction, first order in reac-
zero-order reactions (see the following discussion on reaction tant A and first order in reactant B. Equation 13.5, under these
order). In determining transport with mechanistic rate laws, conditions, would represent a second-order irreversible elemen-
one attempts to describe simultaneously transport-controlled tary reaction. To measure initial rates, one must have available
and chemical kinetics phenomena. One is thus trying to explain a technique that can measure rapid reactions, such as a chemi-
accurately both the chemistry and physics of the system. cal relaxation method or a rapid molecular scale spectroscopic
technique and an accurate analytical detection system to deter-
mine product concentrations. Recently, Parikh et al. (2008) used
13.3.3  Determination of Reaction Order a novel real-time ATR–FTIR spectroscopic technique to mea-
and Rate Constants/Coefficients sure the initial rates of As(III) oxidation on Mn oxides. Using
There are three basic ways to determine rate laws and rate a rapid scan technique, IR spectra were collected with a time
constants/coefficients (Bunnett, 1986; Skopp, 1986; Sparks, resolution of up to 2.55 s. Ginder-Vogel et al. (2009) and Landrot
1989, 1995, 1998, 1999a, 1999b, 2002): (1) initial rates, (2) directly et al. (2010) have employed state-of-the-art QXAS to investi-
using integrated equations and graphing the data, and (3) using gate initial rates of As(III) oxidation on hydrous Mn oxide and
nonlinear least-squares analysis. Cr(III) oxidation on hydrous Mn oxide, respectively. In the
Let us assume the following elementary reaction between study of Ginder-Vogel et al. (2009), QXAS scans were collected
species A, B, and Y: every 0.98 s, while scans were collected every 0.75 s in the study
of Landrot et al. (2010).
⎯⎯k⎯
1
→ Y. Integrated rate equations can also be used to determine rate
A+B ← ⎯ (13.4)
k −1 constants/coefficients. If one assumes that reactant B in Equation
13.5 is in large excess of reactant A, which is an example of the
A forward reaction rate law can be written as method of isolation to analyze kinetic data, and Yo = 0, where Yo
is the initial concentration of product Y, Equation 13.5 can be
d[ A] simplified to
= −k1[ A][B], (13.5)
dt
d[ A]
where = −k1ʹ[ A], (13.8)
dt
k1 is the forward rate constant
α and β (see Equation 13.2) are each assumed to be 1 where k1ʹ = k1[B].
The first-order dependence of [A] can be evaluated using the
The reverse reaction rate law for Equation 13.4 is integrated form of Equation 13.8 using the initial conditions at
d[ A] t = 0, A = Ao:
= + k−1[Y ], (13.6)
dt
k1ʹt
log[ A]t = log[ A]o − . (13.9)
where k−1 is the reverse rate constant. 2.303
Kinetics and Mechanisms of Soil Chemical Reactions 13-5

1.6 is assumed but the reaction is first order, upward curvature

is observed. Curvature can also be due to fractional, third,
[Mn2+]o = 40 μM higher, or mixed reaction order. Nonattainment of equilibrium
1.4 y = 1.61 – (8.65 × 10–3)x, R2 = 0.998 often results in downward curvature. Temperature changes
during the study can also cause curvature; thus, it is impor-
log Mn2+, μM

1.2
tant that temperature be accurately controlled during a kinetic
experiment.

[Mn2+]o = 25 μM
1.0

y = 1.38 – (8.57 × 10–3)x, R2 = 0.999

13.4  Kinetic Models
0.8
20 30 40 50 60 13.4.1  Ordered Models
Time, ms
First-order kinetic models often describe reactions at the soil
FIGURE 13.3  Initial reaction rates depicting the first-order depen- mineral/water interface. Both single first-order and multiple
dence of Mn2+ sorption as a function of time for initial Mn2+ concen-
first-order reactions have been described by many investigators
trations ([Mn2+]o) 25 and 40 μM. (Reprinted from Fendorf, S.E. et al.
(Sparks, 1989, 1991, 2002; Sparks et al., 1993).
1993. Soil Sci. Soc. Am. J., 57:57–62. With permission of the Soil Science
Society of America.) It is not uncommon to observe biphasic kinetics, namely,
a rapid reaction rate followed by a much slower reaction rate.
The half-time (t1/2) for the above reaction is equal to 0.693/k1�and Such data can often be described by two first-order reactions.
is the time required for half of reactant A to be consumed. Some investigators have interpreted such biphasic kinetics to
If a reaction is first order, a plot of log [A]t versus t should suggest reactions on two types of sites, such as external, read-
result in a straight line with a slope = k1ʹ/2.303 and an intercept ily accessible sites (Slope 1) and internal, difficult to access sites
of log [A]o. An example of first-order plots for Mn 2+ sorption (Slope 2) (Jardine and Sparks, 1984; Comans and Hockley, 1992)
on δ-MnO2 at two initial Mn 2+ concentrations, [Mn 2+]o (25 and or molecular sites of differing reactivity such as high-reactivity
40 μM), is shown in Figure 13.3. One sees that the plots are inner-sphere complex sites and low-reactivity outer-sphere com-
linear at both concentrations, which would indicate that the plex sites (Grossl et al., 1994, 1997).
sorption process is first order. The [Mn 2+]o ­v alues obtained However, it is unsound to conclude anything about mecha-
from the intercepts in Figure 13.3 were 24 and 41 μM, which nisms based solely on multiple rate constants that are calculated
are in good agreement with the two [Mn 2+]o values, and the from multiple slopes of kinetic plots. There are other ways to
rate constants were 3.73 × 10 −3 and 3.75 × 10 −3 s−1, respectively. definitively ascertain reaction mechanisms, such as calculating
The fact that the rate constants do not significantly change energies of activation, elucidating rate-limiting steps through
with concentration is a good indication that the ­reaction in stopped flow and interruption approaches, using independent
Equation 13.8 is first order under the imposed experimental or direct methods to determine mechanisms such as spectro-
conditions. scopic and microscopic techniques, and employing blocking
It is dangerous to conclude that a particular reaction order agents that are specific for certain reaction sites. An example
is correct, based simply on the conformity of data to an inte- of the latter approach is found in the research of Jardine and
grated equation. As illustrated above, multiple initial concentra- Sparks (1984) who studied K–Ca exchange on a Delaware soil
tions that vary considerably should be employed to see if the rate at three temperatures and observed two apparent simultane-
is independent of concentration. One should also test multiple ous first-order reactions at 283 and 298 K (Figure 13.4). They
integrated equations. It may also be useful to show that reaction hypothesized that the first, more rapid reaction was predomi-
rate is not affected by a species whose concentration does not nantly due to adsorption on external planar sites of the organic
change considerably during an experiment, such as substances matter and kaolinite in the soil. The slower reaction was
not consumed or present in large excess (Bunnett, 1986; Sparks, ascribed to vermiculitic clay sites that promoted slow pore and
1989, 1991, 1995, 1998, 1999a, 1999b). surface diffusion. These hypotheses were seemingly validated
Least-squares analysis can also be used to determine rate using a large organic polymer, cetyltrimethylammonium bro-
constants/coefficients. With this method, one fits the best straight mide (CTAB), which because of its size is sterically hindered
line to a set of points that are linearly related as y = mx + b, where from internal sites. Thus, CTAB should only block external pla-
y is the ordinate and x is the abscissa datum point, respectively. nar sites. When CTAB was applied to the soil, the first slope was
The slope (m) and the intercept (b) can be calculated by least- eliminated, while the second slope was still present, suggesting
squares analysis. multireactive sites.
When kinetic data are plotted, curvature may be observed While first-order models have been used widely to describe
due to an incorrect assumption of reaction order. If first- the kinetics of CRs on natural materials, a number of other sim-
order kinetics is assumed and the reaction is really second ple kinetic models have also been employed. These include vari-
order, downward curvature results. If second-order kinetics ous ordered equations such as zero, second, and fractional order;
13-6 Properties and Processes

Time, min
0 50 100 150 200 250 300 350
0

–0.2 = 283 K
= 298 K
= 313 K
–0.4

–0.6
log, l – Kt/K∞

–0.8
Time, min
–1.0 0 10 20 30 40 50
0
–0.04 = 298 K
–1.2 = 313 K
log(l – Kt/K∞)

r = –999
–0.12
–1.4 r = –0.994
–0.20
r = –0.999
–0.28

–0.36
–1.8

FIGURE 13.4  First-order kinetics for potassium adsorption at three temperatures on Evesboro soil with inset showing the initial 50 min of the
first-order plots at 298 and 313 K. (Reprinted from Jardine, P.M., and D.L. Sparks. 1984. Potassium-calcium exchange in a multireactive soil system.
I. Kinetics. Soil Sci. Soc. Am. J. 48:39–45. With permission of the Soil Science Society of America.)

TABLE 13.1  Linear Forms of Kinetic Equations Commonly Used 13.4.2  Elovich Equation
in Environmental Soil Chemistry
The Elovich equation was originally developed to describe the
Zero ordera
kinetics of heterogeneous chemisorption of gases on solid sur-
[ A]t = [ A]o − k1ʹt faces (Low, 1960). It seems to describe a number of reaction
First order mechanisms including bulk and surface diffusion and activation
k1ʹt and deactivation of catalytic surfaces.
log[ A]t = log[ A]o − In soil chemistry, the Elovich equation has been used to
2.303c
describe the kinetics of sorption and desorption of various inor-
Second orderb
ganic materials on soils (Sparks, 1989, 1995, 1998, 1999a, 1999b,
1 1 2002). It can be expressed as (Chien and Clayton, 1980)
= + kt
[ A]t [ A]o
Elovich ⎛ 1⎞ ⎛ 1⎞
q = ⎜ ⎟ ln(αβ) + ⎜ ⎟ ln t , (13.10)
⎝ β⎠ ⎝ β⎠
⎛ 1⎞ ⎛ 1⎞
q = ⎜ ⎟ ln(αβ) + ⎜ ⎟ ln t
⎝ β⎠ ⎝ β⎠
where
Parabolic diffusion q is the amount of sorbate per unit mass of sorbent at time t
⎛ 1 ⎞ ⎛ Qt ⎞ 4 ⎛ D⎞
1/2
1 D α and β are constants during any one experiment
⎜⎝ t ⎟⎠ ⎜⎝ Q ⎟⎠ = π1/2 ⎜⎝ r 2 ⎟⎠ −
∞ t 1/2 r 2
A plot of q versus ln t should give a linear relationship if the
Power function Elovich equation is applicable with a slope of (1/β) and an inter-
  ln qt = ln k + v ln t cept of (1/β)ln(αβ). An application of Equation 13.10 to P sorp-
Source: Sparks, D.L., Environmental Soil Chemistry, Academic Press, tion on soils is shown in Figure 13.5.
San Diego, CA, 1995. Some investigators have used the α and β parameters from
Terms in equations are defined in the text of the chapter. the Elovich equation to estimate reaction rates. For example, it
a Describing the reaction A → Y.

b ln x = 2.303 log x is the conversion from natural logarithms (ln) to base

has been suggested that a decrease in β and/or an increase in α
10 logarithms (log). would increase reaction rate. However, this is questionable. The
slope of plots using Equation 13.10 changes with the concentra-
Elovich; power function or fractional power; and parabolic dif- tion of the sorptive and with the solution-to-soil ratio (Sharpley,
fusion models. A brief discussion of some of these will be given; 1983). Therefore, the slopes are not always characteristic of the
the final forms of the equations are given in Table 13.1. For more soil but may depend on various experimental conditions.
complete details and applications of these models, one may con- Some researchers also have suggested that breaks or multiple
sult Sparks (1989, 1995, 1998, 1999a, 1999b, 2002). linear segments in Elovich plots could indicate a changeover
Kinetics and Mechanisms of Soil Chemical Reactions 13-7

160 and thus, a plot of Qt/Q∞/t versus 1/t1/2 should give a straight line
140 with a slope of

120 r 2 = 0.998 1/ 2
(C0 – C), μmol dm–3

4 ⎛D⎞
100 ⎜ ⎟
Okaihau soil
π1/2 ⎝ r 2 ⎠
80

60 and intercept of −D/r2. Thus, if r is known, D may be calculated

40 r 2 = 0.990
from both the slope and intercept.
Porirua soil The parabolic diffusion equation has successfully described
20 metal reactions on soils and soil constituents (Chute and Quirk,
0 1967; Jardine and Sparks, 1984; Krishnamurti and Huang, 1992;
–2 –1 0 1 2 3 4 5 6
In t, h
Krishnamurti et al., 1997), feldspar weathering (Wollast, 1967),
and pesticide reactions (Weber and Gould, 1966).
FIGURE 13.5  Plot of Elovich equation for phosphate sorption on two
soils where C 0 is the initial phosphorus concentration in the soil solu-
tion at time t. The quantity (C 0−C) can be equated to q, the amount 13.4.4  Fractional Power or Power
sorbed at time t. (Reprinted from Chien, S.H., and W.R. Clayton. 1980. Function Equation
Application of Elovich equation to the kinetics of phosphate release and
This equation can be expressed as
sorption in soils. Soil Sci. Soc. Am. J. 44:265–268. With permission from
the Soil Science Society of America.)
q = kt v , (13.13)

from one type of binding site to another (Atkinson et al., 1970).
However, such mechanistic suggestions may not be correct
where
(Sparks, 1989, 1995).
q is amount of sorbate per unit mass of sorbent at time t
k and v are constants
13.4.3  Parabolic Diffusion Equation v is positive and <1
The parabolic diffusion equation is often used to suggest that
Equation 13.13 is empirical, except for the case where v = 0.5,
diffusion-controlled phenomena are rate limiting. It was origi-
when it is similar to the parabolic diffusion equation.
nally derived from radial diffusion in a cylinder where the ion
Equation 13.13 and various modified forms have been used
concentration on the surface is constant, and initially, the ion con-
by a number of researchers to describe the kinetics of reac-
centration within the cylinder is uniform. It is also assumed
tions in natural materials (Kuo and Lotse, 1974; Havlin and
that ion diffusion through the upper and lower faces of the
Westfall, 1985).
cylinder is negligible. Following Crank (1976), the parabolic
diffusion equation as applied to soils can be expressed as
13.4.5  Z(t) and Diffusion Models
⎛ Qt ⎞ 4 Dt 1/2 Dt 1 Dt 3/2
⎜⎝ Q ⎟⎠ = π1/2 r 2 − r 2 − 3π1/2 r 2 , (13.11) In a number of studies, several simple kinetic models have
∞ described rate data well, based on correlation coefficients and
standard errors of the estimate (Chien and Clayton, 1980;
where
Onken and Matheson, 1982; Sparks and Jardine, 1984; Allen
r is the radius of the cylinder
et al., 1995). Despite this, there is often an inconsistent relation
Q t is the quantity of diffusing substance that has left the
between the equation that gives the best fit and the physico-
cylinder at time t
chemical and mineralogical properties of the sorbent(s) being
Q∞ is the corresponding quantity after infinite time
studied. Another problem with some of the kinetic models is
D is an apparent diffusion coefficient
that they are empirical and no meaningful rate parameters can
be obtained.
For the relatively short times in most experiments, the third and
Aharoni and Ungarish (1976) and Aharoni (1984) noted that
subsequent terms may be ignored and thus
some simple kinetic models are approximations of more general
expressions within certain limited time ranges. They suggested
Qt 4 Dt 1/2 Dt
= 1/2 2 − 2 a generalized empirical equation by examining the applicabil-
Q∞ π r r ity of power function, Elovich, and first-order equations to
or (13.12) experimental data. By writing these as the explicit functions of
the reciprocal of the rate (Z), which is (dq/dt)−1, one can show
1c Qtm 4 Dt 1/2 1 Dt that a plot of Z versus t should be convex if the power function
= 1/2 2 1/2 − 2 ,
t Q∞ π r t r equation is operational (1 in Figure 13.6); linear if the Elovich
13-8 Properties and Processes

3 One of the reasons a particular kinetic model appears to

1
2
be applicable may be that the study is conducted during the
3 time range when the model is most appropriate. While sorp-
tion, for example, decreases over many orders of magnitude
2 before equilibrium is approached, with most methods and
Z, arbitrary units

experiments, only a portion of the entire reaction is measured,

and over this time range, the assumptions associated with a
simple kinetic model (power function, Elovich, and first order)
are valid. Aharoni and Suzin (1982a, 1982b) showed that the
1
S-shaped curves could be well described using homogeneous
and heterogeneous diffusion models. In homogeneous diffu-
sion situations, the final and initial portions of the S-shaped
curves (conforming to the power function and first-order
0
0 1 2 3 4 5 6 7 8 9 10 equations, respectively) predominated, whereas in instances
Time, arbitrary units where the heterogeneous diffusion model was operational, the
linear portion of the S-shaped curve that conformed to the
FIGURE 13.6  Plot of Z versus time implied by (1) power function
Elovich equation predominated. Derivations of homogeneous
model, (2) Elovich model, and (3) first-order model. The equations for
the models were differentiated and expressed as explicit functions of the and heterogeneous diffusion models can be found in Aharoni
reciprocal of the rate, Z. (Reprinted with permission from Aharoni, C., and and Sparks (1991).
D.L. Sparks. 1991. Kinetics of soil chemical reactions: A theoretical treat-
ment, p. 1–18. In D.L. Sparks and D.L. Suarez (eds.) Rates of soil chemical
13.4.6  Implications of Diffusion Models
processes. SSSA, Madison, WI.)
The finding that slower reactions at the soil mineral/liquid inter-
face can be described by diffusional models indicates that the
200 kinetics of chemical processes cannot be considered separately
from physically limited transport phenomena. Thus, such a
combination of processes cannot be treated using first- or other-
150 order chemical kinetic equations. When one states that a reac-
Z, μg P g–1 h–1

tion between the molecular species A and B is first order with

respect to A, one assumes that the molecules of A have equal
100
chances of participating in the reaction, and therefore, the rate
is proportional to the concentration (CA). This reasoning can be
50 extended to a reaction between a sorbing surface and a sorptive.
In this case, CA refers to the number of reactive sites per unit
area, which corresponds to the number of unoccupied sites per
0
0 1 2 3 4 5 unit area (1 − θA). However, by using first-order kinetics (or other
Time, h order kinetics), one tacitly assumes that all the surface sites are
potential reactants at any time and have an opportunity of par-
FIGURE 13.7  Sorption of phosphate by a Typic Dystrochrept soil ticipating in the sorption process. If one assumes that there are
plotted as Z versus time. The circles represent the experimental data of
sites that cannot be reached directly from the fluid phase, but can
Polyzopoulos et al. (1986). The solid line is a curve calculated according
be reached after the sorbate has undergone sorption and desorp-
to a homogeneous diffusion model. (Reprinted with permission from
Aharoni, C., and D.L. Sparks. 1991. Kinetics of soil chemical reactions: tion at other sites, one cannot separate chemical kinetics from
A  theoretical treatment, p. 1–18. In D.L. Sparks and D.L. Suarez (eds.) diffusion-limited kinetics. The overall kinetic process obeys a
Rates of soil chemical processes. SSSA, Madison, WI.) diffusion equation since diffusion is the rate-limiting process.
However, the diffusion coefficient, which reflects the rate at
which the sorbate jumps from one site to another, is determined
equation is appropriate (2 in Figure 13.6); and concave if the by the rate of the CRs by which the sorbent–sorbate bonds are
first-order equation is appropriate (3 in Figure 13.6). However, created and destroyed. Additionally, the activation energy for
such plots for soil systems (Figure 13.7) are usually S-shaped, diffusion is equivalent to the activation energy of the CR.
convex at small, concave at large, and linear at some intermedi-
ate t value suggesting that the reaction rate can best be described
13.4.7  Multiple Site Models
by the power function, first order and Elovich equations in these
ranges of t, respectively. Thus, the S-shaped curve indicates that Based on the previous discussion, it is evident that simple
the above equations may be applicable, each over some limited chemical kinetic models such as ordered reaction, power func-
time range. tion, and Elovich models may not be appropriate to describe
Kinetics and Mechanisms of Soil Chemical Reactions 13-9

reactions in heterogeneous systems such as soils, sediments, (3) sites of differing sorbent type (organic matter and inorganic
and soil components. In these systems where there is a range of mineral surfaces); and (4) sites with different sorption mecha-
particle sizes and multiple retention sites, both chemical kinet- nisms. With chemical nonequilibrium sorption processes, the
ics and transport phenomena are occurring simultaneously, and sorbate may undergo two or more types of sorption reactions,
a fast reaction is often followed by a slower reaction(s). In such one of which is rate limiting. For example, a metal cation may
systems, nonequilibrium models that describe both chemical sorb to organic matter by one mechanism and to mineral sur-
and physical nonequilibrium and that consider multiple compo- faces by another mechanism, with one of the mechanisms being
nents and sites are more appropriate. Physical nonequilibrium is time dependent.
ascribed to some rate-limiting transport mechanism such as FD
or PD, while chemical nonequilibrium is due to a rate-­limiting 13.4.7.1  Chemical Nonequilibrium Models
mechanism at the particle surface (CR). Nonequilibrium ­models Chemical nonequilibrium models describe time-dependent
include two-site, multiple site, radial diffusion (pore diffu- reactions at sorbent surfaces. The one-site model is a first-order
sion), surface diffusion, and multiprocess models (Table 13.2). approach that assumes that the reaction rate is limited by only
Emphasis here will be placed on the use of these models to one process or mechanism on a single class of sorbing sites and
describe sorption phenomena. that all sites are of the time-dependent type. In many cases, this
The term sites can have a number of meanings (Brusseau model appears to describe soil CRs quite well. However, often
and Rao, 1989): (1) specific, molecular scale reaction sites; (2) it does not. This model would seem not appropriate for most
sites of differing degrees of accessibility (external and internal); heterogeneous systems since multiple sorption sites exist.

TABLE 13.2  Comparison of Sorption Kinetic Models

Conceptual Model Fitting Parameters Model Limitations
One-site model kd Cannot describe biphasic sorption/desorption
kd
S→C
Two-site model kd, Kp, X1 May not describe the “bleeding” or slow,
KpDeff reversible, nonequilibrium desorption for
S ʹ → Csʹ → C residual sorbed compounds (Karickhoff, 1980)
Radial diffusion penetration retardation (pore diffusion) Deff = f (n, t )Dmn /(1 − n)ρs K p Cannot describe instantaneous uptake without
model (Wu and Gschwend, 1986) additional correction factor; did not describe
KpDeff kinetic data for times greater than 103 min
S′ ↔ C′ → C (Wu and Gschwend, 1986)
Dual-resistance surface diffusion model (Miller and Pedit, 1992) Ds�kb Model calibrated with sorption data
Dskb predicted more desorption than occurred
S ʹ → Csʹ → C in the desorption experiments
(Miller and Pedit, 1992)
Multisite continuum compartment model (Connaughton α, β Assumption of homogeneous, spherical particles
et al., 1993) and diffusion only in aqueous phase
α
M (t ) ⎛ β ⎞
F (t ) = 1 − = 1− ⎜ ⎟
M ⎝ β + 1⎠
Pore space diffusion model (Fuller et al., 1993) De, ∈, Ks, 1/n, Feq
2
⎛ Sa (1−1/n) ⎞ ∂C(r )
⎛ ∂ C(r ) 2∂C(r ) ⎞
⎜⎝ ∈+ n K sC(r ) ⎟⎠ ∂t = De ⎜ ∂r 2 + r ∂r ⎟
⎝ ⎠

Source: Partially adapted from Connaughton, D.F., J.R. Stedinger, L.W. Lion, and M.L. Shuler. 1993. Description of time-varying desorption kinetics:
Release of naphthalene from contaminated soils. Environ. Sci. Technol. 27:2397–2403.
S, concentration of the bulk sorbed contaminant (g g−1); C, concentration of the bulk aqueous-phase contaminant (g mL−1); kd, first-order desorption rate
coefficient (min−1); S2, concentration of the sorbed contaminant that is rate limited (g g−1); Sl, concentration of the contaminant that is in equilibrium with
the bulk aqueous concentration (g g−1); X1, fraction of the bulk sorbed contaminant that is in equilibrium with the aqueous concentration; Kp, sorption
equilibrium partition coefficient (mL g−1); Deff, effective diffusivity of sorbate molecules or ions in the particles (cm2 s−1); S′, concentration of contaminant
in immobile bound state (mol g−1); C′, concentration of contaminant free in the pore fluid (mol cm−3); n, porosity of the sorbent (cm3 of fluid cm−3);
Dm, pore fluid diffusivity of the sorbate (cm2 s−1); ρs, specific gravity of the sorbent (g cm−3); f(n,t), pore geometry factor; kb, boundary layer mass transfer
coefficient (m s−1); r, radius of the spherical solid particle, assumed constant (m); ρ, macroscopic particle density of the solid phase (g m−3); Cs�, solution-
phase solute concentration corresponding to an equilibrium with the solid-phase solute concentration at the exterior of the particle (g L−1); Ds, surface dif-
fusion coefficient (m s−1); Kp, can be determined independently; Kp, Dm, and ρs can be determined independently; F(t), fraction of mass released through
time t; M(t), mass remaining after time t; M, total initial mass; β, scale parameter necessary for determination of mean and standard deviation of ks; α, shape
parameter; ∈, internal porosity of sorbent; C(r), concentration of sorptive in the aqueous phase in the pore fluid at radial distance r; Sa is the surface of
sorbent per unit volume of solid; 1/n, the adsorption isotherm slope; Ka, adsorption isotherm intercept; Deq, effective diffusion coefficient; a, radius of the
aggregate; Feq, equilibrium fraction of absorption sites.
13-10 Properties and Processes

The two-site (two compartment, two box) or bicontinuum 1.0

model has been widely used to describe chemical nonequilib-
rium (Leenheer and Ahlrichs, 1971; Hamaker and Thompson,
1972; Karickhoff, 1980; Karickhoff and Morris, 1985; McCall 0.8

Fractional mass released

and Agin, 1985; Jardine et al., 1992) and physical nonequilib-
rium (Nkedi-Kizza et al., 1984; Lee et al., 1988; van Genuchten 0.6
and Wagenet, 1989; Table 13.2). This model assumes that there
are two reactions occurring, one that is fast and reaches equi-
librium quickly and a slower reaction that can continue for long 0.4
time periods. The reactions can occur either in series or in paral-
lel (Brusseau and Rao, 1989).
In describing chemical nonequilibrium with the two-site 0.2
S2, 3 month equilibrated, α = 0.31 β = 2.9
model, two types of sorbent sites are assumed. One site involves
S3, α = 0.36 β = 250
an instantaneous equilibrium reaction and the other, the time-
0.0
dependent reaction. The former is described by an equilib- 0 2 4 6 8 10
rium isotherm equation while a first-order equation is usually Time, days
employed for the latter.
With the two-site model, there are two adjustable or fitting FIGURE 13.8  Mass fractional release of naphthalene from two soils,
S2 and S3 (S2 is a freshly contaminated soil, reacted with naphthalene for
parameters: the fraction of sites at local equilibrium (X1), and
3 months and S3 is a field [aged]-contaminated soil) fitted with a multi-
the rate constant (k). A distribution (Kd) or partition coefficient
site continuum compartment (Γ) model. (Reprinted from Connaughton,
(Kp) is determined independently from a sorption/desorption D.F., J.R. Stedinger, L.W. Lion, and M.L. Shuler. 1993. Description of time-
isotherm. varying desorption kinetics: Release of naphthalene from contaminated
To account for the multiple sites that may exist in heteroge- soils. Environ. Sci. Technol. 27:2397–2403. With permission American
neous systems, Connaughton et al. (1993) developed a multi- Chemical Society.)
site compartment (continuum) model (Γ) that incorporates a
continuum of sites or compartments with a distribution of rate and Roberts, 1991; Harmon et al., 1992; Pignatello et al., 1993).
coefficients that can be described by a gamma density func- Wu  and Gschwend (1986) successfully used the pore diffusion
tion. A fraction of the sorbed mass in each compartment is model to describe chlorobenzene congener sorption/desorption
at equilibrium with a desorption rate coefficient or distribu- on soils and sediments. Figure 13.9 shows experimental and
tion coefficient for each compartment or site (Table 13.2). The model fits for tetrachlorobenzene and pentachlorobenzene
multisite model has two fitting parameters α, a shape param- 1.0
eter, and 1/β, which is a scale parameter that determines the
mean standard deviation of the rate coefficients. Figure 13.8
shows application of the Γ model to desorption of naphthalene 0.8
from contaminated soils. The entire desorption process was
(C – Ce)/(C0 – Ce)

described well with this model.

0.6
13.4.7.2  Physical Nonequilibrium Models Pentachlorobenzene

A number of models can be used to describe physical non- 0.4

equilibrium reactions. Since transport processes in the mobile
phase are not usually rate limiting, physical nonequilibrium Tetrachlorobenzene
0.2
models focus on diffusion in the immobile phase or interag-
gregate/diffusion processes such as pore and/or surface dif-
fusion. The transport between mobile and immobile regions 0.0
is accounted for in physical nonequilibrium models in three 10–2 10–1 100 101 102 103 104 105
ways (Brusseau and Rao, 1989): (1) explicitly with Fick’s law Time, min
to describe the physical mechanism of diffusive transfer, (2)
explicitly by using an empirical first-order mass transfer FIGURE 13.9  Experimental and model fitting results for pentachlo-
robenzene and tetrachlorobenzene sorption on Iowa soils where C is
expression to approximate solute transfer, and (3) implicitly
the dissolved concentration of organic chemical in the bulk solution,
by using an effective or lumped dispersion coefficient that
C 0 is the initial concentration, and Ce is the equilibrium concentration.
includes the effects of sink/source differences and hydrody- The points represent experimental data and the solid lines represent fit
namic dispersion and axial diffusion. of the data to the radial diffusion (pore diffusion) model. (Reprinted
A pore diffusion model (Table 13.2) has been used by a num- from Wu, S., and P.M. Gschwend. 1986. Sorption kinetics of hydrophobic
ber of investigators to study sorption processes using batch organic compounds to natural sediments and soils. Environ. Sci. Technol.
systems (Wu and Gschwend, 1986; Steinberg et al., 1987; Ball 20:717–725. With permission from American Chemical Society.)
Kinetics and Mechanisms of Soil Chemical Reactions 13-11

sorption on soils. The sole fitting parameter in this model is the Pedit and Miller (1995) have developed a general multiple
effective diffusion coefficient (De), which may be estimated a pri- particle class pore diffusion model that accounts for differences
ori from chemical and colloidal properties. However, this esti- in physical and sorptive properties for each particle class (Table
mation is only valid if the sorbent material has a narrow particle 13.2). The model includes both instantaneous equilibrium sorp-
size distribution so that an accurate, average particle size can be tion and time-dependent pore diffusion for each particle class.
defined. Moreover, in the pore diffusion model, an average rep- The pore diffusion portion of the model assumes that solute
resentative De is assumed, which means there is a continuum in transfer between the intraparticle fluid and the solid phases is
properties across an entire pore size spectrum. This is not a valid fast vis-à-vis interparticle pore diffusion processes.
assumption for micropores in which there are higher adsorption Surface diffusion models, assuming a constant surface dif-
energies of sorbates causing increased sorption. The increased fusion coefficient, have been used by a number of research-
sorption reduces diffusive transport rates and results in nonlin- ers (Weber and Miller, 1988; Miller and Pedit, 1992). The dual
ear isotherms for sorbents with pores less than several sorbate resistance model (Table 13.2) combines both pore and surface
diameters in size. Other factors can cause reduced transport rates diffusion.
in micropores including steric hindrance, which increases as the
pore size approaches the solute size and greatly increased surface
area to pore volume ratios (which occurs as pore size decreases).
13.5  Kinetics of Important Reactions
Another problem with the pore diffusion model is that sorp- on Soils and Soil Components
tion and desorption kinetics may have been measured over a
In the past several decades, numerous studies have been con-
narrow concentration range. This is a problem since a sorption/
ducted on the kinetics of metal, oxyanion, radionuclide, plant
desorption mechanism in micropores at one concentration may
nutrient, and organic CRs on natural materials. In this section,
be insignificant at another concentration.
emphasis will be placed on the kinetics of sorption/desorption,
Fuller et al. (1993) used a pore space diffusion model (Table
precipitation/dissolution, and oxidation/reduction reactions on
13.2) to describe arsenate adsorption on ferrihydrite that
soils and soil components.
included a subset of sites whereby sorption was at equilibrium.
A Freundlich model was used to describe sorption on these sites.
Diffusion into the particle was described by Fick’s second law 13.5.1  Sorption/Desorption Reaction Rates
of diffusion; homogeneous, spherical aggregates, and diffusion
13.5.1.1  Heavy Metals and Oxyanions
only in the aqueous phase were assumed. Figure 13.10 shows
the fit of the model when sorption at all sites was controlled CRs of heavy metals and metalloids on soil components are
by intraaggregate diffusion. The fit was better when sites that rapid, occurring on a millisecond timescale. For such rapid
had attained sorption equilibrium were included based on the reactions, chemical techniques such as pressure jump (p-jump)
assumption that there was an initial rapid sorption on external relaxation (Hayes and Leckie, 1986; Sparks, 1989; Sparks and
surface sites before intraaggregate diffusion. Zhang, 1991; Grossl and Sparks, 1995; Sparks et al., 1996) and
molecular scale methods such as ATR–FTIR and QXAS (Parikh
0.12 60 and Chorover, 2007; Ginder-Vogel et al., 2009; Landrot et al.,
2010) should be used.
As/Fe molar ratio precipitate, μM

0.10 50 The use of p-jump relaxation to measure the kinetics of ion

sorption/desorption on metal oxide surfaces was pioneered by
0.08 40
% As adsorbed

several Japanese chemists. Their research includes some of the

As(V) Total 1 × 10–4 M
Fe(III) Total 5 × 10–4 M following sorption/desorption kinetic studies: divalent metal ion
0.06 30
pH 8.0; 24 h age; NaNO3 0.1 M (Hachiya et al., 1984), phosphate (Mikami et al., 1983a), chro-
0.04
Adsorption data 20 mate (Mikami et al., 1983c), and uranyl (Mikami et al., 1983b)
Model fit sorption reactions on γ-Al2O3. Hayes and Leckie (1986) were the
With exterior sites first to use p-jump relaxation to study sorption/desorption kinet-
0.02 10
No exterior sites
ics of a metal ion contaminant (Pb2+) on goethite (α-FeOOH).
0 0 Other successive studies monitored the rapid sorption/desorp-
0 50 100 150 200
Time, h tion kinetics of molybdate (Zhang and Sparks, 1989), sulfate
(Zhang and Sparks, 1990a), selenate and selenite (Zhang and
FIGURE 13.10  Comparison of pore space diffusion model fits of Sparks, 1990b), Cu2+ (Grossl et al., 1994), and arsenate and chro-
As(V) sorption with experimental data (dashed curve represents sorp-
mate (Grossl et al., 1997) on goethite. Additional studies have
tion where all surface sites are diffusion limited and the solid curve
investigated borate sorption/desorption kinetics on pyrophyllite
represents sorption on equilibrium sites plus diffusion-limited sites).
(Reprinted from Fuller, C.C., J.A. Davis, and G.A. Waychunas. 1993. (Keren et al., 1994) and on γ-Al2O3 (Toner and Sparks, 1995).
Surface chemistry of ferrihydride: Part 2. Kinetics of arsenate adsorption Details of many of these studies are summarized in Hayes
and coprecipitation. Geochim. Cosmochim. Acta 57:2271–2282. With and Leckie (1986), Sparks (1989, 1995), Sparks and Zhang (1991),
permission from Elsevier.) and Sparks et al. (1996) and will not be detailed here. A study
13-12 Properties and Processes

of Grossl et al. (1997) will be summarized to illustrate rapid CR 500

rates of two environmentally important oxyanions (chromate Fast τ
and arsenate) on goethite. A double relaxation was observed Slow τ
400
for both arsenate and chromate sorption/desorption over a pH
range of 6.5–7.5 for arsenate and 5.5–6.5 for chromate, respec-
tively (Figures 13.11 and 13.12). Based on the double relaxations, 300
a two-step process, resulting in the formation of an inner-sphere

τ–1, s–1
bidentate surface complex (Figure 13.13) was proposed. The first
step involves an initial ligand exchange reaction of the aqueous 200
oxyanion (H2AsO or HCrO4) with goethite, forming an inner-
sphere monodentate surface complex that produces signals asso-
100
ciated with fast τ values. The succeeding step involves a second
ligand exchange reaction, resulting in the formation of an inner-
sphere bidentate surface complex that produces the signal asso- 0
ciated with slow τ values. 5.5 5.7 5.9 6.1 6.3 6.5
To determine if the mechanism displayed in Figure 13.13 was pH
plausible and consistent with the kinetic data, the following lin-
FIGURE 13.12  τ−1 Values determined from p-jump experiments
earized rate equations relating reciprocal relaxation time values (τ1)
for chromate adsorption/desorption on goethite, as a function of pH.
to the concentrations of reactive species were used: (Reprinted from Grossl, P.R., M. Eick, D.L. Sparks, S. Goldberg, and C.C.
−1 −1 Ainsworth. 1997. Arsenate and chromate retention mechanisms on goe-
τ fast + τ slow = k1([XOH] + [ion species]) + k−1 + k2 + k−2 , (13.14)
thite. 2. Kinetic evaluation using a pressure-jump relaxation technique.
−1 . −1
Environ. Sci. Technol. 31:321–326. With permission from American
τ fast τ slow = k1[k2 + k−2 ]([XOH] + [ion species]) + k1k−2 , (13.15) Chemical Society.)

where the ion species are H2AsO4 or HCrO4. The derivation of Step 1
Fe OH HO O
these equations was obtained from Bernasconi (1976) and is based
on the two-step reaction system (A + B ↔ C ↔ D). If the mecha- O + As k1
OH
nism portrayed in Figure 13.13 is accurate, then a plot of τ1fast + τslow
−1
Fe OH
–
O OH k–1
1 . −1 Fe O X O
and τ fast τ slow as a function of the concentration term ([XOH] +
(or HCrO4–)
[ion species]) should be linear. Plots of Equations 13.14 and 13.15 O O–
Goethite surface
were linear for both arsenate and chromate, suggesting that the Fe OH H2O
proposed mechanism was plausible (Figures 13.14 and 13.15).
k2 Monodentate surface species
Fe O O
200
O X
Fast τ k–2
Fe O OH Step 2
Slow τ
OH–
150
Bidentate surface species

FIGURE 13.13  Proposed mechanism for oxyanion adsorption/desorp-

τ–1, s–1

100 tion on goethite. The X represents either As(V) or Cr(VI). (Reprinted

from Grossl, P.R., M. Eick, D.L. Sparks, S. Goldberg, and C.C. Ainsworth.
1997. Arsenate and chromate retention mechanisms on goethite. 2.
Kinetic evaluation using a pressure-jump relaxation technique. Environ.
50
Sci. Technol. 31:321–326. Copyright American Chemical Society.)

From the plots in Figures 13.14 and 13.15, forward and reverse
0 rate constants were obtained for the sorption and desorption
6 6.5 7 7.5 8 reactions of both the monodentate and bidentate steps where
pH k1 = slope (Figure 13.14); k−1 = intercept (Figure 13.14) − slope
(Figure 13.15)/slope (Figure 13.14); k2 = intercept (Figure 13.14) −
FIGURE 13.11  τ −1 Values determined from p-jump experiments
k−1 − k−2; and k−2 = intercept (Figure 13.15)/k−1. The calculated
for arsenate adsorption/desorption on goethite, as a function of pH.
rate constants for both chromate and arsenate adsorption/
(Reprinted from Grossl, P.R., M. Eick, D.L. Sparks, S. Goldberg, and C.C.
Ainsworth. 1997. Arsenate and chromate retention mechanisms on goe- desorption on goethite are listed in Table 13.3.
thite. 2. Kinetic evaluation using a pressure-jump relaxation technique. Overall, the forward rate constants associated with the for-
Environ. Sci. Technol. 31:321–326. With permission from American mation of the inner-sphere oxyanion/goethite surface complexes
Chemical Society.) were more rapid than the reverse rate constants. Therefore, the
Kinetics and Mechanisms of Soil Chemical Reactions 13-13

TABLE 13.3  Calculated Rate Constants for Chromate

2
r = 0.95 and Arsenate Adsorption/Desorption on Goethite
Step 1 Step 2
τ–1 fast + τ–1 slow, s–1

Arsenate kl = 10 L mol s
63 −1 −1 k2 = 15 s−1
k−1 = 8 s−1 k−2 = 8 s−1
keq = 105.35 L mol−1 s−1 keq = 100.26
k1
Chromate k1 = 105.8 L mol−1 s−1 k2 = 16 s−1
k−1 = 129 s−1 k−2 = 38 s−1
keq = 103.7 L mol−1 s−1 keq = 10−0.4
k–1 + k2 + k–2
Source: Reprinted from Grossl, P.R., M. Eick, D.L. Sparks,
S. Goldberg, and C.C. Ainsworth. 1997. Arsenate and
chromate retention mechanisms on goethite. 2. Kinetic
{[SOH] + [H2AsO4–]} × 10–5, mol L–1 evaluation using a pressure-jump relaxation technique.
Environ. Sci. Technol. 31:321–326. With permission from
FIGURE 13.14  Evaluation of the linearized rate Equation 13.14 for American Chemical Society.
the mechanism displayed in Figure 13.13 for arsenate. (Reprinted from
Grossl, P.R., M. Eick, D.L. Sparks, S. Goldberg, and C.C. Ainsworth. 1997. with chromate sorption (slightly less than 1). Thus, the mono-
Arsenate and chromate retention mechanisms on goethite. 2. Kinetic eval- dentate chromate/goethite surface complex is slightly favored
uation using a pressure-jump relaxation technique. Environ. Sci. Technol. over the bidentate surface complex. This is in agreement with
31:321–326. With permission from American Chemical Society.) spectroscopic data obtained from x-ray absorption fine structure
200 (XAFS) analyses (Fendorf et al., 1997), which indicate a mixture
of both monodentate and bidentate arsenate, and chromate sur-
r2 = 0.95 face complexes; but at low-surface coverage, a greater propor-
150 tion of chromate is associated with the monodentate complex
τ1 fast + τ1 slow, s–1

than the bidentate complex. The results from both kinetic and
XAFS experiments suggest that arsenate is more likely to form
100 an inner-sphere surface complex with goethite than chromate.
While p-jump relaxation techniques are useful for measur-
ing rapid reaction rates on soil components, the rate constants
50 are calculated from linearized rate equations, which include
k–1 + k2 + k–2 parameters that are determined from equilibrium and model-
ing studies. Consequently, the rate “constants” are not directly
0 determined.
1.0 2.0 2.5 3.0 3.5 4.0 4.5
The ideal way to measure rapid reaction rates that may often
{[SOH} + [HAsO]} × 104, mol L–1
comprise a major portion of the total reaction process for many
FIGURE 13.15  Evaluation of the linearized rate Equation 13.15 for soil chemical processes, particularly on soil components is to
the mechanism displayed in Figure 13.13 for arsenate. (Reprinted from use real-time molecular scale techniques such as ATR–FTIR and
Grossl, P.R., M. Eick, D.L. Sparks, S. Goldberg, and C.C. Ainsworth. 1997. QXAS. With these techniques, one can not only measure reac-
Arsenate and chromate retention mechanisms on goethite. 2. Kinetic eval- tion rates on millisecond timescales but also at the same time
uation using a pressure-jump relaxation technique. Environ. Sci. Technol. couple these measurements with spectroscopic analyses of the
31:321–326. With permission fromAmerican Chemical Society.) reaction mechanism (Parikh et al., 2008; Ginder-Vogel et al.,
2009; Landrot et al., 2010).
rate-limiting steps were the reverse reactions. The equilibrium
While the initial sorption of heavy metals is rapid, with the
constants listed in Table 13.3 were calculated using the rate con-
CR step occurring on second or millisecond timescales, further
stants for each reaction step in the proposed mechanism (Figure
sorption may be slow (Figure 13.16) occurring over timescales of
13.13) from the following relationship:
days and longer. Such behavior has been observed for some Fe
k1 oxides. This slow sorption has been ascribed to several mecha-
K eq = . (13.16) nisms, including interparticle or intraparticle diffusion in pores
k−1
and solids, sites of low reactivity, and surface precipitation/
The calculated equilibrium constant for Step 1 for arsenate was nucleation (Sparks, 1998; Strawn and Sparks, 2000). With het-
105.35 and for Step 2 was 100.26, while the calculated Keq for Step 1 erogeneous soils and even soil components, there may be a con-
for chromate was 103.7 and for Step 2 was 100.4. The sorption of tinuum between the three sorption mechanisms, for example,
both oxyanions and subsequent formation of inner-sphere sur- between adsorption and surface precipitation/nucleation. While
face complexes are thermodynamically favorable, with the excep- it has generally been assumed that adsorption in comparison
tion of the equilibrium constant for the second step associated with surface precipitation/nucleation is much more rapid, recent
13-14 Properties and Processes

100 100

80
75

Percent Pb sorbed
Relative Ni removal, %

60

Adsorption pH edge
50 Aging time = 0 week
40
Desorption
Aging time = 2 weeks
20 Aging time = 12 weeks
25
Aging time = 21 weeks

0
2 4 6 8 10 12
0 pH
0 50 100 150 200
FIGURE 13.17  Fractional sorption–desorption of Pb2+ to hydrous
Time, h
Fe(III) as a function of pH and HFO–Pb2+ aging time. (Reprinted from
FIGURE 13.16  Kinetics of Ni sorption [%] on pyrophyllite (◾), kaolin- Ainsworth, C.C., J.L. Pilon, P.L. Gassman, and W.G. Van Der Sluys. 1994.
ite (Δ), gibbsite (▲), and montmorillonite (○) from a 3 mM Ni solution Cobalt, cadmium, and lead sorption to hydrous iron oxide: Residence
at pH = 7.5 and an ionic strength I = 0.1M (NaNO3). The last sample of time effect. Soil Sci. Soc. Am. J. 58:1615–1623. With permission from the
each experiment was collected and analyzed by XAFS. (Reprinted from Soil Science Society of America.)
Scheidegger, A.M., G.M. Lamble, and D.L. Sparks. 1997. Spectroscopic
evidence for the formation of mixed-cation hydroxide phases upon Pb2+. With Pb2+ between pH 3 and 5.5 there was slight hysteresis
metal  sorption on clays and aluminum oxides. J.  Colloid Interface Sci. over a 21 week aging process (hysteresis varied from <2% differ-
186:118–128. With permission from Elsevier.) ence between sorption and desorption to ∼10%). At pH 2.5, Pb2+
desorption was complete within a 16 h period and was not affected
studies (Scheidegger et al., 1998) that will be discussed later, have by aging time (Figure 13.17). However, with Cd2+ and Co2+, exten-
shown that surface precipitation/nucleation processes can occur sive hysteresis was observed over a 16 week aging period and the
on timescales as short as 15 min, which indicates that sorption hysteresis increased with aging time (Figures 13.18 and 13.19). After
and nucleation processes can occur simultaneously. However, 16 weeks of aging, 20% of the Cd2+ and 53% of the Co2+ were not
in some cases, depending on reaction conditions and the metal desorbed, and even at pH 2.5, hysteresis was observed. The extent
involved, a particular sorption mechanism can dominate.
Obviously, an important factor affecting the degree of slow 15
sorption/desorption of metals (and for that matter also of 10
100
organic chemicals) is the time period the sorbate has been in
contact with the sorbent (residence time). Bruemmer et al. (1988) 5
Percent Cd sorbed

80
studied Ni2+, Zn2+, and Cd2+ sorption on goethite, a porous Fe 0 Adsorption pH edge
oxide that has defect structures in which metals can be incor- 60 2 3 4 5 6 7
Aging time = 0 week
porated to satisfy charge imbalances. Bruemmer et al. (1988)
found, at pH  6, that as reaction time increased from 2 h to 42 40
Desorption
days (at 293 K), adsorbed Ni2+ increased from 12% to 70% of total Aging time = 2 weeks
Aging time = 4 weeks
adsorption, and total Zn2+ and Cd2+ adsorption over this time 20 Aging time = 11 weeks
increased by 33% and 21%, respectively. The kinetic reactions Aging time = 16 weeks
could be well described using a Fickian diffusion model. Metal 0
uptake was hypothesized to occur by a three-step mechanism: 2 4 6 8 10 12
(1) adsorption of metals on external surfaces, (2) solid-state dif- pH
fusion of metals from external to internal sites, and (3) metal
FIGURE 13.18  Fractional sorption–desorption of Cd 2+ to hydrous
binding and fixation at positions inside the goethite particle.
Fe oxide (HFO) as a function of pH and HFO–Cd 2+ aging time; insert
Ainsworth et al. (1994) studied the adsorption/desorption of shows adsorption–desorption of Cd 2+ to HFO at 2 and 4 week aging
Co2+, Cd2+, and Pb2b+ on hydrous Fe(III) as a function of aging and times. (Reprinted from Ainsworth, C.C., J.L. Pilon, P.L. Gassman,
metal oxide residence time. Oxide aging did not cause hysteresis of and W.G. Van Der Sluys. 1994. Cobalt, cadmium, and lead sorption to
metal cation sorption/desorption. Aging the oxide with the metal hydrous iron oxide: Residence time effect. Soil Sci. Soc. Am. J. 58:1615–
cations resulted in hysteresis with Cd2+ and Co2+ but little with 1623. With permission from the Soil Science Society of America.)
Kinetics and Mechanisms of Soil Chemical Reactions 13-15

100 With increased residence time from 30 min to 24 h, Lehmann

and Harter(1984) speculated that there was a transition of Cu
from low to higher energy sites (as evaluated by release kinet-
80 ics). Incubations for up to 4 days showed a continued uptake of
Cu and a decrease in the fraction released within the first 3 min,
which was referred to as the low-energy sorbed fraction.
Percent Co sorbed

60 Recent studies particularly using surface spectroscopic and

microscopic techniques such as XAS and transmission electron
microscopy (TEM) have shown that the formation of polynuclear
40 Adsorption pH edge surface species (e.g., surface precipitates) on natural materials
Aging time = 0 week such as clay minerals, metal oxides, and in soils is an important
Desorption sorption and sequestration mechanism (Charlet and Manceau,
20 Aging time = 2 weeks 1993; Fendorf et al., 1994; Junta and Hochella, 1994; O’Day et al.,
Aging time = 9 weeks 1994a, 1994b; Wersin et al., 1994; Scheidegger et al., 1996, 1997,
Aging time = 16 weeks
1998; Towle et al., 1997; Xia et al., 1997; Elzinga and Sparks, 1999;
0 Roberts et al., 1999; Thompson et al., 1999a, 1999b; Ford and
2 4 6 8 10 12
Sparks, 2000; Nachtegaal et al., 2005; McNear et al., 2007).
pH The surface precipitates of Co, Cr(III), Cu, and Ni on metal
FIGURE 13.19  Fractional adsorption of Co2+ to hydrous Fe oxide oxides and clay minerals have been observed at metal surface
(HFO) as a function of pH and HFO–Co2+ aging time. (Reprinted from loadings far below a theoretical monolayer coverage and in a pH
Ainsworth, C.C., J.L. Pilon, P.L. Gassman, and W.G. Van Der Sluys. 1994. range well below the pH where the formation of metal hydroxide
Cobalt, cadmium, and lead sorption to hydrous iron oxide: Residence precipitates would be expected according to the thermodynamic
time effect. Soil Sci. Soc. Am. J. 58:1615–1623. With permission from the solubility product. In Al-bearing soil components, the precipi-
Soil Science Society of America.) tates are mixed metal–Al hydroxide phases of the layered double
hydroxide type. Recent studies using microfocused x-ray fluores-
of reversibility with aging for Co2+, Cd2+, and Pb2+ was inversely cence (micro-XRF) and x-ray absorption spectroscopy (micro-
proportional to the ionic radius of the ions, namely, Co2+ < Cd2+ XAS) have shown that Zn–Al layered double hydroxides (LDH)
< Pb2+. Ainsworth et al. (1994) attributed the hysteresis to Co and (Nachtegaal et al., 2005) and Ni–Al hydroxide LDH (McNear
Cd incorporation into a recrystallizing solid (probably goethite) et al., 2007) precipitates occur in field-contaminated soils.
by isomorphic substitution and not to micropore diffusion. In general, the formation of surface precipitates has been con-
Strawn and Sparks (2000) investigated the role that residence sidered a slow phenomenon. However, Scheidegger et al. (1998)
time and organic matter content had on Pb desorption kinetics have demonstrated that the rate of surface precipitate formation
from a Matapeake soil. Residence time had little effect on the can be quite rapid. The appearance of surface precipitates dur-
amount of Pb desorbed, but marked hysteresis was observed at ing sorption of Ni to pyrophyllite at pH 7.5 occurred over time
all residence times, which was ascribed to diffusion of Pb into scales less than 1 h. Similar results were observed for Ni sorption
the organic matter and strong metal–soil complexes. to kaolinite. However, the kinetics of Ni sorption onto gibbsite,
Fuller et al. (1993) combined kinetic sorption and desorp- and subsequent surface precipitate formation, were slower than
tion experiments with spectroscopic observations (Waychunas for pyrophyllite (Figures 13.16 and 13.20). Time-resolved XAFS
et al., 1993) to study As sorption on ferrihydrite. Using XAFS studies demonstrated continued growth of the surface precipi-
spectroscopy, they found that As was sorbed predominantly as tate during Ni uptake as the structure and Ni:Al stoichiometry
inner-sphere bidentate complexes, regardless of whether the As of the sorption complex approached that of a takovite-like phase
was adsorbed after the mineralization of the ferrihydrite or (Scheidegger et al., 1998).
it was present during precipitation. No As surface precipitates
were observed. Slow As sorption and desorption were explained 13.5.1.2  Organic Contaminants
as slow diffusion of the As to or from interior surface complex- Numerous studies on the kinetics of organic chemical sorp-
ation sites that exist within disordered aggregates of crystal- tion/desorption reactions on soils and soil components have
lites. The kinetic reactions could be described using a Fickian shown that sorption/desorption is characterized by a rapid,
diffusion model. reversible stage followed by a much slower, nonreversible
Slow metal sorption/desorption has also been ascribed to con- stage (Karickhoff et al., 1979; DiToro and Horzempa, 1982;
version of the metal sorbate from a high- to a low-energy state Karickhoff and Morris, 1985; Kan et al., 1997; Xing and
(Kuo and Mikkelsen, 1980; Padmanabham, 1983; Schultz et al., Pignatello, 2005), or biphasic kinetics. The rapid phase has
1987; Backes et al., 1995). Lehmann and Harter (1984) measured been ascribed to retention of the organic chemical in a labile
the kinetics of chelate-promoted Cu2+ release from a soil to assess form that is easily desorbed. However, the much slower reac-
the strength of the bond formed. Sorption/desorption was bipha- tion phase involves the entrapment of the chemical in a non-
sic, which was attributed to high- and low-energy bonding sites. labile form that is difficult to desorb. The labile form of the
13-16 Properties and Processes

Theories proposed by a number of researchers (Weber and

Huang, 1996; Xing and Pignatello, 1997; Pignatello, 2000) have
620 h explained the slow diffusion of organic chemicals into SOM by
considering SOM as a combination of “rubbery” and “glassy”
polymers. The rubber-like phases are characterized by an
Transform magnitude

224 h
expanded, flexible, and highly solvated structure with pores of
subnanometer dimensions (holes) (Xing and Pignatello, 1997;
109 h Pignatello, 1998, 2000). Sorption in the rubbery phases results in
linear, noncompetitive, and reversible behavior. The glassy phases
have pores that are of subnanometer size, and sorption in this
33 h phase is characterized by nonlinearity and is competitive (Xing
and Pignatello, 1997). These theories, relating slow diffusion into
organic matter to diffusion in polymers, are somewhat validated
40 min
in some studies measuring energies of activation (Ea) for organic
chemical sorption. Cornelissen et al. (1997) studied the tempera-
0 2 4 6 8 ture dependence of slow adsorption and desorption kinetics of
R, Å some chlorobenzenes, polychlorinated biphenyls (PCBs), and
polycyclic aromatic hydrocarbons (PAHs) in laboratory- and
FIGURE 13.20  Radial structure functions for Ni sorption to gibbsite
field-contaminated sediments and obtained Ea values of 60–70 kJ
for reaction times up to 620 h demonstrating the appearance and
mol−1, which are in the range for diffusion in polymers. These
growth of second shell contributions due to surface precipitation and
growth of a hydrotalcite-like phase. (Reprinted from Scheidegger, A.M.,
values are much higher than those for pore diffusion (20–40 kJ
D.G. Strawn, G.M. Lamble, and D.L. Sparks. 1998. The kinetics of mixed mol−1) suggesting that intraorganic matter diffusion may be a
Ni–Al hydroxide formation on clay and aluminum oxide minerals: A more important mechanism for slow organic chemical sorption
time-resolved XAFS study. Geochim. Cosmochim. Acta 62:2233–2245. than interparticle pore diffusion.
With permission from Elsevier.) However, Chang et al. (1997) who studied sorption of toluene
(TOL), n-hexane, and acetone on pressed humic acid disks found
chemical is available for microbial attack, while the nonlabile an insignificant amount of irreversibly bound residue with acti-
portion is resistant to biodegradation. vation energies in the range of 42.3–65.8 kJ mol−1, suggesting a
This slower sorption/desorption reaction has been ascribed to physical sorption process with little diffusion.
intraparticle and interparticle diffusion of the chemical into soil An example of the biphasic kinetics that is observed for many
organic matter (SOM) and inorganic soil components (Wu and organic CRs in soils/sediments is shown in Figure 13.21. In this
Gschwend, 1986; Steinberg et al., 1987; Ball and Roberts, 1991). study, 55% of the labile PCB was desorbed from sediments in

1
0.8
0.8
Fraction PCB
Fraction PCB

0.6
0.6

0.4
0.4

0.2 0.2

0 0
0 20 40 60 80 100 120 140 160 0 2 4 6 8 10 12
(a) Desorption time, h (b) Desorption time, mo

FIGURE 13.21  (a) Short-term polychlorinated biphenyl (PCB) desorption in hours (h) from Hudson River sediment contaminated with 25 mg kg−1
PCB. Distribution of the PCB between the sediment (ν) and XAD-4 resin (ο) as well as the overall mass balance (D) is shown. The resin acts as a sink
to retain the PCB that is desorbed (Carroll et al., 1994). (b) Long-term PCB desorption in months (mo) from Hudson River sediment contaminated
with 25 mg kg−1 PCB. Distribution of the PCB between the sediment (▪) and XAD-4 resin (•) is shown. The line represents a nonlinear regression
of the data by a two-site model. (Reprinted from Carroll, K.M., M.R. Harkness, A.A. Bracco, R.R. Balcarcel. 1994. Application of a permeant/polymer
diffusional model to the desorption of polychlorinated biphenyls from Hudson River sediments. Environ. Sci. Technol. 28:253–258. With permission
from American Chemical Society.)
Kinetics and Mechanisms of Soil Chemical Reactions 13-17

a 24 h period, while little of the remaining 45% nonlabile frac- TABLE 13.4  Sorption Distribution Coefficients for Herbicides
tion was desorbed in 170 h (Figure 13.21a). Over another 1 year in Freshly Aged and Aged Soils
period, ∼50% of the remaining nonlabile fraction desorbed Herbicide Soil Kd (L kg−1)a Kapp (L kg−1)b
(Figure 13.21b).
Metolachlor Cva 2.96 39
Pavlostathis and Mathavan (1992) observed a biphasic
CVb 1.46 27
desorption process for field soils contaminated with trichloro-
W1 1.28 49
ethylene (TCE), tetrachloroethylene (PCE), TOL, and xylene
W2 0.77 33
(XYL). A fast desorption reaction occurred in 24 h followed by a
Atrazine Cva 2.17 28
much slower desorption reaction beyond 24 h. In 24 h, 9%–29%,
CVb 1.32 29
14%–48%, 9%–40%, and 4%–37% of the TCE, PCE, TOL, and
W3 1.75 4
XYL, respectively, were released. However, the apparent irre-
versibility or hysteresis may be an artifact caused by not reach- Source: Adapted from Pignatello, J.J., and L.Q. Huang. 1991.
ing a true sorption equilibrium. For example, DiVincenzo and Sorptive reversibility of atrazine and metolachlor residues in field
soil samples. J. Environ. Qual. 20:222–228. With permission of the
Sparks (1997), studying pentachlorophenol sorption/desorption
American Society of Agronomy.
on a soil, found that if desorption was initiated after an appar- a Sorption distribution coefficient (L kg–1) of freshly aged soil based

ent sorption equilibrium (i.e., slow sorption was measured) was on a 24 h equilibration period.
reached, hysteresis or irreversibility was significantly reduced. b Apparent sorption distribution coefficient (L kg−1) in contaminated

A number of studies have also shown that with aging the soil (aged soil) determined using a 24 h equilibration period.
nonlabile portion of the organic chemical in the soil/sediment
becomes more resistant to release (McCall and Agin, 1985; inaccurate since 24 h Kd values often overestimate the amount of
Steinberg et al., 1987; Pignatello and Huang, 1991; Pavlostathis organic chemical in the solution phase.
and Mathavan, 1992; Scribner et al., 1992; Alexander, 1995; The finding that many organic chemicals are quite persistent in
Loehr and Webster, 1996). However, Connaughton et al. (1993) the soil environment has both good and bad features. The benefi-
did not observe the nonlabile fraction increasing with age for cial aspect is that the organic chemicals are less mobile and may
naphthalene-contaminated soils. not be readily transported in groundwater supplies. The negative
One way to gauge the effect of time on organic contaminant aspect is that their persistence and inaccessibility to microbes
retention in soils is to compare Kd (sorption distribution coef- may make decontamination more difficult, particularly if in situ
ficient) values for freshly aged and aged soil samples. In most remediation techniques such as biodegradation are employed.
studies, Kd values are measured based on a 24 h equilibration
between the soil and the organic chemical. When these values
13.5.2  Kinetics of Mineral Dissolution
are compared to Kd values for field soils previously reacted with
the organic chemical (aged samples), the latter have much higher 13.5.2.1  Rate-Limiting Steps
Kd values, indicating that much more of the organic chemical Dissolution of minerals involves several steps (Stumm and
is in a sorbed state. For example, Pignatello and Huang (1991) Wollast, 1990): (1) mass transfer of dissolved reactants from the
measured Kd values in freshly aged (Kd) and “aged” soils (Kapp, bulk solution to the mineral surface, (2) adsorption of solutes,
apparent sorption distribution coefficient) reacted with atrazine (3) interlattice transfer of reaction species, (4) surface CRs,
and metolachlor, two widely used herbicides. The aged soils had (5) removal of reactants from the surface, and (6) mass transfer
been treated with the herbicides 15–62 months before sampling. of products into the bulk solution. Under field conditions, min-
The Kapp values ranged from 2.3 to 42 times higher than the Kd eral dissolution is slow and mass transfer of reactants or prod-
values (Table 13.4). ucts in the aqueous phase (Steps 1 and 6) is not rate limiting.
Scribner et al. (1992) studying simazine (a widely used tri- Thus, the rate-limiting steps are either transport of reactants and
azine herbicide for broadleaf and grass control in crops) desorp- products in the solid phase (Step 3) or surface CRs (Step 4) and
tion and bioavailability in aged soils found that Kapp values were removal of reactants from the surface (Step 5).
15 times higher than Kd values. Scribner et al. (1992) also showed Transport-controlled dissolution reactions or those con-
that 48% of the simazine added to the freshly aged soils was bio- trolled by mass transfer or diffusion can be described using a
degradable over a 34-day incubation period while none of the parabolic rate law given later (Stumm and Wollast, 1990):
simazine in the aged soil was biodegraded.
One of the implications of these results is that while many dC
r= = kt −1/2 , (13.17)
transport and degradation models for organic contaminants dt
in soils and waters assume that the sorption process is an equi-
librium process, the above studies clearly show that kinetic where
reactions must be considered when making predictions about r is the reaction rate
the mobility and fate of organic chemicals. Moreover, calcula- C is the concentration in solution
tion of Kd values based on a 24 h equilibration period, which t is time
are commonly used in fate and risk assessment models, can be k is the reaction rate constant
13-18 Properties and Processes

Integrating, C increases with t1/2,

C = C0 + 2kt 1/2 , (13.18) pH = 2.5

16 3.0
where C0 is the initial concentration in solution. 3.5
14
If the surface reactions are slow compared to the transport

[Al(III)], 10–5 mol L–1

reactions, dissolution is surface controlled, which is the case for 12
most dissolution reactions of silicates and oxides. In surface- 10 4.0
controlled reactions, the concentrations of solutes next to the 8
surface are equal to the bulk solution concentrations and the 4.3
dissolution kinetics are zero order if steady-state conditions are 6
operational on the surface. Thus, the dissolution rate (r) is 4
2
dC
r= = kA, (13.19)
dt 0
0 10 20 30 40
and r is proportional to the mineral’s surface area, A. Thus, for Time, h
a surface-controlled reaction, the relationship between t and C FIGURE 13.23  Linear dissolution kinetics observed for the dissolu-
should be linear. Figure 13.22 compares transport- and surface- tion of γ-Al2O3. Representative of processes whose rates are controlled by
controlled dissolution mechanisms. a surface reaction and not by transport. (Reprinted from Furrer, G., and
Intense arguments have ensued over the years concerning W. Stumm. 1986. The coordination chemistry of weathering. I. Dissolution
the mechanism for mineral dissolution. Those that supported kinetics of γ-Al2O3 and BeO. Geochim. Cosmochim. Acta 50:1847–1860.
a transport-controlled mechanism believed that a leached layer Copyright 1986. With permission from Elsevier.)
formed as mineral dissolution proceeded and that subsequent
dissolution took place by diffusion through the leached layer that although some incongruency may occur in the initial dis-
(Wollast, 1967; Petrovic et al., 1976). Advocates of this theory solution process, which may be diffusion controlled, the over-
found that dissolution was described by the parabolic rate law all reaction is surface controlled. Energies of activation from
(Equation 13.18). However, the apparent transport-controlled 60 to 86 kJ mol−1 have been observed for dissolution of oxides
kinetics may be an artifact caused by dissolution of hyperfine and silicates, further suggesting surface-controlled dissolution
particles formed on the mineral surfaces after grinding that are (Lasaga, 1984; Jordan and Rammensee, 1996). An illustration of
highly reactive sites or by the use of batch methods that cause the surface-controlled dissolution of γ-Al2O3 resulting in a linear
reaction products to accumulate causing precipitation of second- release of Al3+ with time is shown in Figure 13.23. The dissolu-
ary minerals. These experimental artifacts can cause incongruent tion rate (r) can be obtained from the slope of Figure 13.23.
reactions and pseudoparabolic kinetics. Studies employing x-ray Scanning force microscopy (SFM), which has also been used
photoelectron spectroscopy (XPS) and nuclear resonance profil- increasingly as an in situ technique for imaging mineral surfaces
ing (Schott and Petit, 1987; Casey et al., 1989) have demonstrated immersed in aqueous solution during the course of dissolution
(Hellman et al., 1992; Hillner et al., 1992a, 1992b; Johnsson et al.,
1992; Bosbach and Rammensee, 1994; Maurice et al., 1995), per-
C
mits a direct measure of surface-controlled dissolution rates by
Csurface
providing 3D data on changes in microtopography. In situ SFM
Cbulk has the unique ability to detect separate processes, such as dis-
Cbulk
Distance Distance solution and secondary phase formation, occurring simultane-
ously on a mineral surface (Maurice, 1998).
C C
13.5.2.2  Surface-Controlled Dissolution Mechanisms

Rate
Dissolution of oxide minerals through a surface-controlled
1 reaction by ligand- and proton-promoted processes has been
Time Time described by Furrer and Stumm (1986), Zinder et al. (1986), and
Rate = kt –1/2 Rate = k [surface area]
(a) C = C0 +2kt1/2 (b) C = C0 + kt Stumm and Furrer (1987) using a surface coordination approach.
The important reactants in these processes are H2O, H+, OH,
FIGURE 13.22  (a) Transport- versus (b) surface-controlled dis- ligands, and reductants and oxidants. The reaction mechanism
solution. Schematic representation of concentration in solution, C, as occurs in two steps (Stumm and Wollast, 1990):
a function of distance from the surface of the dissolving mineral. In
the lower part of the figure, the change in concentration is given as a Surface sites + reactants(H + , OH −, ligands) ⎯fast
⎯→ surface species,
function of time. (Reprinted with permission from Stumm, W. 1992.
Chemistry of the solid–water interface. Wiley, New York.) (13.20)
Kinetics and Mechanisms of Soil Chemical Reactions 13-19

OH OH2
M M
O OH

Enhancement of dissolution Inhibition of dissolution

OH2+ OH2 OH O OH OH OH2 CH3 (CH2)-COOH
–
M M M M M M M M CH3 (CH2)n-COOH
OH+ OH2+ O O O O OH– O OH
P
OH O O OH O–
M M M M
O OH O OH
2–
O O– OH OCr+
M M M M
O– OH O O

Surface protonation Surface complex- Surface complex- Blocking of surface groups by hydrophobic moieties
Surface deprotonation formation with formation to of fatty acids, humic acids or macromolecules
bidentate (mono- bi- or multinuclear
nuclear) ligands, complexes or surface
e.g., oxalate, films, blockage of
salicylate, citrate, surface groups by
diphenol, etc. metal cations

FIGURE 13.24  The dependence of surface reactivity and of kinetic mechanisms on the coordinative environment of the surface groups.
(Reprinted from Stumm, W., and R. Wollast. 1990. Coordination chemistry of weathering. Kinetics of the surface-controlled dissolution of oxide
minerals. Rev. Geophys. 28:53–69. With permission from American Geophysical Union.)

The reason for these differences may be that bidentate spe-

slow
Surface species ⎯detachment
⎯⎯⎯⎯⎯⎯ → M(aq). (13.21)
of metal ( M )
cies that are mononuclear promote dissolution while binuclear
bidentate species inhibit dissolution. With binuclear bidentate
Thus, the attachment of the reactants to the surface sites is fast, complexes, more energy may be needed to remove two central
and detachment of metal species from the surface into solution atoms from the crystal structure. With phosphate and arse-
is slow and rate limiting. nate, at low pH, mononuclear species are formed while at higher
pH (∼pH 7), binuclear or trinuclear surface complexes form.
13.5.2.3  Ligand-Promoted Dissolution
Mononuclear bidentate complexes are formed with oxalate while
Figure 13.24 shows how the surface chemistry of the mineral binuclear bidentate complexes form with CrO4 2− . Additionally,
affects dissolution. One sees that surface protonation of the the electron donor properties of CrO4 2− and oxalate are also dif-
surface ligand increases dissolution by polarizing interatomic ferent. With CrO4 2− , a high redox potential is maintained at the
bonds close to the central surface ions that promote the release oxide surface, which restricts reductive dissolution (Stumm and
of a cation surface group into solution. Hydroxyls that bind to Wollast, 1990; Stumm, 1992). Dissolution can also be inhibited
surface groups at higher pHs can ease the release of an anionic by cations such as VO2+, Cr(III), and Al(III) that block surface
surface group into the solution phase. functional groups (Bondietti et al., 1993).
Ligands that form surface complexes by ligand exchange One can express the rate of the ligand-promoted dissolution
with a surface hydroxyl add negative charge to the Lewis acid (R L) as
center coordination sphere and lower the Lewis acid acid-
ity. This polarizes the M–O bonds causing detachment of the RL = kLʹ (≡ ML) = kLʹ CLs , (13.22)

metal cation into the solution phase. Thus, inner-sphere sur- where
face complexation plays an important role in mineral dissolu- kL�is the rate constant for ligand-promoted dissolution (t−1)
tion. Ligands such as oxalate, salicylate, F−, EDTA, and NTA ML is the metal–ligand complex
increase dissolution, but others, such as SO4 2− , CrO4 2− , and CLs is the surface concentration of the ligand (mol m−2)
benzoate, inhibit dissolution. Phosphate, arsenate, and selenite
enhance dissolution at low pH, and dissolution is inhibited at Equation 13.22 adequately describes ligand-promoted dissolu-
pH > 7 (Bondietti et al., 1993). tion of γ-Al2O3 (Figure 13.25).
13-20 Properties and Processes

O O
–8.0
Al
O
O
–8.2

e
15

t
la
xa
O
O
O

3
l2 O
Al –8.4
RL, 10–9 mol m–2 h–1

δ–A
1 O

log RH
10 O
te 3.1
na –8.6
kL alo
M

O –8.8 1
5 O
inate Al
Succ
O
–9.0 s
O log C H

0
0 0.5 1.0 1.5 –6.0 –5.8 –5.6 –5.4
s
C L , 10–6 mol m–2
6 5 4 3 pH
FIGURE 13.25  The rate of ligand catalyzed dissolution of γ-Al2O3 by
the aliphatic ligands oxalate, malonate, and succinate, RL (nmol m−2 h−1), FIGURE 13.26  The dependence of the rate of proton-promoted
can be interpreted as a linear dependence on the surface concentrations dissolution of γ-Al 2O3, R H (mol m−2 h−1) on the surface concentra-
of the ligand complexes, CLs . In each case, the individual values for CLs tion of the proton complexes, CHs (mol m−2). (Reprinted from Furrer,
were determined experimentally. (Reprinted from Furrer, G., and W. G., and W. Stumm. 1986. The coordination chemistry of weathering. I.
Stumm. 1986. The coordination chemistry of weathering. I. Dissolution Dissolution kinetics of γ-Al2O3 and BeO. Geochim. Cosmochim. Acta
kinetics of γ-Al2O3 and BeO. Geochim. Cosmochim. Acta 50:1847–1860. 50:1847–1860. With permission of Elsevier Science, Amsterdam, the
With permission from Elsevier.) Netherlands.)

13.5.2.4  Proton-Promoted Dissolution

R = kLʹ (CLs ) + kHʹ (CHs ) j + kOH s
ʹ (COH )i + kHʹ 2O . (13.24)
Under acid conditions, protons can promote mineral dissolu-
tion by binding to surface oxide ions, causing bonds to weaken
which is followed by detachment of metal species into solution. Equation 13.24 is valid if dissolution occurs in parallel at vary-
The proton-promoted dissolution rate (RH) can be expressed as ing metal centers (Furrer and Stumm, 1986).
(Stumm and Wollast, 1990)
13.5.2.6  Dissolution Kinetics of Metal
RH = kHʹ (≡ MOH2 + ) j = kHʹ (CHs ) j , (13.23) Hydroxide Precipitates

where The formation of metal hydroxide surface precipitates appears
kH� is the rate constant for proton-promoted dissolution to be an important way to sequester metals. As the surface pre-
MOH2 + is the metal–proton complex cipitates age, metal dissolution is greatly reduced (Figure 13.27).
CHs is the concentration of the surface-adsorbed proton com- Thus, the metals are less prone to leaching and being taken up
plex (mol−2) by plants and microbes. Peltier et al. (2010) reacted two soils of
j corresponds to the oxidation state of the central metal ion varying mineralogy and organic matter content with 3 mM Ni
in the oxide structure (i.e., j = 3 for Al(III) and Fe(III) in at two pHs, 6 and 7.5, and evaluated Ni bioavailability using
simple cases) a biosensor. At pH 6, where surface precipitates did not form,
60% of the Ni was bioavailable. However, at pH 7.5, where pre-
If dissolution occurs by only one mechanism, j is an integer. cipitates were observed to form from XAFS analyses, Ni bio-
Figure 13.26 shows an application of Equation 13.23 for the availability was markedly reduced to 25%. Similar results were
­proton-promoted dissolution of γ-Al2O3. found by Everhart et al. (2006).
The decrease in metal release and bioavailability is linked to
13.5.2.5  Overall Dissolution Mechanisms the increasing silication of the interlayer of the LDH phases with
The rate of mineral dissolution, which is the sum of the ligand, increased residence time, resulting in a mineral transformation
proton, and deprotonation-promoted (or bonding of OH from a LDH phase to a precursor phyllosilicate surface precipi-
ligands) dissociation [ROH = kOH s
ʹ (COH )i ] rates along with the pH- tate (Ford et al., 1999; Ford and Sparks, 2000). The mechanism for
independent portion of the dissolution rate (kH�2O ), which is due this transformation is thought to be due to diffusion of Si, origi-
to hydration, can be expressed as (Stumm and Wollast, 1990) nating from weathering of the sorbent, into the interlayer space
Kinetics and Mechanisms of Soil Chemical Reactions 13-21

100
Mn(IV)O2 (s) + 4 H + + 2 e − = Mn2 + + 2 H2O, E 0 = +1.23 V.

(13.26)
80
Relative Ni remaining on surface, %

Changes in the oxidation state of the metals associated with the

oxides above can greatly affect their solubility and mobility in
60 soil and aqueous environments. The reductants can be either
inorganic or organic.
There are a number of natural and xenobiotic organic func-
tional groups that are good reducers of oxides and hydrox-
40
ides. These include carboxyl, carbonyl, phenolic, and alcoholic
functional groups of SOM. Microorganisms in soils and sedi-
ments are also examples of organic reductants. Stone (1987a)
20
showed that oxalate and pyruvate, two microbial metabolites,
could reduce and dissolve Mn(III/IV) oxide particles. Inorganic
reductants include As(III), Cr(III), and Pu(III).
0
0 100 200 300 400 13.5.3.1  Mechanisms for Reductive Dissolution
Reaction time, h of Metal Oxides/Hydroxides
FIGURE 13.27  Kinetics of Ni detachment from surface precipitates at The reductive dissolution of metal oxides/hydroxides appears
pH = 4. Relative Ni remaining on the surface (%) is shown for the con- to occur in the following sequential steps (Stone, 1986, 1991):
ventional method (O) and the replenishment method (■) as a function (1)  diffusion of the reductant molecules to the oxide surface,
of the reaction time. Ninety-eight percent of the initial Ni was sorbed (2)  a surface CR, and (3) release of reaction products and dif-
in the beginning of the detachment experiment. The dissolution of an fusion away from the oxide surface. Steps (1) and (3) are transport
equivalent amount of crystalline Ni(OH)2 (in mol) at pH = 4 is given for
steps. The rate-controlling step in reductive dissolution of oxides
comparison (▲). (Reprinted from Scheidegger, A.M., and D.L. Sparks.
appears to be surface CR control. Reductive dissolution can be
1996a. Kinetics of the formation and the dissolution of nickel surface pre-
cipitates on pyrophyllite. Chem. Geol. 132:157–164. With permission of
described by both inner- and outer-sphere complex mechanisms
Elsevier Science, Amsterdam, the Netherlands.) that involve (1) precursor complex formation, (2) electron trans-
fer, and (3) breakdown of the successor complex (Figure 13.28).
of the LDH, replacing the anions such as NO3. Polymerization Inner-sphere and outer-sphere precursor complex formations
and condensation of the interlayer Si slowly transform the LDH are adsorption reactions that increase the density of reductant
into a precursor metal–Al phyllosilicate. The metal stabilization molecules at the oxide surface, which promotes electron trans-
that occurs in surface precipitates on Al-free sorbents (e.g., talc) fer (Stone, 1991). In the inner-sphere mechanism, the reductant
may be due to Ostwald ripening, resulting in increased crystal- enters the inner coordination sphere by ligand exchange and
lization; however, microscopic analyses have shown that Ni–Al bonds directly to the metal center prior to electron transfer.
LDH phases appear to be amorphous (Livi et al., 2009). Peltier With the outer-sphere complex, the inner coordination sphere
et al. (2006), using acid-solution calorimetry and results from is left intact and electron transfer is enhanced by an outer-
previous calorimetry studies, showed that the enthalpy of for- sphere precursor complex (Stone, 1986). Kinetic studies have
mation of LDH phases is more exothermic, indicating great sta- shown that high rates of reductive dissolution are favored by
bility, on the order of Cl < NO3 < SO4 < CO3 < Si of interlayer high rates of precursor complex formation (i.e., large k1 and low
anionic composition, and that LDH phases were much more k−1 values), high electron transfer rates (i.e., large k2), and high
stable than a Ni(OH)2 phase. rates of product release (i.e., high k3; Figure 13.28).
Specifically, adsorbed cations and anions may reduce reductive
dissolution rates by blocking oxide surface sites or by causing release
13.5.3  Redox Kinetics
of Mn(II) into solution. Stone and Morgan (1984a) showed that
It is well known that Mn(III/IV), Fe(III), Co(III), and Pb(IV) PO4 3− inhibited the reductive dissolution of Mn(III/IV) oxides
oxides/hydroxides are thermodynamically stable in oxygen- by hydroquinone. Addition of 10−2 M PO4 3− at pH 7.68 caused
ated systems at neutral pH. However, under anoxic conditions, the dissolution rate to be only 25% of the rate when PO4 3− was
reductive dissolution of oxides/hydroxides by reducing agents not present. Phosphate had a greater effect than Ca 2+.
occurs as shown below for MnOOH and MnO2 (Stone, 1991):
13.5.3.2  Oxidation of Pollutants
As mentioned earlier, Mn oxides can oxidize a number of envi-
Mn(III)OOH(s) + 3 H + + e − = Mn2 + + 2 H2O, E 0 = +1.50 V,
ronmentally important ions that can be toxic to humans and ani-
(13.25) mals. Chromium and plutonium are similar in their chemical
13-22 Properties and Processes

Inner-sphere Outer-sphere

k1 k1
(a) Precursor MIII (H2O)63+ + HA MIII (A) (H2O)52+ + H3O4 MIII (H2O)63+ + HA MIII (H2O)63+, HA
complex k–1 k–1
formation

k2 k2
(b) Electron MIII (A) (H2O)52+ MIII (A) (H2O)52+ MIII (H2O)63+, HA MII (H2O)62+, A +H+
transfer k–2 k–2

k3 k3
(c) Breakdown MII ( A)(H2O)52+ + H2O MII (H2O)62+ + A MII (H2O)62+, A MII (H2O)62+ + A
of successor k–3 k–3
complex

FIGURE 13.28  Reduction of M(H2O)63+ by phenol (HA) in homogeneous solution. (Reprinted with permission from Stone, A.T. 1986. Adsorption
of organic reductants and subsequent electron transfer on metal oxide surfaces, p. 446–461. In J.A. Davis and K.F. Hayes (eds.) Geochemical processes
at mineral surfaces. American Chemical Society, Washington, DC.)

behavior in aqueous settings (Rai and Serne, 1977; Bartlett and first hour. At higher temperatures, there was a rapid oxidation
James, 1979). They can exist in multiple oxidation states and as rate, followed by a slower rate. Fendorf and Zasoski (1992)
both cationic and anionic species. Chromium(III) is quite stable found that Cr(III) oxidation on δ-MnO2 was more rapid at
and innocuous and occurs as Cr3+ and its hydrolysis products or as pH  5 than pH 3 with overall production of Cr(VI) being
CrO2 − . Chromium(III) can be oxidized to Cr(VI) by Mn(III/ IV) greater at pH 3 at a Cr(III) concentration of 770 μM. The rate
oxides (Bartlett and James, 1979; Fendorf and Zasoski, 1992). and extent of Cr(III) oxidation are affected by a number of
Chromium(VI) is mobile in the soil environment and is a sus- factors including formation of surface precipitates at higher
pected carcinogen. It occurs as the dichromate (Cr2O7 2− ) or chro- pHs and Cr(III) concentrations that effectively inhibit oxida-
mate (HCrO 4 − and CrO2 −) anions (Huang, 1991). tion (Fendorf et al., 1992).
Figure 13.29 shows the oxidation kinetics of Cr(III) to Plutonium can exist in the III to VI oxidation states as Pu3+,
Cr(VI) in a soil. Most of the oxidation occurred during the Pu4+, PuO2 + , and PuO22+ in strongly acid solutions (Huang, 1991).
Plutonium(VI), which can result from oxidation of Pu(III/IV)
by Mn(III/IV) oxides (Amacher and Baker, 1982), is very toxic
[soil] = 12.5 g L–1 and mobile in soils and waters.
[Cr(III)]0 = 192 μmol L–1 Arsenic (As) can exist in several oxidation states and forms
5.0 pH = 5.5 in soils and waters. In waters, As can exist in the +5, +3, 0, and
301 K
−3 oxidation states. Arsenite, As(III), and arsine (AsH3, where
the oxidation state of As is −3) are much more toxic to humans
296 K
Cr(VI) formed, μmol L–1

4.0 than arsenate, As(V). Manganese(III/IV) oxides can oxidize

As(III) to As(V) as shown later where As(III) as HAsO2 is added
323 K to MnO2 to produce As(V) as H3AsO4 (Oscarson et al., 1983):
3.0

HAsO2 + MnO2 = (MnO2 )HAsO2 , (13.27)

275 K
2.0
(MnO2 )HAsO2 + H2O = H3AsO4 + MnO, (13.28)

1.0 H3AsO4 = H3AsO4 − + H + , (13.29)

H2 AsO4 − = HAsO4 2 − + H + , (13.30)

10 20 30 40
Time, min
(MnO2 )HAsO2 = 2 H + = H3AsO4 + Mn2+ . (13.31)
FIGURE 13.29  Effect of temperature on the kinetics of Cr(III) oxi-
dation in moist Hagerstown silt loam soil. (Reprinted with permission Equation 13.28 involves the formation of an adsorbed layer.
from Amacher, M.C., and D.E. Baker. 1982. Redox reactions involv- Oxygen transfer occurs and HAsO2 is oxidized to H3AsO4
ing chromium, plutonium, and manganese in soils. DOE/DP/04515 (Equation 13.28). At pH ≤ 7, the predominant As(III) species is
Pennsylvania State University, University Park, PA.) arsenious acid (HAsO2), but the oxidation product, H3AsO4, will
Kinetics and Mechanisms of Soil Chemical Reactions 13-23

100
0 min: 75 mM As(III) 5 min
90 0.25 min 18 min
0.5 min 300 min
80 1 min

860
873
70
Concentration, μM

60

791
906
50
40
pH 9
30
As(V)
20

IR absorbance
Mn(II)
10 As(III)

0
0 1000 2000 3000 4000 5000 6000 pH 8
Time, s

FIGURE 13.30  Experimental behavior of aqueous As(III), As(V),

and Mn(II) following 99.6 μM As(III) addition to a 0.21 g L−1 of γ-MnO2 pH 7
particle suspension at pH 4, 25°C, and 0.1 M NaClO4. (Reprinted from
Scott, M.J., and J.J. Morgan. 1995. Reactions at oxide surfaces. 1. Oxidation
of As(III) by synthetic birnessite. Environ. Sci. Technol. 29:1898–1905.
With permission from American Chemical Society.)

dissociate and form the same quantities of HAsO4 − and HAsO4 2−

pH 6
with little H3AsO4 present at equilibrium (Equations 13.29 and
13.30). Each mole of As(III) oxidized releases about 1.5 mol H+. The 950 925 900 875 850 825 800 775
H+ produced after H3AsO4 dissociation reacts with the adsorbed Wavenumber, cm–1
HAsO2 on MnO2, forming H3AsO4, and leads to the reduction
and dissolution of Mn(IV) (Equation 13.31). Thus, every mole FIGURE 13.31  ATR–FTIR spectra for HMO reacted with 75 mmol
of As(III) that is oxidized to As(V) results in 1 mol of Mn(IV) in kg−1 As(III) at pHs 6, 7, 8, and 9. Within 1 min of reaction, As(V) peaks
(860, 873, and 906 cm−1) are observed and only minimal changes in
the solid phase being reduced to Mn(II) and partially dissolved
spectra are observed in a subsequent 300 min period. (Reprinted
in solution (Oscarson et al., 1981).
from Parikh, S.J., B.J. Lafferty, and D.L. Sparks. 2008. An ATR–FTIR
Oscarson et al. (1980) studied the oxidation of As(III) to spectroscopic approach for measuring rapid kinetics at the mineral/
As(V) in sediments from five lakes in Saskatchewan, Canada. water interface. J. Colloid Interface Sci. 320:177–185. With permission
Oxidation of As(III) to As(V) occurred within 48 h. In gen- from Elsevier.)
eral, >90% of the added As was sorbed on the sediments within
72 h. Scott and Morgan (1995) studied the oxidation of As(III) in peak intensities. The reaction process is almost complete in
by synthetic birnessite. The depletion of As(III) was rapid with 5 min. Figure 13.32 shows QXAS and traditional batch data for
50% of the initial As(III) removed from solution in 10 min, and after As(III) oxidation on hydrous Mn oxide. An initial concentra-
90 min, the As(III) concentration was below the detection limit. tion of 1.5 mM of As(III) was used. After 1 s of reaction, the
Arsenic(V) was released into solution as fast as As(III) was As(V) concentration, indicating oxidation of As(III), reached
depleted and the total concentration of aqueous As was about 0.37 mM and continued to increase rapidly for 45 s to reach a
constant over the duration of the experiment (Figure 13.30). concentration of 1 mM. The As(V) concentration continued to
Scott and Morgan (1995) concluded that the process of electron increase for the remainder of the reaction, reaching the initial
transfer and release of As(V) were fast compared to the sorption 1.5 mM concentration after 300 s of reaction time (Ginder-Vogel
of As(III), the rate-limiting step. et al., 2009). The initial apparent As(III) depletion rate constants
Recently, Parikh et al. (2008), Ginder-Vogel et al. (2009), (t < 30 s) measured with QXAS were nearly twice as large as rate
and Landrot et al. (2010) have used real-time molecular scale constants measured with traditional analytical techniques such
ATR–FTIR and QXAS techniques to elucidate the rapid redox as the batch method (Ginder-Vogel et al., 2009). Being able to
kinetics and mechanisms of As(III) oxidation (Parikh et al., measure the initial reaction rates with these techniques allows
2008; Ginder-Vogel et al., 2009) and Cr(III) oxidation (Landrot one to measure chemical rate constants that are independent of
et al., 2010) on Mn oxides. Figure 13.31 shows that the oxida- concentration, and, thus, important mechanistic information
tion of As(III) on hydrous Mn oxide at pHs of 6–9 is extremely can be gleaned (Landrot et al., 2010).
rapid with 50% of the reaction occurring within 1 min. Spectra Manganese oxides and hydroxides (e.g., Mn3O4 and MnOOH)
for times >1 min are very similar with only small differences may also catalyze the oxidation of other trace metals such as Co2+,
13-24 Properties and Processes

2.0 TABLE 13.5  Inorganic Redox Reactions with Manganese Dioxides

Driving
As(V) concentration, mM

1.5 Time to Force at pH 4

System Oxidize 50% Δe° (V)a Source

1.0 δ-MnO2: As(III) 10 min +0.529 Scott and Morgan

→ As(V) (1995)
As(V) from Q-XAS pH 4, 25°C, 14 m2 L−1
0.5 As(V) from batch reactions 10 days
δ-MnO2: Se(IV)
→ Se(VI)
0.0 pH 4, 35°C, 14 m2 L−1
pH 4, 25°C, 28 m2 L−1 16 days +0.092
As(III) concentration, mM

5.0 pH 4, 25°C, 14 m2 L−1 30 days

As(III) from Q-XAS β-MnO2: Cr(III) 95 days +0.011 Eary and Rai (1987)
4.5
As(III) from batch reactions → Cr(VI)
4.0 pH 4, 25°C, 71 m2 L−1
Source: Reprinted from Scott, M.J., and J.J. Morgan. 1995. Reactions at
3.5
oxide surfaces. 1. Oxidation of As(III) by synthetic birnessite. Environ. Sci.
3.0 Technol. 29:1898–1905. With permission American Chemical Society.
a The activity ratio for each oxidant/reductant pair is taken as unity.

2.5
0 50 100 150 200 250 300 oxidation of Se(IV) by synthetic birnessite. Se(IV) was oxidized
Time, s to Se(VI) with Se(VI) first appearing in the aqueous suspension
FIGURE 13.32  As(V) and As(III) concentrations determined from
after 12 h and was produced at a constant rate over the duration
traditional batch and QXAS reactions. Error bars represent the SD of the experiment (28 days). Scott and Morgan (1996) suggested
of three measurements made at each time point. (Reprinted from the following oxidation mechanisms: (1) birnessite directly oxi-
Ginder-Vogel, M., G. Landrot, J.S. Fischel, and D.L. Sparks. 2009. dized Se(IV) through a surface complex mechanism; (2) the
Quantification of rapid environmental redox processes with quick- rate-limiting step in the production of Se(VI) was the electron
scanning X-ray absorption spectroscopy (Q-XAS). Proc. Natl Acad. transfer step involving a transfer of two electrons from the anion
Sci. U. S. A. 106:16124–16128. With permission National Academy of to the metal ion, breaking of two Mn–O bonds, and addition of
Sciences, USA.) an O from water to Se(VI); and (3) the reaction products Se(VI)
and Mn(II) were released from the surface by different steps.
Co3+, Cu2+, Ni2+, Ni3+, and Pb2+ by disproportionation to Mn2+ Scott and Morgan (1996) compared their results with those of
and MnO2 (Hem, 1978). The disproportionation results in vacan- Eary and Rai (1987) who studied Cr(III) oxidation by pyrolusite
cies in the Mn oxide structure. Since the Mn2+ and Mn3+ in the (β-MnO2) between pH 3.0 and 4.7 and Scott and Morgan (1995)
oxides have similar physical sizes as Co2+, Co3+, Cu2+, Ni2+, Ni3+, who studied As(III) oxidation by birnessite (δ-MnO2) at pH val-
and Pb2+, these metals can occupy the vacancies in the Mn oxide ues between 4.0 and 8.2 (Table 13.5). The Cr(III) redox trans-
and become part of the structure. With disproportionation or formation on pyrolusite was slowest which Scott and Morgan
with other redox processes involving the Mn oxides, the solubil- (1996) attributed to unfavorable adsorption on both a positively
ity of the metals can be affected. For example, if during the dis- charged surface and aqueous species and the small thermody-
proportionation process Co3O4, the oxidized form of the metal namic driving force. Also, the transfer of three electrons from
forms from Co2+, the reaction can be expressed as (Hem, 1978) Cr(III) to Mn(IV) requires the involvement of more than one
Mn(IV) atom per Cr(III) atom.
2Mn3O4 (s) + 3Co2 + + 4H + Manganese oxides also appear to play an important role in
ligand-facilitated metal transport. Using soil columns that
→ MnO2 (s) + Co3O4 (s) + 5Mn2 + + 2H2O, (13.32) consisted of fractured saprolite coated with amorphous Fe and

Mn oxides, Jardine et al. (1993) studied the transport of Co(II)
and the equilibrium constant (Ko) is (Hem, 1978) EDTA2−, a mixture of Co(II) EDTA2− and Co(III) EDTA− and
Sr EDTA2−. The Mn oxides oxidized Co(II) EDTA 2− into
( Mn2 + )5 Co(III) EDTA−, a very stable complex (log K value of 41.4; Xue
= 1018.73. (13.33)
(Co2 + )3 (H + )4 and Traina, 1996). The formation of this complex resulted in
enhanced transport of Co.
Thus, the oxidation of Co(II) to Co(III) reduces its solubility Xue and Traina (1996) found that an aerobic goethite suspen-
and mobility in the environment. Using XPS analyses (Murray sion catalyzed oxidation of Co(II) EDTA2− to Co(III) EDTA− by
and Dillard, 1979), this reaction has been shown to occur. More dissolved O2. The kinetics were described using a pseudo-first-
recent evidence for heterogeneous redox reactions of trace metals order rate constant, k1 of 0.0078 ± 0.0002 h−1 at pH 5 and a goe-
is discussed in Chapter 19. Scott and Morgan (1996) studied the thite concentration of 3.09 g L−1.
Kinetics and Mechanisms of Soil Chemical Reactions 13-25

A number of investigators have studied the reductive dissolu- Aharoni, C., and Y. Suzin. 1982b. Application of the Elovich equa-
tion of Mn oxides by organic pollutants such as hydroquinone tion to the kinetics of occlusion: Part 3. Heterogenous micro-
(Stone and Morgan, 1984a), substituted phenols (Stone, 1987b), and porosity. J. Chem. Soc., Faraday Trans. 1 78:2329–2336.
other organic compounds (Stone and Morgan, 1984b). With sub- Aharoni, C., and M. Ungarish. 1976. Kinetics of activated chemi-
stituted phenols, the rate of dissolution was proportional to substi- sorption. Part 1. The non-Elovichian part of the isotherm.
tuted phenol concentration and the rate increased as pH decreased J. Chem. Soc., Faraday Trans. 1 72:400–408.
(Stone, 1987b). Phenols containing alkyl, alkoxy, or other electron- Ainsworth, C.C., J.L. Pilon, P.L. Gassman, and W.G. Van Der
donating substituents were more slowly degraded; p-nitrophenol Sluys. 1994. Cobalt, cadmium, and lead sorption to hydrous
reacted slowly with Mn(III/IV) oxides. The increased rate of reduc- iron oxide: Residence time effect. Soil Sci. Soc. Am. J.
tive dissolution at lower pH may be due to more protonation reac- 58:1615–1623.
tions that enhance the creation of precursor complexes or increases Alexander, M. 1995. How toxic are toxic-chemicals in soil.
in the protonation level of the surface precursor complexes that Environ. Sci. Technol. 29:2713–2717.
increase electron transfer rates (Stone, 1987b). Further discussions Allen, E.R., D.W. Ming, L.R. Hossner, and D.L. Henninger. 1995.
on this topic can be found in Chapter 19. Modeling transport kinetics in clinoptilolite–phosphate
rock systems. Soil Sci. Soc. Am. J. 59:248–255.
Amacher, M.C. 1991. Methods of obtaining and analyzing kinetic
13.6  Conclusions
data, p. 19–59. In D.L. Sparks and D.L. Suarez (eds.) Rates of
Research on the kinetics and mechanisms of soil CRs will be a soil chemical processes. SSSA, Madison, WI.
common theme in soil and environmental sciences for decades to Amacher, M.C., and D.E. Baker. 1982. Redox reactions involv-
come. This research emphasis is in large part due to the need ing chromium, plutonium, and manganese in soils. DOE/
to more accurately understand and predict the long-term fate DP/04515 Pennsylvania State University, University Park, PA.
and transport of contaminants in the subsurface environment. Atkinson, R.J., F.J. Hingston, A.M. Posner, and J.P. Quirk. 1970.
Without such data, economically sound decisions about soil Elovich equation for the kinetics of isotope exchange reac-
remediation cannot be made and risk assessment models are tions at solid–liquid interfaces. Nature 226:148–149.
incomplete and most probably inaccurate. Backes, E.A., R.G. Mclaren, A.W. Rate, and R.S. Swift. 1995.
While some very fine and informative research on rates and Kinetics of cadmium and cobalt desorption from iron and
mechanisms of soil CRs/processes has been conducted in the manganese oxides. Soil Sci. Soc. Am. J. 59:778–785.
past few decades, there are many gaps that need to be filled. The Ball, W.P., and P.V. Roberts. 1991. Long-term sorption of haloge-
following research is needed: (1) more accurate kinetic models nated organic chemicals by aquifer material: 1. Equilibrium.
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surfaces; (2) long-term sorption and particularly, desorption Bartlett, R., and B. James. 1979. Behavior of chromium in soils.
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their effect on nutrient/contaminant mobility and bioavailabil- solution. Colloids Surf. A 79:157–167.
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Stumm, W. 1992. Chemistry of the solid–water interface. Wiley, Wersin, P., M.F. Hochella, Jr., P. Persson, G. Redden, J.O. Leckie,
New York. and D.W. Harris. 1994. Interaction between aqueous ura-
Stumm, W., and G. Furrer. 1987. The dissolution of oxides and nium (VI) and sulfide minerals: Spectroscopic evidence
aluminum silicates: Examples of surface-coordination- for sorption and reduction. Geochim. Cosmochim. Acta
controlled kinetics, p. 197–219. In W. Stumm (ed.) Aquatic 58:2829–2843.
surface chemistry. Wiley Interscience, New York. Wollast, R. 1967. Kinetics of the alteration of K-feldspar in buff-
Stumm, W., and R. Wollast. 1990. Coordination chemistry of ered solutions at low temperature. Geochim. Cosmochim.
weathering. Kinetics of the surface-controlled dissolution Acta 31:635–648.
of oxide minerals. Rev. Geophys. 28:53–69. Wu, S., and P.M. Gschwend. 1986. Sorption kinetics of hydro-
Tang, L.Y., and D.L. Sparks. 1993. Cation-exchange kinetics on phobic organic compounds to natural sediments and soils.
montmorillonite using pressure-jump relaxation. Soil Sci. Environ. Sci. Technol. 20:717–725.
Soc. Am. J. 57:42–46. Xia, K., A. Mehadi, R.W. Taylor, and W.F. Bleam. 1997. X-ray
Thompson, H.A., G.A. Parks, and G.E. Brown. 1999a. Dynamic absorption and electron paramagnetic resonance stud-
interactions of dissolution, surface adsorption, and precipi- ies of Cu(II) sorbed to silica: Surface-induced precipita-
tation in an aging cobalt(II)–clay–water system. Geochim. tion at low surface coverages. J. Colloid Interface Sci.
Cosmochim. Acta 63:1767–1779. 185:252–257.
Thompson, H.A., G.A. Parks, and G.E. Brown. 1999b. Ambient- Xing, B., and J.J. Pignatello. 1997. Dual-mode sorption of low-
temperature synthesis, evolution, and characterization polarity compounds in glassy poly (vinyl chloride) and soil
of cobalt–aluminum hydrotalcite-like solids. Clays Clay organic matter. Environ. Sci. Technol. 31:792–799.
Miner. 47:425–438. Xing, B., and J.J. Pignatello. 2005. Sorption of organic chemicals.
Toner, C.V., IV, and D.L. Sparks. 1995. Chemical relaxation and In D. Hillel (ed.) Encyclopedia of soils in the environment,
double-layer model analysis of Boron adsorption on alu- p. 537–548. Vol. 3. Elsevier Ltd., Oxford, U.K.
mina. Soil Sci. Soc. Am. J. 59:395–404. Xue, Y., and S.J. Traina. 1996. Oxidation kinetics of Co(II)-
Towle, S.N., J.R. Bargar, G.E. Brown, Jr., and G.A. Parks. 1997. EDTA in aqueous and semi-aqueous goethite suspensions.
Surface precipitation of Co(II) (aq) on Al2O3. J. Colloid Environ. Sci. Technol. 30:1975–1981.
Interface Sci. 187:62–82. Zhang, P.C., and D.L. Sparks. 1989. Kinetics and mechanisms
van Genuchten, M.Th., and R.J. Wagenet. 1989. Two-site/two- of molybdate adsorption/desorption at the goethite/water
region models for pesticide transport and degradation: interface using pressure-jump relaxation. Soil Sci. Soc. Am.
Theoretical development and analytical solutions. Soil Sci. J. 53:1028–1034.
Soc. Am. J. 53:1303–1310. Zhang, P.C., and D.L. Sparks. 1990a. Kinetics and mechanisms of
Waychunas, G.A., B.A. Rea, C.C. Fuller, and J.A. Davis. 1993. sulfate adsorption desorption on goethite using pressure-
Surface chemistry of ferrihydrite: Part 1. EXAFS studies jump relaxation. Soil Sci. Soc. Am. J. 54:1266–1273.
of the geometry of coprecipitated and adsorbed arsenate. Zhang, P.C., and D.L. Sparks. 1990b. Kinetics of selenate and sel-
Geochim. Cosmochim. Acta 57:2251–2269. enite adsorption/desorption at the goethite/water interface.
Weber, W.J., Jr., and J.P. Gould. 1966. Sorption of organic pesti- Environ. Sci. Technol. 24:1848–1856.
cides from aqueous solution. Adv. Chem. Ser. 60:280–305. Zinder, B., G. Furrer, and W. Stumm. 1986. The coordination
Weber, W.J., and W.L. Huang. 1996. A distributed reactivity model chemistry of weathering. II. Dissolution of Fe(III) oxides.
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geneity and phase-distribution relationships under non-
equilibrium conditions. Environ. Sci. Technol. 30:881–888.
 14
Oxidation–Reduction Phenomena
14.1 Concepts, Principles, and Theories......................................................................................14-1
Nature of the Electron and Proton in Soil Solutions  •  Thermodynamic Relationships
for Electron Activity in Soils  •  Kinetic Derivation of Thermodynamic Parameters
for Redox  •  Microbiological and Enzymatic Controls for Redox State and Processes in Soils
14.2 Methods and Procedures.....................................................................................................14-12
Uses of pe–pH Thermodynamic Information  •  Use of pe–pH Diagrams  •  Measurement
of Soil Redox and Acid–Base Status  •  Proposed Alternative Strategies for More Accurate
Measurement of Soil Redox Status
14.3 Applications of Redox Methods and Concepts to Ecological, Engineered,
and Agricultural Soil Systems............................................................................................ 14-17
Rhizosphere Processes  •  Soil Remediation and Pollutant Speciation  •  Soil Fertility and
Nutrient Cycling  •  Soil Organic C Dynamics and Climate Change  •  Wetland Delineation
Bruce R. James and Function  •  Riparian Soil-Vegetation Systems and Groundwater Nitrate Concentrations
University of Maryland
14.4 Earlier Reviews and Prescient Work on Oxidation–Reduction
Dominic A. Brose Processes in Soils........................................................................................................... 14-19
University of Maryland References..........................................................................................................................................14-20

14.1  Concepts, Principles, and Theories To understand and characterize the nature of “electron activity”
and oxidation–reduction reactions in biotic and abiotic, heteroge-
14.1.1  Nature of the Electron and Proton neous, multiphase soils and soil solutions, an appreciation of the
in Soil Solutions characteristics of electrons and closely allied protons is needed
(James, 1989; Stumm and Morgan, 1996; Bartlett, 1998; Bartlett
Electrons are subatomic particles with wave-like properties that
and Ross, 2005). An examination of the complementary nature of
have defied exact characterization since their discovery in 1897,
electrons and protons affirms the importance of hydrogen ion and
despite their central role in chemical reactions (Castellan, 1983).
electron activities as master variables in soils (Sillén, 1967).
Electrons are considered fundamental subatomic particles, but
The H atom comprises one proton and one electron, and it may
recent findings suggest that they may possess a substructure of
be visualized as a spherical puff of cotton candy with a radius
leptoquarks, that electron orbitals do not exist, and that the role of
of approximately 10 cm and a proton nucleus with a radius of
electrons in predicting periodicity of the elements is only approxi-
5 μm; essentially an invisible fleck of unspun sugar in the center.
mate (Scerri, 1997). In addition, new frontiers are expanding to
The remaining volume of the atom is occupied by the electron
explain electron-transfer processes at interfaces (Tributsch and
and the density of the spun sugar represents the probability of
Pohlmann, 1998). Studying and understanding electron-transfer
finding the electron in any one location. It becomes increasingly
processes in soils, therefore, is challenging and must be based on
less dense (less probable) with distance away from the positively
sources of information from relatively simple aqueous systems and
charged proton (Castellan, 1983). The radius of the H atom
natural waters, as well as on a large base of empirical studies using
(0.3 Å), therefore, is approximately 20,000 times greater than
soils. Electron-transfer processes in microbial cells are central to
that of the proton (~1.5 × 10−5 Å). The proton also may be visual-
nutrient and pollutant chemical reactions, especially oxidation
ized as the size of a 0.1 μm colloidal clay particle, compared to a
state changes governed by intra- and extracellular enzymes (Paul,
2000 μm sand grain in a soil. In contrast to the large proportion
2007). Recent developments in environmental microbiology have
of the volume of the H atom occupied by the negatively charged,
found that bacteria form biofilms almost ubiquitously in aqueous
wave-like electron, the electron has only negligible mass equal
and colloidal environments, such as natural waters, soils, and the
to approximately 550 μg mol−1, 1/1836 of the mass of the H atom
human body (Stoodley et al., 2004). Therefore, understanding the
(106 μg mol−1).
role of microbes in controlling redox processes in soils requires
The tiny, heavy proton persists in hydrated form in aqueous
an appreciation of such “matrix enclosed accretions that adhere
media as H3O+, the hydroxonium or hydronium ion. The H atom
to biological and nonbiological surfaces” (Stoodley et al., 2004).

14-1
14-2 Properties and Processes

can only form the H+ ion when its compounds are dissolved in (Eo) associated with the electron transfers are +5.2 and +1.04 V,
media that solvate protons, so the H+ cannot exist in solid phases respectively, where n is the number of moles of electrons and F is
(Cotton and Wilkinson, 1980). The solvation enthalpy of −1091 kJ the Faraday constant [96,487 C (coulombs) mol−1 or J V−1 mol−1].
mol−1 provides the energy for bond rupture. Protons migrate rap- The concept of H+ activity and pH also can be described in terms
idly between water molecules, and an individual H3O+ ion has of thermodynamic work (Δw) defined as the product of an intensive
a lifetime of approximately 10−13 s. Its concentration and activ- property and extensive variation, such as P (ΔV), where P is pressure
ity can, therefore, be measured and understood in terms of the and ΔV is change in volume (Stumm and Morgan, 1996). Similarly,
hydration of a cation in solution. The single ion activity coefficient electron activity may be defined as E (Δe), where E is potential and
can be calculated based on ionic strength, temperature, effective Δe is change in charge of the system. Proton and electron activities
diameter, and solvent characteristics; and H+ activity can be cal- also may be defined as chemical work, μ (Δn), where μ is chemical
culated or measured (Westcott, 1978; Bates, 1981). potential and Δn is change in moles (Sposito, 1981).
The extremely large “charge-to-size ratio” of the electron pre- Viewing the sibling concepts of “proton activity” and “electron
vents it from persisting in free form in aqueous systems, as does activity” in soils, they must not be considered twins. Recognition
the solvated H+. The ephemeral “hydrated electron” is a powerful must be given to similarities and differences in the formulation
reducing agent with a potential of −2.7 V relative to the H+/H2 of conceptual and operational definitions for these key variables,
reference potential of 0.0 V and has a half-life of <1 ms. It reacts and such comparisons are based on the differences in the nature
rapidly with second-order rate constants of 108–1010 M−1 s−1, near of the proton and electron, as described above. In both cases, how-
the diffusion-controlled limit (Sullivan et al., 1976). Hydrated ever, their thermodynamic activities in a given system are relative
electrons may be transferred to aqueous solution from photoex- to their activities under standard-state conditions. In the case of
cited hydrocarbons as •eaq−. Such “free” or “aqueous” electrons the e−, the standard state is at (H+) = 1 M, a partial pressure of H2 =
react with H2O and H3O+ at femtosecond rates (10−15 s) to form 1 atm, and a temperature of 298 K, characteristics of the standard
the “conjugate acid” of the electron, H•, and the reaction with hydrogen electrode (SHE) with 0 V under these conditions (Lindsay,
H3O+ is approximately 107 times faster than with water (Leffler, 1979; Compton and Sanders, 1996; Stumm and Morgan, 1996). For
1993). The role of such aqueous electrons in soils remains H+ activity, the reference state is 1 M or pH 0 (Bates, 1981).
unstudied, and photochemical studies of soils may reveal their The familiar concept of buffer capacity for pH is defined as
presence and importance. the change in acid or base added (capacity factor) to effect a one
In soil chemical calculations and theory, one considers the unit change in pH (intensive variable; Stumm and Morgan, 1996).
electron as a “species,” designated “e−,” with negligible mass and Similarly, the “capacity factor” in redox is referred to as poise and is
thermodynamically as a ligand, reactant, and product (Sposito, defined as the change in added equivalents of reductant or oxidant
1981). The electron is not ionic, but it is “negatively charged” as to bring about a one unit change in pe (−log of electron activity) or
the carrier of negative electricity (Thompson, 1923). Its “activ- an Eh (voltage relative to the SHE) change of 59 mV, as discussed in
ity” is conceptually analogous to that of H+, but its concentration Section 14.1.2. Poise in soils and natural waters has been less inten-
in “mol L−1” is undefined. All these caveats about the electron sively studied than pH buffering, but it is a central concept governed
require that one understand that electron activity in soils and by reductant and oxidant activities and microbial processes.
natural waters should be regarded as related strictly to energy The choice of oxidant or reductant to add in a redox titra-
functions. Such functions can be described simply as “the ability tion will affect the calculated poise (resistance to change in pe
to do work,” “electrochemical potential,” and more colloquially, as measured by the Pt electrode), and poise will be operationally
“electron pressure.” defined by the couple interacting with the Pt wire. For instance,
Generically, for a reduction half-reaction: ox + ne− = red, the if the soil is titrated with Cr(VI), the Cr(VI)–Cr(III) couple will
electron activity, (e−), equals [(red)/K(ox)]1/n, in which “ox” is the be potential determining, so the poise will reflect that pe range.
oxidized species, “red” is the reduced species, n is the number of If Fe(II) were added, the Fe(III)–Fe(II) couple would set a lower
moles of electrons, and K is the equilibrium constant. Therefore, pe range than would Cr(VI)–Cr(III). Heron et al. (1994) titrated
electron activity is a function of the ratio of reduced-to-oxidized aquifer sediments with the reducing agent, Ti3+ EDTA, to deter-
species activities and of the equilibrium constant [or Gibbs free mine the poise associated with oxidants, such as Fe(III) and
energy for the reaction, since ΔGro = −RT ln K, where R is the gas Mn(III,IV) (hydr)oxides. Barcelona and Holm (1991) titrated
law constant (8.313 J K−1 mol−1) and T is the absolute tempera- with Cr2+ to quantify poise due to oxidants, and with Cr2O72− to
ture measured in Kelvin (298 K under standard conditions)]. determine poise governed by reductants in the soil, respectively.
A “favorable reaction” with a large positive value for K (or large Bauer et al. (2007) measured electron-transfer capacities and
negative �Gro) will therefore be associated with low electron reaction kinetics of peat-dissolved organic matter, an organic
activity. For example, a value of the equilibrium constant, matter analog for soil C. They used Zn and H2S oxidation and
K = 6 × 108, corresponds to ΔGro = −50 kJmol −1 and K = 57 cor- complexed Fe(III) reduction to show that dissolved organic mat-
responds to −10 kJ mol−1 (Compton and Sanders, 1996). That is, ter is a redox poising system between −0.9 and 1.0 V.
such reactions will proceed spontaneously at relatively low elec- Redox intensity measurements (Eh or pe) and estimates of
tron activities or pressures, corresponding to positive electrode poise as the redox capacity of soils and sediments are also dis-
voltages. In these examples, since ΔGro = −nFEo, the voltages tinguished from those only associated with H+ in that microbial
Oxidation–Reduction Phenomena 14-3

catalysis controls the rates of many of the oxidation and reduc- The number of electrons needed for reduction is calcu-
tion reactions governing soil redox status (Russell, 1973; Banerjee, lated from the oxidation numbers or states of the elements
2008). Also, the adaptation and growth of higher plants and algae in the oxidized and reduced species (Vincent, 1985). In
in soils affects redox intensity and capacity. Examples of such this example, the oxidation numbers are III+ and VI+ for
microbial processes governing redox in soils include Fe(III) and Fe and S in FeOOH and SO42−, respectively.
SO42− reduction in sediments (Coleman et  al., 1993), denitri- 2. Add H 2O to the equation (usually to the right side) to
fication in soil microenvironments (Højberg et al., 1994), N2 balance the moles of O:
fixation in flooded soils (e.g., due to pH and pe changes by the
Anabaena–Azolla symbiosis in rice or that of the Frankia sp. FeOOH + e − = Fe2 + + 2H2O, (14.3)
actinomycete infection of alder (Alnus spp.; Buresh et al., 1980;
Madigan and Martinko, 2006), methane oxidation in flooded rice SO4 2 − + 8e − = H2S + 4H2O. (14.4)

soils (Wang et  al., 1997), the reactions of H2 in anoxic ground-
water (Lovley et  al., 1994), methanogenesis (Welsch and Yavitt, 3. Then add H+ to balance moles of H, usually on the left side
2007; Goldhammer and Blodau, 2008; Saggar et al., 2008), and of the equation:
the formation of oxidized root channels (rhizospheres) in soils
(Mendelssohn et al., 1995). FeOOH + e − + 3H + = Fe2 + + 2H2O, (14.5)

The poise and pe of soils also differ from natural waters in that
the solids-to-solution ratio is high; and subsequently, redox reac- SO4 2 − + 8e − + 10H + = H2S + 4H2O. (14.6)

tions across colloid–solution interfaces are centrally important.
Biofilm–water interfaces may be especially important in the case 4. Check charge and mass balances for the equations.
of microbially governed redox processes. Relatively few studies
have been reported on redox reactions across soil colloid–water These equations can now be used to develop expressions for elec-
interfaces, but this area is critically important for predicting tron activity based on equilibrium expressions and free energy
­oxidation state and potential mobility of nutrients and pollutants of formation (�G of ) data.
in soil environments. Examples include reductive dissolution of The principles for doing this can be understood by starting
Fe(III) and Mn(III,IV) (hydr)oxides and redox reactions on such with a generic reduction half-reaction:
surfaces or with constituent ions (Bartlett and James, 1979; Stone
and Morgan, 1987; Suter et al., 1991; Stumm and Sulzberger, 1992; Aox + Be − + CH + = Dred + EH2O (14.7)
Postma and Jakobsen, 1996; White and Peterson, 1996).
where A, B, C, D, and E are the stoichiometric coefficients. The
expression for the equilibrium constant (K) is as follows:
14.1.2  Thermodynamic Relationships
for Electron Activity in Soils ⎡(red)D (H2O)E ⎤
Since electrons are transferred from reductants (e− donors or reduc- K = ⎣ A − B + ⎦C (14.8)
⎡(ox) (e ) (H ) ⎤
ing agents) to oxidants (e− acceptors or oxidizing agents) and do not ⎣ ⎦
persist free in soil solution, reduction reactions must be coupled to
oxidation reactions to describe complete oxidation–reduction pro- where
cesses (redox reactions). By convention, reduction half-reactions () denotes activity
can be written and thermodynamic relationships derived from (H2O) has a value of 1, by convention
them, despite the fact that they do not occur in isolation. The log K
values (where K is the equilibrium constant for the half-reaction) for Taking the log of both sides of the equation,
the coupled reactions may be compared to predict the likelihood of
a reaction occurring spontaneously as written. ⎡ (red)D ⎤ ⎡ 1 ⎤ 1
log K = log ⎢ A ⎥
+ log ⎢ − B ⎥ + log + C (14.9)
For example, development of reduction half-reactions to pre- ⎣ (ox) ⎦ ⎣ (e ) ⎦ (H )

dict whether gaseous H2S could reduce colloidal FeOOH across
a sulfidic–aerobic interface in a wetland soil may be completed and
in the following manner:
log K = D log (red) − A log(ox) + Bpe + CpH (14.10)

1. Write the oxidized and reduced species on the left and right
sides of the equation, respectively, with the appropriate where
number of electrons per mole of oxidant written on the left pe and pH are defined as −log electron activity
side. Balance moles of elements other than O and H: H+ activity, respectively.

FeOOH + e − = Fe2 + , (14.1) The “p” notation means power and denotes the exponent for the

H+ activity (pH 4 or 10−4 mol H+ kg−1 water). Therefore, (H+) = 10−pH.
SO4 2 − + 8e − = H2S. (14.2) In contrast, the exponent for e− activity is not 10−pe, since the electron
14-4 Properties and Processes

activity is not defined in terms of “mol e− L−1.” Both pe and pH are Converting to log10 (ln K = 2.303 log K) yields the following:
analogous, though, if viewed as related to the ability of e− and H+ to
do thermodynamic work (Section 14.1.1). ΔGro
Further rearrangement of Equation 14.10 yields a pe–pH = log K. (14.15)
−5.70
relationship of the following form:
log K may therefore be estimated simply from knowledge of free
⎡⎛ 1 ⎞ ⎛ D⎞ ⎛ A⎞ ⎤ ⎛ C⎞ energies of formation of H2O, the red, and the ox; since those
⎢⎜⎝ ⎟⎠ log K − ⎜⎝ ⎟⎠ log(red) + ⎜⎝ ⎟⎠ log (ox)⎥ − ⎜⎝ ⎟⎠ pH = pe,
B B B B of H+ and e− are zero, by convention. To relate log K directly to
⎣ ⎦
(14.11) pe as defined by Equation 14.11 for one-electron transfers, log
K values must be divided by B, the mol of e− consumed in the
which gives a straight line with slope C/B and the intercept in reaction. Therefore, pe at a given pH and other defined condi-
square brackets that is a function of log K for the half-reaction tions is equivalent to log K, and the parameter pe + pH couples
and the activities of the oxidized and reduced species. the master variables in defining the equilibrium redox state of a
For a one-electron transfer (B = 1) coupled with one-proton soil–water system.
consumption (C = 1), and when D = A and (red) = (ox), Log K values also are related to thermodynamic electro-
chemical potentials (Eh) according to the following expressions
(Compton and Sanders, 1996):
pe + pH = log K. (14.12)

And when pH = 0 (standard state), ΔGro = −nFEh (14.16)

pe = log K. (14.13) where

n is the number of e− transferred mol−1
Knowledge of pe and pH is pertinent to describing the equilibrium F is the Faraday constant (96.5 kJ V−1 equivalent−1 or 96,487 C
condition of a soil as defined by the master variables, pe, pH, and mol−1 where C is coulombs, derived from 1.60 × 10−19 C/e− ×
their sum (Lindsay, 1979). The concepts of electron activity and 6.02 × 1023 e−/mol)
hydrogen ion activity are closely coupled and cannot be separated
in assessing the oxidation–reduction status of a soil system. The Since both Equations 14.16 and 14.14 are expressions for �Gro,
pe + pH parameter has been described metaphorically by Bartlett
(1998) as a seesaw with a hungry baby bird on one side (the electron- −nFEh = −RT lnK (14.17)

deficient player) and earthworms on the other (the electron-rich
source). The parent bird carries the earthworms to the baby, repre- and, when T = 298 K,
senting electron transfer and causing a shift in the position of the
seesaw, quantified by the pe–pH balance. As worms are transferred, RT 2.303 log K
the pe increases and the pH decreases, counteracting and interact- Eh = = 0.0592 log K. (14.18)
nF
ing controls on the redox equilibrium. As the worms are consumed
by the baby, the seesaw shifts back again, representing a dynamic,
If n = 1, (red) = (ox), and pe = log K at a given pH (Equation
metastable system governed by the flow of energy and the cycling of
14.12), then
nutrients, characteristics of ecosystems. The position of the seesaw
governed by pe and pH reflects the equilibrium condition of a soil, Eh (V) = 0.0592 pe
(14.19)
and the values of pe and pH are intensity measures of redox sta-
tus. The change in measured pe and pH per mole of electrons plus or
H+ (H atoms in principle) transferred reflects the buffer capacity or Eh
poise of the system, Δ(pe + pH)/Δ (mol H atoms transferred). = pe. (14.20)
0.0592
To relate the concept of log K to the Gibbs free energy change
(�Gro) for a given half-reaction in the soil, the following expres-
Therefore, calculating or interpreting Eh values rigorously and
sions are pertinent:
linking soil measurements to thermodynamics require knowl-
ΔGro = −RT lnK (14.14) edge of the pH of the soil–water system.
Applying these principles to the H2S–FeOOH problem above
where (Equations 14.5 and 14.6), the following pe–pH expressions can
�Gro is Gibbs free energy of reaction under standard condi- be derived:
tions (298 K and 1 atm) For FeOOH–Fe2+:
R is the universal gas law constant (0.00831 kJ K−1 mol−1)
T is absolute temperature (298 K) pe = log K Fe − log(Fe2 + ) − 3pH (14.21)
Oxidation–Reduction Phenomena 14-5

where activity of FeOOH is assumed to be 1, an assumption the positions of the lines are shifted to higher pe values for the
that may or may not be valid for redox processes (Stumm, 1993; lower activities of the reduced species; the effect being greater for
White and Peterson, 1996). the FeOOH–Fe2+ couple than for SO42−–H2S, due to the greater
For SO42−–H2S: oxidation state change per mole for S than for Fe. This effect of
changing the activity ratio on pe values is an easy way to per-
1 1 ⎡ P ⎤ 5 form a sensitivity analysis for these thermodynamic models and
pe = log K S − log ⎢ H22S− ⎥ − pH (14.22) to plot a family of curves representative of a range of activities
8 8 SO
⎣ 4 ⎦ 4 relevant to any soil system or conditions. Similar calculations
can be performed for variations in the values of �G of , since the
where conditions (e.g., temperature, pressure, and ionic strength)
K Fe and KS are the equilibrium constants for the FeOOH and under which these values are determined may result in a range
SO42− reduction half-reactions of values of up to 10 or more kJ mol−1. The �G of values tabulated
P H2S is the partial pressure of H2S by Lindsay (1979) were reviewed and selected for their accuracy
and their relevance to soils and natural waters.
Calculating log K values and substituting into Equations An important use of pe–pH diagrams is for predicting thermo-
14.21 and 14.22 yield the following: dynamically whether or not the oxidized species in one reduction
half-reaction will oxidize the reduced species in a second reduc-
pe = 13.0 − log(Fe2 + ) − 3pH (14.23) tion half-reaction (i.e., when the second half-reaction is reversed

to become the oxidation half-reaction and is added to the first
and reduction half-reaction). When the line for a pe–pH couple is
above another over a pH range, the calculated Δpe or ΔEh values
⎛ 1⎞ ⎡ P ⎤ ⎛ 5⎞ will be >0 (and corresponding �Gro values <0), signifying that the
pe = 5.21 − ⎜ ⎟ log ⎢ H22S− ⎥ − ⎜ ⎟ pH. (14.24) reaction is spontaneous as written. In the above example, FeOOH
⎝ 8⎠ ⎣ SO4 ⎦ ⎝ 4 ⎠
is expected to oxidize H2S over the pH range 0–6.6 for the activ-
ity ratio = 1 but only up to pH 4.6 for the activity ratio = 10−4.
At defined activities for the ions and partial pressure for H2S, pe Theoretically, above the crossover pH values, SO42− would be
may be calculated, and if pe for Fe(III) reduction > pe for SO42− expected to oxidize Fe2+ to FeOOH, while being reduced to H2S;
reduction, then FeOOH will be reduced to Fe2+ and H2S oxidized the opposite of the reaction at pHs < the crossover value.
to SO42− at equilibrium and at the hypothetical soil interface. The Calculations of myriad pe–pH relationships are conveniently
same result will be obtained if after subtracting the log K value performed using a spreadsheet template that incorporates bal-
for S from that for Fe, a positive answer is obtained. anced half-reactions, appropriate �G of values to calculate log K,
The Equations 14.23 and 14.24 can be plotted on an x–y-graph chosen activity ratios, and Equation 14.11. Using such a spread-
called a pe–pH diagram (Figure 14.1). In this graph, each reduc- sheet, numerous pe values for common reduction half-reactions
tion half-reaction is plotted for (red)/(ox) = 1 and 10−4. Note that pertinent to soil chemical and biochemical processes were cal-
culated and are presented in Table 14.1. Table 14.1 also includes
30 1.8 numerous pe values derived from Eh data in various published
A = FeOOH–Fe2+ (red)/(ox) = 10–4 databases, especially for coenzymes and some intermediates
B = FeOOH–Fe2+ (red)/(ox) = 1
governing microbial respiration. This list provides a quick, semi-
1.3
20 quantitative means of assessing what the products of selected,
C = SO42––H2S (red)/(ox) = 10–4
A coupled reduction and oxidation half-reactions are likely to be.
D = SO42––H2S (red)/(ox) = 1
0.8 The U.S. Environmental Protection Agency developed
10 MINTEQ (for “Mineral Thermal Equilibria”), a DOS-based
B
computer program that calculates the distribution of myriad
Eh (V)

C 0.3
pe

species based on minimizing the Gibbs free energy of a system

D
0 of multiple chemical equilibria. Different from earlier such pro-
–0.2 grams, such as GEOCHEM, it incorporates algorithms for redox
reactions and allows the estimation of pe, pH, and reductant and
–10 oxidant activities in conjunction with dissolution and exchange
–0.7
equilibria. The use of MINTEQ also permits an easy way to con-
duct a sensitivity analysis for estimated pe, pH, or ion activities
–20 –1.2 when just one value for a given parameter is varied (Allison and
0 1 2 3 4 5 6 7 8 9 10
Brown, 1995). Visual MINTEQ was written and is updated for
pH
Microsoft Windows by J.P. Gustafsson, and version 3.0 (as of
FIGURE 14.1  pe–pH diagram for FeOOH–Fe2+ and SO42−–H 2S August 2010) is now available free online at http:/www.lwr.kth.
equilibria at two activity ratios. se/English/OurSoftware/vminteq/
14-6 Properties and Processes

TABLE 14.1  Reduction Half-Reactions for Soils

Log Ka peb
(pe at pH 0) pH 5 pH 7
Nitrogen species
1
2 N2 O + e − + H + = 1
2 N2 + 1
2 H2 O 29.8 22.9 20.9
NO + e + H = − + 1
2 N 2O + 1
2 H2 O 26.8 19.8 17.8
1
2 NO2 + e + − − 3
2 H + + 1
4 N 2O + 3
4 H2O 23.6 15.1 12.1

5 NO3 + e + 5 H = N 2 + 3 5 H2O 21.1 14.3 11.9

1 − − 6 + 1
10

NO2 − + e − + 2H + = NO + H2O 19.8 9.8 5.8

1
4 NO3 + e + − − 5
4 H = + 1
8 N2O + 5
8 H2O 18.9 12.1 9.6
1
6 NO2 + e + − − 4
3 H = + 1
6 NH 4 + + 1
3 H2O 15.1 8.4 5.7

8 NO3 + e + 4 H = 8 NH 4 + 8 H2 O 14.9 8.6 6.1

1 − − 5 + 1 + 3

1
2 NO3 + e + H =
− − + 1
2 NO2 + − 1
2 H2O 14.1 9.1 7.1
1
6 NO3 + e + − − 7
6 H = + 1
6 NH2OH + 1
3 H2O 11.3 5.4 3.1
1
6 N2 + e + 3 H =
− 4 + 1
3 NH 4
+
4.6 −0.7 −3.3

Oxygen species
OH• + e− + H+ = H2O — — 36.8
O3•− + e− + 2H+ = H2O + O2 —c — 30.5d
1O3 + e − + H + =
2
1
2 O2 + 1
2 H2O 35.1 28.4 26.4
OH• + e− = OH− 33.6 33.6 33.6
O2−+ e− + 2H+ = H2O2 32.6 22.6 18.6
1 H 2 O2 + e − + H + = H 2 O
2 30.0 23.0 21.0
HO2• + e− + H+ = H2O2 — — 17.9d
O3 + e− = O3•− — — 15.1d
1O + e− = O •− (singlet) — — 14.1d
2 2
1
4 O2 + e − + H + = 1
2 H2O 20.8 15.6 13.6
H2O2 + e− + H+ = OH• + H2O — — 7.8
2 O2 + e + H = 2 H 2 O2
− +
1 1
11.6 8.2 6.2
3O + e− = O •− (triplet, ground state) −9.5 −6.2 −6.2
2 2
3O + e− + H+ = HO • (triplet, ground state) — — −7.8
2 2

Sulfur species
1
8 SO4 2− + e − + 5 4 H + = 1
8 H2S + 1
2 H2O 5.2 −1.0 −3.5
2−
1
6 SO4 + e + − 4
3 H = + 1
6 S+ 2
3 H2O 5.3 −1.4 −4.0

2S+e +H = 2 H2S
− +
1 1
4.9 −0.1 −2.1
2−
1
2 SO4 + e + 2H = − + 1
2 SO2 + H2O 2.9 −7.1 −11.1
Iron and manganese compounds
1
2 Mn3O4 + e − + 4H + = 3
2 Mn2+ + 2H2O 30.7 16.7 8.7
2+
1
2 Mn2O3 + e + 3H = Mn + 3 2 H2O
− +
25.7 14.7 8.7
Mn + e = Mn 3+ − 2+ 25.5 25.5 25.5
γ-MnOOH + e− + 3H+ = Mn2++ 2H2O 25.4 14.4 8.4
0.62MnO1.8 + e− + 2.2H+ = 0.62 Mn2++ 1.1H2O 22.1 13.4 8.9
1
2 Fe3 (OH)8 + e − + 4H + = 3
2 Fe2+ + 4H2O 21.9 7.9 −0.1
2+
1
2 MnO2 + e + 2H = − + 1
2 Mn + H2O 20.8 12.8 8.8
[Mn (PO4)2] + e = [Mn (PO4)2]
3+ 3− − 2+ 4− 20.7 20.7 20.7
Fe(OH)2+ + e− + 2H+ = Fe2+ + 2H2O 20.2 10.2 6.2
1
2 Fe3O4 + e − + 4H + = 3
2 Fe2+ + 2H2O 17.8 3.9 −4.1
MnO2 + e− + 4H+ = Mn3+ + 2H2O 16.5 0.54 −7.5
Oxidation–Reduction Phenomena 14-7

TABLE 14.1 (continued)  Reduction Half-Reactions for Soils

Log Ka peb
(pe at pH 0) pH 5 pH 7
Fe(OH)3 + e + 3H = Fe + 3H2O
− + 2+ 15.8 4.8 −1.2
FeOH2+ + e− + H+ = Fe2+ + H2O 15.2 10.2 8.2
1
2 Fe2O3 + e − + 3H + = Fe2+ + 3 2 H2O 13.4 2.4 −3.6
FeOOH + e + 3H = Fe + 2H2O
− + 2+ 13.0 2.0 −4.0
Fe3+ + e− = Fe2+ (phenanthroline) 18.0 —c —
Fe3+ + e− = Fe2+ (H2O only) 13.0 13.0 13.0
Fe3+ + e− = Fe2+ (acetate) — 5.8 —
Fe3+ + e− = Fe2+ (malonate), pH 4 — 4.4 —
Fe3+ + e− = Fe2+ (salicylate), pH 4 — 4.4 —
Fe3+ + e− = Fe2+ (hemoglobin) — — 2.4
Fe3++ e− = Fe2+ (EDTA) — — 2.0d
Fe3+ + e− = Fe2+ cyt b3 (plants) — — 0.68
Fe3+ + e− = Fe2+ (DTPA) — — 0.51
Fe3+ + e− = Fe2+ (oxalate) — — 0.034
Fe3++ e− = Fe2+ (pyrophosphate) −2.4 — —
Fe3+ + e− = Fe2+ (peroxidase) — — −4.6
Fe3+ + e− = Fe2+ (spinach ferredoxin) — — −7.3
Fe3++ e− = Fe2+ (ferritin) — — −3.2d
1
3 KFe3 (SO4 )2 (OH)6 + e − + 2H + = Fe2+ + 2H2O + 2 3 SO4 2− + 1
3 K+ 8.9 6.9 2.9

[Fe(CN)6 ]3− + e − = [Fe(CN)6 ]4− — — 6.1

Carbon species
CH3CH2• + e− + H+ = CH3CH3 — — 32.2d
RO• + e− + H+ = ROH (aliphatic) — — 27.1d
CO3•− + e− + H+ = CO32− — — 25.1d
Tryptophan• + H+ + e− = tryptophan — — 16.9
Catechol-O• + e− + H+ = catechol — — 9.0d
Benzosemiquinone + e− + H+ = hydroquinone — — 7.8d
1
2 Ubiquinone + H + + e − = ubiquinone-H 2 — — 1.7
1
2 o-quinone + e + H = − + 1
2 diphenol — — 5.9
1
2 p-quinone + e + H = − + 1
2 hydroquinone — 4.7
Cu2+ + H+ + e− = Cu+ (superoxide dismutase) — — 7.1
Mn3+ + H+ + e− = Mn2+ (superoxide dismutase) — — 5.2
Fe3+ + H+ + e− = Fe2+ (superoxide dismutase) — — 4.7
1
2 CH3OH + e − + H + = 1
2 CH 4 + 1
2 H2O 9.9 4.9 2.9
1
12 C 6 H12O6 + e + H = − + 1
4 C 2 H5OH + 1
4 H2O 4.4 −1.9
1
8 CO2 + e + H =
− + 1
8 CH 4 + 1
8 H2O 2.9 −2.1 −4.1
1
2 CH2O + e + H = − + 1
2 CH3OH 2.1 −2.9 −4.9
1
2 HCOOH + e − + H + = 1
2 CH2O + 1
2 H2O 1.5 −3.5 −5.5
1
4 CO2 + e + H =
− + 1
24 C 6 H12O6 + 1
4 H2O −0.21 −5.9 −7.9
1
2 Dehydroascorbate + e + H = − + 1
2 ascorbic acid 1.0 −3.5 −5.5
1
2 Methylene blue(ox) + H + e = + − 1
2 methylene blue(red) — — 0.2
FAD + H + e = + − 1
2 FADH2 — — −3.0
1
2 Pyruvate + H + e = + − 1
2 lactate — — −3.2

2 NAD + H + e = 2 NADH + 2H — — −5.4

1 + + − 1 1 +

(continued)
14-8 Properties and Processes

TABLE 14.1 (continued)  Reduction Half-Reactions for Soils

Log Ka peb
(pe at pH 0) pH 5 pH 7
1
2 Pyruvate + 1
2 CO2 + H + e = + − 1
2 malate — — −5.6
Ferredoxin-Fe + e = ferredoxin-Fe 3+ − 2+ — — −7.3
1
4 CO2 + e − + H + = 1
4 CH2O + 1
4 H2O −1.2 −6.1 −8.1
1
2 CO2 + e + H = − + 1
2 HCOOH −1.9 −6.7 −8.7
1
2 Acetate + H + e = + − 1
2 acetaldehyde — — −10.1
1
2 Acetate + CO2 + H + e = + − 1
2 pyruvate — — −11.8
CO2 + e− = CO2•− — — −30.5
Pollutant/nutrient group
Co3+ + e− = Co2+ 30.6 30.6 30.6
2+
1
2 NiO2 + e + 2H = − + 1
2 Ni + H2O 29.8 21.8 17.8
PuO2+ + e− = PuO2 26.0 22.0 22.0
2+
1
2 PbO2 + e + 2H =
− + 1
2 Pb + H2O 24.8 16.8 12.8
PuO2 + e + 4H = Pu + 2H2O
− + 3+ 9.9 −6.1 −14.1
1
3 HCrO 4 − + e − + 4 3 H + = 1
3 Cr(OH)3 + 1
3 H2O 18.9 10.9 8.2
1
2 H 2 AsO 4 + e + 2 H =
− − 3 + 1
2 H 3 AsO3 +
1
2 H2O 11.2 3.7 0.7
Hg 2+ + e − = 1
2 Hg 22+ 15.4 13.4 13.4
2−
1
2 MoO4 + e + 2H = − + 1
2 MoO2 + H2O 15.0 3.0 −1.0
2− 2−
1
2 SeO4 + e + H = − + 1
2 SeO3 + 1
2 H2O 14.9 9.9 7.9
2−
1
4 SeO3 + e + − 3
2 H = + 1
4 Se + 3
4 H2O 14.8 6.3 3.3
2−
1
6 SeO3 + e + − 4
3 H = + 1
6 H2Se + 1
2 H2O 7.62 1.0 −1.7
1
2 VO2 + e +
+ − 1
2 H 3O = + 1
2 V(OH)3 6.9 2.4 1.4
Cu2+ + e− = Cu+ 2.6 2.6 2.6
PuO2 + e− + 3H+ = PuOH2+ + H2O 2.9 −8.1 −14.1
Paraquat + e− = paraquat•− — — –7.6
Analytical couples
CeO2 + e− + 4H+ = Ce3+ + 2H2O 47.6 31.6 23.6
1
2 ClO + e + H =
− − + 1
2 Cl + − 1
2 H2O 29.0 24.0 22.0
HClO + e − + H + = 1
2 Cl 2 + H 2 O 27.6 20.6 18.6
1
2 Cl 2 + e = Cl
− −
23.0 25.0 25.0
6 IO3 + e + H = 6I + 2 H2O 18.6 13.6 11.6
1 − − + 1 − 1

1
2 Pt(OH)2 + e + H = − + 1
2 Pt + H2O 16.6 11.6 9.6
1
2 2 I +e =I − −
9.1 11.1 11.1
1
2 Hg 2 Cl 2 + e − = Hg + Cl − 4.5 3.9 3.9
AgCl + e = Ag + Cl − −
3.8 3.2 3.2e
e +H =
− + 1
2 H2 0 −5 −7
1
2 PtS + e − + H + = 1
2 Pt + 1
2 H2 S −5.0 −10.0 −12.0
a Calculated for reaction as written according to Equation 14.14. Free energy of formation data were

taken from Lindsay (1979) as a primary source, and when not available from that source, from Garrels and
Christ (1965) and Loach (1976).
b Calculated using tabulated log K values, (red) and (ox) = 10−4 mol/L soluble ions and molecules, activi-

ties of solid phases = 1, and partial pressures for gases that are pertinent to soils: 10−4 atm for trace gases,
0.21 atm for O2, 0.78 for N2, and 0.00032 for CO2. Note: pe × 59.2 = Eh (mV) at the specified pH.
c Values not listed by Loach (1976) or Larson (1997).

d Values from Larson (1997).

e Value for 4 M Cl− in Ag/AgCl reference electrode.

Oxidation–Reduction Phenomena 14-9

14.1.3  K inetic Derivation of Thermodynamic but linear free energy relationships (LFERs) are useful plots
Parameters for Redox of observed rate constants versus equilibrium constants or Eh
values (Stumm and Morgan, 1996; Bürge and Hug, 1997). Such
This thermodynamic derivation of log K and its relationship to information could affirm the reliability of using thermodynamic
pe and pH of soils is based on free energy of formation data for data to predict bioavailability of nutrients and pollutants, and
oxidants and reductants, and it is not related to reaction mecha- to estimate true reactivity of electron donors and acceptors in
nisms or rates. An alternate procedure to obtain log K values, nonequilibrium, kinetically governed soil chemical and micro-
in theory, is the kinetic approach suggested by Sparks (1985) bial environments.
for cation exchange and by Harter and Smith (1981) for adsorp- Given the constraining limitation of irreversibility of most
tion processes. This approach has been little used in redox soil redox reactions in soils, especially microbial ones, for using
chemistry, probably due to difficulties in obtaining rate coeffi- experimental data to calculate values for thermodynamic
cients for many electron-transfer processes in soils and due to parameters, the use of kinetic knowledge on soil redox processes
the irreversibility of most redox reactions. The application of is less widely used than are pe (and Eh) and pH for assessing
such approaches should, however, be appropriate for certain equilibrium conditions of soils. Empirical studies in relatively
reversible redox reactions in soils, especially in situations where pure, aqueous systems, and complex soil suspensions have, how-
metastability and lack of chemical equilibrium prevail or when ever, provided pertinent information on the kinetics of redox
accurate free energy of formation data is unavailable for oxi- processes and their relation to thermodynamic parameters and
dants and reductants. reaction pathways (Stumm, 1992, 1993; Stumm and Morgan,
In principle, this is the method for calculating kinetic param- 1996; Hug et al., 1997; Typrin, 1998).
eters: the equilibrium constant (K) for redox equilibria can be
estimated from the ratio of forward and reverse rate coefficients
for a given reversible reaction in soils:
14.1.4  Microbiological and Enzymatic Controls
k for Redox State and Processes in Soils
K= f (14.25)
kr
Bacterial metabolism, the process of producing adenosine tri-
where k f and k r are the rate constants for forward and reverse phosphate (ATP) through a series of catabolic reactions and
reactions, respectively. The standard Gibbs free energy for the building cell constituents with anabolic reactions, requires
reaction then can be calculated by substituting ln K into Equation energy, electrons, nutrients, and either oxygen or another highly
14.14. Preparation of Arrhenius plots of the rate coefficients as a oxidized compound to serve as a terminal electron acceptor
function of 1/T permits estimation of activation energies for the (TEA; Sylvia et al., 2005). Bacteria that use O2 as the electron
forward and reverse reactions, and standard enthalpies for the acceptor are aerobic, those that utilize another oxidized com-
reactions can be calculated as pound in the absence of oxygen are anaerobic, and those capable
of both are facultative anaerobes. The use of external TEAs intri-
ΔHo = E*f − E*r (14.26)
cately links bacteria to important geochemical processes, such
where as denitrification, methane production, and metal reduction
ΔHo is enthalpy for the redox reaction (Salminen et al., 2006; Banerjee, 2008).
E*f and E*r are the activation energies for the forward and The metabolic classification of bacteria is based on the energy
reverse reactions source, electron source (reducing equivalents), and carbon
source used in catabolic and anabolic processes. Bacteria can
With knowledge of ΔGo and ΔHo, standard entropy of the reac- derive energy from natural sunlight or from chemical reac-
tion can be calculated as tions. Phototrophy is the process of using natural light for
energy, as employed by photosynthesizing algae or cyanobac-
ΔHo − ΔG o teria, whereas chemotrophy requires a chemical reaction for
ΔSo = . (14.27) metabolic growth (Madigan and Martinko, 2006). All nonpho-
T
tosynthetic cellular organisms utilize this pathway to derive
Since the e− and H+ are key reactants and products in the thermo- the energy needed for metabolic reactions. Electrons (reducing
dynamic sense, a refined knowledge of mechanisms for particu- equivalents) can be derived from either organic or inorganic
lar redox reactions is needed because of our current limitations compounds. Organotrophy is the process of using organic com-
in understanding how similar or different e− and H+ reactions are pounds, and lithotrophy is that of using inorganic compounds.
in soils and natural waters. Knowledge of thermodynamic stabil- Organotrophic bacteria are generally associated with chemot-
ity for a redox system does not necessarily predict kinetic labil- rophy; however, lithotrophic bacteria can be either phototrophs
ity, a concept directly pertinent to reactivity of different types of or chemotrophs. Cellular C needed for metabolic processes
complexes (Cotton and Wilkinson, 1980). The kinetic lability of can be derived from organic compounds, which is referred to
redox processes in soils has not been compared systematically as heterotrophy, or from CO2 (dissolved CO2, H2CO3, HCO3−,
with predictions of stability based on thermodynamic data, or CO32− in natural waters and soil solution; the predominant
14-10 Properties and Processes

species depending on pH), which is autotrophy. Autotrophy is species can react with cell constituents, thereby allowing aerobic
generally linked with lithotrophy, and heterotrophy is associated respiration to proceed. Hydroxyl radicals are rarely formed in
with organotrophy (Sylvia et al., 2005). microbial cells due to the efficiency of H2O2 dismutation to H2O
The oxidation of an organic or inorganic compound and reduc- and O2, following reduction of HO2•. Deficiencies of some or all
tion of O2 or other oxidized species during bacterial metabolism of these enzymes render soil microbes incapable of respiration
is the coupling of oxidation–reduction half-reactions (redox pro- under fully aerobic conditions but better adapted to microaero-
cesses) and is the basis for bioenergetics. Biologically mediated philic or anaerobic conditions (Madigan and Martinko, 2006).
redox reactions in soils are linked to metabolic processes and In aerobic respiration, the coupling of C oxidation to O2 reduc-
will follow a thermodynamic sequence based on the energetic tion occurs within the bacterial cell either by substrate-level
possibility of the reaction (Stumm and Morgan, 1996). Aerobic phosphorylation or oxidative phosphorylation, which is carried
chemoorganoheterotrophs use organic C compounds as a source out by an intermediate compound such as the coenzyme nico-
of energy, electrons, and C; and they use O2 as the TEA. The half- tinamide adenine dinucleotide (NAD+) or nicotinamide ade-
reactions for the reduction of O2 and oxidation of an organic nine dinucleotide phosphate (NADP+) Madigan and Martinko,
compound (generically represented by CH2O with the oxidation 2006). Although intermediaries are utilized in oxidative phos-
state of C = 0) from Table 14.1 can be coupled to show that the phorylation, the overall net change in energy is the difference
overall ΔGro = −130 kJmol −1. An anaerobic chemoorganohetero- in reduction potential between the primary electron donor
troph present in an O2-depleted environment, such as a wetland and TEA. The electron-carrying coenzyme NADH or NADPH
soil, can utilize the same C source but would require another transfers electrons to a series of four complexes of the mito-
TEA. Using Fe(OH)3 instead of O2 from Table 14.1 would result chondrial respiratory chain, which conserves energy by proton
in an overall ΔGro = −102 kJmol −1. This example illustrates how pumping, which further drives the synthesis of ATP (Banerjee,
the use of O2, when available, is thermodynamically more favor- 2008). It is at complex IV, the final complex of electron transfer
able for metabolic growth than other oxidized species. in oxidative phosphorylation, that oxygen is reduced to water
The reduction of O2 to H2O in aerobic respiration involves by cytochrome c oxidase in a four-electron, one-step reaction
four, one-electron reduction steps, shown with pe values at pH 7: (Equations 14.28 through 14.31). In substrate-level phosphoryla-
tion, ATP is directly produced in the enzymatic oxidation of an
O2 + e − + H + = HO2 i organic substance but with much lower yields than obtained via
Formation of superoxide radical (pe = −7.8), (14.28) oxidative phosphorylation (Madigan and Martinko, 2006).
Calculating the Gibbs free energy of a reaction may indicate
that the use of an electron donor and acceptor in a reaction is
HO2 i + e − + H + = H2O2 thermodynamically favorable, but it does not indicate at what
Formation of hydrogen peroxide (pe = 17.9), (14.29) rate the reaction would occur. The use of a substrate, although
energetically favorable, may not occur at a biologically relevant
i rate without the catalytic action of an enzyme. Enzymes are pro-
H2O2 + e − + H + = HO + H2O teins configured in secondary, tertiary, or quaternary structures
Formation of hydroxyl radical (pe = 7.8), (14.30) that allow for specific binding properties and often contain non-
protein prosthetic groups, cofactors, and coenzymes that par-
ticipate in the catalytic functions of the enzyme (Madigan and
HO i + e − + H + = H2O Martinko, 2006). In order to obtain substrates located outside of
Formation of water (pe = 36.8), (14.31) the cell, enzymes (e.g., hydrolases) can be excreted to break down
insoluble polymers such as cellulose, starch, and proteins. These
degraded macromolecules are then transported into the cell for
1 1
O2 + e − + H + = H 2O use in metabolic reactions (Sylvia et al., 2005). Soil microorgan-
4 2 isms using extracellular enzymes are important in the initial
Overall reaction (pe = 13.6). (14.32) depolymerization of cellulose. White rot and brown rot fungi
are key microorganisms in the breakdown of cellulose, hemicel-
An examination of the pe values for the stepwise reduction of lulose, and lignin in woody plant tissue in contact with soil.
O2 to H2O demonstrates that even though the overall reaction Either through intracellular or extracellular mechanisms,
has a pe = 13.6 (confirming that it is a good oxidizing agent), once substrates are in the cell; oxidative phosphorylation
superoxide, hydrogen peroxide, and hydroxyl radical inter- requires a TEA, and in oxygen-depleted environments, bacte-
mediates are more powerful oxidants than O2. Superoxide ria must use alternative oxidized species. Nitrate (NO3−), Fe(III)
dismutase or reductase, catalase or peroxidase, and glucose-6- (hydr)oxides, Mn(III,IV) (hydr)oxides, SO42−, and CO2 are oxi-
dehydrogenase are essential enzymes used by aerobic cells. They dized species found in soil, which can be reduced in the termi-
dismutate superoxide and hydrogen peroxide and subsequently nal step of oxidative phosphorylation, and the reduced forms
reduce hydroxyl radicals more rapidly than the reactive oxygen are excreted from the cell (Sylvia et al., 2005). The reduction of
Oxidation–Reduction Phenomena 14-11

nitrate coupled to the oxidation of pyrite in anoxic groundwater The electron-donating kinetics of dissolved organic matter in
sediments was recently demonstrated to be a biologically driven aquatic systems was shown to occur within the course of 1 day
redox process (Jorgensen et al., 2009). and capable of shuttling electrons to SO42− and Fe(III) (Bauer
In addition to soluble constituents, such as NO3− or SO42−, et al., 2007).
as TEAs, the use of less soluble minerals, such as Fe(III) (hydr) Quinone moieties in natural organic matter can serve
oxides or Mn(III,IV) (hydr)oxides, can also be accomplished. as TEAs in microbial respiration, cycling electrons from
The mechanism by which microbial cells interact with the bacteria to mineral surfaces (Lovley et al., 1996; Bond and
molecular lattice of minerals is yet to be fully understood. It is Lovley, 2002). Soil bacteria reduced the humic acid analog,
speculated that structural or chemical defects, or points in the ­a nthraquinone-2,6-disulfonate (AQDS), which then shuttled
solid where energy has been perturbed, can serve as regions of electrons to reduce Fe(III) (Fredrickson et al., 1998; Kappler
reactivity or possibly access sites for organisms (Fredrickson and et al., 2004). The shuttling activity of AQDS was demonstrated
Zachara, 2008). further with G. sulfurreducens shuttling electrons to ferrihy-
Nonenzymatic, extracellular strategies for moving electrons drite in solution (Straub and Schink, 2003). This use of humic
from inside the cell to the outside in electron-transfer processes substances as a TEA may allow for more efficient respiration
have been observed. One such strategy is the use of a protein on than directly using a mineral. The rate of electron transfer
the cell wall surface that extends away from the cell or a mole- between reduced humic substances to ferrihydrite is approxi-
cule that passes between the cell and substrate when a bacterium mately 27 times faster than the rate of G. sulfurreducens directly
lacks the c-type cytochrome necessary to reduce a metal inter- transferring electrons to ferrihydrite (Jiang and Kappler, 2008).
nally (Rawlings, 2005; Gralnick and Newman, 2007; Dittrich The biological reduction of electron shuttles, such as soluble
and Luttge, 2008). When at a distance from a mineral, Geobacter humic acids, is important in soils, but abiotic reduction ­pathways
sulfurreducens develops pili, or nanowires, which are localized also significantly contribute to the natural redox cycling of met-
to one side of the cell wall, and extend out to allow electron als and nutrients. Lactic acid, tartaric acid, and citric acid were
transfers to the mineral surface of Fe(III) (hydr)oxides (Reguera shown to reduce AQDS, which then shuttled electrons to enhance
et al., 2005). the reduction of Cr(VI) in solution (Brose  and James,  2010).
In addition to localizing proteins to the exterior of the outer ­Low-molecular-weight organic acids, such as these, are pro-
membrane, another strategy bacteria use in extracellular respi- duced naturally by microbial activity or plant root exudates
ration is to utilize small organic shuttles to transfer electrons to and can be important reducing agents for quinone moieties in
substrates at a distance from the cell. Quinones are ubiquitous soils and soluble humic acids, thus further contributing to natu-
structures found in nature and are principal constituents of soil ral redox process in soils. Figure 14.2 illustrates the conceptual
organic matter (SOM). In the human body, coenzyme Q or ubi- model of how citric acid reduces the electron shuttle AQDS to
quinone is present in every cell, and the ubiquinone/ubiquinol AH2DS, which ultimately reduces Cr(VI) to Cr(III).
redox couple plays a role in shuttling electrons between com- Electrons are in constant flux in soils, being transferred from
plex II and III of the mitochondrial electron transport chain electron donors to electron acceptors, often mediated by soil
during oxidative phosphorylation (Table 14.1; Banerjee, 2008). microorganisms, which results in metastable redox conditions in
Ubiquinone also acts as a lipid-soluble antioxidant by accepting soils. Though thermodynamic equilibrium models may predict
one electron and forming a stable radical anion semiquinone. steady-state conditions, in reality, a dynamic nonequilibrium
This same quinone structure is present in soils and natural state is a more accurate representation of natural systems (Stumm
waters as the primary abiotic electron-donating and accept- and Morgan, 1996). Often, redox reactions in soils are moving
ing moiety of humic and fulvic acids in natural organic matter
(Scott et al., 1998; Ratasuk and Nanny, 2007). 1.5 Citric acid 1.5 3-Ketoglutarate
Phenolic groups are abundant in natural organic matter and
are important in complexation reactions with metals. Phenolic
groups can be biologically oxidized by the enzymes phenolase 3e–
and laccase to produce quinones (Tan, 2003). Converse to this
oxidation, a one-electron transfer to quinone forms the same, 1.5 AQDS 1.5 AH2DS
highly reactive intermediate semiquinone as with ubiquinone
and then the second electron transfer forms hydroquinone 3e–
(Larson, 1997). Hydroquinone is then capable of donating its two
electrons in further reduction reactions, making the ­quinone–
hydroquinone species a very dynamic redox constituent in
Cr(III)(hydr)oxide Cr(VI)
soils. The natural reducing capacities of International Humic
Substance Society (IHSS) humic acids were shown to increase FIGURE 14.2  The stoichiometric transfer of electrons from citric acid
several-fold following microbial reduction and were significant to AQDS, reducing it to the hydroquinone form AH2DS, which ultimately
even under aerobic conditions (Peretyazhko and Sposito, 2006). reduces Cr(VI) to Cr(III).
14-12 Properties and Processes

toward equilibrium, but the reactions are constantly being per- 14.2  Methods and Procedures
turbed by the influx and efflux of chemical species and soil biota,
thus shifting activities and reestablishing new, partial equilibria. 14.2.1  Uses of pe–pH Thermodynamic
Dioxygen is the most ubiquitous electron acceptor in natural sys- Information
tems, when available, and the electron activity and type of micro-
Values of log K derived from Gibbs free energy of formation
organisms present in a soil depend, in part, on its presence.
data or kinetic evaluations of redox reactions provide tools for
Because a saturated soil restricts the diffusion of O2, satu-
predicting if a reduction half-reaction coupled with an oxida-
rated soils allow for more electron flow to other electron accep-
tion half-reaction will allow the spontaneous transfer of elec-
tors, such as Fe(III) (hydr)oxides and SO42− (Bartlett and James,
trons from reductant to oxidant. Since soils are only metastable
1993). When a soil becomes submerged, pe decreases, and the
and highly heterogeneous in nature, such predictive capability
rate of decrease will be a function of easily oxidized SOM,
is necessary to formulate hypotheses for many processes that
temperature, time submerged, and nature of available electron
may occur in the field, even if they require microbial catalysis
acceptors (Sparks, 2003), which are also important metabolic
or other coupled reactions to occur at ambient temperatures and
requirements of soil microorganisms. Though soils host a vari-
pressures of soil–water–plant systems.
ety of microorganisms using a diverse array of electron acceptors
The reduction half-reactions listed in Table 14.1 are biological
for respiration, such as Fe(III) (hydr)oxides in anoxic sediments,
and abiotic species of N, O, Mn, Fe, S, C, various pollutants sensi-
SOM is the dominant electron donor and can be fully oxidized
tive to redox conditions in soils and several reactions pertinent
to CO2 (Lovley, 2000), or partially to organic acids. Aerobic
to the analysis or characterization of redox conditions. Within
microorganisms will thrive until O2 is depleted, and then facul-
groups, the half-reactions are arranged in descending order of
tative and obligate anaerobic microorganisms will be the domi-
log K values, calculated as described above. These values are pe at
nant biological mediators.
pH = 0 when activities of oxidant and reductant are 1 and may be
Bacteria and their electron-shuttling systems are widely used
considered standard, reference pe values for the reactions (formal
in remediation strategies for organic and inorganic pollutants.
potentials). The pe values listed at pH 5 and 7 are calculated to
Humus and other quinone analogs were used in the reductive
represent typical activities of ions and partial pressures of gases in
biotransformation of nitroaromatic compounds and to dechlo-
soil environments.
rinate organic pollutants (Field et al., 2000; Becker, 2006). In the
Higher log K or pe values indicate greater “ease of reduction”
anaerobic oxidation of phenol and p-cresol, it was shown that
of an oxidant (left side of equation) to its reduced form than do
the addition of the quinone analog AQDS diverted electrons
lower values. This means that for predictive purposes, an oxi-
from methanogenesis to quinone reduction, a more thermody-
dant in a particular reduction half-reaction is able to oxidize the
namically favorable reaction (Cervantes et al., 2000).
reductant in another half-reaction with a lower pe, at a speci-
The bioremediation of metals, such as Cr(VI) and U(VI) has
fied pH, as demonstrated quantitatively for the FeOOH–Fe2+ and
also proven to be an effective strategy for treating contaminated
SO42−–H2S couples. Another example shows Mn(III,IV) (hydr)
soils and groundwater (Gu and Chen, 2003; Nyman et al., 2007;
oxides would be expected to oxidize Cr(OH)3 to Cr(VI) at pH 5
Wu et al., 2007). The cell wall of Arthrobacter oxydans con-
since the range of pe values for reduction of Mn (12.8–16.7) is
tains an acid-soluble protein with a positive charge, as shown
greater than that for Cr(VI) reduction (10.9). This has been dem-
by electrophoresis, capable of reducing Cr(VI) to an insoluble
onstrated to occur in most field-moist soils in the pH range of
Cr(III) (hydr)oxide (Asatiani et al., 2004). Bacteria can trans-
4–7 containing oxides of Mn(III,IV) (Bartlett and James, 1979;
form Hg compounds to either less toxic or less bioavailable spe-
James and Bartlett, 1983). Conversely, these oxides would not be
cies. Desulfovibrio desulfuricans API strain degrades CH3Hg+ by
expected to oxidize N2 to N2O (pe at pH 5 = 22.9).
producing H2S that reacts with CH3Hg+ forming the insoluble
Even though the log K or pe for one reduction half-reaction
species (CH3Hg)2S (Hobman et al., 2000). The dissimilative
is less than that for a second half-reaction, the reduced form in
reduction of Se(VI), a soluble, toxic form of Se, to the insoluble
the first reaction may still be oxidized by the oxidized species in
Se(0) by anaerobic bacteria in anoxic environments has impor-
the second half-reaction (the reverse of the above concept). For
tant implications for the continued irrigation of seleniferous
example, the pe at pH 5 for reduction of CO2 to C6H12O6 is −5.9
soils and industrial applications such as the production of pesti-
and that for reduction of O2 to H2O is 15.6. Based on this differ-
cides and semiconductors (Oremland and Stolz, 2000).
ence, one would predict that reduction of O2 to H2O would be
As bacterial metabolic activities are continually studied, more
coupled to oxidation of C6H12O6 to CO2, and coupling oxidation
ways will be discovered to apply the use of microorganisms to
of H2O to O2 with reduction of CO2 to C6H12O6 would not be
transform pollutants to less toxic or less bioavailable forms. The
thermodynamically probable. In fact, both respiration (the pre-
adaptation of bacteria to a wide variety of electron donors and
dicted reaction) and photosynthesis (the second, “improbable”
acceptors provides almost unlimited application of biologically
reaction) occur together, and the balance of the two is respon-
mediated redox reactions. Understanding how bacteria link the
sible for the existence of the aerobic lifestyle and the persistence
oxidation of electron donors to the reduction of electron accep-
of SOM. Photosynthesis (represented simply as CO2 → C6H12O6)
tors will provide insight into further utilizing these mediated
is made possible by a complex series of coupled reactions that
reactions to improve ecosystems and natural waters.
Oxidation–Reduction Phenomena 14-13

make an overall thermodynamically improbable reaction occur- TABLE 14.2  Sensitivity of Calculated pe at pH 0 to Variation in �G of
ring rapidly in sunlight. and Activities of Oxidant and Reductant in Selected Half-Reactions
Similarly, a reaction predicted to be thermodynamically prob- Pertinent to Soils
able may not occur at any appreciable rate under natural condi- −log
tions. The pe for NO3− reduction to N2 at pH 5 (14.3) is greater than Activity �G of
that for HCrO4− reduction to Cr(OH)3 (10.9), but this NO3− oxida- Couple Ox Red Ox Red pe Δpea
tion of Cr(III) has not been demonstrated in soils or plants, prob-
O2/H2O 0.68 0 0.00 −237.01 20.61
ably because the reduction of NO3− requires enzymatic catalysis to
2.68 0 0.00 −237.01 20.11 −0.50
lower the energy of activation at such a high pH.
0.68 0 0.00 −278.81 24.20 3.59
The order of log K values for reduction half-reactions also has
NO3/N2 4 0.11 −110.48 0.00 20.30
been used to predict the sequence of reduction reactions carried
6 0.11 −110.48 0.00 19.90 −0.40
out by respiring soil microorganisms following saturation of a
4 0.11 −152.28 0.00 18.80 −1.50
soil (Ponnamperuma, 1972). The descending order of prefer-
Mn3O4/Mn2+ 0 4 −1279.92 −227.39 36.70
ence (pe) for the electron acceptors at pH 7 (proportional to free
0 6 −1279.92 −227.39 39.70 3.00
energy derived from the reduction) is O2–H2O (13.6), NO3−–N2
0 4 −1321.72 −227.39 33.00 −3.70
(11.9), MnO2 –Mn2+ (8.8), Fe(OH)3–Fe2+ (−1.2), SO42−–H2S (−3.5),
MnO2/Mn2+ 0 4 −464.40 −227.39 22.80
and CO2–CH4 (−4.1). Heterotrophic bacteria are using organic
0 6 −464.40 −227.39 23.80 1.00
compounds as the electron donors and their energy source (che-
0 4 −506.20 −227.39 19.10 −3.70
moorganoheterotrophs) in their respiration to produce CO2 MnOOH/Mn2+ 0 4 −556.36 −227.39 29.40
or organic acids (pe range at pH 7 of −8.7 to −3.1), so most of 0 6 −556.36 −227.39 31.40 2.00
the organic compounds can be used throughout the reduction 0 4 −598.16 −227.39 22.10 −7.30
sequence following depletion of atmospheric O2. CO2/C6H12O6 3.5 4 −394.01 −913.66 −0.91
3.5 6 −394.01 −913.66 −0.83 0.08
3.5 4 −394.01 −955.46 −0.60 −0.31
14.2.2  Use of pe–pH Diagrams Fe(OH)3/Fe2+ 0 4 −712.27 −91.12 19.80
0 6 −712.27 −91.12 21.80 2.00
14.2.2.1  Oxygen Species
0 4 −754.07 −91.12 12.40 −7.40
While the pe for reduction of O2 to H2O ranges from 20.8 at pH Fe2O3/Fe 0 4 −740.28 −91.12 17.40
0 to 13.6 at pH 7 (Table 14.1), the intermediates associated with 0 6 −740.28 −91.12 19.40 2.00
one-electron transfers show a wide fluctuation in their oxidizing 0 4 −782.08 −91.12 13.70 −3.70
power (Equations 14.28 through 14.32), a property of O2 that is SO42−/H2S 4 4 −743.83 −33.52 5.20
pertinent to understanding the transition in soils from “aerobic” 6 4 −743.83 −33.52 5.50 0.30
to “anaerobic” conditions. Anaerobic respiratory enzymes are 4 4 −702.03 −33.52 6.10 0.90
typically produced when PO2 reaches approximately 1% of atmo- a Change in calculated pe resulting from a change in activity of the ox or red
spheric levels (0.0021 atm). The data in Table 14.2 also indicate species (column 1 or 2) or resulting from use of a �G of value that is 44 kJ mol−1
that the pe for reduction of O2 is relatively insensitive to the O2 (10 kcal) different from the published value (first row, column 3 or 4).
partial pressure in this range.
Ozone (O3) and the hydroxyl free radical (HO•) are the most
powerful oxidants among the oxygen species (Table 14.1), and the conditions under which the O2–H2O system may rarely attain
latter may be formed during stepwise, four-electron reduction equilibrium. Therefore, only metastable conditions and a slow
of O2 to O2−, H2O2, and H2O (Fridovich, 1978; Equations 14.28 approach to chemical equilibrium characterize O2 behavior,
through 14.32). The high and low pe values for superoxide reduc- making thermodynamic predictions difficult for aerobic soils
tion to H2O2 and for superoxide oxidation to O2 indicate that both (Bartlett, 1981).
a powerful oxidant and a powerful reductant agent are formed in
14.2.2.2  Nitrogen Species
the first of four, one-electron steps in the reduction of O2 to H2O.
The enzyme superoxide dismutase scavenges superoxide in liv- Most reduction reactions of N species (Table 14.1) are not revers-
ing cells using O2 as the TEA (respiring aerobically), but relatively ible, are biologically mediated, and therefore are not well defined
little is known about its reactivity in biological and chemical pro- by thermodynamic pe–pH relationships. The series of half-
cesses in soils that may be pertinent to our understanding of the reactions composing the process of denitrification, though, is
formation of highly reduced components such as SOM and highly instructive in that it identifies the wide range in pe for reduction
oxidized species such as NO3− that coexist in soil under non- or of each of the intermediates believed to form in the sequence of
quasi-equilibrium conditions. electron acceptors used by microbes:
The wide range of reduction potentials for O2 and its partially
reduced intermediates, coupled with biological processes con- NO3 − ⎯(⎯ → NO2 − ⎯(⎯ → NO ⎯(⎯ → N2O ⎯(⎯ → N2
1) 2) 3) 4)
trolling the partial pressure of this gas in soil solution, create Steps
14-14 Properties and Processes

Step (1) of the sequence occurs at pe values less than those aerobic conditions. The kinetic lability of these species is poorly
for reduction of O2 to H2O, while those for steps (2), (3), and understood and new knowledge could contribute significantly
(4) are increasingly higher. The overall reduction of NO3− to N2 to predictions of bioavailability and toxicity of numerous plant
is almost identical to that for the O2–H2O couple. The similar nutrients and pollutants in a range of soil types from rice pad-
pe range for the O2 and NO3− reduction intermediates indicates dies and wetlands to well-drained agricultural and forest soils.
that denitrification and aerobic respiration may occur at the
same time under certain conditions when organic C is used as 14.2.2.4  I ron Species
the electron donor. They may not be mutually exclusive as pre- While predictions of redox behavior of Fe(II) and Fe(III) species
dicted from log K values for the overall reactions, O2 to H2O and indicate that they fall below most Mn(III,IV) (hydr)oxide spe-
NO3− to N2. cies (lower pe values and less free energy released per equiva-
lent upon reduction), intermediate hydrolysis products, such as
14.2.2.3  Manganese Oxide Species Fe(OH)2+, theoretically can oxidize Cr(III) to Cr(VI) at pH
Manganese exists in soils in the II+, III+, and IV+ oxidation values <4 (Table 14.1). In addition, thermodynamically more
states, and the latter two are most stable as oxides or oxyhy- stable complexation of Fe3+ by organic and inorganic ligands
droxides. Trivalent Mn may exist as Mn(H2O)63+, especially if such as OH−, relative to complexation of Fe2+, lowers the pe at
stabilized by ligands, such as pyrophosphate or citrate. The pe which Fe3+ is reduced to Fe2+. These Fe(II)–Fe(III)-ligand reduc-
values (Table 14.1) predict that different oxidation states of Mn tion potentials are similar to those of Fe(III) (hydr)oxides in
in Mn3O4, MnOOH, and MnO2 affect the pe at which Mn2+ the pH range 5–7 (Table 14.1). This phenomenon suggests that
would be expected to form at pH 5 (pe values of 16.7, 14.4, and Fe(II)–Fe(III)-ligand systems create Fe(II) species that are more
12.8, respectively), but they are all similar at pH 7 (8.7, 8.4, and powerful reductants than hexaquo Fe2+ if the Fe(III)-ligand
8.8). The Mn3+–Mn2+ couple indicates that at pH ≈ 5, Mn3+ is a complex is more thermodynamically stable than the Fe(II)-
powerful oxidant (pe 25.5) similar to superoxide (pe 22.6) if in ligand complex. Conversely, if the complex with Fe(II) is more
equilibrium with Mn2+. At pH ≈ 6.5, Mn3+ in equilibrium with stable than that with Fe(III) (e.g., with phenanthroline), the
MnO2 is a powerful reductant similar to H2 and again, superox- Fe(II) becomes a less powerful reductant than hexaquo Fe2+. This
ide. This predicted reducing energetics of Mn3+ may be pertinent may explain the ability of a Fe(II,III) system to act as a cofac-
to anaerobic soils that are exposed to O2, and in which Mn2+ is tor in enzymes involved in redox processes, such as peroxidases
oxidizing to form Mn(III,IV) (hydr)oxides via Mn3+. In oxidized and superoxide dismutases. These enzymes reduce or dismutate
soils containing MnO2, flooding and the process of becoming H2O2 and superoxide. The application of such concepts to abiotic
reduced may produce Mn3+, which is a powerful reducing agent. redox processes in soils remains a key area for future research.
The trivalent Mn species may be ephemeral intermediates in
such processes at redox interfaces, such as in the rhizosphere of 14.2.2.5  Carbon and Sulfur Species
plant roots or between the vadose zone and groundwater. Reduced forms of C and S are normally viewed as reductants in
Since many Mn(III,IV) (hydr)oxides are nonstoichiomet- soils, either in abiotic or biological processes. Thermodynamic
ric and no compound with the exact composition of MnO2 is predictions support this idea for carbohydrates produced in pho-
known (Arndt, 1981), predictions of their redox properties as tosynthesis, CH4 from methanogenesis, and H2S from reduction
a function of mineralogy or oxidation state in heterogeneous of SO42− (Table 14.1). The reduction reactions of o- and p-­quinone,
soils may be hard to formulate. Despite the uncertainty of suggest that these compounds may be reduced at higher pe values
thermodynamic predictions for the redox behavior of Mn, the than are CO2 and SO42−. These pe values, however, coincide with
chemistry of this element is pertinent to a number of processes the MnO2/Mn3+ couple at pH 7, suggesting that Mn3+ may act as
governing speciation and oxidation state of trace elements and a reducing agent for certain organic species in near neutral soils.
pollutants found in soils (Bartlett and Ross, 2005). The pe–pH The coupling of reduction of the organic species with oxidation
data indicate that oxides of Mn may oxidize Pu(III) to Pu(IV), of Mn may result in formation of free radical species. This is per-
V(III) to V(V), As(III) to As(V), Se(IV) to Se(VI), N(III) to tinent to understanding the formation and persistence of SOM
N(V), and Cr(III) to Cr(VI) since the pe for each of these cou- in high pH soils that may contain reactive forms of Mn(III,IV)
ples falls below that for Mn oxides (Table 14.1). The oxidations (hydr)oxides (Bartlett and Ross, 2005).
of Pu(III), As(III), Se(IV), N(III), and Cr(III) all have been Reactions of H2S and H2Se are predicted to be similar with
demonstrated to occur in soils containing Mn(III,IV) (hydr) respect to SO42− and SeO32− formation (Table 14.1). While SeO42−
oxides or by synthetic Mn(III,IV) (hydr)oxides (Bartlett and and SO42− are similar chemically, the oxidation of SeO32− to
James, 1979; Amacher and Baker, 1981; Bartlett, 1981; Moore SeO42− is predicted to occur at higher pe values than that of
et al., 1990; Blaylock and James, 1994). H2S to SO42− (Table 14.1). Blaylock and James (1994) observed
The instability of Mn3+ and its ability to dismutate, similar that Mn(III,IV) (hydr)oxides in soils or in pure form will oxi-
to H2O2 and superoxide, mean that kinetic constraints and dize SeO32− to SeO42−, as predicted by thermodynamics. They
very low steady-state concentrations in soil solution may be also observed that adding reducing phenolic acids, such as gal-
particularly important in understanding the redox behavior lic and ascorbic acids, actually enhanced this oxidation reaction
of Mn in soils undergoing transitions between anaerobic and of SeO32−. They hypothesized that partial reduction of MnO2
Oxidation–Reduction Phenomena 14-15

in soils converted the Mn(IV) (hydr)oxide into a Mn(III) (hydr) low impedance, drift will be observed in the voltage readings
oxide or ion that is a more powerful oxidant for SeO32− than is (Rabenhorst et al., 2009), and redox reactions may take place at
Mn(IV) oxide. Such a hypothesis is supported by the relative the electrode–soil solution interface. Such reactions may form
oxidizing power of MnO2, MnOOH, and Mn3O4, where the lat- interfering redox couples on the Pt metal (e.g., Pt(OH)2–Pt or
ter two oxides contain Mn(III) (Table 14.1). PtS–Pt; see Table 14.1). Commercially available pH meters typi-
cally have high input impedance, but inexpensive voltmeters
that are sometimes used in field studies with multiple Pt elec-
14.2.3  Measurement of Soil Redox
trodes do not.
and Acid–Base Status
Generally, Pt electrode measurements are only semiquantita-
The most common method for quantifying electron activity of tive for assessments of redox status, especially of aerobic soils
soils and natural waters is to measure the potential difference in the field (Whitfield, 1974; Bartlett, 1981; Grenthe et al., 1992;
between a Pt indicator electrode and a calomel or Ag/AgCl ref- Hostettler, 1992; Grundl, 1994). Other methods that employ
erence electrode, both connected to a voltmeter or a pH meter analysis of soil solution analytes indicative of redox status, along
(Pearsall and Mortimer, 1939; Patrick and DeLaune, 1972; with thermodynamic half-reactions, as discussed above, may
Rowell, 1981; Bricker, 1982; Patrick et al., 1996; Rabenhorst prove more reliable for calculating pe ranges for aerobic and
et al., 2009). In this method, the Pt electrode is presumed to anaerobic soil systems (Peiffer et al., 1992; Kludze et al., 1994;
be inert and does not react chemically while coming into equi- Lovley et al., 1994; Stumm and Morgan, 1996; Typrin, 1998).
librium with electroactive species in soil solution and on soil
colloids (Compton and Sanders, 1996). Figure 14.3 illustrates 14.2.3.1  Construction and Use of Pt Electrodes
how a Pt electrode establishes an equilibrium condition with
Platinum and suitable reference electrodes are relatively easy
soil solution. When the electrode contacts the soil solution
and inexpensive to construct (Mueller et al., 1985; Farrell
(and while coupled to a reference electrode), a tiny quantity of
et  al., 1991), but measurement technique may significantly
electrons jumps either from the soil solution to the electrode
alter measured voltages (Bartlett, 1981; Bricker, 1982; Matia
(when soil is more reduced than the electrode) or in the oppo-
et al., 1991). These researchers have described several aspects
site direction when the soil solution is more oxidized. In the
of electrode use and misuse with respect to the reliability of
first case, the Pt electrode becomes more negative relative to
recorded voltages for natural systems. Comparisons have been
the soil, and this lowers the voltage at the electrode–soil solu-
made between H2 and Eh measurements for redox status in a
tion interface. In the second, the electrode surface and the
contaminated aquifer (Chapelle et al., 1996). Quantification of
potential become more positive.
H2 was more reliable than Eh measurements for identifying
A high input impedance (≥20 mΩ) is needed to obtain precise
anoxic redox process, especially when considered with respect
and accurate electrode potentials, because if current flows under
to electron acceptor availability. The limits and limitations of
Eh measurements have been described for natural systems,
Solution Metal
especially with respect to how long the electrodes may be left
e– in place in the soil or water (Mansfeldt, 1993; Norrström, 1994)
and with respect to interpreting the Eh values obtained (Baas-
Fermi level Becking et al., 1960; Whitfield, 1974; Lindberg and Runnells,
Energy
(of electron) 1984; Yu, 1992). Platinum electrode systems also have been
Filled
Fe3+ conduction incorporated into potential-controlling systems for long-term
band laboratory studies (Patrick, 1966; Petrie et al., 1998).

Final 14.2.3.2  I nadequacies of Pt Electrode Potentials

Solution Metal Assessing “electron activity” in soils relates strictly to an evalu-
– + ation of the ability of the electron to be transferred, or do ther-
modynamic work, and not of its concentration or activity in
Original position
of Fermi level soil solution, as can be defined for H+. Because of the nature of
the electron and its differences from H+, a number of caveats
must be described and recognized when evaluating Pt electrode
Fe3+ Fe2+ Filled
Original position of
conduction
potentials.
solution energy levels
band
14.2.3.2.1  Dissolved Oxygen Status
FIGURE 14.3  The energy of electrons in ions in solution and in the While a stable potential can be obtained for a Pt-reference elec-
Pt electrode. (Taken from Compton, R.G., and G.H.W. Sanders. 1996. trode pair immersed in an oxygenated soil suspension, this
Electrode potentials. Oxford Science Publications, Oxford, U.K. p. 4, potential is unreliable as a measure of dissolved oxygen status
Fig. 1.2.) (Bricker, 1982; Stumm and Morgan, 1996). The Pt surface may
14-16 Properties and Processes

react with O2 to form Pt(OH)2 that develops a potential with 14.2.3.2.4  Coupling of pH and pe
elemental Pt with a pe of 9.6 at pH 7 (Table 14.1). In addition, Based on the complementary nature of pH and pe (Stumm and
the measurement may not be that of the O2–H2O couple but may Morgan, 1996) summing pe + pH to describe log K for soils is pos-
be responding to O2 reduction intermediates, such as H2O2 and sible theoretically, as described above. Due to the fact that the Pt
superoxide (Bricker, 1982). In addition, predicted pe values are electrode responds to pH (almost in Nernstian fashion) as well as
relatively insensitive to changes in dissolved O2 between 0.21 to electron activity, pH should always be measured and reported
and 0.0021 atm (Table 14.2), the range of O2 partial pressures in with pe. The negative slopes of the pe–pH relationships (Figure
which aerobic respiration occurs (Russell, 1973). For these rea- 14.1) of many of the reduction half-reactions also indicate that
sons, Pt electrode potentials cannot be used reliably as a measure the energy change associated with a particular reduction reac-
of redox status for aerobic soils, but empirical values for pe may tion decreases with increasing pH. Therefore, an Eh measure-
be obtained for comparison purposes (Bartlett, 1981, 1998). ment cannot be used to predict the presence of a particular redox
While more faith is placed in measurements of soil pH, it couple unless pH is known. Since higher pe values at lower pHs
also should be considered an empirical measurement because correspond to larger releases of free energy, reduction reactions
of uncertainty about the form of the H+ ion in colloidal envi- are expected to be more likely to occur at lower pH. That is, such
ronments and about the behavior of the glass electrode in such systems are ones in which “reduction is favored.” In contrast, loss
systems. For these reasons, both pe and pH measured with elec- of electrons from reductants of a particular couple is favored at
trodes in soils may be very uncertain for accurate descriptions of higher pH, or the system is more “prone to oxidation.”
the redox status of soil environments containing air-filled pores.

14.2.3.2.2  Irreversibility of Redox Couples

14.2.4  Proposed Alternative Strategies
Many of the important redox processes involving C, H, N, O, for More Accurate Measurement
and S (the “light” elements, relative to the “heavy” metals) are of Soil Redox Status
irreversible in the thermodynamic sense, and nonelectroactive
gases and molecules may be consumed or formed. As a result, 14.2.4.1  Using Electrochemical Relations in Reverse
potentials generated by redox couples for these elements are dif- Given the uncertainty associated with measured Pt electrode
ficult to obtain and interpret using a Pt electrode. In addition, potentials in soils to quantify Eh or pe, actual measurements of
many of these reactions do not reach true chemical equilib- reductant and oxidant activities, along with a reliable pH mea-
rium, and activities measured in soil solution may be kineti- surement, may be a better approach (Stumm and Morgan, 1996;
cally constrained (Liu and Narasimhan, 1989). Since soil redox Typrin, 1998). The activities are substituted into appropriate
status is often set by “microbial potentials,” as discussed earlier, half-reactions relating pe and pH, and pe is thereby obtained by
consuming or producing compounds or ions containing one or calculation.
more of these elements may render Pt electrode measurements As shown in Table 14.2, the pe predicted by such a tech-
inaccurate. nique will be inaccurate to different degrees for different half-­
reactions. For example, an error of two log units for H2S or O2
14.2.3.2.3  Mixed Potentials partial pressures will only produce errors of 0.3–0.5 pe units.
Measured redox potentials in soils normally are governed by In contrast, similar errors in measurement of Mn2+ or Fe2+ will
more than one redox couple (“mixed potentials”), and these result in pe errors of 1.0–3.0 pe units. Since Mn and Fe are rela-
couples usually are not at true chemical equilibrium. Therefore, tively easy to measure accurately by atomic absorption or colo-
thermodynamic interpretations of measured Pt electrode poten- rimetric methods and mineralogy of associated oxides can be
tials in soil suspensions need to consider several couples, and made with infrared or x-ray techniques, assessing pe for Mn and
analyses of soil solution concentrations of redox active species Fe oxide-dominated systems could be reliable. Detailed research
may be indicative of the couples controlling the potential at is needed to prove this hypothesis. In contrast, dissolved gases
the Pt surface (Typrin, 1998). For example, a Fe2+–Fe3+ couple are harder to measure accurately, and qualitative estimates may
at activities greater than 10−5 M generates sufficient anodic and be sufficient to obtain accurate evaluations of pe.
cathodic currents to obtain a measurable voltage for the system, If calculated pe values obtained with this “reverse electro-
and this may coexist with the relatively nonelectroactive couple, chemical technique” are equal for two different reduction half-
O2–H2O in heterogeneous soils. reactions, then chemical equilibrium may be assumed to exist. If
The establishment of a measurable balance between the the pe values are unequal, then disequilibrium and a metastable,
cathodic and anodic current at the Pt electrode at the point of kinetically limited soil system probably exists. This latter condi-
zero applied voltage requires activities of >10−5 M, a condition tion is common in soils due to spatial heterogeneity of soil solu-
that may not exist for many redox active species of interest in tion, oxide mineralogy, organic matter reactivity, and microbial
soils. Activities <10−6 M may be common, especially for certain controls on key reactions. New thinking and hands-on research
plant nutrients and soil pollutants. For this reason, application are needed to provide new ideas for evaluation of the “electron
of measured Pt electrode potentials to predicting soil composi- activity” for soils by this combination of analytical and ther-
tion may not be possible. modynamic approaches. A key to its accuracy is knowing what
Oxidation–Reduction Phenomena 14-17

redox couples are contributing to the electron activity, assumed 14.3  Applications of Redox Methods
to exist as a quantifiable parameter at chemical equilibrium.
and Concepts to Ecological,
14.2.4.2  Redox Ranges for Empirical pe Values Engineered, and Agricultural
These limitations to assessing soil pe based on Pt electrode and
Soil Systems
reverse electrochemical methods indicate that our sense of accu- The principles and theories of oxidation–reduction processes in
racy for soil redox status must be modified. If we surrender in soils, and methods for defining them operationally, have many
our efforts to conceptualize and operationally define soil redox applications that relate to root–soil interactions in the rhizo-
status, we will have lost a challenging scientific crusade. This sphere, to pollutant oxidation state in and remediation of con-
means that while new ideas are being developed, we accept a lack taminated soils, to nutrient management and soil fertility in
of knowledge of pe values more accurate than ranges bracketed agricultural and wild ecosystems, to the role of soils in global C
by whole numbers. balances affecting the earth’s climate, to the study of wetlands and
Liu and Narasimhan (1989) have described “redox zones” in hydric soils, and to understanding groundwater chemical com-
which a range in Eh or pe defines an electron activity condi- position at the interface with surface waters. A brief discussion of
tion. The oxygen–nitrogen range is defined by Eh values of +250 each of these applications follows, coupled to specific examples.
to +100 mV, the iron range is +100 to 0.0 mV, the sulfate range
is 0.0 to −200 mV, and that for methane–hydrogen is defined
at < −200 mV. Sposito (1989) proposed “oxic” soils as those with 14.3.1  R hizosphere Processes
pe > 7, “suboxic” ones in the range of pe between +2 and +7. and
Root exudates (rhizodeposition), especially those containing
“anoxic” soils with pe < +2; all at pH 7. These ranges correspond
C compounds, are key constituents that influence microbial
roughly to redox control by oxygen–nitrogen, manganese–iron,
metabolism and chemical processes in the rhizosphere (Jones
and sulfur couples.
et al., 2009). These exudates may be the result of cell sloughing,
Berner (1981) proposed categories for redox named “oxic, pos-
establishment and maintenance of microsymbionts, gaseous
toxic, sulfidic, and methanic” controlled by transformations of
loss (e.g., O2 and CO2), and mucilage production. Carbon com-
oxygen/nitrogen, iron, sulfur, and methane–hydrogen, respec-
pounds typically act as electron donors (and in the case of qui-
tively. James (1989) has proposed these names be assigned to
none functional groups as electron acceptors) for heterotrophic
ranges in EMpe (empirical pe; Bartlett, 1981, 1998) of +7 to +13,
microbes, and HCO3− acts as the C source for autotrophs.
+2 to +7, −2 to +2, and −6 to −2 (at pH 7). The appropriateness of
The diffusion of O2 from the atmosphere through aerenchyma
these categories and names will require further evaluation of new
tissue formed in stems and roots in response to the develop-
operational definitions for the concept of “redox status” in soils.
ment of anaerobic soil conditions favors the formation of oxi-
Bartlett and James (1995) proposed a new system for categoriz-
dized rhizospheres in plants adapted to grow in anaerobic soils.
ing soil redox status using chemical field tests such as tetrameth-
Examples are rice paddies, freshwater and tidal wetlands, and
ylbenzidine for Mn status, Cr oxidation–reduction reactions, Fe
other poorly drained soils (Marschner, 1995). In plants poorly
speciation, sulfide levels, and pH. They proposed the following
adapted to growth in anaerobic soils, redox changes related to
categories: superoxic, manoxic, suboxic, redoxic, anoxic, and
denitrification, reductive dissolution of Mn(III,IV) (hydr)oxides
sulfidic, which relate to electron lability in heterogeneous soil
and Fe(III) (hydr)oxides, sulfate reduction, and methanogen-
systems under field conditions. Bartlett (1998) has refined this
esis can significantly affect plant growth, the maintenance of a
system of redox classification and applied it to interfacial pro-
symbiotic relationship with N2-fixing bacteria and mycorrhizal
cesses in soils pertinent to wetlands, hydric soils, and other soil–
fungi (Marschner, 1995).
water systems containing contrasting zones of redox status.
The formation of the products of organic matter decomposi-
tion and fermentation of glucose to lactate or ethanol can affect
14.2.4.3  Use of “Indicator of Reduction rhizosphere chemistry and microbial activity. Formation of
in Soils” (IRIS) Tubes ethylene, volatile fatty acids, and phenolic compounds activity
A novel method for assessing whether or not a soil may become affects vascular tissue conductivity and root growth (Marschner,
reducing for Fe(III) (hydr)oxides to Fe(II) is to coat 21 mm, poly- 1995). Ethylene production in root tissues in response to water
vinyl chloride (PVC) tubes with paints made from Fe(III) (hydr) logging is responsible for the formation of aerenchyma tissue in
oxide suspensions of known mineralogy. The coated tubes are plants tolerant of anaerobic soil conditions.
placed in soil columns in the laboratory or in the field, and after The rhizosphere is a soil environment that is hard to study in
a period of incubation, the extent of removal of Fe(III) from the situ but one that is critically important in plant nutrition, soil
tubes by reduction to Fe(II) is quantified by image processing fertility, plant pathology, soil biochemistry, microbial ecology,
(Rabenhorst et al., 2008 and references therein). Such in situ, and pedology. The August, 2009 issue of Plant and Soil com-
empirical methods may prove useful in delineating wetlands, prises 21 articles dedicated to reviewing current knowledge of
hydric soils, and the extent of reducing conditions for Fe(III) rhizosphere processes, many of which are redox based (Dessaux
under various soils conditions. et al., 2009).
14-18 Properties and Processes

14.3.2  Soil Remediation and Pollutant state under ambient biological temperatures and pressures
Speciation remains V+, but reduction of Fe(III) (hydr)oxides and the oxi-
dation of Fe(II) control, in complex ways, the presence of an
In recent years, much emphasis has been placed on the remedia- important sorbent for orthophosphate in soils (H2PO4− and
tion of soils contaminated with organic or inorganic industrial HPO42−, the dominant inorganic forms of P between pH 4 and 9;
waste products (Clapp et al., 2001). Examples of these contami- Young and Ross, 2001; Sims and Pierzynski, 2005).
nants are synthetic organic chemicals, such as dense nonaque-
ous phase liquids (DNAPLs); benzene, toluene, ethylbenzene,
and xylenes (BTEX); and pesticides (herbicides, insecticides, 14.3.4  Soil Organic C Dynamics
and fungicides) (Schwarzenbach et al., 1993). The oxidation or and Climate Change
reduction of functional groups, aliphatic chains, and aromatic The oxidation state of C varies from IV− to IV+ in natural envi-
rings results in changes in solubility and toxicity (Schwarzenbach ronments, and enzymatic processes govern transformations
et al., 1993; Clapp et al., 2001). among them. Examples of the classes of C compounds represent-
The oxidation state of contaminant metals and metalloids ing the range of oxidation states are alkanes (IV− in methane,
can be transformed through microbiological or chemical redox CH4), alcohols (II− in methanol, CH3OH), aldehydes (0 in form-
processes. Such redox-based remediation changes their specia- aldehyde or general representations of SOM, CH2O), carboxylic
tion, solubility, bioavailability, and toxicity (Sauvé and Parker, acids (II+ in formic acid, HCOOH, i.e., hydrated CO), and carbon
2005). In such cases, the total, unspeciated concentration of the dioxide (IV+ in CO2; and when hydrated as H2CO3, HCO3−, and
element in question remains the same; only the oxidation state CO32−, depending on pH). The speciation of C in soils is governed
is changed. In these cases, the development of new methods for by myriad anabolic and catabolic processes in cells (Clapp et al.,
speciation and fractionation (Sauvé and Parker, 2005) based on 2005; Table 14.3).
oxidation state of the element has contributed to novel methods The knowledge of C speciation and the reactions governing
for remediation that do not involve removal of the element from it are central to many contemporary environmental, engineer-
the soil and that allow novel, in situ methods of remediation ing, and agricultural concerns. Greenhouse gas and particu-
(James, 1996). late releases into the atmosphere (CO2, CH4, black C and other
An example of an ongoing remediation-by-reduction are soils C-rich particulates) has encouraged research on C sequestration
contaminated with chromate [Cr(VI)] from industrial plating related to balances between methanogenesis and methanotro-
operations and chromite ore processing residue (James, 1996). phy (Sylvia et al., 2005). Concern about climate change due to
In situ or ex situ conversion of toxic, soluble Cr(VI) to much greenhouse gas releases is linked to the kinetics of formation
less toxic and insoluble Cr(III) species has been effective in and degradation of SOM and to effects of tillage practices and
laboratory, pilot, and field-scale studies. Methods studied have plant and animal waste decomposition dynamics (Ussiri and
included elemental Fe in permeable reactive barriers (PRBs; Lal, 2009). Balances between sources of SOM (via photosynthe-
Rivero-Huguet and Marshall, 2009), steel wool (James, 1994), sis and oxidation polymerization processes) and its decomposi-
ascorbic acid (Xu et al., 2005), animal manures (Bartlett and tion to simple organic acids and CO2 are keys to how soils may
Kimble, 1975), polysulfides (Graham et al., 2005), and FeSO4 sequester organic C.
(Geelhoed et al., 2003). Central to the acceptance of these meth- Clapp et al. (2005) provide an encyclopedic treatise on SOM,
ods by government regulatory agencies has been the refinement its structure, reactions, and roles in soils as a base for under-
of an analytical method for soils that selectively dissolves Cr(VI) standing organic matter and C dynamics. Lal (1999) provides a
from the solid matrix without reducing it and without method- brief description, with examples, of the role of soils in the green-
induced oxidation of Cr(III) in the soil (Vitale et al., 1997). house effect. He includes relevant information on greenhouse
emissions, with particular reference to rice paddies and organic
soils. Falkowski et al. (2008) provide excellent perspective on
14.3.3  Soil Fertility and Nutrient Cycling
the microbial redox processes that govern nonequilibrium bio-
Redox transformations are central to the biological controls logical systems, using what they call “nanobiological machines.”
of the N cycle, including N2 fixation (N2 to NH4+), nitrification They also describe how redox processes integrate sediments,
(NH4+ to NO3−), denitrification (NO3− to N2O and N2). These water, and the atmosphere through interconnected, biologically
processes govern the speciation of N in all ecosystems, whether mediated cycles for H, C, N, O, S, and Fe.
in wild biomes, engineered soils, or domesticated agricultural
ecosystems. Redox processes also govern speciation, bioavail-
14.3.5  Wetland Delineation and Function
ability, and solubility of Mn, Fe, C and S, cofactors in many
of the enzymes that catalyzed these N redox changes (Sylvia The delineation and redox-based functioning of freshwater and
et al., 2005). tidal wetlands (and their constituent hydric soils) are current chal-
In soils and natural waters, high levels of P contribute to the lenges as a result of increasing interest in preventing loss of wet-
growth of cyanobacteria and are therefore a concern related to lands due to human development and sea level rise linked to global
eutrophication of freshwaters (Howarth, 1988). The oxidation climate change and crustal subsidence (Hurt and Vasilas, 2006).
Oxidation–Reduction Phenomena 14-19

TABLE 14.3  Reduction Half-Reactions for Environmentally Relevant Species

Species Equations Eo (V) Log K �Gro (kJ/eq)

A γ-MnOOH γ-MnOOH + e− + 3H+ → Mn2+ + 2H2O 1.50 25.4 −145.0

B CrO42− 1/3CrO42− + e− + 5/3H+ → 1/3Cr(OH)3 + 1/3H2O 1.24 21.0 −119.9
C MnO2 1/2MnO2 + e− + 2H+ → 1/2Mn2+ + H2O 1.23 20.8 −118.8
D HCrO4− 1/3HCrO4− + e− + 4/3H+ → 1/3Cr(OH)3 + 1/3H2O 1.11 18.9 −107.9
E AQDS 1/2AQDS + e− + H+ → 1/2AH2DS 0.22 3.9 −22.3
F Lactate ½Pyruvate + e− + H+ → 1/2lactate 0.23 3.9 −22.3
G CH2O 1/4CO2 + e− + H+ → 1/4CH2O + 1/4H2O −0.07 −1.2 6.9
Examples
γ-MnOOH reduction by AH2DS (A and E) 21.5 −122.8
HCrO4− reduction by CH2O (D and G) 20.1 −114.8
HCrO4− reduction by lactate (D and F) 15.0 −85.7
HCrO4− reduction by AH2DS (D and E) 15.0 −85.7
Cr(OH)3 oxidation by γ-MnOOH (A and D) 6.5 −37.1
AQDS reduction by CH2O (E and G) 5.1 −29.1
AQDS reduction by lactate (E and F) 0.0 0.0
Sources: Data from Bartlett, R.J., and B.R. James. 2000. Redox phenomena, p. 169–193. In M.E. Sumner
(ed.) Handbook of soil science, 1st Ed. CRC Press, Washington, DC; Milazzo, G., V.K. Sharma, and S. Caroli.
1978. Tables of standard electrode potentials. Wiley, New York; Loach, P.A. 1976. Oxidation–reduction
potentials, absorbency bands, and molar absorbency of compounds used in biochemical studies, p. 122–130.
In G. Fasman (ed.) Handbook of biochemistry and molecular biology. Chemical Rubber Co., Cleveland, OH.
These reactions can be combined to form redox reactions, many of which are energetically favorable as
indicated by negative Gr values in the given examples.

The definition of hydric soils (Hurt and Vasilas, 2006) and wet- Correll, 1984; Allan et al., 2008). The role of trees, understory veg-
lands are linked to redox conditions and dynamics associated etation, and planted grasses in riparian ecosystems has shown that
with the position and fluctuations of the water table. A so-called black locust trees (Pseudoacacia spp.) act as a source of NO3− in
technical standard for defining wetlands is based on Eh and pH groundwater that occurs following N2 fixation, NH4+ release into
measurements associated with the oxidation and reduction of the soil, and nitrification. When black locust trees were cut and
Fe(II,III) (Rabenhorst and Castenson, 2005; Hurt and Vasilas, replaced with planted tall fescue, NO3− concentrations in ground-
2006; NTCHS, 2007). Recent research on IRIS tubes and the con- water beneath the riparian zones decreased, whereas when non-
cept of “biological zero” have contributed new methods and con- leguminous trees (red oak, loblolly pine, and sassafras) were cut,
ceptual thinking on this technical standard and how to define a NO3− concentrations increased. These results demonstrated the
wetland (Rabenhorst, 2005; Rabenhorst et al., 2008). important roles played by vegetation–microbe–soil–groundwater
The chemistry of tidal marshes that are diurnally inundated interactions affecting N speciation (James et al., 1991).
with SO42−-rich seawater leads to the accumulation of numer-
ous iron sulfide minerals, including iron monosulfides (e.g.,
FeS) and pyrite (FeS2) (Rabenhorst and James, 1992). In addi- 14.4  Earlier Reviews and Prescient
tion, the dynamics of organic C accumulation, methanaogen- Work on Oxidation–Reduction
esis and methane oxidation are important applications of redox Processes in Soils
concepts because of the importance of CH4 as a greenhouse gas
(Liverman, 2007). There are numerous general reviews and examples of redox mea-
surements, processes, applications, and data in soils and natural
waters. Interested readers are referred to the following sources:
14.3.6  R iparian Soil-Vegetation Systems and
Lindsay (1979), Buxton et al. (1988), Neta et al. (1988), Wardman
Groundwater Nitrate Concentrations
(1989), Sawyer (1991), Bartlett and James (1993), Schwarzenbach
Redox transformations of NO3− in groundwater have been major et al. (1993), Helz et al. (1994), Blough and Zepp (1995), Compton
societal concerns due to the potential for eutrophication of natu- and Sanders (1996), Stumm and Morgan (1996), Bartlett (1998).
ral waters, especially of by non-N2 fixing, green algae in saline Bartlett and Ross (2005) provide novel and heuristic ideas
waters of estuaries, such as the Chesapeake Bay of the Coastal surrounding a central role played by Mn in soil redox processes,
Plain of the United States (James et al., 1991). The reduction of N including formation of humic compounds, free radical reactions,
in NO3− (oxidation state V+) to N2O (oxidation state I+) and N2 nutrient cycling, rhizosphere chemistry, photochemistry, and
(oxidation state 0) via denitrification in riparian ecosystems has wetlands. Other chapters in this book tie in soil acidity, chemical
been extensively studied (Lowrance et al., 1984; Peterjohn and kinetics, and other topics related to oxidation–reduction.
14-20 Properties and Processes

Extensive redox-based research conducted by the late William Bartlett, R., and B. James. 1979. Behavior of chromium in soils.
Patrick and coworkers at the Wetland Biogeochemistry Institute III. Oxidation. J. Environ. Qual. 8:31–35.
at Louisiana State University (Baton Rouge, LA) has been central Bartlett, R.J., and B.R. James. 1993. Redox chemistry of soils. Adv.
to much of current knowledge related to Eh and pH as master Agron. 50:151–208.
variable controlling the chemistry and biochemistry of tidal Bartlett, R.J., and B.R. James. 1995. System for categorizing
marshes and freshwater wetlands. soil redox status by chemical field testing. Geoderma
Remarkable, almost prescient, insight is provided in several 68:211–218.
references on electron activity and its measurement by the Pt elec- Bartlett, R.J., and B.R. James. 2000. Redox phenomena, p. 169–
trode in the first four decades of the twentieth century following 193. In M.E. Sumner (ed.) Handbook of soil science, 1st Ed.
the discovery of the electron in 1897 (Gillespie, 1920; Willis, 1932; CRC Press, Washington, DC.
Pearsall and Mortimer, 1939). These researchers linked thermo- Bartlett, R.J., and J.M. Kimble. 1975. Behavior of chromium in
dynamic theory, biological processes in soils, and applications of soils. II. Hexavalent forms. J. Environ. Qual. 5:383–386.
redox chemistry to societal needs of their times—an accomplish- Bartlett, R.J., and D.S. Ross. 2005. Chemistry of redox processes
ment that can serve as a guide for future studies on the elusive in soils, p. 461–487. In M.A. Tabatabai and D.L. Sparks
electron in soil environments. Research and teaching related (eds.) Chemical processes in soils. Soil Sci. Soc. Am. Book
to oxidation–reduction processes in myriad soil environments Ser. 8. SSSA, Madison, WI.
remains a vital and dynamic field of study with many applica- Bates, R.G. 1981. The modern meaning of pH. Crit. Rev. Anal.
tions for future soil chemists and environmental scientists inter- Chem. 10:247–278.
ested in addressing complex biological and chemical systems. Bauer, M., T. Heitmann, D.L. Macalady, and C. Blodau. 2007.
Electron transfer capacities and reaction kinetics of
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 15
Soil Colloidal Behavior

Sabine Goldberg 15.1 Nature of Soil Colloids...........................................................................................................15-1

Significance of Colloidal Phenomena  •  Types of Soil Colloids  •  Properties of Soil
United States Department
of Agriculture Colloids  •  Thermodynamics of Colloid Surfaces
15.2 Interparticle Forces..............................................................................................................15-16
Inmaculada Lebron Electrical Double Layer  •  Attractive Force  •  Repulsive Force
Centre for Ecology & Hydrology 15.3 Colloidal Stability.................................................................................................................15-18
Flocculation and Dispersion  •  Factors Affecting Colloidal Stability  •  Measurement
John C. Seaman of Colloidal Stability
University of Georgia
15.4 Colloid Transport.................................................................................................................15-25
Donald L. Suarez Colloid Transport Modeling  •  Colloid-Mediated Contaminant Transport  • 
United States Department Effect of Colloid Transport on Hydraulic Conductivity and Soil Formation
of Agriculture References..........................................................................................................................................15-30

15.1  Nature of Soil Colloids understanding the processes of adsorption, flocculation, dis-
persion, and transport in soils and the resultant changes in soil
15.1.1  Significance of Colloidal Phenomena hydraulic properties, as well as chemical migration. Since the
major part of the surface area is in the colloidal fraction of the
The importance of colloids in soil science has been appreciated
soil, almost all surface-controlled processes including adsorp-
for many years. However, recent understanding that organic
tion reactions, nucleation, precipitation, and dissolution involve
and inorganic contaminants are often transported via colloidal
colloids. Colloids are reactive not only because of their total sur-
particles has increased interest in colloid science. Essentially,
face area but also because of enhanced reactivity related to rough
all chemicals and individual species are to some extent reac-
surfaces and highly energetic sites, as well as the effects of elec-
tive with soils, including species such as chloride ions, which
trostatic charge. Colloid charge is associated with substitution of
undergo repulsion from negatively charged surfaces. With few
lower charge cations for those of higher charge in the mineral
exceptions, soil chemistry is primarily the chemistry of colloids
lattice (which results in a net permanent charge) as well as sur-
and surfaces. The primary importance of colloids in soil science
face charge associated with broken bonds. The charge associated
stems from their surface reactivity and charge characteristics.
with broken bonds is characterized as variable charge in as much
The overwhelming majority of surface area and electrostatic
as the solution influences the surface speciation (Chapter 16).
charge in a soil resides in the less than 1 μm size fraction with
In addition to these chemical processes, colloids are mobile in
particles with radii between 20 and 1000 nm constituting the
soils and thus not only affect the chemical transport of other-
major part of the soil surface area (Borkovec et al., 1993). A sig-
wise immobile chemicals but also exert a strong influence on soil
nificant fraction of reactive soil colloidal material falls within the
hydraulic properties.
<100 nm size range and thus is relevant to the growing interest
in the properties and behavior of nanoparticles. Furthermore,
soil is often the ultimate repository for anthropogenic nanoma-
terials of environmental concern (Hochella, 2008; Theng and
15.1.2  T ypes of Soil Colloids
Yuan, 2008; Waychunas and Zhang, 2008). The unique aspects of Colloidal particles are defined as having an equivalent spheri-
“nanoscience” as a discipline separate from colloid science reflect cal radius smaller than 1 μm (van Olphen, 1977). A homoge-
deviations in material properties in the nanoparticle size range, neous dispersion of colloidal particles in a liquid is called a
especially for materials <10 nm, and in many cases the lack of a colloidal dispersion. If the particles are large and settle rapidly,
natural bulk analog in the larger size fractions, for example, fer- the dispersion is called a suspension. A colloidal dispersion is
rihydrite (Hochella, 2008; Waychunas and Zhang, 2008). defined as a system where particles of colloidal dimensions are
Characterizations of size, shape, surface area, surface dispersed in a continuous phase of a different composition (van
charge density, and changes in surface charge are required for Olphen, 1977).

15-1
15-2 Properties and Processes

15.1.2.1  Oxides be inherited from parent materials or formed pedogenically in

Oxides, including hydroxides and oxyhydroxides, are ubiquitous warm climatic regions (Brown et al., 1978). The two magnetic Fe
constituents of soils, occurring as both discrete particles and as minerals, magnetite and maghemite, occur in soils; the former is
coatings on other soil surfaces. Oxide minerals that are com- inherited from parent rock, while the latter is formed pedogeni-
monly found in the soil clay fraction are discussed in Chapter 22. cally in highly weathered soils (Brown et al., 1978). Ferrihydrites
Hydroxylation of oxide minerals can either be structural are poorly crystalline, have indefinite composition, and occur as
and/or occur by chemisorption of water in an aqueous medium very small particles with high surface area (Schwertmann and
(Schwertmann and Taylor, 1977). Edge hydroxyl groups on oxides Taylor, 1977). Ilmenite is an uncommon mineral usually inher-
and clay minerals represent the most abundant and reactive sur- ited from igneous or metamorphic parent rocks (Brown et al.,
face functional groups in soils (Sposito, 1984). Any one type of 1978). Iron oxides play an important role in ion adsorption and
oxide mineral contains various groups of surface hydroxyls that in aggregation and cementation of soil particles.
are distinguishable by crystal plane location and/or extent of Manganese oxides occur widely in soils as minor constitu-
coordination to the cations of the bulk structure. However, as ents, mainly as dark coatings on particle surfaces. Manganese
a simplification, it is often assumed that each oxide mineral has oxides are chemically complex, existing as a continuous range
a single set of homogeneous reactive functional groups. Surface of compositions between MnO and MnO2 (Brown et al., 1978).
hydroxyl groups on most oxide minerals are amphoteric, exhib- Birnessite, vernadite, lithiophorite, and hollandite are the most
iting positive charge at low pH and negative charge at high pH. common crystalline manganese minerals in soils (McKenzie,
For this reason, oxide minerals are often referred to as variable 1989). Birnessite occurs in both acid and alkaline soils, while
charge soil minerals. Table 15.1 provides densities of surface lithiophorite occurs mainly in neutral to acid soils (Brown et al.,
hydroxyl groups for some common oxide minerals in soils. 1978). These oxides supply Mn for plant nutrition. Manganese
Boehmite and gibbsite are the only crystalline Al oxides oxides exhibit a strong adsorption capacity for metal cations,
common in soils. Aluminum oxides are the products of intense especially copper, due to their pH-dependent charge, small par-
weathering of aluminosilicate minerals and are most abundant ticle size, and large surface area (McKenzie, 1989).
in tropical soils. Gibbsite can also be found in volcanic ash soils Rutile and anatase are the common titanium oxides occur-
of humid regions (Brown et al., 1978). Noncrystalline Al oxides, ring in soils. Rutile is a high-temperature form occurring in
which have similar structure and chemical characteristics but igneous and metamorphic rocks (Hutton, 1977). Anatase is
smaller particle size than crystalline varieties, often domi- a low-temperature form occurring as an alteration product of
nate the chemical reactions with anions in soils (Hsu, 1977). titanium containing minerals such as ilmenite and is much less
Aluminum oxides play an important role in ion adsorption, abundant than rutile (Brown et al., 1978). Titanium oxides are
stabilization of soil aggregates, and flocculation of soil particles. present in both the coarse and fine fractions of soils and are very
Iron oxides are found in most soils and provide soil horizons insoluble (Hutton, 1977).
with their red, yellow, and brown colors (Brown et al., 1978). Quartz is not only the most abundant silicon oxide but also
Most iron oxides are the weathering products of iron-contain- the most abundant mineral in most soils. Most quartz is found
ing silicates. Goethite, which is the most common Fe oxide in predominantly in the sand, silt, and coarse clay fractions of soils
temperate, subtropical, and tropical soils, is usually thermody- (Wilding et al., 1977). Silicon oxides are generally considered
namically the most stable (Schwertmann and Taylor, 1977). Soil inert having a small surface area and little surface charge.
goethites are usually fine grained and contain appreciable sub- 15.1.2.2  Clay Minerals
stituted Al. Lepidocrocite is a minor constituent of waterlogged
temperate soils undergoing alternating oxidizing and reducing The clay fraction of most soils is dominated by various layer sili-
conditions, whereas hematite is a common soil mineral that can cate clay minerals. Layer silicate clay minerals are classified as 1:1
where each layer consists of one tetrahedral silica sheet and one
TABLE 15.1  Densities of Surface Hydroxyl octahedral alumina sheet, 2:1 where each layer consists of one
Groups on Oxide Minerals octahedral sheet sandwiched between two tetrahedral sheets, or
Site Density Range 2:1:1 where a metal hydroxide sheet is sandwiched between the
Solid (Sites nm−2) 2:1 layers. Layer silicate minerals common in soils are discussed
Gibbsite 2–12 in Chapter 21. A discussion of silicate structures is provided by
Goethite 2.6–16.8 Schulze (2002).
Hematite 5–22 Layer silicate clay minerals are characterized by isomorphic
Ferrihydrite 1.1–10.1 substitution of lower valence cations in either or both the tetra-
MnO2 6.2 hedral and the octahedral sheets. This excess of negative charge
TiO2 2–12 is balanced by other cations, either inside the crystal or on the
Amorphous SiO2 4.5–12 external surfaces (McBride, 1994). Layer charge is an electro-
Source: Adapted from Davis, J.A., and D.B. Kent.
static charge balanced outside of the structural unit and deter-
1990. Surface complexation modeling in aqueous mines the strength and type of bonding occurring between the
geochemistry. Rev. Mineral. Geochem. 23:177–260. basal planes. Charge arising from isomorphic substitution is
Soil Colloidal Behavior 15-3

TABLE 15.2  Charge Characteristics and Cation Exchange Vermiculite is an important clay mineral in soils that is
Capacities of Clay Minerals formed as an alteration product of muscovite and biotite micas
Charge per Unit Half Cell (Douglas, 1977). Vermiculite is widely distributed and has a
Cation Exchange
wide particle size range. Vermiculites contain hydrated magne-
Solid Tetrahedral Octahedral Capacity (cmolc kg−1)
sium cations that can be readily exchanged by K and ammonium
Kaolinite 0 0 1–10
ions, resulting in collapse of the clay layers and fixation of these
Smectite 80–120
nutrient ions. Vermiculites have high CEC and high surface area
Montmorillonite 0 −0.33
but exhibit limited swelling.
Beidellite −0.5 0
Chlorites are 2:1:1 layer silicates that occur extensively in
Vermiculite −0.85 +0.23 120–150
soils. The hydroxide interlayer sheet is usually dominated either
Mica 20–40
by brucite [Mg(OH)2] or by gibbsite [Al(OH)3]. This interlayer
Muscovite −0.89 −0.05
sheet restricts swelling, decreases effective surface area, and
Chlorite 10–40
decreases effective CEC (McBride, 1994). Chlorites are non-
Sources: Bohn, H.L., B.L. McNeal, and G.A. O’Connor. 1985. Soil chem- swelling silicates.
istry. John Wiley & Sons, New York; McBride, M.B. 1994. Environmental
chemistry of soils. Oxford University Press, New York.
15.1.2.3  Organic Matter
Soil organic matter (SOM) refers to the mixture of products result-
called permanent charge because it is independent of solution
ing from microbial and chemical transformations of organic resi-
pH. Layer silicate clay minerals also possess variable charge
dues and is discussed in Chapter 11. An important component of
located at the broken edges of the particles. At the edges of the
SOM is called humus, a complex and microbially resistant mix-
octahedral sheet, hydroxyl ions attached to Al cations are called
ture of amorphous and colloidal substances. These substances are
aluminol groups. Similar to the hydroxyl groups on oxide min-
the result of modifications of original tissues or synthesis by soil
erals, aluminol groups are amphoteric. At the edges of the tet-
microorganisms. Humic substances are subdivided into humic
rahedral sheet, hydroxyl groups attached to Si cations are called
acid, fulvic acid, and humin using a separation scheme based
silanol groups. Silanol groups do not undergo protonation, but
on solubility in strong acid and base (McBride, 1994). The struc-
dissociate and become negatively charged at high pH. Adsorbed
ture and composition of humus are complex and incompletely
cations on clay minerals balance both pH dependent and per-
known. The structure contains a variety of reactive functional
manent charges. Table 15.2 provides charge characteristics and
groups including carboxyl R–COOH, phenol C6H5OH, alcohol
cation exchange capacities (CEC) for some common clay miner-
R–CH2OH, enol R–CH=CH–OH, ketone R–CO–R′, quinone
als in soils.
O=C6H4=O, ether R–CH2–O–CH2–R′, and amino R–NH2
Kaolinite is one of the most widespread clay minerals in soils,
(Stevenson, 1982). Humus is amorphous and highly colloidal;
being most abundant in soils of warm moist climates (Dixon,
its surface area, ion adsorption, and CEC are greater than those
1977); while halloysite is formed through acid weathering and
of layer silicate clay minerals (McBride, 1994). The presence of
in soils of volcanic origin. The halloysite structure is the same as
humus usually promotes aggregation of soil particles.
the kaolinite structure but contains a sheet of water molecules
between the layers. Both minerals have low colloidal activity, low
surface area, and low CEC and anion exchange capacity (AEC) 15.1.3  Properties of Soil Colloids
(Dixon, 1977). The CEC and AEC of the 1:1 minerals are pre-
dominantly pH dependent (McBride, 1994). 15.1.3.1  Particle Size and Shape
Micas are abundant in soils, occurring as primary miner- Colloids in natural systems are characterized by a continuous
als inherited from soil parent materials. Micas strongly retain particle size distribution (PSD; polydispersivity) of extreme com-
interlayer potassium ions, rendering them nonexchangeable plexity and diversity. Organisms, organic macromolecules, min-
and reducing the CEC of these minerals. Through weathering, erals, clays, oxides, and combinations of any of them constitute
micas release K and provide an important natural source of this the colloidal fraction in soils. The distribution of shapes, densi-
plant nutrient (Fanning and Keramidas, 1977). Illite is a second- ties, surface chemical properties, and chemical composition vary
ary mineral that is less crystalline, contains less K, and contains widely with size. Some fractions of the size spectrum may be liv-
more water than muscovite mica (McBride, 1994). Micas and ing, and all particulates are subject to diverse physical, chemical,
illites are nonswelling minerals. and biological processes that can alter size distribution, shape, or
Smectites constitute an important group of 2:1 clay miner- chemical composition (Kavanaugh and Leckie, 1980).
als. Members that are important in soils include montmorillon- Colloids are dynamic particles, subject to constant altera-
ite, beidellite, and nontronite. Smectites are most significant in tion; the distribution of particle sizes in natural systems is the
moderately weathered soils and have high colloidal activity and result of a number of processes, which either bring the particles
high surface area. Smectites are responsible for a large part of the together (coagulation) or disrupt existing aggregates (disper-
CEC and the majority of the shrink/swell properties of smectitic sion) (Filella and Buffle, 1993; Buffle and Leppard, 1995a, 1995b).
soils (Borchardt, 1977). Particle size is an important parameter in the characterization
15-4 Properties and Processes

of colloids. Sequential gravimetric sedimentation has been the techniques are able to accurately measure the full scale of size
classical method for measuring PSDs in soils. However, this ranges for colloids in polydisperse samples. Furthermore, most
technique has proven to be unreliable for particle sizes in the of the colloidal-sizing techniques do not measure size directly,
colloidal range (1–1000 nm). The reason for the lack of reli- but rather determine a physicochemical property from which
ability is the combination of Brownian motion and convection the size is calculated (Lead and Wilkinson, 2007). For example,
currents, which each exert a significant influence on settling at scanning and transmission electron microscopic techniques
diameters below ∼1 μm in water. determine the physical dimensions of the projected area of the
Awareness of the environmental importance of colloids, particles (Lebron et al., 1999), light scattering and flow-FFF
for example, remediation schemes using engineered nanopar- generally determine the diffusion coefficients (Lead et al., 2000;
ticles, and studies on the ecotoxicology of the products created Hassellov et al., 2007), and sedimentation-FFF (Sd-FFF) and
by the emerging nanotechnology industry have accelerated the other centrifugation-based techniques measure the buoyant mass
development of analytical techniques for nanoscale research (Hassellov et al., 2007). Although particle size can be estimated
(Wilkinson and Lead, 2007). These analytical techniques pro- from projected areas, diffusion coefficients, and buoyant mass,
vide quantification, analyses, and characterization of the size, the calculations are based on a number of assumptions, which
shape, and distribution of colloids in polydisperse systems if not met, will reduce the quality of the results (i.e., sphericity,
within the environment (Handy et al., 2008). Some of the tech- homogeneous charge distribution, absence of coulombic interac-
niques more commonly used in soil science for colloid char- tions among particles). Therefore, it is not uncommon to obtain
acterization and determination of PSD are reviewed in the different PSDs for the same sample when using different tech-
following section. These include centrifugation, particle size niques (Lead and Wilkinson, 2007). Even more direct techniques
analysis using the Coulter principle, field flow fractionation like scanning electron microscopy (SEM) and environmental
(FFF), atomic force microscopy (AFM), electron microscopy scanning electron microscopy (ESEM) have their limitations.
(EM), and acoustic spectroscopy. A recent publication by the Doucet et al. (2004) observed differing colloidal morphologies
International Union of Pure and Applied Chemistry (IUPAC) in preparations obtained from the same sample with SEM and
Wilkinson and Lead (2007) provides more detailed information AFM. They attributed these differences to the sample prepara-
on the various techniques. tion required for each technique. The difficulty in obtaining
It is important to consider that each particle size measurement similar PSDs using different techniques indicates the limitation
technique has different accuracy and precision. In other words, of the individual techniques. Therefore, it is good practice to use
detection limits and detection windows, corresponding to dif- the results of several characterization techniques simultaneously
ferent size ranges, are technique dependent (Table 15.3). Not all (Lead and Wilkinson, 2007; Hassellov et al., 2008).

15.1.3.1.1  Measurement Methodology

TABLE 15.3  Operational Range of Colloid Particle Size Minimization of sample handling and processing is recom-
Characterization for a Variety of Analytical Techniques and the mended when analyzing colloidal systems. Currently, no in
Inferred Colloidal Dimension Quantified by Each Technique situ technique allows direct measurement of the PSD for soils.
Approximate Analysis Furthermore, measurement of colloid particles cannot be com-
Analytical Technique Quantified Parameter Size Range (nm) pared to standard samples to evaluate the quality of measure-
Filtration Equivalent pore size 100–>1000 ments made because there are no accepted standards or reference
diameter materials for natural colloids (Lead and Wilkinson, 2007).
Ultrafiltration Equivalent molar mass 1–100
Centrifugation Equivalent spherical 10–>1000 15.1.3.1.2  Electron Microscopy
volume diameter EM is one of the few techniques capable of measuring the size
Dialysis Equivalent molar mass 0.5–100 of particles across the entire colloidal range (Table 15.3). Both
ESEM Projected area 40–>1000
transmission electron microscopy (TEM) and SEM require
SEM Projected area 10–>1000
deposition of aqueous suspensions, sample evacuation, and in
TEM Projected area 1–>1000
the case of SEM, sample coating with a conducting material,
AFM Three dimensions 0.5–>1000
typically graphite or gold, to reduce charging from the beam.
Fl-FFF Hydrodynamic diameter 1–1000
Hence sample preparation can, and most likely will, alter the
Sd-FFF Equivalent spherical 50–1000
original particle morphology and size distribution (Buffle and
volume diameter
Leppard, 1995a, 1995b; Chanudet and Filella, 2006). However,
DLS Hydrodynamic diameter 3–>1000
Acoustic Equivalent particle 5–>1000
new sample preparation techniques are constantly being
spectroscopy diameter developed to counteract artifacts generated by dehydration.
For example, freeze-drying techniques or the use of hydrophilic
Source: Adapted from Hassellov, M., J.W. Readman, J.F. Ranville, and
K. Tiede. 2008. Nanoparticle analysis and characterization methodologies in
resins and multimethod TEM sample generation techniques can
environmental risk assessment of engineered nanoparticles. Ecotoxicology be used to stabilize the three-dimensional structure of colloids
17:344–361. (Mavrocordatos et al., 2007).
Soil Colloidal Behavior 15-5

ESEM can, in theory, be used to quantify colloids under ambi- where u is the velocity. If R E ≤ 0.2, the fluid conditions are
ent conditions, as can AFM that is generally used only to deter- described as streamlined or laminar, and the drag on the particle
mine the dimensions and characteristics of individual colloids. is due mainly to viscous force within the fluid. Particles with
While minimal sample manipulation is an advantage, the disad- high densities or large particle diameters may be moving with
vantage is a reduction in the resolution of the techniques; both velocities that exceed R E = 0.2, and in this situation, they are
ESEM and AFM produce much better resolution at lower relative likely to enter the region of turbulent flow, where velocities are
humidity. Another serious problem in AFM imaging of liquids more difficult to calculate. In a centrifugal field, Stokes’ equation
is the alteration of the AFM-derived signal due to the uptake has the form:
of nanoparticles onto the AFM cantilever (Lead et al., 2005).
Applications and new sample preparation techniques for envi- (ρ − ρ0 )ω 2d 2p ln(r/s0 )
ronmental colloids using AFM are discussed by Balnois et al. u= = (15.2)
18η t
(2007). Force-volume mode AFM has been used to evaluate the
heterogeneous distribution of charge on clay surfaces (Taboada-
Serrano et al., 2005). where
Microscopy, despite being a very powerful technique, is ω is the rotational velocity (rad s−1)
not widely used for routine particle size analysis. The reasons t is the time (s) required for a particle of diameter dp to
for its limited use are the high cost of the equipment and the move from its starting point radius (s 0) to the analytical
small sample volumes that can be scanned at any given mag- radius (r)
nification. Image analysis software facilitates the quantification
of the different particle metrics in the micrographs. However, Application of the Stokes equation requires certain assump-
obtaining sufficient particles to allow representative and robust tions that are not always achieved. All of these assumptions
statistics requires the scanning of many micrographs of the are critical to the measurement of the size of the sedimenting
specimen. Nevertheless, the determination of morphology and particles. The first assumption is that the particles are spheri-
particle shape factor still remains the strength of microscopic cal, smooth, and rigid. Since this assumption is almost never
techniques. Automated instrumental analysis routines that take valid, the diameter calculated is an equivalent or Stokes diam-
advantage of enhanced beam stability combined with image eter (dSt). It is assumed that the particle terminal velocity is
analysis software, and greater computing capacity have the reached instantly, although calculations show that a finite but
potential to address such limitations (Seaman, 2000; Laskin and small time is actually required before this condition is reached.
Cowin, 2001). Additionally, SEM, ESEM, and TEM coupled with The particle is assumed to be moving without interference or
energy dispersive x-ray (EDX) spectroscopy can provide valu- interaction from other particles in the system. This assump-
able chemical information about individual particles. It must be tion is only true at high dilutions (<1%) that ensure consid-
recognized that the resulting x-ray signal in SEM may be gen- erable separation between particles. Also, it is assumed that
erated from a sample region larger than the particle of interest inertial effects are not present and that the fluid exhibits only
(Goldstein et al., 1992; Seaman, 2000). Furthermore, TEM can Newtonian flow properties. Since water is generally the dilu-
also, by measuring the x-ray spectra emitted by the specimen, tion medium in soils and colloidal particles are <1 μm, these
resolve crystal spacing. Selective area electron diffraction can be assumptions are usually valid. A more detailed analysis of the
used to identify colloidal minerals and to determine their degree methodology as well as a description of different centrifuga-
of colloid crystallinity. tion methods is provided by Bunville (1984), Groves (1984),
Koehler et al. (1987), Holsworth et al. (1987), and Coll and
15.1.3.1.3  Centrifugation Oppenheimer (1987).
A particle falling through an infinite fluid will eventually travel
at a terminal constant velocity determined by the size of the par- 15.1.3.1.4  Coulter Effect
ticle and the resistance offered by the fluid. The terminal veloc- The increase in the resistance across a small aperture produced
ity in a centrifugal field is not constant, but rather a function of by a nonconducting particle in a conducting medium is called
distance from the axis of rotation. Measurement of this radius the Coulter effect. The magnitude of this increase in resistance
is necessary in order to calculate the particle size. The relation- (ΔR) for a spherical particle of diameter (dp) suspended in an
ship between the movement of the particle and the movement of aperture of diameter (Da) is
fluid around that particle may be reduced to the Stokes equation.
For fluid moving past a particle of diameter (dp), the ratio of the ⎡ 4 ⎛ d p ⎞2 24 ⎛ d p ⎤
8 Pf d p ⎞
inertial transfer is described by the dimensionless parameter, ΔR = ⎢1 + ⎜ ⎟ + ⎜ ⎟ + ⎥ (15.3)
the Reynolds number (R E): 3πDa4 ⎢⎣ 5 ⎝ Da ⎠ 35 ⎝ Da ⎠ ⎥⎦

ρ0ud p
RE = (15.1) where Pf is the resistivity of the conducting medium. This resis-
η
tance pulse (ΔR) results in a voltage pulse (iΔR) for a sphere
15-6 Properties and Processes

of diameter dp, where i is the current across the aperture. The Like chromatography, FFF is an elution methodology in which
resulting voltage pulses are counted and scaled using a multi- constituents are differentially retained, and thus separated in a
channel analyzer. flow channel (Beckett et al., 1997). With this technique, a col-
Instruments utilizing the resistive pulse technique require loidal sample is introduced into a stream of liquid and subjected
calibration using standard particles with known diameter to to a field (such as gravitational, centrifugal, third cross-flow,
assign a particle size to each of the thresholds. This procedure thermal gradient, electrical, or magnetic) acting perpendicular
takes into account the dimensions and electrical characteristics to the stream direction (Beckett and Hart, 1993). According to
of the aperture and the conducting medium. theory, the rate at which particles are displaced downstream,
The advantage of the resistive pulse technique is that no other measured as emergence times, can be related exactly to particle
properties of the particle, such as refractive index or specific properties such as mass, size, and density. However, since differ-
gravity, are required for the interpretation of the data in terms of ent kinds of particles move at different velocities in this system,
a PSD. Developments in instrumentation for particle size analy- broad particle populations are sorted into graded size (or mass)
sis using the resistive pulse technique allow the analysis of par- distributions along the length of the flow channel. Observation
ticle sizes <1 μm but the range is limited (typically 0.4–<1 μm) of the shape of the emerging distribution, combined with theory,
(Bunville, 1984). yields PSD curves called fractograms.
If applied as indicated above, FFF provides highly detailed
15.1.3.1.5  D
 ynamic Light Scattering or Photon size distribution curves and is a very flexible technique that can
Correlation Spectroscopy be adapted to different particle types in almost any suspend-
Dynamic light scattering (DLS), also called photon correlation ing medium. The more commonly used FFFs in environmen-
spectroscopy, or quasielastic light-scattering measures the fluc- tal applications are Sd-FFF and flow-FFF (Fl-FFF). Sd-FFF uses
tuation in scattered intensity of a laser beam over small-time a centrifugal field to aid the separation of the colloids, while
intervals when it passes through a small volume of particles Fl-FFF uses a cross flow. For detailed information about FFF,
under Brownian motion. These fluctuations are dependent on Giddings (1993) provides a detailed explanation of this family of
the diffusion coefficient of the particles. techniques and Hassellov et al. (2007) highlight the latest accom-
When the particles have a regular shape other than spherical, plishments of FFF for aquatic colloids and macromolecules.
the depolarized component can be used to study the particle Detection limits for colloid chemical analyses have been lim-
rotational diffusion coefficient. The rotational and translational ited using traditional analytical techniques because the amount
diffusion coefficients obtained in conjunction with theoreti- of colloids collected for analysis is generally limited. Presently,
cal, hydrodynamic relationships contain information about the with the availability of low detection limit chemical analysis
particle dimensions. For a nonspherical particle larger than the instrumentation such as graphite furnace atomic absorption
incident wavelength, light is scattered from different parts of spectrometer (GFAAS) and inductively coupled plasma-mass
the same particle producing interferences, which are dependent spectrometry (ICP-MS), concurrent particle size determination
on the angle of the scattered intensity and characteristic of a and chemical analyses can be conducted. Instruments can be
particular particle shape (Pecora, 1983). assembled either off-line (disconnected) or online (connected)
Limitations of DLS are due to the assumptions made in cal- to achieve a more complete description of the colloid nature.
culating the particle radius from the diffusion coefficients. These Blo et al. (1995) used GFAAS as an off-line detector for Sd-FFF,
assumptions include sphericity, nonpenetrable spheres, and non- while Contado et al. (1997) coupled online GFAAS to Sd-FFF
columbic forces existing among the particles. A more major limi- to characterize suspended particulate matter from rivers. When
tation, when applied to colloidal systems, is the strong particle analyzing colloidal fractions, techniques like inductively cou-
size dependence of the scattered light intensity. Larger particles pled optical emission spectrometry (ICP-OES) or ICP-MS that
have a much larger influence than smaller particles, biasing size allow the simultaneous collection of multiple element signals are
quantification toward larger particle sizes. Consequently, previ- preferable. Sd-FFF was coupled with ICP-MS for the first time
ous sample fractionation is advised, since small fractions of dust by Beckett (1991). Since then, many scientists have produced
or other micrometer-sized particles will overshadow the signal detailed chemical information about colloidal size fractions and
of the particles in the colloidal range (Hassellov et al., 2008). associated elements (Murphy et al., 1993; Ranville et al., 1999).
Despite limitations, DLS is quick and easy to use, is available in As per Table 15.3, Sd-FFF is only capable of separating particles
most laboratories, and is very useful for monitoring changes in down to ∼50 nm. Since many colloids of interest are smaller,
colloid aggregation. It has been applied successfully to measure Chittleborough et al. (2004) developed the Fl-FFF-ICP-MS tech-
particle sizes of colloids in natural systems (Rees, 1990; Ryan and nique that can operate across the entire colloidal size range.
Gschwend; 1990; Lebron et al., 1993; Ledin et al., 1993, 1994; Finsy,
1994; Perret et al., 1994; Newman et al., 1994; Filella et al., 1997). 15.1.3.1.7  Acoustic Spectroscopy
Acoustic spectroscopy methods measure the propagation veloc-
15.1.3.1.6  Field-Flow Fractionation ity and attenuation of sound waves (i.e., 1–100 MHz) passing
FFF is a group of separation techniques capable of fractionating through a colloidal suspension, providing information about the
and characterizing the PSD of colloids in the range 0.01–1 μm. PSD, rheology, and electrokinetic behavior of the suspension.
Soil Colloidal Behavior 15-7

Dukhin and Goetz (2002) provide a thorough discussion of inherently unstable suspensions, such as materials close to their
acoustic methods and the six mechanisms of acoustic attenu- zero point of charge (ZPC) and/or critical coagulation concen-
ation associated with a colloidal suspension: viscous, thermal, tration (CCC) (Babick et al., 2000; Dukhin and Goetz, 2002;
scattering, intrinsic, electrokinetic, and structural signal dissi- Kosmulski et al., 2002; Guerin and Seaman, 2004; Guerin et al.,
pation. The application of acoustic spectroscopy to colloid char- 2004; Delgado et al., 2005). Furthermore, the relatively large
acterization assumes that each attenuation process functions sample volume allows for the collection of subsamples through-
independently and that the overall attenuation is the summation out acoustic analysis for characterization by other analytical
of the independent processes. methods (Seaman et al., 2003).
Viscous and thermal dissipation are the most important Acoustic spectrometers for use in characterizing colloi-
because colloids mainly interact with sound waves hydrody- dal suspensions became commercially available in the 1990s.
namically through the generation of oscillating shear waves and Despite several advantages when compared to light-scattering
thermodynamically through temperature losses. The resulting techniques, the application of acoustic-based methods to the
acoustic spectra are generally insensitive to the electrical con- study of soil colloids has generally been restricted to the char-
ductivity of the solution and the charge of suspended particles acterization of mineral standards or synthesized mineral ana-
and provide no information concerning particle morphology logs, such as goethite and hematite (Gunnarsson et al., 2001;
(Dukhin and Goetz, 2002; Seaman et al., 2003). Kosmulski, 2002; Kosmulski et al., 2002, 2003; Appel et al., 2003;
Acoustic attenuation attributed to the suspension is gener- Guerin and Seaman, 2004; Guerin et al., 2004; Delgado et al.,
ally determined by measuring the relative change in signal at 2005). However, acoustic methods of suspension characteriza-
each frequency with precise changes in gap distance or sample tion rely on the interpretation of macroscopic sample properties,
path length in spectroscopic terms. Thermal losses dominate in that is, the acoustic attenuation spectrum of a suspension, using
emulsions and low-density dispersions, so that viscous losses idealized model algorithms with various simplifying assump-
may be neglected. For rigid submicron particles (i.e., soil clays, tions and a few known system parameters, such as suspension
oxides), viscous attenuation dominates and limited informa- concentration and particle density. The limited information can
tion regarding composition of the particles (density), the media often result in systems that are “ill defined” and can be described
(solution density and shear viscosity), and the relative volume by multiple answers, that is, PSDs (Dukhin and Goetz, 2001;
fraction of the two phases is required for estimating particle Babick and Ripperger, 2002), a problem that also plagues light-
size, providing a minimum detectable particle size of approxi- scattering techniques (Schurtenberger and Newman, 1993). As
mately 10 nm. For complex environmental samples, however, such, acoustic methods are most suitable for evaluating relative
such information may be lacking. Acoustic scattering becomes changes in colloid aggregation and surface charge for suspen-
more important with increasing particle size, and sound speed sions in response to known changes in solution chemistry rather
must also be considered. When characterizing “soft” particles than for comparing subtle differences between poorly defined
having a limited density contrast compared to the suspend- environmental samples.
ing solution, such as latex particles and polymers, additional
information concerning their thermal expansion properties is 15.1.3.1.8  Applications of Particle Size Methods
required for interpretation of the attenuation spectra (Dukhin PSD is a fundamental soil property, affecting soil surface area,
and Goetz, 1996, 1998, 2002). bulk density, porosity, water retention, and hydraulic behavior.
Acoustic methods offer several advantages compared to other Furthermore, precise information about colloidal size and shape
instrumental techniques for evaluating colloid size and surface is important because submicron-size colloids often act as vehi-
charge properties. Ultrasound can propagate through suspen- cles that control the transport and fate of adsorbed pollutants
sions to a much greater degree than light. Therefore, acoustic (hydrophobic organic compounds, toxic trace metals, and radio-
analysis can be conducted at relatively high solid to solution nuclides [de Jonge et al., 2004a]). Bacteria and viruses are part
ratios (up to 30% solids by volume) that are more analogous to of the colloidal pool in natural environments; their character-
soil conditions in the field. However, the analysis may require ization and transport are significant for understanding biogeo-
more colloidal material than may be readily available. Analysis chemical processes (Rockhold et al., 2004), epidemic evolution
may be indicative of particle interaction within the intact sus- (Bertuzzo et al., 2008), and the spread of diseases in general
pension, lessening the impact of trace artifacts, that is, dust, (Khilar and Fogler, 1984; McDowell-Boyer et al., 1986; Kia et al.,
bubbles, suspension heterogeneity due to particle segregation, 1987; Ryan and Elimelech, 1996; Kretzschmar et al., 1999; de
and filtration artifacts that can bias sizing methods such as Jonge et al., 2004a; McCarthy and McKay, 2004; Tufenkji, 2007).
SEM and DLS. The applicable sizing range is much larger than Submicron-size colloids have been insufficiently studied in the
light-scattering methods, that is, ≈5 nm–1000 μm. It is also less past because methods for their isolation, detection, and char-
biased with respect to larger particles, making it more suit- acterization have been inadequate, with the exception of a few
able for complex polydisperse systems. Acoustic methods are examples (Kaplan et al., 1993; Kretzschmar et al., 1993; Chanudet
insensitive to sample convection, allowing stirring or agitation and Filella, 2006). However, with the new fractionation methods
of the sample during analysis as required for reactive titration and the coupling with low detection limit analytical instruments
(e.g., Sun et al., 2006) or for the characterization of low charge, (FFF-ICP-MS), a new era in the characterization of soil colloids
15-8 Properties and Processes

is commencing (Chittleborough et al., 2004; Ranville et al., 2005; physical adsorption. Physical adsorption is characterized by
Lead and Wilkinson, 2007). low heats of adsorption without structural changes at the sur-
Despite the new advances in the characterization and analy- face, fully reversible and rapid reactions since no activation
sis of colloids, many unanswered questions exist in regard to in energy is required, coverage of the entire surface rather than
situ colloidal behavior in natural environments, in particular, specific sites, little or no adsorption at elevated temperatures,
the chemical nature of colloids present and their structure, size, and potential coverage by more than one layer of adsorbate
and shape distributions (Filella et al., 1997; Lead and Wilkinson, (Lowell, 1979). Chemisorption is characterized by high heats of
2007). New methods of in situ visualization of colloids in porous adsorption, localization of adsorption at specific surface sites,
media are the research focus of several recent publications; light and irreversible reaction. The term “specific surface area” has
transmission and epifluorescent microscopy are some of the been used to denote the surface area of a material expressed on
new techniques developed by Crist et al. (2004) and Baumann a mass basis (m2 g−1).
and Werth (2004) for the observation and modeling of colloidal
transport in porous media. 15.1.3.2.2  Gas Adsorption Using the BET Equation
The BET equation is commonly used in conjunction with physi-
15.1.3.2  Surface Area cal gas adsorption to measure surface area. The BET equation is
Surface area must be regarded as a relative term, in as much as named after Brunauer, Emmett, and Teller (1938), who extended
it is scale dependent, as well as often dependent on the chemical the Langmuir theory for monolayer gas adsorption to multi-
and physical conditions of a system. Determinations of surface layer adsorption. The Langmuir equation (Langmuir, 1918) is
area range from particle size calculations assuming smooth sur- given by:
faces and simplified geometry, generally termed geometric surface
area, to possible molecular level calculations based on the dis- P 1 P
= + (15.4)
tances between surface ions in a mineral structure. Because the V kVm Vm
measurement is scale and system dependent, there is no univer-
sally accepted way to measure surface area. Determination as to where
which measurement system to utilize should consider the scale P is the pressure
and chemical conditions required by the application. Kinetic V is the volume of gas adsorbed per kilogram of adsorbent at
reactions that are diffusion controlled should likely consider geo- that pressure
metric surface area, while surface-controlled reactions (such as k is a constant
some adsorption and some dissolution/precipitation reactions) Vm is the volume of gas adsorbed per kilogram of adsorbent at
should consider surface area at the scale of the reacting molecule. monolayer surface coverage
In most instances, surface area is related to surface reactivity,
either adsorption or surface-controlled kinetic processes. The surface area is obtained by determination of 1/Vm, which is
15.1.3.2.1  Measurement Methodology the slope of the P/V versus P plot. The specific surface area is then
equal to 1/Vm multiplied by the cross-sectional area of the adsor-
The results of surface area determinations must be interpreted bate and the number of molecules in volume Vm.
within the context of the size and orientation of the adsorbate, The BET relation assumes that there is a dynamic equilibrium
as well as the attractive forces between the surface and the adsor- between the molecules in the various layers such that the num-
bate. This distinction is particularly important for clays such as ber of molecules in each layer remains constant, although differ-
smectites, which can be considered to have internal as well as ent sites may or may not be occupied at any given time. Use of
external surface area. Internal surface area is representative of the equation enables calculation of the number of molecules in
the surface area of the interlayers. Inert gases such as N2 are not a monolayer despite the fact that complete monolayer coverage
able to enter the interlayer positions, and thus, measure only may not have occurred. The BET equation is written as (Lowell,
external surface area of clay particles. In contrast, polar mol- 1979):
ecules such as ethylene glycol, ethylene glycol monoethyl ether
(EGME), and water are able to cause expansion of the layers and
1 1 C −1 P
penetrate into interlayer positions. Use of such molecules results = + (15.5)
in measurement of internal and external surface area. Since W[P0 /P ] WmC WmC P0

water is the solvent in environmental systems, these total sur-
face area measurements are appropriate for adsorption studies. where
Soil surface area measurements obtained using N2, water, and P is the adsorbate gas pressure
EGME were highly correlated with each other and with clay con- P0 is the adsorbate pressure at saturation for the temperature
tent when considering soils with similar mineralogy but not for of the experiment
soils with differing mineralogy (de Jong, 1999). W is the weight adsorbed in the monolayer
To characterize adsorption methods of surface area deter- Wm is the weight adsorbed in the complete monolayer
mination, it is useful to distinguish between chemical and C is the BET constant
Soil Colloidal Behavior 15-9

Multipoint BET plots are created by plotting 1/(W(P0/P − 1)) to nonpolar molecules until at least two layers of water are pres-
on the y axis and P/P0 on the x axis. The value of Wm is calcu- ent (Quirk and Murray, 1991).
lated from the slope and intercept. The specific surface area is
determined by dividing the total surface area by the sample 15.1.3.2.3  Organic Molecules
weight. The region of P/P0 between 0.05 and 0.35 is usually lin- 15.1.3.2.3.1  Ethylene Glycol  Ethylene glycol was utilized by
ear and within the region of pressures corresponding to suffi- Dyal and Hendricks (1950) for determination of total surface
cient adsorption to complete monolayer coverage, and thus, best area of clays. The method consists of adding excess ethylene gly-
suited for determination of Wm (Lowell, 1979). col to soil or clays and allowing the excess to evaporate under
Often the BET surface area can be determined from a single vacuum. It is assumed that when the rate of weight loss of the
pressure measurement without much loss of accuracy. For rela- sample decreases, only a monolayer of ethylene glycol remains.
tively high values of C, the intercept value is small relative to the Dyal and Hendricks (1950) calibrated the method assuming a
slope and can be approximated by zero. The BET equation is thus bentonite surface area of 810 m2 g−1 and calculated that 0.31 mg of
reduced to (Lowell, 1979): adsorbed ethylene glycol corresponded to each square meter of
surface area. The method was modified by Bower and Goertzen
⎛ P ⎞ (1959) using CaCl2-monoglycolate to maintain an ethylene gly-
Wm = W ⎜ 1 − ⎟ (15.6) col vapor pressure just below that of the saturation vapor pres-
⎝ P0 ⎠
sure. In this method, the sample and the liquid are placed in
separate open vessels in an evacuated system and the sample is
Soil and mineral surface areas are most commonly measured by weighed until it is in equilibrium with the vapor pressure of the
N2 adsorption, using the BET equation. The calculation is made ethylene glycol.
using the N2 cross-sectional area of 0.162 nm2 (Gregg and Sing,
15.1.3.2.3.2  Ethylene Glycol Monoethyl Ether  Ethylene glycol
1982). Often this area is referred to as the effective or occupied
monoethyl ether (EGME) has replaced ethylene glycol as the
area. Alternatively for surface area <1 m2 g−1 the use of Kr is
polar solvent of choice for determination of surface area. Since
recommended.
EMGE has a higher vapor pressure than ethylene glycol, it
Most commonly, the BET method consists of adsorption of
requires a shorter reaction time to equilibrate the sample (Carter
N2 at a fixed partial pressure P in a He–N2 mixture and mea-
et al., 1986). A solvate of EGME and CaCl2 is used in the evacu-
surement of the desorbed N2 in a pure He gas stream using gas
ated chamber to lower the vapor pressure of EGME to just below
chromatography. Alternative methods include measurement of
the saturation pressure. Open vessels of EGME/CaCl2 and soil
the mass of N2 adsorbed. In this method, the sample is evacu-
are placed in the chamber and the soil is periodically weighed
ated to high vacuum, heated, then cooled to liquid N2 tempera-
until no further weight gain is observed. It is assumed that the
ture, and weighed. Quantities of N2 are then added to the system
EGME surface coverage is 5.2 × 10−19 m2 per molecule and that
and a series of weighings is made at various pressures. In this
0.286 mg adsorbed corresponds to 1 m2 of surface area (Carter
instance, the N2 partial pressures are equal to the total pressure
et al., 1986). The method is limited in that the EGME affinity
in the system.
for cations results in greater than monolayer coverage at those
Surface area can also be determined from the sorption of
sites, the assumption that EGME covers all surfaces cannot be
water at one or more vapor pressures (Newman, 1983). In this
properly evaluated, and the large size of the molecule may pre-
instance, air-dried samples are reacted in evacuated desiccators
vent coverage in small surface voids. A serious reservation of
containing saline solutions with relative vapor pressures on the
the procedure is the assumption that the average EGME occu-
order of 0.2–0.4. Samples are equilibrated until there is no fur-
pancy of smectite surface applies equally well to all soil surfaces,
ther weight change, then samples are dried at 105°C and weighed
regardless of mineralogy (Tiller and Smith, 1990). These authors
again. Sorbed water is taken as the difference between the oven-
found that more EGME was retained per unit area by nonex-
dry weight and the desiccator-equilibrated weight. Surface area
panding soil clays such as illites and kaolinites than by smec-
is then calculated as with N2, using Equation 15.5. This method
tites resulting in an overestimation in surface area of 50%–100%
gives values comparable to EGME values for nonexpanding
when using smectite as a reference. Measurement of total surface
clays but underestimates surface area for smectites due to lim-
area of soils with mixed mineralogy using EGME and a single
ited water uptake in the interlayers (de Jong, 1999). For smec-
conversion factor based on smectite leads to significant under-
titic soils, de Jong (1999) recommended using the Langmuir
and overestimation of surface area of many soils, even including
equation (monolayer) for water sorption indicating that the
smectitic soils (Tiller and Smith, 1990).
reduced BET equation (Equation 15.6) is not applicable because
interlayer water uptake is limited. de Jong (1999) demonstrated 15.1.3.2.3.3  Methylene Blue  Methylene blue, an organic cation,
a correspondence close to 1:1 between surface area determined is reacted at various concentrations with soil suspensions (typi-
with EGME using the BET equation and with water using the cally with organic material removed) under pH-buffered con-
Langmuir expression. It can be argued that water sorption val- ditions. Measurement of methylene blue concentration before
ues may be more realistic than EGME values (Pennell et al., and after reaction with soil is made spectrophotometrically at a
1995), since the interlayer spaces of smectites are not accessible wavelength of 665 nm. The adsorbed concentration of methylene
15-10 Properties and Processes

blue is used to calculate surface area assuming an area of 1.3 nm2 where

per methylene blue molecule (Hang and Brindley, 1970). This Iq is the scattering intensity
surface area corresponds to the molecule attaching parallel to A is a proportionality constant
its long axis. This method can only be used in hydrated systems. B is the background correction
Aringhieri et al. (1992) found surface areas determined with
methylene blue to be unrealistically lower than those obtained Values of Ds obtained for soils using this method are in relatively
with water adsorption and suggested that the major limitation of good agreement with values calculated from gas adsorption sur-
the method is its dependence on the soil surface charge charac- face area (a) for soil particle radii (r) using the relation (Borkovec
teristics. Alternatively, Borkovec et al. (1993) obtained relatively et al., 1993):
good agreement between methylene blue and N2 BET surface
areas for four soil samples assuming a methylene blue surface a = C λ 2 − Ds r Ds − 3 (15.8)

area of 0.247 nm2, corresponding to a molecular attachment
of methylene blue perpendicular to its long axis. Orientation
where
of the organic molecules may be related to surface site char-
λ is the size of the probing molecules
acteristics, as well as concentration of adsorbing molecules.
C is the proportionality constant
These differences illustrate one of the disadvantages of using
charged molecules for surface area determination; their use is
not recommended. 15.1.3.2.6  Negative Adsorption
Negative adsorption refers to a deficiency in the concentration of
15.1.3.2.4  Electron Microscopy Image Analysis
an ion in solution adjacent to a solid surface relative to the con-
Transmission electron microscopy as well as SEM can be used for centration of the ion in the bulk solution. The deficit is caused
determination of geometric surface area using a variety of meth- by electrostatic repulsion between ions and surfaces of simi-
ods, including calculation of planar surface area and assump- lar charge. Since most charged surfaces in soils are negatively
tions regarding geometry to calculate total external surface charged, negative adsorption usually relates to solution anion
area. With this method, only edge roughness can be measured. concentrations and negative surfaces. For a 1:1 electrolyte, the
The SEM method, which offers the possibility of measuring the diffuse double layer model produces the following approxima-
external surface roughness, consists of collecting two images tion (Sposito, 1984):
at different sample tilt angles and constructing a three-dimen-
sional representation of the surface. Surface area is calculated 2
within a grid of fixed lines by summation of the planar surfaces de ≈ −δ (15.9)
βc
in the grid. The ratio of the calculated surface to the area within
the grid gives a measure of surface roughness. Measurements
can also be made at different scales, providing information where
about the size distribution of the surface features. Since these de is the exclusion distance
measurements are typically made at the micrometer scale, and c is the concentration of the bulk electrolyte
measure external surface area, it is not surprising that the values β is a constant equal to 1.08 × 1016 m mol−1
are intermediate between geometric surface areas based on par- δ is the distance between two planes
ticle size and BET values. Determination of specific surface area
requires conversion of particle surface area to a mass basis using The exclusion volume and area (Se) are related by
the particle density. The assumption that the particle density is
equal to the density of specimen samples of the mineral is rea- Ve = Sede (15.10)
sonable and introduces relatively minor errors in comparison to
other assumptions made in the calculation. Increasing computer where Ve is the exclusion volume (the hypothetical volume
capacity and suitable software makes this method the most use- from which the ion is completely excluded). Substituting into
ful of the geometric methods. Equation 15.9 yields

15.1.3.2.5  Small Angle X-Ray Scattering 2Se

Ve ≈ − δSe (15.11)
In this application, Kα radiation from a conventional x-ray tube βc

is scattered by freeze-dried samples in glass capillary tubes.
The background-corrected x-ray-scattering intensity is plotted
The exclusion volume is calculated by first removing the bulk
against the scattering vector (q) to obtain the apparent surface
solution, determining the remaining liquid volume, displacing
fractal dimension (Ds) using the relation (Borkovec et al., 1993):
the liquid, and analyzing for the bulk solution and extract con-
centration. The exclusion volume is then equal to the mass deficit
I q = Aq Ds −5 + B (15.7) in the extract divided by the concentration in the bulk solution.
Soil Colloidal Behavior 15-11

A plot of Ve vs. c−0.5 should yield a straight line whose slope is This definition is similar to the one provided by Sposito (1984)
proportional to the exclusion specific surface area as shown by with the exception that total net surface charge results from iso-
inspection of Equation 15.11. morphic substitution and is generated by specifically adsorbing
This method was first described by Schofield (1949), who ions (Hunter, 1981). An inner-sphere surface complex contains
used it to determine montmorillonite surface area from reac- no water between the adsorbing ion and the surface functional
tions with NaCl, NaNO3, and Na 2SO4 solutions. Subsequent group; while an outer-sphere surface complex contains at least
work by Edwards et al. (1965a, 1965b) demonstrated that the one water molecule between the adsorbing ion and the surface
specific surface area determined with this method varied with functional group (Sposito, 1984). Examples of surface functional
cation selected. Calculated values for illites ranged from values groups are reactive surface hydroxyl groups on oxide minerals,
close to the N2 BET values with Li to 0 with Cs. In contrast, for aluminol and silanol groups on clay minerals, and carboxyl and
montmorillonite, LiCl exclusion volumes were 10 times greater phenol groups on SOM.
than N2 BET surface areas, while Cs values were comparable
to those obtained by N2 BET. Trends in surface area values 15.1.3.3.1  Measurement Methodology
measured using anion exclusion for Li, Na, K, NH4, Cs, and The total net surface charge can be measured directly using
Ca-montmorillonites were in agreement with those calculated electrokinetic experiments. The point of zero charge (p.z.c.) of a
from a tactoid model (Schramm and Kwak, 1982a, 1982b). particle is the solution pH value where total net particle charge
is zero. The p.z.c. can be measured directly using electrokinetic
15.1.3.2.7  Applications
experiments or indirectly from potentiometric titrations under
Surface area measurements are required for a variety of calcula- certain experimental conditions (Sposito, 1984).
tions. In most soils, the bulk soil surface area is dominated by Electrokinetic phenomena are processes where a relative
the surface area of the clay minerals. Surface charge density, velocity exists between two parts of the electrical double layer
which requires measurement of both surface area and par- (Hiemenz, 1977; Hiemenz and Rajagopalan, 1997). In this
ticle charge, has been related to cation exchange selectivity. As motion, a thin layer of liquid remains with the solid and a shear
expected, increasing surface charge density favors adsorption plane is located between the solid and liquid phases at some
of the higher valence cation in heterovalent exchange (Maes distance from the solid surface (van Olphen, 1977). The electric
and Cremers, 1977). Surface charge density is also required for double layer potential at the shear plane is called the zeta poten-
calculation of double layer thickness and for use in a variety of tial (ζ). The assumption that ζ is equal to or very close to the dif-
adsorption relationships. Determination of specific surface area fuse double layer potential (ψd) is supported indirectly by a large
is required for chemical studies on many different minerals. In body of data on a variety of surfaces (Hunter, 1981, 1989). The
this case, bulk surface area is not appropriate. Controlled labora- principle electrokinetic phenomena that measure zeta potential
tory studies are often performed using addition of quantities of are discussed later.
a well-­characterized mineral having a known surface area. This
method is used to study a variety of chemical reactions, such 15.1.3.3.2  Electrophoresis
as kinetics of calcite, gypsum, and dolomite dissolution, sur- Electrophoresis measures the movement of a suspended charged
face area of calcite for prediction of phosphate adsorption, and particle in response to an applied electric field. This move-
addition of various Fe or Mn oxides for study of adsorption and ment is called electrophoretic mobility (μE) and is given by the
redox processes. Among the various applications of the EGME Smoluchowski equation (Hunter, 1989):
method, Ross (1978) related shrink/swell properties of soils to
surface area and Supak et al. (1978) related the specific surface εζ
area of clays to the adsorption of the pesticide aldicarb. μE = (15.13)
η
15.1.3.3  Surface Charge
The total net surface charge on a particle (Φp) is where
ε is the relative permittivity

σ p = σ s + σ H + σis = σos − σd
(15.12) η is the viscosity

where The Smoluchowski equation applies when the particle dimensions

σs is the permanent structural charge are much greater than the double layer thickness (Hunter, 1987).
σH is the proton surface charge resulting from the specific The complete formula relating ζ and μE is derived by the theoreti-
adsorption of protons and hydroxyl ions cal evaluation of the electric force on the charged particle ( f1), the
σis is the inner-sphere complex charge resulting from specific hydrodynamic frictional force on the particle by the liquid ( f2), the
ion adsorption electrophoretic retardation force ( f3), a frictional force resulting
σos is the outer-sphere complex charge resulting from non- from the movement of water with the counterions, and the relax-
specific adsorption ation force ( f4), caused by distortion of the double layer around
σd is the dissociated charge the particle (van Olphen, 1977). Additional considerations arise
15-12 Properties and Processes

for nonspherical particles and those carrying two double layers one measures either (1) the colloid vibration potential (CVP) or
such as clays. For these reasons, the Smoluchowski equation is, colloid vibration current (CVI), the induced dipole moment cre-
in general, only approximate and it is advisable to report electro- ated by the displacement or polarization of the electrical double
phoresis results as electrophoretic mobility rather than to attempt layer in response to an acoustic wave, or (2) the electrokinetic
to convert to zeta potential (van Olphen, 1977). sonic amplitude (ESA) generated by the movement of a charged
Electrophoresis is the most common method of determin- particle in response to an electrical field as indicators of colloi-
ing zeta potential. For colloidal systems, the most appropri- dal zeta potential. The individual dipole moments created by the
ate technique is microelectrophoresis where the movement of interaction of sound waves with a colloidal suspension can be
individual particles is followed directly by microscopy (Hunter, measured as an alternating electrical field that varies with the
1981). Microelectrophoresis is only applicable at very low par- amplitude of the sound wave. Conversely, the electrophoretic
ticle concentrations. Electrophoresis can also be studied using movement of charged particles in response to an applied elec-
laser Doppler velocimetry and photon correlation spectroscopy. trical field gives rise to sound waves, known as the ESA effect.
The mass transport mobility apparatus measures electrophoretic Although electroacoustic spectroscopy can provide PSD, such
mobility from the mass of colloids transported to a suitable elec- information is best derived from the conventional acoustic spec-
trode compartment (Hunter, 1981). This apparatus can be used at tra (Dukhin and Goetz, 2002; Seaman et al., 2003).
much higher particle concentrations than microelectrophoresis. In contrast to microelectrophoretic light-scattering methods,
electroacoustic measurement of zeta potential can be conducted
15.1.3.3.3  Electroosmosis at much higher suspension concentrations (30%–50% solids),
Electroosmosis measures the movement of the liquid adjacent an obvious advantage given that sample dilution and changes
to a flat, charged surface in response to an electric field applied in solution chemistry can impact the expression of zeta poten-
parallel to the surface. This movement is called electroosmotic tial and apparent particle size (Dukhin et al., 2001; Dukhin and
velocity (veo) and is also obtained from the Smoluchowski equa- Goetz, 2002; Delgado et al., 2005). Acoustic methods have been
tion (Hunter, 1987): used to evaluate shifts in the isoelectric point (IEP) of materials
at high-ionic strengths as indicators of specific and nonspecific
−εζE sorption mechanisms (Kosmulski, 2002; Kosmulski et al., 2002;
veo = (15.14)
η Greenwood, 2003). Such applications are best used in combina-

tion with other surface active spectroscopic methods for deter-
mining sorption mechanisms. In comparing various techniques
where E is the electric field strength. While it is possible to mea-
for evaluating the IEP and p.z.c. of Fe (hydr)oxides, Kosmulski
sure electroosmotic velocity directly using microscopy, it is
et al. (2003) noted that electroacoustic methods produced higher
more common to measure the volume of liquid transported per
IEP values than observed for potentiometric titration methods.
unit time (Hunter, 1981):
The cause of the discrepancy was not discussed.
V εζ 15.1.3.3.5  Streaming Potential
= (15.15)
i ηλ 0
The streaming potential is an electric potential difference gener-
ated when liquid adjacent to a charged surface is set in motion
where by an applied pressure gradient (Hunter, 1987). The streaming
V is volume potential (Φst) is also governed by the Smoluchowski equation
i is the electric current and given by (Sposito, 1984)
λ0 is the electrical conductivity
εζ
Φ st = ΔP (15.16)
The material whose zeta potential is being measured is formed λ 0η
into a porous plug and the transport of liquid across a tube in
response to an electric field may be obtained by measuring the where ΔP is the applied pressure difference. The streaming
movement of an air bubble in the capillary providing the return potential can be measured in similar fashion as the electroos-
path (Adamson, 1976). It is also possible to measure the elec- motic velocity. Liquid is forced under pressure through a porous
troosmotic flow by applying a counter pressure until the flow is plug and Φst is measured by electrodes in the solution on either
exactly compensated (Hunter, 1981). end (Adamson, 1976).

15.1.3.3.4  Electroacoustic Spectroscopy 15.1.3.3.6  Sedimentation Potential

A general discussion of the application of acoustic spectroscopy When particles having charged surfaces settle in a liquid under
for characterizing colloidal suspensions was presented earlier in the force of gravity, a plane of shear is developed. As the particles
this chapter (Section 15.1.3.1). Both acoustic and electroacoustic settle, the interfacial charge is separated since a portion inside
spectrometers are commercially available separately or com- the shear plane moves with the particle and the remainder is left
bined in a single instrument. In electroacoustic spectroscopy, behind (Sposito, 1984). An electric potential difference arises
Soil Colloidal Behavior 15-13

from the separation of charge called the sedimentation poten- dissolution of solid phases, or complexation with surfaces whose
tial. The gradient for the sedimentation potential, dΦsed, is given charge is not pH dependent (Parker et al., 1979). Without these
by (Sposito, 1984) corrections, no surface chemical significance can be provided by
Equation 15.19. A detailed description of the use of potentiometric
dΦ sed εζ titration to determine surface charge is provided by Huang (1981).
= nΔρg (15.17)
dz λ 0η
15.1.3.3.8  Applications
where One of the most important applications of electrokinetic experi-
n is the number of particles per unit volume ments and potentiometric titrations is the determination of the
Δρ is the difference in mass density between the particles and p.z.c. A characteristic of variable charge minerals is the p.z.c.
the liquid phase obtained in the presence of an inert electrolyte. This p.z.c. is
g is gravitational acceleration determined electrokinetically as the pH value where the zeta
z is distance potential is zero or indirectly from the point of zero net proton
charge (p.z.n.p.c.) or from the point of zero salt effect (p.z.s.e.)
The potential difference is measured by inserting reversible elec- obtained potentiometrically. The p.z.n.p.c. and the p.z.s.e. are
trode probes at two different heights in the column of settling discussed in detail in Chapter 16. The p.z.n.p.c. and the p.z.s.e.
particles (Hunter, 1981). For low particle concentration, the sedi- are equivalent to the p.z.c. in the absence of surface complex
mentation potential is also governed by the Smoluchowski equa- formation. Table 15.4 provides characteristic values of p.z.c.
tion (Hunter, 1981). obtained using electrokinetic experiments and potentiometric
titrations for a variety of variable charge minerals.
15.1.3.3.7  Potentiometric Titration
Potentiometric titration measures the surface density of proton TABLE 15.4  Representative Points
surface charge (σH) defined as (Sposito, 1984) of Zero Charge for Various Minerals
Solid p.z.c.
F
σH = (qH − qOH ) (15.18) Electrophoresis
A
Goethite 8.8
Hematite 8.5
where
Magnetite 6.9
F is the Faraday constant
Amorphous iron oxide 8.0
A is the specific surface area
Gibbsite 9.8
qH is the complexed proton charge (mol)
Bayerite 9.2
qOH is the complexed hydroxyl charge (mol) per unit mass of
Boehmite 9.4
solid
Pseudoboehmite 9.2
Amorphous aluminum oxide 9.3
Titration data consist of pH readings obtained while known
δ-MnO2 2.3
amounts of acid or base are added to a solid suspension. A net
Rutile 4.8
titration curve is obtained by subtracting a calibration curve
Anatase 5.9
obtained by titrating the equivalent supernatant solution. The
Kaolinite 2.9
values of qH − qOH are given by (Sposito, 1984)
Streaming potential
C A − C B − [H ] + [OH ]
+ − γ-Al2O3 9.1
qH − qOH = (15.19) α-Al2O3 9.2
Cs
Titration
where Goethite 8.7
CA is the molar concentration of acid added Hematite 8.6
CB is the molar concentration of base added Magnetite 6.9
[H+] is the molar proton concentration Gibbsite 9.8
[OH−] is the molar hydroxyl concentration obtained from pH Boehmite 8.5
measurement Pseudoboehmite 9.3
Amorphous aluminum oxide 9.5
Cs is the particle concentration
δ-MnO2 3.6
SiO2 3.0
In order for Equation 15.19 to be valid, added protons and hydroxyl
Rutile 5.8
ions must only react with surface-reactive functional groups
Anatase 6.0
whose charge is pH dependent. Usually, other reactions that are
Kaolinite 2.9
also pH dependent occur, such as soluble complex formation,
15-14 Properties and Processes

4 100
0 ppm Mo
Electrophoretic mobility (μm s–1 V cm–1)

28 ppm Mo
3

Proportion of dispersed clay (%)

48 ppm Mo 80
100 ppm Mo
2
60

1
40

0
20 Kaolinite
Illite
–1 Smectite
0
–20 –25 –30 –35 –40 –45
–2
1 2 3 4 5 6 7 8 9 10 11 12 Zeta potential (mV)

FIGURE 15.1  Shifts in p.z.c. and charge reversal of gibbsite in the FIGURE 15.2  Relation between zeta potential and dispersible clay
presence of molybdate. (Adapted from Goldberg, S., H.S. Forster, and of Na-clay minerals obtained using electrophoresis. (Reprinted from
C.L. Godfrey. 1996. Molybdenum adsorption on oxides, clay minerals, Chorom, M., and P. Rengasamy. 1995. Dispersion and zeta potential of
and soils. Soil Sci. Soc. Am. J. 60:425–432.) pure clays as related to net particle charge under varying pH, electrolyte
concentration and cation type. Eur. J. Soil Sci. 46:657–665. With per-
Electrokinetic experiments and potentiometric titrations can be mission of Blackwell Science Ltd.)
used to infer adsorption mechanisms for adsorbing ions on sur-
faces. Adsorption of ions that form inner-sphere surface complexes –150
is characterized by shifts in the p.z.c. of the particles and reversals
of their electrophoretic mobility with increasing ion concentration
(Hunter, 1981). Adsorption of ions that form outer-sphere surface
complexes does not produce p.z.c. shifts since they are assumed
to lie outside the shear plane. Figure 15.1 presents the shifts in
p.z.c. and charge reversals observed for gibbsite upon the specific –100
Zeta potential (mV)

adsorption of increasing amounts of molybdate. These results are

indirect evidence for inner-sphere surface complexation of this ion.
Net particle surface charge is a primary factor in dispersion of
clay minerals. Zeta potential as a measure of particle surface charge
was also related to percentage of dispersible clay (Chorom and
Rengasamy, 1995). Figure 15.2 indicates the relationship between –50
zeta potential measured using electrophoresis, and dispersible clay
for Na-saturated kaolinite, montmorillonite, and illite.
The plane interface technique determines the electroosmotic Silica–silica system
velocity at large plane interfaces and can be used to determine Mica–silica system
the zeta potential of two different surfaces at the same time
0
under the same conditions (Nishimura et al., 1992). These 2 4 6 8 10
authors used the plane interface technique to simultaneously pH
study silica plates and muscovite mica basal planes. The zeta
potential values for silica presented in Figure 15.3 indicate that FIGURE 15.3  Zeta potentials as a function of solution pH for muscovite
mica basal plane– and silica plate–aqueous solution interfaces obtained
the asymmetric silica–mica cell provides results comparable to
using electroosmosis. (Reprinted from Nishimura, S., H.  Tateyama,
those of the symmetrical silica–silica cell.
K. Tsunematsu, and K. Jinnai. 1992. Zeta potential measurement of mus-
Zeta potentials of clay minerals have also been determined covite mica basal plane-aqueous solution interface by means of plane
using a flat plate streaming potential apparatus for muscovite interface technique. J. Colloid Interface Sci. 152:359–367. With permis-
mica (Scales et al., 1990), saponite, and hectorite (Nishimura sion of Academic Press, Inc.)
et al., 2002a). Zeta potential of clays becomes less negative
with increasing electrolyte concentration as a result of double found to be dependent on the salt concentration of the permeat-
layer compression (Figure 15.4). The resulting charge reduction ing solution (Heister et al., 2005).
causes clay flocculation. Streaming potential measurements of A vastly different application of electrokinetic experiments
sodium montmorillonite using a flexible wall permeameter were is the application to dewatering and decontamination of soils
Soil Colloidal Behavior 15-15

0
CaCl
–20 KCl Phase
NaCl
LiCl
–40
Zeta potential (mV)

Interfacial
Gibbs
–60
surface
Region
–80

–100
Phase

–120

FIGURE 15.5  Representation of the interfacial region and the Gibbs

–5 –4 –3 –2 –1 surface.
Log (electrolyte conc.) [mol m–2]
Volume: V = V α − V β
FIGURE 15.4  Relation between zeta potential and electrolyte
concentration for various 1:1 electrolytes obtained from streaming Internal Energy : E = E α + E β + E σ
(15.20)
potential. (Reprinted with permission from Scales, P.J., F. Grieser,
Entropy : S = S α + Sβ + S σ
and T.W. Healy. 1990. Electrokinetics of the muscovite mica–aqueous
solution interface. Langmuir 6:582–589. Copyright 1990 American Moles : ni = ni α + ni β + ni σ

Chemical Society.)
where
α and β denote the bulk phases
and clays. For example, electroosmosis has been used for
σ denotes the Gibbs surface (Adamson, 1976)
removing organic contaminants from kaolinite and soil clays
(Shapiro and Probstein, 1993; Schultz, 1997; Kim et al., 2001).
Additional variables of state are defined as the surface tension
These authors present applications for in situ hazardous waste
or surface free energy (γ) and the area of the Gibbs surface (A).
remediation of soils. Economic analysis indicated that electro-
The three fundamental thermodynamic relationships of
osmosis compared favorably with the cost of excavation and
surface chemistry are the Young–Laplace equation, the Kelvin
ex situ treatment (Schultz, 1997).
equation, and the Gibbs equation (Adamson, 1976). The Young–
A potentiometric titration method has been developed to
Laplace equation is the fundamental equation of capillarity for a
account for changes in solubility of the solid with changes in pH
curved Gibbs surface:
(Schulthess and Sparks, 1986). This is a batch method where the
reference for each sample is the supernatant specific to that sam- ⎛1 1⎞
ple back titrated to pH 7. This method is considered to account Pβ − P α = γ ⎜ + ⎟ (15.21)
⎝ r1 r2 ⎠
for all sources of proton consumption (Schulthess and Sparks,
1986). where
Pβ − Pα is the capillary pressure
15.1.4  Thermodynamics of Colloid Surfaces r1 and r2 are the radii of curvature

To develop the thermodynamic treatment of the surface region, The Kelvin equation gives the effect of surface curvature on
a few definitions are useful. The interfacial region is a space the molar free energy of a substance. The free energy of a sub-
between two adjoining phases (gas–liquid, gas–solid, liquid–­ stance can be related to its vapor pressure assuming the vapor to
liquid, liquid–solid, solid–solid), which is characterized by inho- be ideal (Adamson, 1976). The Kelvin equation is
mogeneity in its properties. The Gibbs surface is a mathematical
dividing surface, without volume, drawn parallel to the bound- ⎛ P ⎞ γV ⎛ 1 1 ⎞
ln ⎜ ⎟ = ⎜ + ⎟ (15.22)
aries of the interfacial region, which is used to define the volumes ⎝ P0 ⎠ RT ⎝ r1 r2 ⎠

of the two adjoining bulk phases. A schematic of the interfa-
cial region and the Gibbs surface is presented in Figure 15.5. where
The actual values for the system as a whole will differ from the P0 is the normal vapor pressure of the liquid
sum of the values for the bulk phases by an excess or deficiency P is the vapor pressure observed over the curved surface
due to the Gibbs surface (Adamson, 1976). The following rela- R is the molar gas constant
tions hold for the variables of state: T is temperature
15-16 Properties and Processes

For a small, reversible change dE in the energy of the system

(Adamson, 1976)

dE = dE α + dE β + dE σ

Ion concentration, C
= TdS α + ∑ μ dn i i
α
− P αdV α + TdSβ c΄,

+ ∑ μ dn
i i
β
− P βdV β + TdS σ + ∑ μ dn i i
σ
− P σdV σ + γdA
c΄,= c΄,= c΄
c΄, c΄,
c΄,
(15.23) c,΄
c,΄ c,΄ c,΄= c,΄= c΄

where μi is chemical potential. Substituting for dE α and dE β c c

c, c, = c, = c c, c, = c, = c
and manipulating the equation for dE σ lead to the expression 0 0
0 x 0 x
(Adamson, 1976) (a) (b)

FIGURE 15.6  Distribution of ions in the electric double layer at

S αdT = Ad γ + ∑n dμ = 0
i
σ
i (15.24)
two electrolyte concentrations (c′ > c). (a) Constant potential surface.
(b) Constant surface charge. (Adapted from van Olphen, H. 1977. An
At constant T and A, the Gibbs equation is introduction to clay colloid chemistry, 2nd Ed. John Wiley & Sons,
New York.)
ni σ

−d γ = ∑ A
dμi = ∑Γ i
σ
dμi

(15.25) where
ψ(x) is the inner potential at a distance x from the surface
ε0 is the permittivity of free space
where Γ i σ is a surface excess concentration per unit area defined D is the dielectric constant of water
as Γ i σ = ni σ /A. The Gibbs equation can be applied to ­liquid–liq- c is the concentration
uid and liquid–vapor interfaces where the surface tension can be R is the gas constant
measured to calculate the surface concentration of the adsorbed T is the temperature (K)
species causing the surface tension change. Similarly, if the sur- F is the Faraday constant
face concentration can be measured directly but the surface zi is the valence of the charged species (Sposito, 1984)
tension cannot, the Gibbs equation can be used to calculate the
lowering of γ from the measured adsorption in solid–gas and Figures 15.6 and 15.7 present the ion distribution and the elec-
solid–liquid systems (Hunter, 1987). tric potential distribution, respectively, in the double layer at two
electrolyte concentrations. The extent of the double layer is given
15.2  Interparticle Forces by the distance (1/κ) in units of meters:

15.2.1  Electrical Double Layer 1 ε0 RT

= (15.27)
Double layer theory describes the distribution of ionic concen- κ 2000F 2 I
trations near electrostatically charged particles. The charge on
the colloidal particles is due to isomorphic substitution in the
particle lattices or arises from the preferential adsorption of one
where I is the ionic strength = 1/2 ( ∑ c z ). Important findings
2
i i

of diffuse double layer theory are (1) the excess cations near
ionic species from the solution phase (Babcock, 1963). Such a
the negative surface neutralize more of the charge than the
charge requires the presence of a layer of ions of opposite charge.
anion deficit, (2) the electric potential decreases as the electro-
The double layer consists of an excess of ions of opposite sign
lyte concentration increases, and (3) the double layer distance
and a deficiency of ions of the same sign that are electrostati-
(1/κ) decreases as the electrolyte concentration increases. Some
cally repelled by the particle. Double layer theory assumes that
important limitations of double layer theory are that it applies
the surface of the colloidal particles is represented by an infinite
only to infinitely dilute suspensions and to low surface charge
flat surface having continuous and uniform electrostatic charge
densities (Babcock, 1963).
density immersed in an electrolyte with a uniform dielectric
constant (Babcock, 1963). All electrolyte ions are assumed to be
point charges. The electrical potential, ion charge, and ion distri- 15.2.2  Attractive Force
butions can be calculated from the Poisson–Boltzmann equation:
The attractive force acting on colloidal particles is called the
van der Waals force and acts to bring particles closer together.
d 2ψ 1
dx 2
=−
ε0D ∑ cFz exp (−z F ψ(x)/RT )
i i (15.26) The basis of the attractive force is that the fluctuating dipole
of one atom polarizes another one and the two atoms attract
Soil Colloidal Behavior 15-17

Retarded
–100
Electric potential

Force radius (μN/m)

–200

ed
Low concentration c

etard
–300
High concentration c΄

Nonr
–400
0
(a) 0 x
–500
0 5 10
Distance d (nm)
Electric potential

FIGURE 15.8  van der Waals forces between two mica surfaces in
aqueous electrolyte solutions. The measured Hamaker constant is
A  =  2.2 × 10−20 J. Retarded van der Waals forces are observed above
Low concentration c 5 nm. (Reprinted from Israelachvili, J.N. 1992. Intermolecular and sur-
face forces, 2nd Ed. Academic Press, San Diego, CA. With permission
High concentration c΄ of Academic Press Ltd.)
0
(b) 0 x 15.2.3  Repulsive Force
FIGURE 15.7  Electric potential distribution in the electric double The electrostatic force results from the charge on the colloidal
layer at two electrolyte concentrations. (a) Constant potential surface.
particles and acts to repel them. A force operates on charged sur-
(b) Constant surface charge. (Adapted from van Olphen, H. 1977. An
faces as a result of their interacting double layers. This force is
introduction to clay colloid chemistry, 2nd Ed. John Wiley & Sons,
New York.)
repulsive if the charges on the particles are the same. The repul-
sion described in terms of interaction energy per unit area (ΦR)
is given by the force times the distance through which it oper-
each other. This attraction between atom pairs is additive, and, ates (Hiemenz, 1977; Sposito, 1984; Hiemenz and Rajagopalan,
therefore, the energy of interaction between particles decreases 1997):
much more slowly with distance than that between individ-
ual atoms (Quirk, 1994). The interaction energy per unit area 64a2
between two opposing planar solids for the van der Waals force ΦR = − cRT exp(−z κd ) (15.30)
z
(ΦvdW) is (Israelachvili, 1992)
where
AH
Φ vdW = − (15.28) a = tanh(zψ0/4RT)
12πd 2
z is the charge on the electrolyte ions
c is the concentration of the electrolyte ions
where κ is the inverse double layer distance
AH is the Hamaker constant d is half of the surface separation
d is the distance separating the solid surfaces
This equation is valid only when the surface separation 2d >> 1/κ
At distances >5 nm, the correlations between the induced dipole and a ≈ 1. The electrostatic force between two plates for different
distributions weaken and the interaction energy per unit area electrolyte concentrations is presented in Figure 15.9.
corresponds to the retarded van der Waals force (ΦRvdW): When surfaces are brought closer together, an additional repul-
sive force becomes important. This force is called the solvation
BrH force or, when water is the medium, the hydration force. Solvation
Φ RvdW = − (15.29)
3d 3 forces are of short range and oscillatory and arise whenever liq-
uid molecules are induced to order between surfaces. Between
where BrH is the retarded Hamaker constant. Figure 15.8 shows colloid surfaces, repulsive hydration forces arise when water mol-
values of the van der Waals force obtained experimentally ecules strongly bind to hydrogen bonding surface groups such as
between two mica surfaces. Attractive forces were observed hydrated ions or hydroxyl groups (Israelachvili, 1992). The effec-
between mica particles in the range of 0.6–2 nm in CaCl2 solution tive range of hydration forces in clays and silicas is 3–5 nm. The
both experimentally and theoretically with statistical mechanics interaction of mica surfaces in dilute solution obeys double layer
and Monte Carlo simulations (Kjellander et al., 1990). theory, but at higher electrolyte concentration, a hydration force
15-18 Properties and Processes

Clay swelling is the result of double layer repulsion between

the surfaces of individual particles. Under confining conditions,
1000
a fluid pressure or swelling pressure is created that is a direct
measure of the balance of forces between particles (van Olphen,
500
1977). The swelling pressure is obtained by measuring the con-
0.0010 M
2 fining force that must be applied to keep the clay layers at a given
(K = 0.6 nm)
distance. The swelling pressure (Π) is
R (N m–2)

100 Π = PvdW + PR (15.31)

0.0032 M
0.0100 M (K 2 = 5.4 nm)
50
(K 2 = 3.0 nm) where
0.0060 M
PvdW is the van der Waals force
(K 2 = 4.3 nm)
PR is the electrostatic force (Greathouse et al., 1994)

10 At short distances, hydration forces become significant in the

10 20 30 40 50 60
swelling pressure. At greater distances, measured swelling pres-
2d (nm)
sures are of similar magnitude to calculated double layer repul-
FIGURE 15.9  Repulsive force between two plates for different con- sions (van Olphen, 1977).
centrations of a 1:1 electrolyte where κ is the inverse double layer dis- Interparticle forces can be measured experimentally using the
tance. (Reprinted from Hiemenz, P.C. 1977. Principles of colloid and surface force apparatus (SFA), total internal reflectance micros-
surface chemistry. Marcel Dekker Inc., New York. With permission of copy, and the AFM (Israelachvili, 1992). The SFA can measure
Marcel Dekker, Inc.) forces between surfaces at the 10−10 m level of resolution. This
apparatus has been used to measure attractive van der Waals
develops due to the energy needed to dehydrate surface-bound cat- forces, repulsive double layer forces, and repulsive hydration
ions. The strength of the hydration force, which increases with the forces in aqueous solutions (Israelachvili, 1992). Because of its
hydration number of the cation: Mg2+ > Ca2+ > Li+ ≈ Na+ > K+ > Cs+ smooth surface and ease of handling, mica has been the primary
(Pashley and Quirk, 1984; Israelachvili, 1992), is illustrated for two solid used in SFA studies. Total internal reflection microscopy
mica surfaces in Figure 15.10. has been used to study forces between a surface and an indi-
vidual colloidal particle. AFM has been used to measure both
short- and long-range forces (Ducker et al., 1991; Nishimura
106 et  al., 2002b; Zhao et al., 2008). Interactions between charged
mica surfaces have been investigated using a combination of SFA
and AFM experiments. Results from both methods agree with
theoretical predictions (Kékicheff et al., 1993).
105
15.3  Colloidal Stability
F/R (μN m–1)

15.3.1  Flocculation and Dispersion

The International Union of Pure and Applied Chemistry defines
104 flocculation as “a process of contact and adhesion whereby the
particles of a dispersion form larger-size clusters,” other terms
used interchangeably with flocculation are agglomeration and
coagulation (IUPAC, 2009). The stability of colloidal suspen-
sions is a balance between repulsive and attractive forces act-
103
1 2 3 4 5 6 7 8 ing among the suspended particles. If net repulsive forces
d (nm) predominate, particles do not coagulate and remain dispersed.
When the attractive forces are dominant, interacting particles
FIGURE 15.10  Forces between two mica surfaces in 7 mmol L−1 NaCl
coagulate and the resulting floccules settle more rapidly from
electrolyte. F is the total force scaled by the radius (R) of the curved
the suspension than the smaller dispersed particles. Different
surfaces. At distances > 1.5 nm, the forces are described by double
layer theory. Hydration forces are observed at distances < 1.5 nm.
theories in the literature attempt to describe colloid behavior
(Reprinted with permission from Ducker, W.A., and R.M. Pashley. (Sogami and Ise, 1984; Smalley, 1990; Ise and Smalley, 1994;
1992. Forces between mica surfaces in the presence of rod-shaped McBride and Baveye, 2002). A classical continuum scale theory
divalent counterions. Langmuir 8:109–112. Copyright 1992 American of the forces between particles is the DLVO theory named after
Chemical Society.) Derjaguin, Landau, Verwey, and Overbeek, largely responsible
Soil Colloidal Behavior 15-19

for its development (Hunter, 1987). Through the use of the SFA, properties and geometry, and should only be applied to dilute
it has been shown that the DLVO theory is an oversimplification systems (Sogami and Ise, 1984).
of the forces acting at the mineral surface. For example, DLVO The potential barrier preventing particles from coagulat-
theory does not take into account short-range solvation forces ing is defined by the stability ratio (W), which is the fraction
(Israelachvili, 1992). of the total number of collisions between particles that result in
Continuum DLVO theory provides a simplified assump- coagulation. The rate of coagulation in the absence of a potential
tion of a phyllosilicate surface with permanent negative charge. barrier or rapid coagulation (Rf) is limited only by the rate of dif-
Conceptually, the negative charge is developed from isomor- fusion of the particles toward one another. When the particles
phous substitution of lower valent cations for higher valent cat- have a potential barrier to overcome, the rate of coagulation (Rs)
ions in either the tetrahedral or octahedral layers of the crystal. is slow and is related to Rf by
With regard to soils, a further complication exists in terms of
mineral/organic interaction. Mounting evidence suggests that Rf
Rs = (15.32)
the primary reactive phases in soils are complex mineral assem- W
blages where phyllosilicates are coated by natural organic mat-
ter and Fe-oxyhydroxide phases (Bertsch and Seaman, 1999). In Rapid coagulation occurs when no significant repulsive forces
this case, the theoretical models are too simplified to provide act between particles and van der Waals or long-range coulombic
a good representation of natural colloids. Advanced computer attractions predominate. The quantification of the coagulation
molecular simulations must be used to begin to understand the rate under these conditions was examined by von Smoluchowski
complexities of mineral/fluid and mineral/mineral interaction, (1916, 1917) and is discussed by Overbeek (1952).
even for clean systems, for surface force behavior on the colloi- Slow coagulation occurs over distances of the order of
dal scale (Hsu, 1999). Consequently, DLVO theory, acknowledg- 1–100 nm when the approaching particles experience a barrier
ing its simplifications, will be used as a frame of reference for the as their double layers overlap. Diffusion over this distance results
discussion of flocculation dispersion. from many individual Brownian events, some of which bring the
Flocculation is a thermodynamically favorable process; how- particles closer together and some of which take them further
ever, the kinetics of coagulation determine the stability of col- apart. Since the rates of rapid and slow coagulation are directly
loidal suspensions. Generally, all colloidal suspensions will proportional to the number of particles diffusing in the direc-
spontaneously flocculate given sufficient time, but potential tion of a central particle (J), it follows from Equation 15.32 that
energy barriers retard the rate of flocculation. These barriers are the stability ratio is given by
analogous to activation energies considered in chemical kinetics
(Hiemenz and Rajagopalan, 1997). Particles in a primary mini- R f Jf
∞
⎛ E ⎞ dr
mum are adhesive and are not readily separated. In contrast, the
dispersion/flocculation transition is the result of a secondary
W=
Rs
=
Js ∫
= 2r exp ⎜ T ⎟ 2
⎝ K BT ⎠ d
(15.33)
2r
minimum, involves card-house type structures (Figure 15.11),
and is readily reversible (Quirk, 1994). where
There are many examples in the literature showing that r is the particle radius
DLVO theory can account for the observed kinetic behavior d ≅ 2r
of dispersed colloidal systems (e.g., Napper and Hunter, 1974).
However, this theory must be applied with caution since it treats Verwey and Overbeek (1948) showed that W was determined
ions exclusively as point charges ignoring their surface chemical almost entirely by the value of the total potential energy (ET) at
the maximum (Figure 15.12). In Figure 15.12 ER and EA are the
potential energies due to repulsive and attractive forces. A more
complete analysis of the kinetics of colloid flocculation is pre-
sented in Hunter (1987).
Gravity removes suspended particles by sedimentation
while inducing differential sedimentation coagulation, thereby
decreasing Brownian coagulation rates. Ultimately, sedimenta-
tion limits the time of a flocculation series test. The test should
be long enough to detect relative changes in suspended particle
numbers, but not so long that all dispersed particles settle from
a stable suspension (Hesterberg and Page, 1990a).
The reverse of flocculation is called dispersion. Ideally, the
amount of energy required to separate two particles coagu-
FIGURE 15.11  Representation of card-house structure. (Reprinted lated into a potential energy minimum is approximately equal
from Hunter, R.J. 1987. Foundations of colloid science, Vol. 1. Oxford to the difference between the interaction energy at the mini-
University Press, New York by permission of Oxford University Press.) mum and that at the adjacent maximum (van Olphen, 1977).
15-20 Properties and Processes

The electrical potential at the edge surface strongly depends

on the electrolyte concentration and the ratio of the face to edge
charge density. The extent of spillover also is a weak function of
the particle shape (Secor and Radke, 1985). This study implies
that attraction between positively charged edges and negatively
E charged faces of phyllosilicate mineral particles will depend on
ER the extent of the edge protonation, electrolyte concentration, and
shape of the particle. A phyllosilicate structure that is collapsed
in the c-dimension, such as mica, should be able to acquire a
ET
larger edge surface charge density than a layer silicate like smec-
ES
0
tite where structural expansion increases the distance between
2 4 6 10 edge surface aluminol groups (Hesterberg, 1988).
Kd
When there is a reduction in the thickness of the double layer,
particles can associate among themselves in three different ways:
EA face–face, face–edge, or edge–edge. Face–face association is also
called parallel aggregation and does not produce floccules, while
the other two associations do produce three-dimensional struc-
tures called card houses (see Figure 15.11).
In concentrated suspensions of clay, the edge–edge and edge–
face associations form a continuum, with chains of particles in
FIGURE 15.12  Total potential energy of interaction of two colloidal the card-house structures mentioned above. The rigidity of the
particles. ET = ES + ER + EA, where ES is the potential energy of repulsion gel depends on the number and strength of the bonds in the con-
due to the solvent layers, ER is the potential energy due to the repulsive
tinuum structure. Some attempts to characterize the gel struc-
forces, EA is the potential energy due to the attractive forces, and κd is
ture using freeze-drying techniques have been made (Norrish
particle separation. (Reprinted from Hunter, R.J. 1987. Foundations of
colloid science, Vol. 1. Oxford University Press, New York by permis-
and Rausell-Colom, 1961). When the water is eliminated from
sion of Oxford University Press.) the suspension, the volume of the system does not change and
the final product is a dry clay structure with some strength that
Under constant chemical conditions, separation of particles has been called aerogel (van Olphen, 1977).
could presumably be induced by an input of kinetic energy
(e.g., thermal or mechanical shear). Alternatively, changing the 15.3.1.1.2  Domains and Quasicrystals
chemical conditions of the bulk solution surrounding coagu- Some colloidal systems may, under certain circumstances, show
lated particles could provide chemical and/or electrochemical a reversible clustering among particles. The earliest reported
energy to produce dispersion. example is the Fe-hydroxide sol described by Cotton and Mouton
(1907). The term tactoid was first used by Freundlich (1932) and
15.3.1.1  Modes of Particle Association
was more precisely defined by Overbeek (1952) as the association
15.3.1.1.1  Edge–Edge, Edge–Face, Face–Face of particles at a certain distance affected by electrolyte concen-
Clay crystals have a net negative surface charge as a consequence tration and pH. Quirk and Aylmore (1971) proposed the term
of isomorphic substitutions of electropositive ions for ions with a quasicrystal to describe the regions of parallel alignment of indi-
lower valence. This negative charge generates an ionic reorganiza- vidual aluminosilicate lamellae in montmorillonite and the term
tion in the solution medium that has been described above as the domain to describe the regions of parallel alignment of crystals
diffuse double layer. Clay particles also have edge surfaces with for illite. This terminology is adopted in the present chapter.
atomic structure different from the faces. At the edge of the platelet, The distribution model of adsorbed ions in mixed mono- and
the tetrahedral layer of Si and the octahedral layer of Al exhibit bro- divalent systems for smectite quasicrystals was described by
ken bonds, which, in turn, generate another electric double layer. Shainberg and Otoh (1968) and Bar-on et al. (1970). According
Double layer theory assumes that the surfaces of the clay min- to this theory, called the ion demixing model, when Na is added
erals are of semi-infinite spatial extent and show no edge effects, to Ca saturated montmorillonite, most of the adsorbed Na will
a simplification that is not always satisfactory. Clay mineral concentrate on the external surfaces of the quasicrystals until
particles have finite dimensions. Below the p.z.c., edge surfaces 10% of the adsorbed Ca has been replaced by Na. Initially, the
carry a positive charge due to specific adsorption of protons. size and shape of the particles are not altered by the addition
Using the Poisson–Boltzmann equation, Secor and Radke (1985) of adsorbed Na. As further Na is added to the system, Na pen-
calculated the effect of edge–face corners on the electrical poten- etrates into the quasicrystals and brings about disintegration of
tial distribution around an idealized, symmetrical montmoril- the clay packets (Bar-on et al., 1970).
lonite disk. Spillover of the negative electrical potential from the Lebron and Suarez (1992a) used electrophoretic mobility
particle faces into the edge region can result in a negative poten- experiments to show that the demixing model can be applied
tial everywhere around the particle. to micaceous clays. The electrophoretic mobility of micaceous
Soil Colloidal Behavior 15-21

TABLE 15.5  Critical Coagulation Concentrations of Phyllosilicates under Various Conditions

Solids Concentration
Mineral CCC (molc L−1) Background Electrolyte pH (g kg−1)
Kaolinite-4 2–40 NaNO3 4–10 0.025
Kaolinite-9 8, 30 NaHCO3, Na2CO3 8.3, 9.5 0.6–0.9
Kaolinite (Georgia) 5, 245, 75 NaCl, NaHCO3, Na2CO3 7, 8.3, 9.5 0.6–0.9
Kaolinite (KGa-1) <0.19–54.6 NaCl 5.8–9.1 0.67
Kaolinite-4 0.1–0.3 Ca(NO3)2 4–10 0.025
Kaolinite (KGa-1) <0.19–0.85 CaCl2 5.5–9.3 0.67
Montmorillonite-23 1–10 NaNO3 3.8–10 0.25
Montmorillonite-23 20, 48, 68 NaCl, NaHCO3, Na2CO3 7, 8.3, 9.5 0.6–0.9
Montmorillonite-27 14, 47, 17 NaCl, NaHCO3, Na2CO3 7, 8.3, 9.5 0.6–0.9
Montmorillonite (SAz-1) 14–28 NaCl 6.4–9.4 0.67
Montmorillonite (SAz-1) 1.09, 1.56 CaCl2 6.1, 7.6 0.67
Montmorillonite (SAz-1) 0.93, 2.02, 0.88 MgCl2 6.1, 8.4, 9.0 0.67
Vermiculite 38, 58, 30 NaCl, NaHCO3, Na2CO3 7, 8.3, 9.5 0.6–0.9
Illite-36 9, 185, 95 NaCl, NaHCO3, Na2CO3 7, 8.3, 9.5 0.6–0.9
Illite (Grundy) 7.24 NaCl ∼6 1
Illite (Grundy) 0.2 CaCl2 ∼6 1
Source: Adapted from Hesterberg, D.L. 1988. Critical coagulation concentrations and rheological properties of
illite. Ph.D. Thesis. University of California, Riverside, CA by Oxford University Press.

domains increased when the sodium adsorption ratio (SAR) agrees well with experimental results if ψ0 ∝ 1/z. When calcu-
increased from 5 to approximately 10. lating the CCC in soils, one must consider that soils consist of
mixtures of permanent and variable charge minerals. The net
15.3.1.2  Critical Coagulation Concentration surface charge, and consequently, the electrical potential around
the mixture of particles are dependent upon variables such as
The CCC, sometimes called the critical flocculation concentra-
pH, specifically adsorbed ions, ionic strength, and mineralogy.
tion (CFC), is the minimum concentration of indifferent elec-
A more detailed evaluation of the effect of these variables on the
trolyte that induces rapid coagulation. The CCC is strongly
stability of colloids is presented below.
dependent on counterion valence (Table 15.5). This observation
is known as the Schulze–Hardy rule. An estimate of the CCC
(mol L−1) is given by (Hunter, 1987) 15.3.2  Factors Affecting Colloidal Stability
15.3.2.1  Solution Composition
0.107ε3 (kBT )5 Z 4
CCC = (15.34) The magnitude of the repulsion barrier is determined by the
N A AH2 (ze)6
nature of the material adsorbed on the particle surface. In the
case of a charged colloid, repulsion depends on the magnitude
where of the surface charge and on the extent of the electrical double
Z = tanh(zeψ0/4kBT) layer, which, in turn, depends on the total electrolyte concen-
NA is Avogadro’s number tration. It is necessary here to distinguish between the concen-
AH is the Hamaker constant tration of the potential determining ions and that of other ions
ε is the relative dielectric constant that have no direct interaction with the surface. If the surface
kB is the Boltzmann constant potential of the particles is determined by the concentration
e is the proton charge of potential determining ions, the magnitude of this potential
is not affected by the addition of an indifferent electrolyte. For
The variation of CCC with counterion valence depends this type of double layer, when salt concentration increases,
approximately on the inverse sixth power of z. At 25°C in water, the double layer thickness decreases, the surface charge of the
using the experimental observation that coagulation usually particles increases, and the surface potential remains constant
occurs between low-potential surfaces, the result is (Figure 15.7a).
If the surface charge of the particle is determined by
ψ04 isomorphic substitution, the surface charge does not change
CCC ∝ (15.35)
z2 with increasing electrolyte concentration. The diffuse double
layer compresses, but in this case, the surface potential decreases
where now the CCC depends on the inverse of the square of with increasing electrolyte concentration (Figure 15.7b) (van
the valence. However, the CCC calculated with Equation 15.35 Olphen, 1977).
15-22 Properties and Processes

15.3.2.2  Exchange Complex Composition

As explained above, clay particles are surrounded by cations as
a consequence of the net negative electrical charge on the sur- Secondary
minerals
face. Cations bonded to the surface can be exchanged for other
Layer silicate clays,
cations in solution. Consequently, the cations on the exchange

Relative amount
Primary oxides, noncrystalline
complex are dependent on the solution composition. aluminosilicates
minerals
There is an equilibrium between the cations on the exchange
complex and the cations in the solution. Not all cations are Quartz, feldspars,
adsorbed with the same affinity. Cations with larger hydrated micas, etc.
radii are less strongly adsorbed than those with smaller hydrated
radii. In solutions with equal initial concentration of different
cations, the amounts of Ca and Mg adsorbed are several times
greater than the amount of Na adsorbed. In general, polyvalent Sand Silt Clay
50 2
cations are adsorbed more strongly than monovalent cations and
Particle size (μm)
are not easily displaced by other cations. The order of adsorption
strength is Al > Ca > Mg > H > K > Na (Duchaufour, 1970). FIGURE 15.13  Typical abundance of primary and secondary miner-
The flocculation/dispersion behavior of soil colloids depends als in different size fractions of the soil. (Reprinted from McBride, M.B.
on salt concentration, exchange complex cation, cation valence, 1994. Environmental chemistry of soils. Oxford University Press, New
and dominant clay mineralogy. In general, divalent cations are York by permission of Oxford University Press.)
more effective in flocculating colloids than monovalent cations.
For example, Quirk and Schofield (1955) found that the floccu- 15.3.2.4  M ineralogy
lating power of CaCl2 is 50–100 times higher than that of NaCl. The colloidal fraction of a soil consists primarily of secondary
For monovalent cations, there is also a difference, with KCl minerals (Figure 15.13). Layer silicate minerals differ in chemical
showing greater flocculation power than NaCl (Pashley, 1981). composition and charge characteristics leading to different phys-
icochemical behavior (Table 15.5). The stoichiometry of each
15.3.2.3  pH mineral varies due to isomorphic substitutions in the crystal lat-
The pH is an important determinant of the electrical potential of tice during the formation or evolution of the mineral structure.
the clay surface. Changes in pH affect the edge charge on clays The siloxane (Si–O–Si) surfaces of 2:1 layer silicates without
and the surface charge of variable charge minerals such as Fe and structural charge are hydrophobic. Therefore, the surface oxy-
Al oxides. There is considerable variability depending on struc- gens coordinated to Si show little tendency to hydrogen bond
tural composition and degree of crystallinity, but Fe and Al oxides with water molecules. Smectites, such as montmorillonite,
generally undergo a surface charge reversal around pH 7–9 (posi- form weak hydrogen bonds between structural charge located
tively charged below that pH and negatively charged above). This mainly in the octahedral sheet and water. Such bonds are the
is also the region in which kaolinite exhibits its edge charge rever- result of the delocalization of some structural charge into the
sal as evidenced by Cl− adsorption studies (Schofield and Samson, surface oxygens (Farmer, 1978). Smectites, such as beidellite,
1954). Soil colloids consist of a mixture of minerals, each with a with a high proportion of charge in the tetrahedral sheet, form
different p.z.c. At low pH, edge to face bonding, as well as bonding stronger hydrogen bonds. The siloxane surfaces of vermiculite
of positive Fe and Al oxides to negative clay surfaces, is expected are the most hydrophilic of the 2:1 layer silicate clays because
to occur (van Olphen, 1977; Kretzschmar et al., 1993, 1997). This they possess a large tetrahedral charge partially distributed
type of bonding should hinder dispersion and should thus result onto surface oxygens (Farmer, 1978). Tetrahedral charge is
in flocculation. With increasing pH, as the p.z.c. is approached, much more localized on fewer surface oxygens than octahedral
edge to face clay bonding decreases and Fe and Al oxide bond- charge, explaining the stronger hydrogen bonding of adsorbed
ing to clays is also expected to decrease (Suarez et al., 1984). In water on vermiculite (McBride, 1989). An extensive study of the
variable charge systems, flocculation is at a maximum at the p.z.c. structural characteristics of soil minerals can be found in Dixon
CCC increased at high SAR values with increasing pH for and Weed (1989).
three soil clays whose clay mineralogy was dominantly kaolin- An example of how these mineral differences affect the floc-
ite, montmorillonite, or illite (Goldberg and Forster, 1990). culation/dispersion behavior of soil colloids is shown in Table
Hesterberg and Page (1990b) also found an increase in CCC for a 15.5. An overview of the data reveals that reported CCC values
Na- and a K-illite with increasing pH. Similar results were found of kaolinite, montmorillonite, vermiculite, and illite are quite
for illite and three micaceous soil clays when SAR > 15 (Lebron variable within and between these mineral groups.
and Suarez, 1992a, 1992b). The electrophoretic mobility of these Many of the differences in Table 15.5 are due to differences in
materials increased when the SAR was greater than 20 and the methodology in the determination of CCC and/or differences in
pH was above the p.z.c. No pH effect was observed at SAR < 15 the stoichiometry of the silicate minerals. However, these fac-
for either mobility or CCC. tors do not account for all of the variability. Lebron and Suarez
Soil Colloidal Behavior 15-23

(1992a) found substantial differences in CCC within samples 200

from the same soil type. Differences in content of organic mat-
ter and other minerals can drastically change the behavior of soil
colloids. Consequently, general guidelines for reclamation of agri- 150
cultural land or the use of amendments to maintain colloids in a
flocculated state must be implemented with caution because soils Na-clay

CCC (mM)
usually require higher electrolyte concentrations than the corre- 100
sponding pure clay minerals to maintain a flocculated condition.

15.3.2.5  Organic Matter pH 8

50
pH 6
Organic matter constitutes a small portion of the soil mass
(0.5%–10%) but is intimately associated with inorganic particles
Ca-clay
and plays an important role in the improvement of soil struc- 0
ture (Nelson and Oades, 1998). Aeration, water-holding capac- 0 10 20 30 40
ity, and permeability increase with increasing soil SOM content. Humic acid concentration (mg L–1)
However, adsorbed organic matter can promote dispersion of
soil particles. Organic coatings, under certain conditions, main- FIGURE 15.14  Effect of the humic acid concentration on the CCC of a
tain a dispersed state for soil colloids in suspension through a Na-clay and a Ca-clay. (After Tarchitzky, J., Y. Chen, and A. Banin. 1993.
combination of electrostatic and steric mechanisms (Stevenson, Humic substances and pH effects on sodium and calcium-montmoril-
1982). Table 15.6 shows the spatial extensions for nonionic poly- lonite flocculation and dispersion. Soil Sci. Soc. Am. J. 57:367–372.)
mer molecules of different molecular weights. Like electrical Tarchitzky et al. (1993) showed similar comparisons between Na-
double layers, macromolecules of at least a few thousand molec- and Ca-montmorillonite suspensions with varying additions of
ular weight also extend in space over distances comparable to, or humic and fulvic acids (Figure 15.14). The effect of organic matter
greater than, the van der Waals attraction. In general, it has been on stability of soil colloids is a function of its size. Large organic
shown that organic matter coatings modify the surface proper- materials such as polysaccharides and hyphae act to bind colloid
ties of minerals, increasing their CEC, generating hydrophobic particles together. Small organic molecules such as fulvic acid
and hydrophilic surfaces (Hunter, 1987), and significantly alter- and organic acids increase dispersion of soil colloids through
ing the point of zero net charge (p.z.n.c., pH at which the CEC their effect on particle charge. A more detailed review of organic
and AEC are equal) (Heil and Sposito, 1993; Kaplan et al., 1997; matter chemistry and its effect on soils is provided in Stevenson
Kretzschmar et al., 1997; Bertsch and Seaman, 1999). (1982) and Nelson and Oades (1998).
Goldberg and Forster (1990) and Kretzschmar et al. (1993) found
that the removal of SOM enhanced soil flocculation (decreased
15.3.3  Measurement of Colloidal Stability
the CCC). Similarly, addition of small amounts of organic mate-
rial substantially increased dispersion of Na-saturated soil or 15.3.3.1  Flocculation Series Test
clay in the order: humic acid > soil polysaccharide ≥ anionic CCC are commonly determined using the flocculation series
polysaccharide (Gu and Doner, 1993; Kretzschmar et al., 1997). test. The experiment can be performed by taking a series of test
Using smectite, kaolinite, and three soils whose clay fractions tubes containing the same concentration of the colloid and add-
were dominated by one of these minerals, Frenkel et al. (1992) ing varying amounts of the coagulating electrolyte. The tubes are
showed that the CCC values of Na-soils were much higher, and then shaken and allowed to stand for a given time. If the electro-
much more affected by organic matter than those of Ca-soils. lyte range has been properly chosen, the CCC is defined as the
concentration above which the settling material leaves behind a
TABLE 15.6  Spatial Extensions of Electrical Double perfectly clear supernatant solution. Below the CCC, the super-
Layers and Polymers of Different Molecular Weight natant retains some of the uncoagulated colloid. The concentra-
1:1 Electrolyte Double-Layer Polymer Spatial tion of colloidal particles at which the flocculation test must be
Concentration Thickness, Molecular Extension performed should not exceed 10 g L−1, thus avoiding interferences
(mol L−1) 1/κ (nm) Weight (nm) from different particle interactions such as gel formation.
10−5 100 1,000,000 60
15.3.3.2  Dispersion Indices
10−4 30 100,000 20
10−3 10 10,000 6 There are several methods (qualitative, semiquantitative, and
10−2 3 1000 2 quantitative) to determine the dispersion or flocculation status
10−1 1 of soil colloids. Qualitative analyses of the dispersion state are
those based on direct observation of small particles when the
Source: Reprinted from Hunter, R.J., Foundations of
Colloid Science, Vol. 1, 1987 by permission of Oxford soil is immersed in water. This observation can be made with
University Press. the optical microscope or with the naked eye, as is the case for
15-24 Properties and Processes

the test of Emerson (1967). Methods based on turbidity of a sus-

pension of dispersed soil can be considered semiquantitative a b c
when comparative measurements are made. Normally, a stan-
dard curve is constructed using known amounts of dispersed
clay. The soil under evaluation is assigned a dispersion value by
comparison with the standard. The most commonly used quan-

Shear rate
titative method to determine soil flocculation state is the disper-
sion index. This index is the ratio of the amount of soil colloids
in water to the amount of soil colloids in solution when the soil
has been treated with a dispersant. This procedure is recom-
mended by the Soil Conservation Service (Sherard et al., 1977).
Different variations regarding particle size, dispersing agent,
and manipulation of samples are found in the methods proposed
by El-Swaify et al. (1970) and Dong et al. (1983), among others. τ1 τ2 τ3
Shear stress
15.3.3.3  Bingham Yield Stress
FIGURE 15.15  Shear rate versus shear stress relationships. Curve a rep-
Rheology is the study of the flow and deformation of colloidal
resents Newtonian flow, curve b represents ideal plastic flow, and curve c
systems under the influence of mechanical forces (van Olphen, represents Bingham flow. (Adapted from van Olphen, H. 1977. An intro-
1977). A Newtonian liquid when confined between two paral- duction to clay colloid chemistry, 2nd Ed. John Wiley & Sons, New York.)
lel plates moves at a constant shear rate (γ⋅) proportional to the
applied shear stress (τ):
1000
τ = ηγ (15.36)
800
Shear rate (s–1)

Non-Newtonian fluids obey different relations between shear mmolg L–1

stress and shear rate. Plastic flow is flow that occurs only above 600
a certain finite stress (τ0) called the yield stress. Ideal plastic 0.01
400 1
flow exhibits a linear relationship between shear rate and shear 3
stress over all rates of shear. Many colloidal dispersions exhibit 300
Bingham flow, which is characterized by the equation 200 1000
3000

τ = τB − ηΔ γ (15.37) 0
0 0.8 1.6 2.4 3.2 4.0
Shear stress (N m–1)
where
FIGURE 15.16  Shear rate versus shear stress for Na-kaolinite. The
τB is the Bingham yield stress found by extrapolating Equation
open symbols represent dispersed systems and ideal plastic flow.
15.37 to zero shear rate
The closed symbols represent coagulated systems and Bingham flow.
ηΔ is the differential or plastic viscosity (Adapted from Yong, R.N., A.J. Sadh, H.P. Ludwig, and M.A. Jorgensen.
1979. Interparticle action and rheology of dispersive clays. J. Geotech.
The differential viscosity is the derivative of shear stress with Eng. Div. 105:1193–1209.)
respect to shear rate at a given shear rate (van Olphen, 1977).
Shear rate versus shear stress relationships for Newtonian flow, Ohtsubo et al., 1991; Hesterberg and Page, 1993), montmorillon-
ideal plastic flow, and Bingham flow are presented in Figure 15.15. ite (Rand et al., 1980; Heath and Tadros, 1983; Keren, 1988, 1989a;
Bingham yield stress is a measure of the degree of coagula- Tombácz et al., 1989; Miano and Rabaioli, 1994; Benna et  al.,
tion of a colloidal suspension and the mode of particle interac- 1999; Duran et al., 2000), laponite (Laxton and Berg, 2006), clay
tion. Bingham yield stress is a function of both the number of mixtures (Yong et al., 1979; Keren, 1989b, 1991), soil clays (Zhao
particle–particle linkages in the coagulated structure and the et al., 1991), and soils (Ghezzehei and Or, 2001; Markgraf et al.,
energy required to break these linkages (Rand and Melton, 1977). 2006). A series of curves of Bingham yield stress as a function of
A stable clay dispersion exhibits ideal plastic flow, while floccu- pH obtained at successively increasing electrolyte concentration
lated suspensions exhibit Bingham flow as can be seen in Figure should coincide at one point. This point is characteristic of the
15.16 for kaolinite. Differential viscosity can also be used to assess pH value of the edge p.z.c. of the mineral (Rand and Melton,
the extent of particle flocculation, but it is a much less sensitive 1977). Edge p.z.c. values have been determined in this manner
parameter than Bingham yield stress (Heath and Tadros, 1983). for various kaolinites and range in value from pH 5.6 to 8.8 (Diz
Rheological studies have been carried out on kaolinite and Rand, 1989). Kaolinite particles occur in edge–face associa-
(Flegman et al., 1969; Rand and Melton, 1977; Yong et al., 1979; tions below the edge p.z.c. and in edge–edge associations around
Diz and Rand, 1989; Ma and Pierre, 1999), illite (Yong et al., 1979; the edge p.z.c. (Rand and Melton, 1977).
Soil Colloidal Behavior 15-25

Montmorillonite exhibits no edge–face associations over transport requires consideration not only of the chemical and
the pH range 4–11; coagulation produced by electrolyte addi- biological processes and reactions but also of the physical prin-
tions is initially the result of edge–edge interactions with face– ciples of filtration and deposition in porous media.
face interactions occurring at high-electrolyte concentrations Several mechanisms have been identified by which colloidal
(Rand et al., 1980). No edge p.z.c. could be determined on materials can be mobilized in the soil environment (Figure
montmorillonite using this method. This is likely because the 15.17) including clay dispersion resulting from changes in
edge area is small and attraction between edges and faces is pore-water chemistry that increase electrostatic repulsion
small compared to repulsion between faces (Rand et al., 1980). between the colloid and collector surfaces, water film expan-
From yield stress and electrophoretic mobility measurements sion and air–water interface scouring during episodic wet-
determined without electrolyte addition, Benna et al. (1999) ting events (imbibition), raindrop impact at the soil surface,
suggested that the p.z.c. of three bentonites occurred in the pH and increased shear forces associated with transient hydrody-
range of 7.5–8.5. namic events (i.e., precipitation, groundwater pumping, sub-
In distilled water, Ca-montmorillonite exhibited Newtonian surface recharge injection). Mobile colloids can also be formed
flow. With increasing exchangeable sodium percentage (ESP), in situ through precipitation reactions resulting from changes
differential viscosity, deviation from Newtonian flow, and in pore-water chemistry. Clearly, colloid mobilization is asso-
Bingham yield stress of montmorillonite all increased (Keren, ciated with a physical and/or chemical perturbation sufficient
1988). These increases are likely due to the increased number to overcome the energy barrier limiting particle detachment
of particles in solution as tactoids break down. Differential vis- (McCarthy and Degueldre, 1993; Ryan and Elimelech, 1996;
cosity and Bingham yield stress decreased with increasing elec- DeNovio et al., 2004).
trostatic charge density of smectites (Keren, 1989a). This result Compared to saturated aquifer systems, chemical and physi-
is attributed to the reduced swelling of higher charge density cal perturbations are common within the soil environment, with
smectites. Kaolinite exhibited Newtonian flow at all ESPs. The the presence of air providing an additional system interface for
introduction of even 5% montmorillonite into the kaolinite sys- colloid partitioning (Wan and Wilson, 1994; Sirivithayapakorn
tems resulted in deviations from Newtonian flow and increased and Keller, 2003). The presence of a dynamic air–water inter-
differential viscosity (Keren, 1989b). Bingham yield stress and face and fluctuating chemical and hydrological conditions
deviations from Newtonian flow of kaolinite–montmorillonite complicate our understanding of colloid transport processes
mixtures also increased with ESP (Keren, 1991). Bingham yield in the soil and vadose environments (Bradford and Torkzaban,
stress of kaolinite, Ca-montmorillonite, Na-montmorillonite, 2008). Preferential flow paths can increase the mobility of col-
and two soils increased exponentially with decreasing water loidal material in close proximity to the pathway, while limiting
content (Ghezzehei and Or, 2001). the reactivity of colloidal sorbents isolated from the flow path
(DeNovio et al., 2004; McCarthy and McKay, 2004).
15.4  Colloid Transport The energy barrier limiting colloid detachment is the dif-
ference between the interaction minimum and the maximum
As previously discussed, colloidal materials found in soils energy potential described in Figure 15.12. In terms of chemi-
include phyllosilicate clays, Al, Fe, and other metal oxides, car- cal perturbations, soil colloid mobilization can result from
bonate minerals, microorganisms, and other biological debris, changes in pore-water pH, ionic strength, and/or Na+/Ca 2+
much of which falls into the “nanoparticle” size range (see ratios (McDowell-Boyer, 1992; Ryan and Gschwend, 1994;
Section 15.1.2). The fundamental processes involved in colloid Gamerdinger and Kaplan, 2001; Bunn et al., 2002; Khaleel et al.,
migration in the soil environment include mobilization, trans- 2002; McCarthy et al., 2002; Grolimund and Borkovec, 2006),
port, and deposition, representing primarily a balance between alteration of surface charge resulting from a chemical dispersing
the two opposing processes of colloid mobilization and deposi- agent or dissolved organic matter (Ryan and Gschwend, 1994;
tion. The study of colloid transport in the subsurface environ- Seaman and Bertsch, 2000; Johnson et al., 2001), or dissolution
ment has received considerable attention in recent years because of carbonate or Fe cementing agents resulting in the release
of concern that mobile colloids may enhance the mobility of and transport of silicate clays (Gschwend et al., 1990; Ryan and
strongly sorbing contaminants (i.e., facilitated transport) and Gschwend, 1990; Ronen et al., 1992; Swartz and Gschwend,
alter the hydraulic properties of soil and aquifer materials. 1998). Furthermore, potentially mobile colloids may precipi-
In addition, the migration of biocolloids such as bacteria and tate in situ due to altered chemical gradients (Gschwend and
viruses has important implications to in situ bioremediation, the Reynolds, 1987; Mashal et al., 2004). In many instances, more
protection of drinking water supplies, and the spread of disease than one of the mechanisms may be operative in order to trigger
(Khilar and Fogler, 1984; McDowell-Boyer et al., 1986; Kia et al., significant colloid mobilization, such as a change in pore-water
1987; Ryan and Elimelech, 1996; Kretzschmar et al., 1999; de chemistry that reduces particle attraction combined with an
Jonge et al., 2004b; McCarthy and McKay, 2004; Tufenkji, 2007). increase in pore-water velocity and shear forces.
However, our ability to predict colloid movement and deposition Under ideal laminar flow conditions, the hydrodynamic shear
is often confounded by the complexities of surface interactions force acting on a spherical particle attached to a flat surface can
in such heterogeneous natural systems. Understanding colloid be expressed as follows:
15-26 Properties and Processes

Water Water Water Water

flow flow flow flow
φax

Mobile
Detached colloid
colloid
dp

Mobile
wam colloid

Mobile
Mobile
colloid
colloid

Immobile
colloid

Colloid Film expansion Air–water interface Shear

dispersion release scouring mobilizatiom

(a)

Water Air Water Water

flow flow flow

Immobile
(around
colloid
bubble)
Immobile
Mobile Immobile colloid
colloid colloid Water Air
flow
Air
bubble
φax
wam

dp
Immobile
colloid Mobile
colloid
Mobile Mobile
colloid colloid

Grain Air–water Pore straining Film straining

attachment attachment attachment attachment

(b)

FIGURE 15.17  Colloid mobilization (a) mechanisms include dispersion due to chemical perturbation, expansion of water film during imbibi-
tion, air–water interface scouring and shear mobilization. Colloid deposition (b) mechanisms include attachment associated with physicochemical
filtration, attachment to the air–water interface, physical pore straining, and water film straining. (Adapted from DeNovio, N.M., J.E. Saiers, and
J.N. Ryan. 2004. Colloid movement in unsaturated porous media: Recent advances and future directions. Vadose Zone J. 3:338–351.)

Fshear = (1.7)6πμrV (15.38) Adhesive forces that oppose shear stress are subject to changes

in solution chemistry. The critical velocity for particle release
decreases with increasing particle size, even though the required
where hydrodynamic force increases for non-Brownian particles, that
V is the flow velocity at the center of the particle is, >1 μm in diameter (Sharma et al., 1992). As one might expect,
μ is the fluid viscosity the amount of particles mobilized should generally increase with
r is the particle radius (Sharma et al., 1992; Ryan and increasing flow velocity, but greater flow velocities are required
Elimelech, 1996; Ryan et al., 1998; DeNovio et al., 2004) to mobilize smaller particles that extend to a lesser degree into
Soil Colloidal Behavior 15-27

the advective stream. However, many assumptions inherent in Hydrodynamic dispersion and dispersivity appear to decrease
applying such a physical approach to soil and aquifer systems with increasing particle size (Sinton et al., 2000; Auset and
are likely in question. In more realistic systems, interrelated fac- Keller, 2004). As the colloidal material moves through porous
tors such as contact area, adhesion strength, and surface charge medium, it may be removed from solution by various physico-
heterogeneity are important in countering shear forces (Sharma chemical filtration processes, with various expressions, such
et al., 1992). as the equilibrium partitioning (Keq), used to describe revers-
In addition to the chemical factors affecting colloid stabil- ible colloid attachment processes in a manner analogous to the
ity, transport of colloids is related to soil physical factors such equilibrium partitioning of solutes. Using a numerical solution
as pore size distribution, geometry, and continuity (Torkzaban to the ADE, equilibrium partitioning can be modified to reflect
et al., 2008; Bradford et al., 2009). Coarse-textured soils have any one of a variety of phenomenological equilibrium partition-
a larger distribution of pore sizes (with larger pores) than ing expressions, that is, Freundlich, Langmuir, etc.
fine-textured soils, suggesting greater potential for colloid In contrast to equilibrium partitioning, colloid attachment
movement. This is not generalizable since some fine-textured is more often viewed as a kinetically controlled process with
materials experience cracking and formation of continuous terms accounting for both attachment (katt) and detachment
structural macropores that provide a preferential pathway for (kdet) rates:
colloid transport.
ρb ∂S ρ
= katt C − b kdet S (15.40)
θ ∂t θ
15.4.1  Colloid Transport Modeling
Physical and chemical processes affect the transport of soil yielding an expression that is mathematically equivalent to the
colloids. Colloid transport can be represented by the physi- reversible first-order kinetic equation for partitioning solutes.
cal processes of molecular diffusion (Brownian movement), Ripening and blocking are terms that are used to describe an
advective flow, and gravitational forces. Molecular diffusion, increase or decrease in colloid attachment efficiency (i.e., katt and
the random motion of particles caused by thermal effects, is kdet) with time or distance.
related to temperature and viscosity. Deposition is the process Figure 15.18 illustrates colloid breakthrough behavior for
whereby moving particles are attached to stationary surfaces irreversible (Figure 15.18a) and reversible (Figure 15.18b) attach-
based on the balance of attractive and repulsive forces, that ment kinetics. Colloid attachment is commonly assumed to be
is, attractive van der Waals forces and the combined influence irreversible (i.e., kdet = 0) as described by clean-bed colloid fil-
of attractive and repulsive electrostatic forces, as described by tration theory (CFT) (O’Melia and Tiller, 1993; Bradford et al.,
DLVO theory of colloid stability (see Sections 15.2.2, 15.2.3, 2003; Simunek et al., 2006; Tufenkji, 2007). For irreversible
and 15.3.1). attachment (i.e., CFT), the kinetic rate coefficient determines
The attachment process involves two steps: transport to the the plateau level of colloid breakthrough, while more complex
collector surface and attachment that binds the two surfaces breakthrough behavior is observed when both attachment and
together. The transport step reflects a combination of diffusion, detachment occur at differing rates. When katt = kdet, colloid
convection, and gravity, with electrostatic and van der Waals behavior becomes analogous to that of a conservative tracer, that
forces controlling colloid binding. Models used in describing is, R = 1. Colloid retention profiles for irreversible attachment
colloid transport are typically extensions of the advection dis- (Figure 15.18c) remain unchanged after the inlet colloid source
persion equation (ADE) for describing solute movement in a is removed and an exponential decrease in retained colloids is
homogeneous saturated porous medium: observed with transport distance. Again, a more complex col-
loid retention profile is observed for reversible attachment that
∂C ρb ∂S ∂2C ∂C depends on both the forward and reverse rate coefficients and
+ =D 2 −ν (15.39)
∂t θ ∂t ∂x ∂x the treatment duration (Figure 15.18d).

The irreversible colloid attachment/depositional rate constant
for a clean-bed filter is
where
C is the aqueous phase concentration for the solute or sus-
pended colloidal material of interest 3(1 − θ)ν
katt = η0α (15.41)
x is distance 2dc
t is time
D is the hydrodynamic dispersion coefficient where
ν is the pore-water velocity dc is the average grain size of the matrix
S is the sorbed concentration of colloids or solutes η0 is the collector contact efficiency for the three transport
ρb is the matrix bulk density mechanisms (diffusion, gravity, convection)
θ is the volumetric water content (Grolimund and Borkovec, α is the attachment efficiency (Yao et al., 1971; Bradford et al.,
2001; Bradford et al., 2003; Tufenkji, 2007) 2003; Li et al., 2004)
15-28 Properties and Processes

kdet = 0.5 h–1

1.0 1.0 All plots katt= 0.5 h–1
10 h = 1 PV
Effluent colloid concentration (c/c0)

0.8 0.8 kdet = 0.1 h–1

katt = 0.1 h–1
0.6 0.6

katt = 1.0 h–1 kdet = 0.05 h–1

0.4 0.4

0.2 0.2
katt = 0.5 h–1 kdet = 0.0 h–1

0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
(a) Time (h) (b) Time (h)

4 4
Ln sorbed colloid concentration

katt = 1.0 h–1

All plots katt= 0.5 h–1
kdet = 0.0 h–1
2 2
katt = 0.5 h–1

0 katt = 0.1 h–1 0 kdet = 0.05 h–1

kdet = 0.1 h–1

t = 120 h t = 120 h
–2 –2
0 20 40 60 80 100 0 20 40 60 80 100
(c) Soil depth (cm) (d) Soil depth (cm)

FIGURE 15.18  Simulated colloid breakthrough for a 1 m column with a saturated flow velocity of 2.4 m day−1 (θ = 0.5, DL = 0.01 m) exposed to a
60 h colloid pulse with kinetically controlled attachment (a = clean-bed filtration theory), and kinetically controlled attachment and detachment
(b). Retained colloid profile for irreversible (c), and reversible attachment (d) after 60 h colloid pulse followed by 60 h of colloid-free inlet solution.

The collector efficiency reflects the colloid collisions with the grain surface. For  particles with the same charge, a deep pri-
stationary matrix resulting from diffusion, advective flow, mary attractive force exists at very short separation distances,
and gravitational forces, and can be calculated (Tufenkji and known as the primary minimum (Figure 15.12). However, elec-
Elimelech, 2004a). The attachment efficiency term (α) is gener- trostatic repulsion supposedly limits particle approach in a man-
ally determined experimentally by fitting colloid breakthrough ner similar to chemical activation energies. Such discrepancies
results to the CFT model based on katt and the calculated η in deposition studies, and in batch aggregation experiments,
(O’Melia and Tiller, 1993; Elimelech et al., 2000; Bradford have been attributed to porous media heterogeneity that can be
et al., 2004; Tufenkji and Elimelech, 2004a; Tufenkji, 2007). difficult to quantify experimentally (i.e., grain size, morphol-
Additional mechanisms of material loss, such as cell motility, ogy, and surface charge) and a secondary energy minimum that
growth, and inactivation, must also be considered when evalu- favors colloid sorption without the necessity to overcome the full
ating the transport of microbes. Furthermore, research in the electrostatic repulsion required to enter the primary minimum
last decade has demonstrated the importance of surface biomol- (Figure 15.12), resulting in an apparent change in the attachment
ecules, which can vary in response to the local environment, rate coefficient (katt) with transport distance (Roy and Dzombak,
and among microbial strains and species in controlling their 1996; Elimelech et  al., 2000; Chen et al., 2001; Bradford et al.,
adhesion properties (Bolster et al., 2000; Walker et al., 2004; 2002, 2003; Tufenkji et al., 2003; Hahn and O’Melia, 2004; Li
Tufenkji, 2007). et al., 2004; Redman et al., 2004; Tufenkji and Elimelech, 2005;
Studies using model colloidal systems indicate that CFT is Tufenkji, 2007). The secondary minimum reflects the exponen-
generally applicable under conditions favoring particle attach- tial decay in electrostatic forces with separation distance, in
ment, that is, no significant electrostatic repulsion. However, contrast to van der Waals forces that decrease more slowly with
the CFT approach fails in describing experimental data under distance. The inability to remobilize particles trapped within the
apparently unfavorable conditions when significant electro- “secondary” minimum by altering solution chemistry, that is,
static repulsion exists between the mobile colloid and matrix reducing ionic strength, further demonstrates the hydrodynamic
Soil Colloidal Behavior 15-29

and physicochemical complexity of colloid retention mecha- collector particle surfaces where the magnitude of fluid velocity
nisms (Bradford and Torkzaban, 2008; Torkzaban et al., 2008; is quite small compared to the bulk solution, analogous to the
Bradford et al., 2009). “immobile” regions evident in solute transport behavior. Within
Verifying the spatial distribution of retained colloids based the immobile regions, greater colloid/colloid and colloid/collector
on the attachment parameter (αBTC) derived from effluent break- surface interactions lead to enhanced colloid immobilization in a
through data is a good method for testing the validity of the CFT manner that depends on both solution chemistry and pore geom-
model. In many instances, the slope of the relationship is greater etry. Furthermore, particles weakly retained in the secondary
than CFT predictions, indicating higher initial colloid reten- minimum can be subsequently funneled to the immobile capture
tion that decreases with increasing transport distance (Li et al., regions by hydrodynamic forces that are insufficient to induce full
2004; Tufenkji, 2007). Such discrepancies have been addressed colloid detachment (Bradford and Torkzaban, 2008; Torkzaban
through the use of multiple deposition rate constants, that is, a et al., 2008; Bradford et al., 2009).
fast and a slow rate, or a defined statistical distribution of ran-
domly assigned particle deposition rates that reflect the inherent
15.4.2  Colloid-Mediated Contaminant
variability in colloidal surface potentials (Li et al., 2004; Tufenkji
Transport
and Elimelech, 2004b; Tufenkji, 2007). It is interesting to note
that the statistical distribution in observed deposition rate coef- Numerous studies have established that organic and inorganic
ficients appears to narrow as colloid deposition becomes more chemicals, which are highly sorbed onto soil nonetheless, are
favorable, for example, reduced flow velocities and increased often transported in the subsurface to a greater degree than
ionic strengths (Li et al., 2004). expected. Such anomalies have been attributed to kinetic effects
Attachment kinetics are highly sensitive to colloid–collector associated with nonequilibrium sorption and bypass flow, as
interaction potentials. Moderate changes with respect to colloid well as contaminant transport associated with a mobile colloi-
surface potentials can result in relatively large changes in col- dal fraction that enhances apparent migration beyond the levels
lision efficiency and attachment rate (Elimelech and O’Melia, controlled by thermodynamically based solubilities or partition-
1990; Ryan and Elimelech, 1996; Elimelech et al., 2000; Li et al., ing reactions. Furthermore, colloidal materials may move at rates
2004). Deviation from the breakthrough plateau with time is that are similar or faster than those of nonreactive solute tracers
indicative of a change in the colloid deposition efficiency dur- because of physical size or electrostatic exclusion from a fraction
ing the course of injection, that is, filter ripening or blocking. In of the saturated pore space (Simunek et al., 2006). In general,
addition, surface modifiers such as Fe oxides and soil organics, colloid-facilitated transport is only significant when the contami-
often present in relatively minor amounts, can alter the expres- nant is strongly sorbed to the mobile colloidal phase, approaching
sion of electrostatic repulsion on soil mineral surfaces (Goldberg irreversible partitioning. Otherwise, the sorbed contaminant will
and Forster, 1990; Kretzschmar et al., 1993; Kaplan et al., 1993, desorb in response to the decrease in the aqueous phase contami-
1997; Bertsch and Seaman, 1999; Franchi and O’Melia, 2003; nant concentration when the colloidal phase travels faster than
Seaman et al., 1995, 2003). the aqueous phase (Grolimund and Borkovec, 2005).
Recent studies indicate that pore structure and particle strain- Models that include colloid-facilitated transport generally
ing may also be more significant than previously recognized for differ in the manner in which they account for the various col-
intermediate colloid and matrix grain sizes. Colloid straining, loid release and attachment processes described in Section 15.4.1
trapping colloids in pore regions that are too small to permit pas- (i.e., reversible vs. irreversible attachment, kinetic vs. equilib-
sage, is generally considered to be an irreversible process. Within rium) (Mills et al., 1991; Dunnivant et al., 1992; Corapcioglu and
a transport model, straining can be addressed by including an Jiang, 1993; Grolimund and Borkovec, 2005) with additional
additional first-order expression to the deposition equation equilibrium or kinetic expressions used to account for con-
given above. In the absence of colloid detachment, the kinetic taminant–colloid interactions. Only recently have models been
deposition model accounting for colloid straining becomes developed that address partially saturated conditions, colloid
straining, and size exclusion (Simunek et al., 2006). The devel-
ρb ∂S opment of such a contaminant transport model, while requiring
= katt C − kstr ψ strC (15.42)
θ ∂t numerous simplifying assumptions (van de Weerd and Leijnse,
1997; Simunek et al., 2006), still results in a significant list of
where parameters required to account for both contaminant sorption
k str is the straining rate constant and colloid attachment. For example, transport and mass bal-
ψstr is the depth-dependent colloid straining function ance expressions must account for the aqueous phase contami-
(Bradford et al., 2002, 2003, 2004) nant, contaminant sorbed to the immobile matrix, contaminant
sorbed to the mobile colloids, and contaminant sorbed to col-
In contrast to straining, traditionally considered a physical phe- loids immobilized by various mechanisms, that is, stationary
nomenon insensitive to solution chemistry, recent hydrodynamic phase attachment, air–water interphase attachment, and strain-
modeling efforts have verified particle capture within hydrody- ing. Additional expressions are required to account for colloid
namically disconnected regions of the porous matrix near two mass balance as well, illustrating the potential level of model
15-30 Properties and Processes

complexity. Simunek et al. (2006) recommend the use of sen- Soil profile development is often affected by colloid move-
sitivity analysis to discern the relative importance of such vari- ment. Among these processes are the formation of impermeable
ables in accurately describing contaminant fate and transport. clay layers in the subsurface and movement of Fe and Al, most
Although subject to numerous sampling artifacts, signifi- probably as organic metal complexes. Moderately to strongly
cant concentrations of mobile colloids have been observed in developed soils are generally characterized by depleted clay
soil and groundwater systems (Ronen et al., 1992; McCarthy contents in the A horizon and larger amounts of clay generally
and Degueldre, 1993; DeNovio et al., 2004). However, contami- in the upper portion of the B horizon. A substantial portion
nant transport models generally fail to account for the impact of the argillic B horizon is related to migration of clays from
of mobile colloids in facilitating the transport of strongly sorb- the upper portion of the profile and subsequent deposition
ing contaminants. For example, colloid-facilitated transport (Birkeland, 1974). Flocculation in the lower part of the profile
has been implicated in the migration of organic contaminants is enhanced by increased electrolyte concentration relative to
(e.g., atrazine, prochloraz, and dichlorodiphenyltrichloroethane the surface horizons. Clay colloid migration is evident by the
[DDT]) (Vinten et al., 1983; Seta and Karathanasis, 1996; Seta presence of clay films over ped surfaces and inside voids and
and Karathanasis, 1997; de Jonge et al., 1998; Roy and Dzombak, presence of oriented clay particles. This process is also observed
1998), metals (e.g., Pb, Ni, Cu, and Zn) (Kaplan et al., 1994b, 1995; in aridisols where low organic matter and elevated exchange-
Grolimund et al., 1996; Roy and Dzombak, 1997; Karathanasis, able Na enhance colloid transport. Clay deposition is enhanced
1999; Grolimund and Borkovec, 2005; Karathanasis et al., 2005), by increasing electrolyte concentration and removal of water by
radionuclides (e.g., 137Cs) (Von Gunten et al., 1988; Kaplan et al., evapotranspiration. In general, formation of argillic horizons
1994a; Kersting et al., 1999; Flury et al., 2002), and sparingly sol- requires that the soil be at least partially dry during some part
uble nutrients, such as phosphate (de Jonge et al., 2004b). Some of the season.
of the general issues concerning contaminant migration via Formation of Fe- and Al-rich layers by translocation (pod-
colloid-facilitated transport are discussed by McDowell-Boyer zolization) is probably caused by transport of metal–fulvic acid
et al. (1986), McCarthy and Zachara (1989), Ryan and Elimelech complexes, rather than movement of the dissolved metals. The
(1996), and Kretzschmar et al. (1999). spodic B horizon marks the location at which these chelates
either flocculate due to increases in electrolyte concentration or
by decomposition of the organic matter (Birkeland, 1974).
15.4.3  Effect of Colloid Transport on Hydraulic
Conductivity and Soil Formation
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 16
Ion Exchange Phenomena
16.1 Introduction............................................................................................................................16-1
16.2 Surface Charge and Ion Exchange Capacities....................................................................16-2
16.3 Ion Exchange Thermodynamics...........................................................................................16-4
16.4 Trends in VK and ex K..............................................................................................................16-5
Smectites  •  Micaceous Minerals  •  Soils and Sediments
16.5 Ion Exchange and Chemical Speciation Models................................................................16-8
Modeling Ion Exchange as a Surface Complexation Process  •  Modeling Ion
Exchange as a Solid-Solution Process
Ian C. Bourg
University of California
16.6 Micro- and Nanoscale Perspectives on Ion Exchange Selectivity..................................16-9
Molecular-Scale Coordination and Dynamics of Exchangeable Ions  •  Coupling between
Garrison Sposito Cation Exchange and Exchanger Structure
University of California, Berkeley References.......................................................................................................................................... 16-11

16.1  Introduction and the physical properties of soils is the heterovalent Na–Ca
exchange reaction:
Ion exchange phenomena involve the population of read-
ily exchangeable ions, the subset of adsorbed solutes that bal- 2 XNa (s) + Ca (aq)2 + = X 2Ca (s) + 2 Na(aq) + . (16.2)
ance the intrinsic surface charge and can be readily replaced
by major background electrolyte ions (Sposito, 2008). These Figure 16.1 shows an experimental ion exchange isotherm for
phenomena have occupied a central place in soil chemistry the binary Na–Ca exchange reaction on a montmorillonitic soil
research since Way (1850) first showed that potassium uptake (Fletcher and Sposito, 1984a), plotted as the fractional contribu-
by soils resulted in the release of an equal quantity of moles of tion of Ca 2+ to the total adsorbed charge of exchangeable cations
charge of calcium and magnesium. Ion exchange phenomena (ECa = qCa/Q, where qi = zini is the adsorbed charge of species i in
are now routinely modeled in studies of soil formation (White molc kg−1 of solid, zi and ni being the valence of i and the moles
et al., 2005), soil reclamation (Kopittke et al., 2006), soil fer- of adsorbed i per kilogram of solid, respectively, and Q = Σiqi)
tilization (Agbenin and Yakubu, 2006), colloidal dispersion/ against its fractional contribution to the charge concentration
flocculation (Charlet and Tournassat, 2005), the mechanics of all cations in solution (ẼCa = zCaCCa/Q̃, where Ci is the molar
of argillaceous media (Gajo and Loret, 2007), aquitard pore concentration of species i [mol dm−3] and Q  = ∑ ziCi). The con-
water chemistry (Tournassat et  al., 2008), and groundwater vexity of the isotherm in Figure 16.1 is typical of the competitive
(Timms and Hendry, 2007; McNab et al., 2009) and contami- adsorption of the higher-valence ion in heterovalent exchange
nant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; reactions. As shown below, however, this convexity does not
Serrano et al., 2009). imply selectivity or thermodynamic preference of the solid
The prototypical chemical reaction equation for the exchange exchanger for Ca 2+ vs. Na+.
of cations Aa+ and Bb+ can be written as follows if X− represents a For practical applications, ion exchange isotherms are fitted
mole of negative charge carried by the solid exchanger: with a variety of empirical one- or two-parameter models. The
most widely used one-parameter models are those introduced by
b+ a+
bX a A(s) + aB(aq) = aX bB(s) + bA(aq) . (16.1) Vanselow (1932), Gapon (1933), and Gaines and Thomas (1953):

Equation 16.1 can be modified in a straightforward manner to

describe anion exchange reactions on positively charged surface xBa (A a+ )b
V
K AB = (Vanselow), (16.3)
sites. An example of Equation 16.1 of importance to sodicity x Ab (B b + )a

16-1
16-2 Properties and Processes

VK ~
= 1 at Q = 0.05 molc dm–3 16.2  Surface Charge and Ion
GK ~
= 1 at Q = 0.05 molc dm–3 Exchange Capacities
1
As noted above, ion exchange phenomena involve adsorption
reactions that balance the intrinsic surface charge of soil par-
0.8
ticles. The intrinsic surface charge density σin (molc kg−1) is the
sum of the net structural surface charge density σ0 (mol kg−1)
0.6
and the net proton surface charge density σH (mol kg−1) (Sposito,
ECa

1998, 2008):
0.4
G ~
K = 1 at Q = 0.5 molc dm–3
0.2 σin ≡ σ0 + σ H . (16.7)
VK = 1 ~
at Q = 0.5 molc dm–3

0 The net structural (“permanent”) surface charge density σ0

0 0.2 0.4 0.6 0.8 1
~ results from crystalline defects, such as isomorphic substitu-
ECa
tions of Si(IV), Al(III), or Mg(II) by lower-valence cations in 2:1
FIGURE 16.1  Binary Na–Ca ion exchange isotherm on a montmo- phyllosilicates (smectites, vermiculites, illites, and micas; Figure
rillonitic soil at Q̃ = 0.05 molc dm−3 (diamonds, Fletcher et al. (1984b)) 16.2a); for these 2:1 phyllosilicates, σ0 contributes dominantly
plotted as ECa vs. Ẽ Ca. Nonselective isotherms were calculated  for the to σin and is invariably negative. The net proton (“variable”)
Vanselow (thick lines) and Gapon conventions (thin lines) at Q̃ = 0.05 surface charge density σH (the difference between the moles of
and 0.5 mol dm−3 (solid lines and dashed lines, respectively). protons and the moles of hydroxide ions complexed by surface
functional groups (σH = qH − qOH)) results from Brønsted acid
surface groups with a pH-dependent charge, such as hydroxyl,
G EB (A a + )1/a carboxyl, or phenol groups (Figure 16.2b); it is predominant in
K AB = (Gapon), (16.4)
EA (B b + )1/b natural organic matter, kaolinite, and oxide minerals and can be
negative, zero, or positive depending on pH, ionic strength, and
GT EBa (A a+ )b other conditions.
K AB = (Gaines and Thomas), (16.5)
EAb (B b+ )a Charge balance at solid–water interfaces imposes that Δq, the
sum of the adsorbed ion charge densities qi of all species except
surface-complexed H+ and OH− ions, equals the opposite of the
where
VK, GK, and GTK are the Vanselow, Gapon, and Gaines–
intrinsic surface charge density (Sposito, 1998, 2008):
Thomas selectivity coefficients, respectively
(Aa+) is the thermodynamic activity of Aa+ in aqueous σ0 + σ H + Δq = 0. (16.8)

solution
xA is the fractional contribution of Aa+ to the total number of
The net adsorbed ion charge Δq can be expressed as a sum of the
moles of exchangeable cations (xA = nA/Σini)
net charge of ions adsorbed in the Stern layer (σS) (ions immo-
bile on timescales >10 ps [Sposito et al., 1999]) or in the diffuse
By definition, nonselective (or nonpreference) Na–Ca binary ion swarm (σd). The Stern layer charge component can be fur-
exchange isotherms are obtained if VK = 1, GK = 1, or GTK = 1; ther divided into the contributions of inner-sphere (σIS) and
examples are plotted in Figure 16.1 for Q̃ = 0.05 mol dm−3 (solid outer-sphere (σOS) surface complexes (formed by direct contact
lines) and Q̃ = 0.5 mol dm−3 (dashed lines). Clearly, despite its name, of surface functional groups or through one or more interposed
nonselective exchange can differ among models and produce a water molecules, respectively) to yield the expression (Sposito,
strong, Q̃-dependent adsorption of the higher-valence ion; caution 1998, 2008):
should therefore be used in assigning underlying mechanistic sig-
nificance to isotherm shapes or selectivity coefficient values.
The most popular two-parameter model is the Rothmund– Δq = σ IS + σOS + σ d . (16.9)

Kornfeld type model, in which the ratio of solute activities in
Equations 16.3 through 16.5 is raised to a fitted power n (Bond, The utility of Equation 16.9 depends on the extent to which the
1995). The Rothmund–Kornfeld model based on Equation 16.3, molecular-scale coordination of adsorbed ions can be deter-
for example, is (Bond, 1995): mined. Equations 16.7 and 16.8 show that σin and Δq can vary
significantly with pH, ionic strength, and other variables that
n influence σH, especially in soils with low permanent structural
VRK x Ba ⎡ (A a+ )b ⎤
K AB = ⎢ b+ a ⎥ . (16.6) charge (i.e., soils poor in 2:1 phyllosilicates). Experimental
x Ab ⎣ (B ) ⎦
data on Δq vs. σH for a kaolinitic tropical soil suspended in
Ion Exchange Phenomena 16-3

(a) (b)

FIGURE 16.2  Major types of ion exchange sites in natural materials: (a) clay siloxane surfaces located near a site of isomorphic substitution
(shown only as the basal surface O atoms (matte gray) and tetrahedral sheet Si atoms (shiny gray) of two stacked smectite lamellae with a K+ ion
(black, forming an inner-sphere surface complex) and nearby water molecules in the interlayer space. (From Sposito, G., N.T. Skipper, R. Sutton,
S.-H. Park, A.K. Soper, and J.A. Greathouse. 1999. Surface geochemistry of the clay minerals. Proc. Natl. Acad. Sci. U. S. A. 96:3358–3364. Copyright
1999 National Academy of Sciences, U.S.A.) (b) pH-dependent sites resulting from the deprotonation of Lewis acid groups on organic matter or
mineral oxide surfaces (here three carboxyl groups of natural organic matter (with O atoms in matte gray) coordinating an almost completely
desolvated Ca 2+ ion (central dark gray atom)). (From Sutton, R., G. Sposito, M.S. Diallo, and H.-R. Schulten. 2005. Molecular simulation of a model
of dissolved organic matter. Environ. Toxicol. Chem. 24:1902–1911. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. With permission.)

LiCl solutions of varying ionic strength and pH (Figure

40 16.3) confirm the inverse relationship between Δq and σH in
Equation 16.8 and the strong dependence of intrinsic surface
35 ++ charge density on experimental conditions. Thus, measured
ion exchange isotherms and Q values for such variable-charge
30
+ soils may be highly sensitive to pH and other conditions that
+
25 determine σH.
++ + The pH dependence of surface charge is characterized by
∆q (mmolc kg–1)

20 points of zero charge, pH values at which one or more of the

+
15
surface charge components in Equations 16.8 and 16.9 vanishes
+
+ +
at fixed temperature, applied pressure, and aqueous solution
10 composition (Sposito, 1998, 2008). For example, the pH value at
+ + ++ which σin = 0 (where adsorbed cation and anion charge densi-
5
ties are equal according to Equations 16.7 and 16.8) is the point
++
0 + of zero net charge (p.z.n.c.). Nomenclature for these points of
+ ++ zero charge is listed in Table 16.1. Unfortunately, previous ter-
–5 + minology for the points of zero charge has been highly erratic
+
(e.g., both the p.z.s.e. and the p.z.n.c. have been termed points
–10
of zero charge, while the p.z.n.p.c. has been termed zero point of
–25 –20 –15 –10 –5 0 5 10 15 20 25
charge). Furthermore, the points of zero charge frequently have
σH (mmolc kg–1)
been indirectly determined from experimental data on electro-
FIGURE 16.3  “Chorover plot” (Chorover and Sposito, 1995) of phoretic mobility or particle flocculation (calculations sensitive
the net adsorbed ion charge against the net proton surface charge
density for a Brazilian oxisol (Manaus soil). The combined data, for TABLE 16.1  Points of Zero Charge
ionic strengths of 0.001 (open circles), 0.005 (crosses), and 0.01 (filled Symbol Name Definition
circles) mol kg−1, can be fit to the regression equation (solid line): Δq = p.z.n.c. Point of zero net charge σin = 0
−1.01(±0.07)σH + 12.5(±0.8), where Δq and σH are in mmolc kg−1. Charge
p.z.n.p.c. Point of zero net proton charge σH = 0
balance is confirmed by the values of the slope and both intercepts
p.z.c. Point of zero charge σp = 0a
(σ0 = 12.5 ± 0.4 mmolc kg−1 in direct measurement). (From Geochim.
p.z.s.e. Point of zero salt effect ∂σH/∂I = 0
Cosmochim. Acta, 59, Chorover, J. and Sposito, G., Surface charge
characteristics of kaolinitic tropical soils, 875–884, Copyright 1995, a σ (≡ σ + σ + σ + σ ) is the net particle surface
p 0 H IS OS
with permission from Elsevier.) charge density.
16-4 Properties and Processes

TABLE 16.2  Typical Cation Exchange between the standard-state chemical potentials μ0[…] of the
Capacities (CEC, in molc kg−1) of Soils and products and reactants in Equation 16.1, termed the standard
Major Soil Constituents Gibbs energy change of the reaction:
Solid CEC
Soils 0.01–1.4 Δ rG 0 = − RT ln ex K AB = a μ 0[X bB] + b μ 0[Aa+ ] − b μ 0[X a A] − a μ 0[Bb+ ],
Natural organic matter 0.8–10a
Vermiculite 1.6–2.5 where
Smectite 0.7–1.7 R is the molar gas constant
Illite 0.2 T is the absolute temperature
Mica 0.1
Kaolinite <0.05 The equilibrium chemical potentials μ of reactants and products
Increasing with pH and in the order peat <
a typically differ from their standard-state values μ0, and this dif-
humic acid. ference must enter Equation 16.10 through the thermodynamic
Source: Sposito, G. 2004. The surface chemistry activities on its right side. For the aqueous species Aa+ and Bb+,
of natural particles. Oxford University Press,
the activity is defined by setting
Oxford, U.K.; Sposito, G. 2008. The surface chemis-
try of soils. 2nd edn. Oxford University Press,
Oxford, U.K. (i) ≡ γ iCi , (16.11)

to the assumed distribution and mobility of ions in the electrical
where γi is an activity coefficient (dm−3 mol), commonly
double layer [Fair and Anderson, 1989; Hunter, 1993]) or from
expressed relative to the infinite dilution reference state at
acid–base titrations of solid suspensions (calculations that often
T  = 298.15 K and P = 1 atm with the semiempirical Davies
use untested assumptions on the initial value of the net proton
equation (Sposito, 1994):
surface charge [Sposito, 1998; Bourg et al., 2007]).
If all adsorbed ions (except surface-complexed H+ and OH−)
are readily exchangeable, then Δq = CEC − AEC, where CEC ⎧⎪ I ⎫⎪
ln γ i = −0.512zi2 ⎨ − 0.3I ⎬ (I < 0.5 mol dm −3 ) (16.12)
is the cation exchange capacity (equal to Q plus the usually
⎩⎪ 1 + I ⎭⎪
small positive equivalent adsorbed charge contributed by anion
exclusion from the vicinity of X− surface sites [Sposito, 2008])
where I is the ionic strength (I = 1/2 ∑ i zi2Ci ). For adsorbed spe-
and AEC is the anion exchange capacity (defined equivalently
cies, if the exchanger phase is pictured as analogous to a solid
for anion exchange on positively charged surface functional
solution of two components Xa A and XbB, an appropriate model
groups). Ranges of the CEC of soils and soil constituents are
of thermodynamic activity should be (Argersinger et al., 1950;
listed in Table 16.2. The AEC of soils is usually less than 0.05 molc
Sposito, 1994)
kg−1 (Sposito, 2008). Major contributors to the CEC of soils are
the widely studied smectite clay minerals (Sposito et al., 1999;
Sposito, 2008) and the less well-characterized soil organic mat- (i) ≡ fi xi , (16.13)

ter (Helling et al., 1964; Curtin et al., 1998; Sutton and Sposito,
2005; Sposito, 2008). Micaceous minerals (illite, mica) also play where the rational activity coefficient f i (dimensionless) is
an important role in the uptake of small quantities of weakly sol- equal to 1 in the conventionally chosen reference state x i = 1,
vated ions, such as K+, NH +4 , and Cs+ (Maes and Cremers, 1986; I = 0, T = 298.15 K, and P = 1 atm (Gaines and Thomas, 1953;
Bradbury and Baeyens, 2000). Sposito, 1994). No model for f i of similar applicability and
simplicity to Equation 16.12 currently exists for f i . However,
16.3  Ion Exchange Thermodynamics Equations 16.3, 16.10, and 16.13, and the Gibbs–Duhem rela-
tion at fixed T, P [xA d ln fA + x B d ln f B = 0] yield closed-form
If Equation 16.1 describes a true chemical equilibrium and expressions for calculating ex K and f i from experimental
the exchanger sites X− are all identical (or are taken to repre- ion exchange isotherms at fixed Q̃ (Argersinger et al., 1950;
sent an average site), a thermodynamic equilibrium constant Sposito, 1994):
or exchange equilibrium coefficient ex K can be defined with the
relation (Sposito, 1994): 1

a
(X B) (A ) a+ b
ex B
A
∫
ln K = ln V K AB dEB , (16.14)
ex
K = b b b+ a ,
B
A (16.10) 0

(X a A) (B )
EB

where (i) represents the thermodynamic activity of species i.

The equilibrium constant ex K is directly related to the difference
b ln f A = EB ln V K AB −
∫ ln
0
V
K AB dEB . (16.15)
Ion Exchange Phenomena 16-5

In the context of the solid-solution picture, the A–B exchange is materials (a series of several acid washes [pH ≈ 4], exchange-
defined as ideal if fA = f B = 1, that is, if VK AB = exK AB , and nonprefer- able cation homogenization [I ≈ 1 M], and rinsing steps followed
ence if exK AB = 1. The Vanselow model in Equation 16.3 therefore by storage in liquid water at low temperature [Duc et al., 2005;
describes ideal binary exchange and the nonselective isotherms Bourg et al., 2007]), and (2) measured qi and Ci for all compet-
with VK = 1 in Figure 16.1 are ideal thermodynamic nonprefer- ing ions (Table 16.3). For the sake of brevity, we focus on results
ence isotherms. Binary exchange ex K values should obey the “tri- obtained at T ≈ 298 K and do not discuss the temperature depen-
angle rule”: c log exK AB + a log exK BC + b log exK CA = 0, as has been dence of VK or the estimation of enthalpic and entropic contri-
verified within ±0.1 log units for montmorillonite (Lewis and butions to the Gibbs energy of exchange (Gast, 1972; Maes and
Thomas, 1963; Gast, 1969), vermiculite (Wild and Keay, 1964), Cremers, 1978; Morel et al., 2007).
and illite (Brouwer et al., 1983).
Since the reference state for surface species includes the ionic
16.4.1  Smectites
strength condition I = 0, Equations 16.14 and 16.15 are strictly
valid only if applied to VK AB vs. EB data measured at several Q̃ Ion exchange reactions on smectites that involve only strongly
values and then extrapolated to Q̃ = 0 (Gaines and Thomas, hydrated cations (Li+, Na+, and divalent metal cations M2+) have
1953). In practice, this extrapolation is rarely done, but VK val- VK values that display no hysteresis (Verburg and Baveye, 1994)

ues for exchange reactions on smectites and soils have been and are independent of Ei within 0.1 log units (Gast, 1969; Sposito
shown to have a rather small Q̃-dependence (≤0.1 log units) if et al., 1981, 1983a, 1983b, 1983c; Tang and Sparks, 1993; Zhang
Q̃ ≤ 0.2 molc dm−3 (Laudelout et al., 1972; Jensen and Babcock, and Sparks, 1996), that is, they are ideal within experimental pre-
1973). Furthermore, the rational activity coefficients fi calculated cision. (Erroneous reports of “nonideal” heterovalent exchange
with Equation 16.15 are strictly valid only for the binary sys- reactions have been based on plots of GT K AB vs. EB [Banin, 1968;
tems in which they were measured; expressions for fi in ternary Keren, 1979; McBride, 1980]; for example, the significant depen-
or more complex exchange systems are much more complicated dence of GT K Na
M
on EM [M = Cu, Cu, Ni, or Zn] observed for mont-
(Chu and Sposito, 1981; Sposito, 1994). However, several mod- morillonite is in fact consistent with an ideal exchange reaction
els of comparable accuracy have been proposed for estimating since V K Na
M
is independent of EM [Sposito and Mattigod, 1979].)
ternary-system activity coefficients from binary ion exchange Exchange reactions between strongly hydrated cations are
isotherm data (Bond and Verburg, 1997). mildly selective (i.e., slightly favor the adsorption of cations of
larger ionic radius or larger valence) and weakly affected by the
16.4  Trends in VK and ex K type of smectite (Table 16.4). As expected from the near ideality
and weak selectivity of cation exchange reactions on smectites
Broad syntheses of ion exchange data for natural materials are in the absence of weakly hydrated ions, chemical speciation in
scarce, despite the large number of reported experimental stud- such systems can be reasonably well described using log KV ≈ 0
ies. This scarcity results in part from the complexity of soils. for all ion exchange reactions, for example, the systems Na–H
Even for smectite minerals (the most widely studied soil con- (Tournassat et al., 2004), Na–Cd, and Na–UO2–UO2(OH)–
stituent), analyses of ion exchange data are complicated by the (UO2)3(OH)5 (Zachara and McKinley, 1993).
difficulty of isolating these clays (exchangeable cation homog- Binary reactions that involve at least one weakly hydrated
enization and removal of carbonate, organic matter, and Al cation (K+, NH 4 + , Rb+, Cs+, large organic cations, and, to a
and Fe hydroxide impurities require a careful choice of sample smaller extent, Ba 2+) are typically nonideal, and they fre-
pretreatment and storage procedures [Duc et al., 2005]) and quently display hysteresis (Verburg and Baveye, 1994; Laird
of accurately calculating the selectivity coefficient (VK calcu- and Shang, 1997; Chatterjee et al., 2008) along with a strong
lated without measuring Ci and qi for all competing ions may dependence of VK on Ei (Gast, 1969; Maes and Cremers, 1978;
be highly imprecise [Pabalan and Bertetti, 1999]). In addition, McBride, 1979; Shainberg et al., 1987; Amrhein and Suarez,
the measured selectivity coefficients may vary with experimen- 1991), especially if the exchanging cations have very different
tal conditions, such as Q̃, pH, solid–liquid ratio ms, or type of hydration energies. This nonideality may result in part (but
background anion because of poorly understood processes, such not entirely [Maes and Cremers, 1978; Laird and Shang, 1997])
as ion-pair adsorption (Sposito et al., 1983a, 1983b; Griffoen from the greater selectivity of octahedral-charge sites vs. tetra-
and Appelo, 1993; Charlet and Tournassat, 2005), adsorption on hedral-charge sites (i.e., sites resulting from isomorphic sub-
variable-charge sites on the edge surfaces of smectite lamellae stitutions in the octahedral or tetrahedral sheet, respectively,
(Fletcher and Sposito, 1989; Chen and Hayes, 1999), or the influ- of phyllosilicate minerals) for weakly hydrated cations (Xu
ence of experimental conditions on exchanger structure (Laird and Harsh, 1992; Onodera et al., 1998). Among alkali metals
and Shang, 1997). and organic cations, the adsorption selectivity of weakly hydrated
In this section, we summarize current knowledge of the ion cations increases with ionic radius (Gast, 1972; Maes and
exchange selectivity of smectites, micaceous minerals, and soils Cremers, 1986; Teppen and Aggarwal, 2007) because larger,
based on reported VK and ex K values. In the case of smectites, less strongly hydrated ions have lower affinity for the aque-
we base our analysis as much as possible on studies that (1) used ous solution phase (Mizutani et al., 1995; Teppen and Miller,
solid pretreatment practices known to produce pure, homoionic 2006; Teppen and Aggarwal, 2007). Selectivity also increases
16-6 Properties and Processes

TABLE 16.3  Compilation of the Best Available Data Sets on Cation Exchange on Smectite Clay Minerals
Reference Solid Cations Comments
Gast (1972) Arizona montmorillonite Na–Li, Na–K, Na–Rb, Q̃  = 1 mmolc dm−3 (Cl− electrolyte); T = 298 K; ms not specified;
and Na–Cs qi values not measured
Maes and Cremers (1977) Otay and RCCBa Na–Ca Q̃  = 10 mmolc dm−3 (Cl− electrolyte); T = 298 K; ms ≈ 10 g kg−1;
montmorillonites qi values not measured
Maes and Cremers (1978) Otay and RCCB Na–Cs Q̃  = 10 mmol dm−3 (Cl− electrolyte); T = 298 K; ms not specified;
montmorillonites, hectorite pH = 5.5–6; clay stored in freeze-dried form; qi values not measured
Sposito et al. (1981) Wyoming montmorillonite Na–Cu Q̃  = 10 mmolc dm−3 (Cl− or ClO4 − electrolytes); T = 298 K;
ms = 13–21 g kg−1; pH = 5–6 to avoid Cu adsorption on oxide-type
edge surface sites
Sposito et al. (1983a, Wyoming montmorillonite Na–Ca, Na–Mg, Q̃  = 50 mmolc dm−3 (Cl− or ClO4 − electrolytes); T = 298 K;
1983b, 1983c) Ca–Mg, and ms = 20–30 g kg−1; pH = 6.8–7.1
Na–Ca–Mg
Xu and Harsh (1992) Cameron montmorillonite Na–Li, Na–K, Na–Rb, Q̃  = 10 mmolc dm−3 (Cl− electrolyte); T = 298 K; ms not specified;
and Na–Cs Ci and qi values not reported; VK values reported only at ENa = 0.5
Tang and Sparks (1993) Wyoming montmorillonite Na–Ca and K–Ca I = 10 mmol dm−3 (Cl− electrolyte); T = 296 K; ms = 10.2 g dm−3;
pH = 6.8; clay stored in freeze-dried form
Zhang and Sparks (1996) Wyoming montmorillonite Na–Cu Q̃  = 20 mmolc dm−3 (ClO4 −, Cl−, NO3 −, or SO4 2− electrolyte); T = 298 K;
ms ≈ 16–17 g dm−3; pH = 5.2–6.5, decreasing with qCu; clay stored in
freeze-dried form
Laird and Shang (1997) Synthetic fluorohectorite Mg–Ba Q̃  = 20 mmolc dm−3 (Cl− electrolyte); T = room temperature;
ms = 10 g dm−3; no acid wash, but the material (a synthetic
magnesium silicate) should not contain Al or Fe hydroxides or
organic impurities; clay stored in freeze-dried form
Charlet and Tournassat Wyoming montmorillonite Na–Fe(II), Ca–Fe(II), Q̃  = 50 or 130 mmolc dm−3 (Cl− electrolyte); T not specified;
(2005) Na–Ca–Fe(II) ms = 4–8 g dm−3; pH = 2.1–3.6 to avoid Fe adsorption on oxide-type
edge surface sites; qFe not measured (estimated by mass balance)
a RCCB montmorillonite: reduced-charge Camp-Berteau (Morocco) montmorillonite. Layer charge was reduced by 5%–41% using the Hofmann–Klemen
effect (Maes and Cremers, 1977, 1978).
The studies by Gast (1972) and Maes and Cremers (1977, 1978) are tentatively included, despite the fact that they did not include measurements of qi values,
because of the good quality of their pretreatment methods. Studies that used smectites stored by freeze-drying also are tentatively included, although storage in
liquid water at low temperature is preferred (Duc et al., 2005). Experimental procedures that may adversely affect the quality of experimental results are reported
in italics in the last column.

with surface charge density (Gast, 1972; Maes and Cremers, The reactivity of external basal surfaces of illite and mica crystals
1978; Shainberg et al., 1987; Xu and Harsh, 1992) (Table 16.4) is thought to be similar to that of smectites (Brouwer et al., 1983),
and perhaps especially with the charge density of octahedral- but the crystals also carry a small population of sites (0.1%–10%)
charge sites (Xu and Harsh, 1992). with a very high affinity for weakly hydrated cations (K+, NH 4 + ,
Metal–ligand complexes also can adsorb by ion exchange, Rb+, and Cs+) (Brouwer et al., 1983; Thellier and Sposito, 1989;
but this process has not been deeply studied. The strong adsorp- Liu et al., 2004; Tournassat et al., 2007). These so-called frayed-
tion of copper-ethylenediamine complexes Cu(en)2+ 2 (Maes edge sites occur at partially propped-open, K+-depleted edges of
and Cremers, 1986) and the complexation of nitroaromatic collapsed interlayers (Rajec et al., 1999; McKinley et al., 2004).
compound with exchangeable cations on smectite surfaces Adsorption on frayed-edge sites may be determined to a cer-
(Chatterjee et al., 2008) are consistent with the expectation that tain extent by nonequilibrium processes, such as diffusion-
metal–organic complexes should have an affinity similar to large controlled adsorption over timescales of weeks or more (Comans
organic cations for smectite surfaces. Divalent metals are known et al., 1991). Such processes can cause difficulties in defining
to coadsorb with anions, such as Cl− (Sposito et al., 1983a, 1983b; and measuring ion exchange selectivity, since the population of
Charlet and Tournassat, 2005) or HCO3− (Griffoen and Appelo, “accessible” frayed-edge sites may vary with time, experimental
1993), but the mechanism of this coadsorption (ion-pair forma- conditions, the type of exchangeable cation, and the choice of
tion or diffuse layer process) and its dependence on experimen- agent used to extract adsorbed cations for measuring qi (Brouwer
tal conditions are not well understood (Sposito, 1991). et al., 1983; Comans et al., 1991; Baeyens and Bradbury, 2004;
Tournassat et al., 2007). Nevertheless, the finding that frayed-
edge sites obey the “triangle rule” (Brouwer et al., 1983) suggests
16.4.2  Micaceous Minerals
that ion exchange on these sites can be reasonably well described
Illites and micas have a lamellar morphology similar to that of on certain timescales as a thermodynamic process. If ion B = K,
smectites but with collapsed, K+-filled interlayers (Sposito, 2008). Rb, or Cs, experimental VK AB values decrease sharply with EB
Ion Exchange Phenomena 16-7

TABLE 16.4  Recommended Values for VK on Smectite Based on the Studies Listed in Table 16.3
Variable log K References
Exchanges of two strongly hydrated cations
V Li
K Na −0.08 ± 0.06 Gast (1972), Xu and Harsh (1992)
V M(II)
K Na 0.11 ± 0.11a (M = Mg, Ca, and Cu) Maes and Cremers (1977), Sposito et al. (1981, 1983a),
Tang and Sparks (1993), Zhang and Sparks (1996)
V Ca
K Mg 0.01 ± 0.02 (ENa = 0, 0.016, or 0.036) Sposito et al. (1983b, 1983c)
V Ca
K Fe(II) ~0.01 Charlet and Tournassat (2005)b
Exchanges involving at least one weakly hydrated cation
ex K
K Na 0.58 ± 0.14c Gast (1972), Xu and Harsh (1992)
ex
K Rb
Na 1.08 ± 0.25c Gast (1972), Xu and Harsh (1992)
ex
K Cs
Na 1.23 × CEC − 0.06 d Gast (1972), Maes and Cremers (1978), Xu and Harsh (1992)
V Ba
K Mg ~0.5 in the three-layer hydrate, increasing Laird and Shang (1997)
to ~1.4 in the two-layer hydrate
Confidence intervals calculated as ±2σ where several VK values were available.
a Neglecting Na–Ca exchange data obtained with reduced-charge montmorillonites, which show V Ca values closer
K Na
to 0 (Maes and Cremers, 1977).
b Charlet and Tournassat (2005) erroneously reported their GTK values as VK values, but for homoionic Ca–Fe(II)

exchange GTK = VK.

ex K ex Rb
c log K Na and log K Na are thought to increase with Q (Shainberg et al., 1987; Xu and Harsh, 1992).
d Linear regression with r2 = 0.91, p < 0.001; CEC = 0.66–1.44 mol kg−1, estimated from the number of octahedral and
c
tetrahedral substitutions in the clay unit cell formula.

when the frayed-edge sites become B-saturated (Brouwer et al., The first type of approximation is exemplified by the ion
1983), a behavior that can be described with a two- or three-site exchange properties of Amazon river suspended matter in the
model, that is, one or two types of highly selective frayed-edge system Na–K–Ca–Mg, which are essentially identical to those
site plus weakly selective basal surface sites (Maes and Cremers, of montmorillonite, even though only half of the CEC of the
1986; Liu et al., 2004; Tournassat et al., 2007). suspended matter originates from its clay-size fraction (Charlet
and Tournassat, 2005). The second type of approximation is well
illustrated by the fact that the Mg–Ca exchange selectivity of soils
16.4.3  Soils and Sediments
is correlated with their ratio of organic carbon to clay content
For highly heterogeneous, multiphase media such as soils and sed- (Curtin et al., 1998). Curtin et al. (1998) successfully described
iments, Equations 16.14 and 16.15 have no clear thermodynamic the Mg–Ca selectivity of several soils with a two-site model
meaning and any selectivity model may be suitable on a case-by- where the soil organic matter and clay fractions were represented
case basis. For example, the Gapon selectivity coefficient has been by log V K Mg
Ca
= 0.6 and 0.1, respectively. Similar additive behavior
found to be less variable than VK over broad ranges of exchanger of soil smectites and soil organic matter has been used to inter-
phase composition for Na–Ca, Mg–K, and Ca–K exchange pret the ion exchange selectivity of montmorillonitic soils in the
reactions in some soils (Naylor and Overstreet, 1969; Jensen system Na–Ca–Mg (Fletcher et al., 1984a; Sposito and Fletcher,
and Babcock, 1973; Evangelou and Coale, 1987; Feigenbaum 1985) and may also explain the Ca–Sr selectivity of soils (Juo
et al., 1991; Agbenin and Yakubu, 2006). Experimental data on and Barber, 1969) and the Ca–Cd and Ca–Zn selectivity of acidic
log V K Ca
M
vs. EM (M = Na,K,or Mg) obtained for a range of con- soils (Voegelin and Kretzschmar, 2003). Additive behavior of
ditions of pH, Q̃, and soil type illustrate the variability of the micaceous materials and other soil constituents may explain the
ion exchange selectivities of soils (Figure 16.4). The scatter of strong adsorption of K+ and Cs+ at low EK or ECs values in numer-
log V K Ca
Na
values at ENa ≤ 0.2 in Figure 16.4b may reflect in part the ous soils and sediments (Feigenbaum et al., 1991; Bradbury and
high sensitivity of VK at small Ei values to sources of error such Baeyens, 2000; Sinanis et al., 2003; Liu et al., 2004; Agbenin and
as the dissolution of soil materials (Carlson and Buchanan, 1973; Yakubu, 2006). The concept that soil ion exchange selectivity is
Sheta et al., 1981). a sum of the selectivities of component phases evidently can be
Despite the inherent complexity of soil and sediment ion quite powerful (Sposito and Fletcher, 1985; Curtin et al., 1998;
exchange properties, these have been modeled conceptually with Bradbury and Baeyens, 2000; Charlet and Tournassat, 2005),
some success assuming their exchange properties result from although it neglects nonadditive behavior such as the enhanced
their smectite constituent (Charlet and Tournassat, 2005) or from (about 0.3 log unit greater) Na–Ca selectivity of smectites when
the sum of their smectite, organic matter (Curtin et al., 1998), their interlayers contain Al-hydroxide polymers (Keren, 1979;
and/or micaceous constituents (Bradbury and  Baeyens,  2000). Janssen et al., 2003).
16-8 Properties and Processes

2.00 2.00
Mg
log VK Ca log VK Ca
Na

1.50 1.50

1.00 1.00

0.50 0.50
EMg ENa
0.00 0.00
0 0.5 1 0 0.5 1
–0.50 –0.50

–1.00 –1.00

–1.50 –1.50
(a) (b)

3.00
log VKCa
K

2.50

2.00

1.50

1.00

0.50
EK
0.00
0 0.5 1
–0.50
(c)
Mg
FIGURE 16.4  Compilation of experimental data on log V K Ca M
vs. EM (M = Mg2+, Na+, or K+) in soils if Q̃ ≤ 0.2 mol dm−3 and T = 298 K; (a) log V K Ca
data for a loam soil (Jensen and Babcock, 1973), calcareous clay soils (Van Bladel and Gheyi, 1980), smectitic soils with 27–96 g kg organic carbon
−1

(Curtin et al., 1998), and a montmorillonitic soil (DeSutter et al., 2006); (b) log V K Ca
Na
for a montmorillonitic soil (Fletcher et al., 1984b), kaolinitic
soils (Levy et al., 1988), a kaolinitic sandy loam soil with 25.7 g kg−1 organic carbon (Rhue and Mansell, 1988), a calcareous, smectitic clay soil
(Amrhein and Suarez, 1991), and an illite–kaolinite clay soil (Bond, 1995); (c) log V K Ca K
for a loam soil (Jensen and Babcock, 1973), kaolinitic soils
(Levy et al., 1988), a kaolinitic sandy loam soil with 25.7 g kg organic carbon (Rhue and Mansell, 1988), an illite–kaolinite clay soil (Bond, 1995),
−1

and a tropical soil (Agbenin and Yakubu, 2006).

16.5  Ion Exchange and Chemical Equation 16.16 can be incorporated into conventional chemical
speciation models using its analogy with surface complexation
Speciation Models or solid-solution reactions, as described below.
Analytical solutions of thermodynamic equations to deter-
mine exchanger phase composition rapidly become intrac- 16.5.1  Modeling Ion Exchange as a Surface
table in systems that involve more than three exchangeable Complexation Process
ions (Bond and Verburg, 1997). For such complex systems, a
numerical solution can be implemented in chemical specia- Most chemical speciation programs include a model of sur-
tion models after dividing Equation 16.1 into two hypothetical face complexation reactions (similar in form to Equation 16.16)
half-reactions involving a fictitious anionic species X− (Sposito where the thermodynamic activities of uncharged surface
and Mattigod, 1977; Shaviv and Mattigod, 1985; Fletcher and species arbitrarily are set equal to their concentrations [X ii]
Sposito, 1989): (Sposito, 2004). On this model, the half-reaction selectivity coeffi-
cients associated with Equation 16.16 are the following (Fletcher
a+ and Sposito, 1989; Stadler and Schindler, 1993):
aX − + A(aq) = X a A(s) , (16.16a)

half [X a A]
b+ KA = , (16.17a)
bX − + B(aq) = X bB(s) . (16.16b) (X − )a (A a + )
Ion Exchange Phenomena 16-9

[X bB] where (X−) is the activity of a fictitious dissolved species. In the

half
KB = . (16.17b) program PHREEQC2, Equation 16.19 can be solved by defin-
(X − )b (B b+ )
ing X−, Aa+, and Bb+ as dissolved species and Xa A and X bB as
solid phases and by setting solubilityK ≪ 1 for a chosen reference
Equation 16.17 can be incorporated into any program that cation, such that X− contributes negligibly to the mass balance
models surface complexation reactions; typically, half K is set to on X. If fA = f B = 1, Equation 16.19 is identical to the Vanselow
a very large value (1010 –1020) for a reference cation, such that model with
the wholly uncomplexed X− sites contribute negligibly to the
total mass balance on X, and the half K values of other cations are
chosen to fit experimental equilibrium constants (Flechter and V ⎡ ( solubility K B )a ⎤
K AB = ⎢ solubility A b ⎥ . (16.20)
Sposito, 1989; Stadler and Schindler, 1993). Certain chemical ⎣( K ) ⎦

speciation programs include a specific model of ion exchange
reactions based on Equation 16.17. For example, in the program
The ideality of ion exchange reactions between strongly hydrated
PHREEQC2 (Appelo and Postma, 2005), the fictitious species
cations on smectite (Table 16.4) suggests that Equation 16.19 may
X− is excluded from the total mass balance on X and Na+ is cho-
be more accurate than Equation 16.17 for multicomponent ion
sen as a reference species with log half KNa = 0. Suggested values of
half K for other cations on smectite are provided in the PREEQC2 exchange reactions on smectite over broad ranges of exchanger
phase composition. However, to our knowledge, Equation 16.19
database (Appelo and Postma, 2005). The use of Equation 16.17
has never been used for this purpose.
with fixed half K values corresponds to an implicit assumption
that GTK is equal to an equilibrium constant, since GTK and half K
are related through
16.6  Micro- and Nanoscale Perspectives
⎡ ( half K B )a ⎤ ⎛ ba ⎞ on Ion Exchange Selectivity
GT
K AB = ⎢ half A b ⎥ ⎜ b ⎟ Q (b − a) . (16.18)
⎣( K ) ⎦⎝ a ⎠ Micro- and nanoscale studies have yielded insight into the
processes that determine VK using theoretical estimates of
Equation 16.17 has been used to model ion exchange reactions long-range electrostatic forces (Barak, 1989; Rytwo et al.,
involving protons, alkali metals, trace metals,  and  actinides 1996), short-range interactions (Shainberg and Kemper, 1966;
on clay minerals (Stadler and Schindler, 1993;  Zachara  and Eberl, 1980), or statistical mechanical quantities (Sposito,
McKinley,  1993; Poinssot et  al.,  1999;  Bradbury and Baeyens 1993; Benjamin, 2002). In the present chapter, we focus on
2000, 2005, 2009; Baeyens and Bradbury,  2004; Charlet and two subfields illustrating micro- and nanoscale studies: (1) the
Tournassat, 2005; Heidmann et al., 2005; Bourg et al., 2007; Gu molecular-scale ­coordination and dynamics of exchangeable
and Evans, 2008). Most of these studies (with the notable excep- ions and (2) the influence of exchanger microstructure on ion
tion of Charlet and Tournassat, 2005) investigated systems where exchange selectivity.
half K should be constant if ion exchange is ideal, either because

the main background electrolyte cation was Aa+ and occupied

most ion exchange sites, such that GT K AB ⊕ V K AB (b/a)a, or because 16.6.1  Molecular-Scale Coordination and
the system studied was homovalent, in which case GT K AB = V K AB. Dynamics of Exchangeable Ions
Spectroscopic and molecular simulation methods have been
widely used to probe the coordination environment and dynam-
16.5.2  Modeling Ion Exchange ics of exchangeable cations in smectites (Sposito and Prost, 1982;
as a Solid-Solution Process Sposito, 2004; Skipper et al., 2006) and have been increasingly
Some chemical speciation programs include a model of solid- applied to other exchanger phases (Skipper et  al., 1995; Kim
solution formation, which is also similar in form to Equation and Kirkpatrick, 1998; Schlegel et al., 2006; Xu  et  al., 2006).
16.16. The “solubility coefficients” associated with Equation 16.16 Spectroscopic techniques can probe the molecular structure
are described as follows in the solid-solution formalism (Appelo of the interface as a function of distance from a solid surface
and Postma, 2005): (by x-ray reflectivity [Schlegel et al., 2006; Park et al., 2008]), the
dynamics of water H atoms (by quasielastic neutron scattering
[QENS] [Marry et al., 2008]), the local coordination environ-
solubility (X − )a (A a+ ) ment of certain atomic probes (such as water or Li by neutron dif-
KA = , (16.19a)
xA fA fraction with isotopic substitution [NDIS] [Skipper et al., 1995;
Powell et al., 1998] or Co, Sr, Pb, Cu, Cs, and other atoms by
x-ray absorption spectroscopy [XAS] [Papelis and Hayes, 1996;
solubility (X − )b (B b+ ) Chen and Hayes, 1999; Strawn and Sparks, 1999; Morton et al.,
KB = . (16.19b)
xB fB 2001; Bostick et al., 2002]), the coordination environment and
16-10 Properties and Processes

rotational dynamics of paramagnetic atoms such as Cu (by et al., 1998; Park and Sposito, 2002; Nakano et al., 2003); the
electron spin resonance [ESR] or electron spin-echo modula- mobility of these cations along smectite basal surfaces is not
tion [ESEM] [McBride et al., 1975; Brown and Kevan, 1988]), well characterized (Kosakowski et al., 2008), but recent results
and the local molecular environment (“chemical shielding”) suggest that they diffuse only 5%–8% as fast as in bulk liquid
of atoms with an odd number of nucleons or protons such as water (Bourg and Sposito, 2010). Clearly, the molecular-scale
23Na, 133Cs, 113Cd, or 35Cl (by nuclear magnetic resonance [NMR] behavior of cations on smectites parallels their ion exchange
[Weiss et al., 1990; Kim and Kirkpatrick, 1998; Xu et al., 2006]). selectivity: The strongly hydrated cations (M 2+, Li+, Na+) adsorb
Molecular simulation techniques, primarily Monte Carlo (MC) mainly as fully solvated OSSC or DL species and display ideal,
and molecular dynamics (MD), have been used for over a decade weakly selective ion exchange behavior, whereas the weakly
to complement spectroscopic results (Chang et al., 1995; Park hydrated ions adsorb mainly as ISSC and display nonideal,
and Sposito, 2002). Most spectroscopic and simulation studies strongly selective ion exchange behavior. The ISSC formed by
have been used to probe homoionic exchangers, but a few studies Li+ and Na+ on tetrahedral-charge sites do not fit this simple
have investigated the behavior of a “reporter” cation doped into a classification, suggesting that Li+ and Na+ may show nonideal
smectite that is almost homoionic in another cation (McBride exchange behavior on smectites with high tetrahedral charge.
et al., 1975; Brown and Kevan, 1988; Marry and Turq, 2003; This point may not have been noticed previously because refer-
Bourg and Sposito, 2010). ence smectites typically carry 80% ± 20% octahedral-charge
Spectroscopic and molecular simulation studies have shown sites (Xu and Harsh, 1992).
that the aqueous phase in smectite interlayers is analogous to Thanks to increases in computational capabilities, MD and
a concentrated ionic solution (Sposito and Prost, 1982; Powell MC simulations may soon be able to “bridge the gap” from the
et al., 1998); in the two- and three-layer hydrates and on external time and length scales (or number of MC simulation steps)
basal surfaces, it diffuses about 30%–40% as fast as bulk liquid required to probe molecular exchanger phase structure and
water (Chang et al., 1997; Marry et al., 2008; Bourg and Sposito, dynamics (<1 ns and ≤1 nm) to the time and length scales
2010). Exchangeable cations in smectite one-layer hydrates form (tens of nanoseconds and nanometers) on which ion exchange
inner-sphere surface complexes (ISSC) for obvious steric rea- equilibria become established (Greathouse and Cygan, 2005;
sons, and they diffuse very slowly (McBride et al., 1975; Chang Rotenberg et  al., 2007). Molecular simulation methods could
et al., 1995, 1997; Bourg and Sposito, 2010); at higher hydration then be used to test Equation 16.13 directly or to predict VK val-
levels, they can be divided into three categories based on their ues (Greathouse and Cygan, 2005; Teppen and Miller, 2006).
interaction with smectite surfaces: divalent metal cations (M2+), Teppen and Miller (2006) showed that the Gibbs energy dif-
strongly hydrated alkali metal cations (Li+, Na+), and weakly ference between K-, Rb-, and Cs-montmorillonite (one com-
hydrated cations (K+, Rb+, Cs+). The divalent cations are adsorbed ponent of the Gibbs energy of exchange) at fixed interlayer
in fully solvated form as outer-sphere surface complexes (OSSC) spacing and interlayer water content could be determined by
or in the diffuse layer (DL) (McBride et al., 1975; Brown and MD simulation. Greathouse and Cygan (2005) found that ten
Kevan, 1988; Papelis and Hayes, 1996; Chen and Hayes, 1999; 1 ns MD simulations of a 4 nm thick Na + −UO22 + −CO23 − aque-
Strawn and Sparks, 1999; Greathouse et al., 2000; Chávez-Páez ous solution on a montmorillonite basal surface were too short
et al., 2001; Morton et al., 2001; Whitley and Smith, 2004); they and small scale to determine VK accurately, but were suffi-
tumble and diffuse slowly, about 1%–10% as fast as in bulk liquid cient to identify important processes, such as the formation of
2−
water (McBride et al., 1975; Brown and Kevan, 1988; Greathouse ⎣⎡ Na 2UO2 (CO3 )3 ⎦⎤ complexes.
et al., 2000; Bourg and Sposito, 2010). The strongly hydrated
monovalent cations (Li+, Na+) also adsorb as OSSC or DL species
16.6.2  Coupling between Cation Exchange
on octahedral-charge sites, but they form inner-sphere surface
and Exchanger Structure
complexes (ISSC) on tetrahedral-charge sites (Chang et al., 1995,
1997; Leote de Carvalho and Skipper, 2001; Marry and Turq, As pointed out above, Equation 16.10 has strict thermodynamic
2003; Marry et al., 2003; Tambach et al., 2004, 2006; Greathouse meaning only if all exchanger sites X− are identical. For smec-
and Cygan, 2005); they diffuse about 20%–60% as fast as in bulk tites (Sposito, 1992; Laird and Shang, 1997) and natural organic
water if adsorbed on octahedral-charge sites, but are essentially matter (Sutton et al., 2005), however, the microstructure of
immobile (on subnanosecond timescales) on tetrahedral-charge the exchanger phase depends on experimental conditions and,
sites (Chang et al., 1995, 1997; Leote de Carvalho and Skipper, therefore, the X− may not be identical at different points along
2001; Marry and Turq, 2003; Bourg and Sposito, 2010). Finally, a binary exchange isotherm, or even in different regions of the
the weakly hydrated cations form primarily ISSC on smec- exchanger phase within a single sample. In the case of smectite
tite surfaces along with small amounts of OSSC or DL species clay minerals, the stacking arrangement of smectite lamellae
(Chang et al., 1998; Nakano et al., 2003; Whitley and Smith, (number of layers per stack, interlayer spacing) is a dynamic,
2004; Tambach et al., 2006; Liu et al., 2008); two populations nonuniform property (several interlayer hydration levels may
of ISSC exist in Cs- and K-smectite interlayers that may corre- coexist [Tamura et al., 2000; Wilson et al., 2004; Ferrage et al.,
spond to cations located above ditrigonal cavities or “triads” 2005]), which depends on the magnitude and location of clay
of O atoms of the siloxane surface (Weiss et al., 1990; Onodera structural charge (Slade et al., 1991; Tambach et al., 2004), the
Ion Exchange Phenomena 16-11

population of adsorbed cations (Schramm and Kwak, 1982; have unequal cation exchange selectivities (Keren, 1979; Sposito
Sposito, 1992; Laird and Shang, 1997; Ferrage et al., 2005; Table et al., 1983a), and the fraction of internal-surface X− sites in con-
16.5), the thermodynamic activity of water (Norrish, 1954; Slade tact with one-, two- or three-layer interlayer hydrates, which
et al., 1991; Laird et al., 1995), as well as the previous history of also may have unequal cation exchange selectivities (Barak,
the clay (Verburg and Baveye, 1994; Laird et al., 1995; Chatterjee 1989; Laird and Shang, 1997; Van Loon and Glaus, 2008). Thus,
et al., 2008) and its degree of compaction (Kozaki et al., 1998). cation exchange on swelling clay minerals involves a feedback
Molecular-scale simulations confirm that homoionic mont- loop among adsorption, exchanger structure, and selectivity
morillonites frequently exhibit several stable states of crys- (Laird and Shang, 1997; Figure 16.5) that is reminiscent of the
talline swelling separated by energy barriers (Whitley and behavior of certain ion-selective pores (Kuyucak et al., 2001).
Smith, 2004; Tambach et al., 2004, 2006; Smith et al., 2006). This  feedback loop may explain the occurrence of exchange-
Transitions between these states are predominantly enthalpic able cation “de-mixing” (Shainberg and Otoh, 1968; Fink et al.,
(Whitley and Smith, 2004), driven by cationic solvation energy 1971; Iwasaki and Watanabe, 1988), increased selectivity for
(Whitley and Smith, 2004)—as opposed to being determined by the preferred cation at high surface loading of the same cation
the hydrogen bond network of interlayer water (Tambach et al., (Shainberg et al., 1980; Laird and Shang, 1997; Janssen et al.,
2006)—strongly hysteretic (Tambach et al., 2006), and in fact 2003), cation exchange hysteresis (Fripiat et al., 1965; Verburg
thermodynamically analogous to a phase transition (Laird and et al., 1995), and increased selectivity for weakly hydrated ions
Shang, 1997; Whitley and Smith, 2004). as smectite charge density increases (Maes and Cremers, 1978;
The stacking arrangement, in turn, determines the fraction of Shainberg et al., 1987). Smectite ex K values would then have
X− sites located on external vs. internal basal surfaces, which may thermodynamic meaning only if defined for a certain particle
arrangement (Laird and Shang, 1997). Thus, the nonideality of
Selectivity Properties cation exchange reactions that involve weakly hydrated cations
of solution
may be related to the fact that these cations cause a sequential
collapse of the interlayer from a three-layer hydrate or more (for
Li+, Na+, and strongly hydrated divalent cations M2+) to a two-
Properties layer hydrate (for K+ and Ba 2+) to a one-layer hydrate (for Cs+;
of cations Interlayer Table 16.5).
cationic
composition

Extent of
swelling
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Na-montmorillonite: Microcalorimetric investigation. cation composition on the size and shape of montmorillonite
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Pabalan, R.T., and F.P. Bertetti. 1999. Experimental and mod- Shaviv, A., and S.V. Mattigod. 1985. Cation exchange equilibria
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Papelis, C., and K.F. Hayes. 1996. Distinguishing between inter- Sodium-calcium exchange in Nile delta soils: Single values
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Sinanis, C., V.Z. Keramidas, and S. Sakellariadis. 2003. Sposito, G., C. Jouany, K.M. Holtzclaw, and C.S. LeVesque. 1983c.
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two alfisols of northern Greece. Commun. Soil Sci. Plant presence of adsorbed sodium. Soil Sci. Soc. Am. J. 47:1081–1085.
Anal. 34:439–456. Sposito, G., and S.V. Mattigod. 1977. On the chemical founda-
Skipper, N.T., P.A. Lock, J.O. Titiloye, J. Swenson, Z.A. Mirza, tion of the sodium adsorption ratio. Soil Sci. Soc. Am. J.
W.S.  Howells, and F. Fernandez-Alonso. 2006. The struc- 41:323–329.
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Chem. Geol. 230:182–196. metal cation exchange on Camp Berteau montmorillonite.
Skipper, N.T., M.V. Smalley, G.D. Williams, A.K. Soper, and Clays Clay Miner. 27:125–128.
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Sposito, G. 2004. The surface chemistry of natural particles. Clays Clay Miner. 48:400–404.
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Tournassat, C., C. Lerouge, P. Blanc, J. Brendlé, J.-M. Greneche, and J.W. Harden. 2005. Chemical weathering rates of a soil
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Macdonald. 2008. Pore water chemistry of acid sulfate soils: Clays Clay Miner. 52:180–191.
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Miner. 42:207–220. Geochim. Cosmochim. Acta 70:4319–4331.
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 17
Chemisorption and
Precipitation Reactions
17.1 Introduction............................................................................................................................ 17-1
17.2 Conceptual Distinctions in Chemisorption and Precipitation....................................... 17-1
Chemisorption  •  Precipitation and Coprecipitation
17.3 Influence of Abiotic and Biotic Processes...........................................................................17-6
17.4 Quantitative Descriptions of Chemisorption and Precipitation Reactions.................. 17-8
Robert G. Ford 17.5 Observations of Cation and Anion Solid-Phase Partitioning in Soils........................... 17-9
United States Environmental Nickel  •  Selenium
Protection Agency References.......................................................................................................................................... 17-15

17.1  Introduction 17.2  Conceptual Distinctions in

The partitioning of dissolved components to a solid surface
Chemisorption and Precipitation
in soils is governed by the competition between sorption and 17.2.1  Chemisorption
desorption reactions. Chemisorption (or chemical adsorption)
of a dissolved component (adsorbate) to a solid surface (adsor- Chemisorption reactions involving formation of mononuclear
bent) has been defined as “adsorption that results from chemi- chemical bond between solutes in the solid solution and reactive
cal bond formation (strong interaction) between the adsorbent surfaces in solid matrix are referred to as surface complexation
and the adsorbate in a monolayer on the surface” (IUPAC, 1997). reactions and are typically categorized by the relative binding
These partitioning reactions may be influenced by electrostatic strength of interaction between the adsorbate (species in solu-
forces between the adsorbate and adsorbent, similar to those tion) and the adsorbent (soil solid). One should note that the
controlling ion-exchange reactions (discussed in this volume). conceptual underpinning that guides our historical and con-
It has also been observed that sorption of solution species may temporary understanding of chemisorption/surface complex-
result in more than monolayer coverage at the surface of solid ation reactions is the notion that reactive surface sites can be
surfaces. In these cases, the adsorbate may form polynuclear viewed as a special type of ligand that coordinates to cations or
surface complexes or surface precipitates (e.g., Scheidegger and exchanges with anions from solution (Schindler et al., 1976; Sigg
Sparks, 1996). Surface precipitation can be considered as a spe- and Stumm, 1981; Sposito, 1998, 1999). While our molecular-
cial form of homogeneous precipitation reaction where a solid level understanding of the physicochemical forces that govern
component in the soil participates in the overall reaction process the characteristics of these surface reactions has improved over
(Chapter 7 in Stumm and Morgan, 1996). In the following dis- the years, the underlying conceptual basis remains technically
cussion, surface precipitation includes all processes that result in sound. The driving force for molecules or ions in soil solution
incorporation of the sorbate into a solid structure that could not to form surface complexes with sites of adsorption in the soil
form in the absence of the adsorbent. This includes (1) formation solid matrix is governed by the physical and chemical properties
of a dilute solid solution with a structure that is distinct from or of the adsorbate, sorption sites, and the soil solution (i.e., “solute,”
shared with the original adsorbent, (2) epitaxial growth of a new “sorbent,” and “solvent” in the more general terminology in
solid phase sharing a structural relationship with the adsorbent, Stumm [1992]). As an example, the probability that a cation
and (3) nucleation of a new solid phase at the solid–water inter- will form an inner-sphere versus an outer-sphere surface com-
face. Background information and discussion of the literature plex will, in part, be governed by the relative free-energy change
(dating up to 1998) addressing chemisorption and precipitation between the cation maintaining a water molecule versus a surface
reactions in soils were provided by McBride (1999). The follow- hydroxyl site within its immediate coordination sphere. Cations
ing discussion provides an update on the current understanding for which coordination with a water molecule is more energeti-
of these reactions in soil systems. cally favorable will tend to favor outer-sphere surface complexes.

17-1
17-2 Properties and Processes

However, the overall tendency for surface complex formation or anion and the surface, the surface complex is referred to as
will be governed by other factors such as electrostatic forces inner sphere and is considered to be “strong” (Sposito, 1984). The
between the adsorbate and sorption site. Therefore, project- propensity of a cation or anion to form either an inner-sphere
ing trends in surface complex formation must be predicated or outer-sphere surface complex is a function of the adsorbate,
on knowledge of the physicochemical properties of the three the surface functional groups of the adsorbent, and the aqueous-
primary components in the reaction (i.e., adsorbate, sorption phase chemistry (e.g., pH and ionic strength).
sites, and solvent), in addition to how the surface complexation For inner-sphere complexation of ions onto solid surfaces,
reaction(s) may be modified by interactions of any or all of these the molecular rationale for the reaction is formation of covalent
primary components with other solution or solid components in bonding within an ion’s first coordination sphere. From this per-
the reaction system. spective, several authors have observed an apparent consistency
There are several recent discussions that provide useful per- between the approach to establish linear free-energy relation-
spective on the fundamental chemical factors that govern the ships (LFER) for aqueous coordination reactions and surface
extent for and relative strength of surface complex bond forma- complexation reactions developed for the formation of surface
tion (e.g., Sverjensky, 2006; Brown, 2009). It should be noted complexes (e.g., Schindler et  al., 1976; Sigg and Stumm, 1981;
that current developments in our understanding of the physi- Tamura and Furuichi, 1997). The apparent systematic correla-
cochemical forces controlling chemisorption reactions have tion captured in an LFER reflects the relationship between the
benefited from exploration of the molecular-level processes con- free energies of complex formation and thermodynamic proper-
trolling ion partitioning onto soil solids, as reflected in discus- ties of ions. For surface complexation reactions, LFER plots of the
sions of bond formation by Sverjensky (2006) and Brown (2009). stability constants of metal complexation with hydroxyl surface
This emphasis is, to some extent, a departure from past efforts sites versus the hydrolysis constant for metals in aqueous solu-
to relate apparent trends in ion partitioning based on periodic tions have been interpreted as providing a thermodynamic basis
properties of the elements (i.e., adsorbate), for example, refer- for the apparent selectivity trends for metal adsorption onto ref-
ence to apparent macroscopic trends with respect to qualita- erence hydrous metal oxides. Recent compilations by Bradbury
tive concepts such as the “lyotropic” or “Hofmeister” series. and Baeyens (2005, 2009) extend these relationships to metal
However, as noted in several studies, deviations in observed ion adsorption onto the phyllosilicate minerals, montmorillonite,
partitioning trends from qualitative concepts specific to the sor- and illite. As stated by the authors, the utility of these relation-
bate support the need to further development of our molecular- ships is their use as a tool to estimate surface complexation con-
level understanding of chemisorption reactions (e.g., Dove and stants for ions in which no data or data of high uncertainty are
Craven, 2005; Teppen and Miller, 2006; Rotenberg et al., 2009; available. In Figure 17.1, LFER plots of published data for cations
Kowacz et al., 2010). (Another form of solid-solution partition- and anions are provided to illustrate the correlations that one
ing, hydrophobic bonding, plays an important role in govern- may observe with similarities in the energetics and molecular
ing uptake of nonpolar organic compounds onto soil solids. This characteristics of homogeneous (aqueous) and heterogeneous
specific partitioning mechanism is not discussed further within (surface) coordination reactions. While these relationships are
this chapter, and the reader is referred to other comprehensive tied to our conceptual understanding of the molecular charac-
reviews [e.g., Karickhoff, 1981; Stumm, 1992; Schwarzenbach teristics of surface-coordination reactions, their use to project
et al., 1993], along with recent developments in the concept of surface complexation trends in soil systems should be limited to
bonding mechanisms intermediate between nonspecific (hydro- qualitative applications. The number of interacting components,
phobic) bonding and chemisorption reactions for organic mol- both aqueous and solid, within a soil system necessitates a more
ecules [e.g., Lambert, 2008; Keiluweit and Kleber, 2009].) comprehensive perspective.
There is a range of binding strength for ion adsorption that Important adsorbent phases commonly found in the envi-
depends on characteristics of the adsorbate, adsorbent, and ronment include phyllosilicate minerals, metal-oxohydroxide
chemistry of the soil solution. However, discussions of binding phases, sulfide phases, and natural organic matter (Dixon and
strength are generally couched in terms of “weak” or “strong” Schulze, 2002). Many phyllosilicate minerals possess a perma-
surface complexation reactions, albeit a common convention in nent negative charge as a result of the substitution of lower-
chemistry would categorize both the covalent and electrostatic valence cations, that is, Mg(II), Fe(II), Li(I) for Al(III) in the
interactions involved in adsorption as “strong” intermolecular octahedral layer and/or Al(III) for Si(IV) in the tetrahedral layer
forces (Israelachvili, 1994). For description of surface complex- (referred to as isomorphic substitution). There are two main
ation reactions, the microscopic distinction that the adsorbate classes of phyllosilicate minerals based on layer structure. The
possesses solvation properties is borrowed from the charac- 1:1 mineral layer type is comprised of one Si-tetrahedral layer
terization of soluble ion pairs (Westall, 1986; Stumm, 1992). If and one Al-octahedral layer, which in soils is commonly repre-
solvating water molecules are interposed between the cation or sented by the mineral kaolinite having the general formula [Si4]
anion and the surface, the surface complex is referred to as outer Al4O10(OH)8 · nH2O. Kaolinite and related minerals generally
sphere and is considered to be “weak.” Conversely, if upon sur- have insignificant degrees of cation substitution within their
face complexation, the adsorbate loses waters of hydration such octahedral and tetrahedral layers, and, thus generally posses
that there are no water molecules interposed between the cation a very low permanent negative charge. The 2:1 mineral type is
Chemisorption and Precipitation Reactions 17-3

Zn
Ni
25 >FehHPO4– vs. FeH2PO42+(aq)
0 Co
Mn
Co*
Cd
>FehPO42– vs. FeHPO4+(aq)
–4 20
logSKx–l (surface)

Co

logsK (surface)
Zn
–8 15
Ni
Cd*
Ni
Mn
–12 >FehCrO4– vs. FeCrO4+(aq)
10

Co >SOMe+ vs. Me(OH)+(aq) >FehSO4– vs. FeSO4+(aq)

–16 Zn o o
>SOMe(OH) vs. Me(OH)2 (aq) 5
Ni >SOMe(OH)2 vs. – Me(OH)3–(aq) >FehSeO3– vs. FeHSeO32+(aq)
Ni
–20
0
–32 –28 –24 –20 –16 –12 –8 0 5 10 15 20 25
(a) logOHKx (aqueous) (b) log K (aqueous)

FIGURE 17.1  Comparison of related formation constants for surface and aqueous complexes for coordination reactions between a selection of
ions and aqueous or surface functional groups. (a) Relationship between the stability constant for cation complexation with surface hydroxyls
of Na-exchanged montmorillonite/illite versus the metal hydrolysis species formation constant in solution (Bradbury and Baeyens, 2005, 2009).
Species stoichiometry noted in legend; starred metal labels indicate surface stability constant is for Ca-exchanged montmorillonite. (b) Relationship
between the formation constant for anion ligand exchange with surface hydroxyls on hydrous ferric oxide versus formation of aqueous complexes
with Fe3+ (Visual MINTEQ, 2009). Species stoichiometry shown next to data point.

comprised of one Al-octahedral layer interposed between two the pH of the bathing solution and on the specific chemical char-
Si-tetrahedral layers comparable to the mica structures. The 2:1 acteristics of the adsorbate.
layer class is represented by a variety of minerals, which are clas- The most important inorganic phases for surface reactions
sified based on the location (tetrahedral versus octahedral layer) with ions in many soil systems are the metal-oxohydroxide
and relative amount of isomorphic substitution. The three major phases. These phases are characterized by hexagonal or cubic
mineral classes within the 2:1 layer type are illite (M x[Si6.8Al1.2] close-packed O or OH anions with Fe(II)/Fe(III), Al(III), and/or
(Al3Fe0.25Mg0.75)O20(OH)4), vermiculite (M x[Si7Al](Al3Fe0.5Mg0.5) Mn(III)/Mn(IV) occupying octahedral sites. These oxides are
O20(OH)4), and smectite (M x[Si8]Al3.2Fe0.2Mg0.6O20(OH)4), which present as discrete phases and as complex mineral assemblages,
display different levels of cation substitution in their tetrahedral being associated with phyllosilicates and primary minerals as
and octahedral layers. The permanent negative charge imparted coatings or with humic macromolecules. In soils, the crystal-
to 2:1 clay minerals by isomorphic substitution is typically bal- linity of these phases typically varies from poorly ordered to
anced through exchange reactions involving major cations in well-crystalline forms and grain size from the nanometer to
soil solution (e.g., Na+, K+, Ca 2+, or Mg2+; represented by “M x” in micrometer scale. Among the most common Fe-oxohydroxide
the formulas listed above). phases found in soils are the poorly ordered phase ferrihydrite
Chemisorption of ions to phyllosilicates may occur via electro- (Fe2O3 · nH2O), and the moderate to well-crystalline phases, goe-
static exchange reactions (on the basal plane or within clay par- thite (α-FeOOH), and hematite (α-Fe2O3). The most common
ticle interlayers) or surface complexation with surface functional Al-oxohydroxide phase found in soils is gibbsite (γ-Al(OH)3).
groups, for example, terminal silanol or aluminol functional Additionally, poorly ordered aluminosilicates can be impor-
groups at the edges of clay particles, for example, montmoril- tant reactive phases in certain soils and these include the very
lonite (Bradbury and Baeyens, 2005) and illite (Bradbury and poorly ordered allophanes (Si/Al ratios 1:2–1:1) and the para-
Baeyens, 2009). Due to differences in the levels of isomorphic crystalline phase, imogolite (SiO2 · Al 2O3 · 2H2O). While Mn
substitution for the 1:1 and 2:1 clay-mineral classes, ion exchange oxohydroxides are less prevalent than Fe and Al oxohydroxides
is usually only significant for 2:1 phyllosilicates. In addition to in soils, they are very important phases in terms of surface-
siloxane oxygen atoms along the basal plane, phyllosilicates pos- mediated redox reactions and because of their propensity for
sess two types of terminal ionizable hydroxyl groups (>OHo), high metal sorption. The mineralogy of Mn is complicated by
aluminol and silanol, protruding from the edge surface. These the range in Mn–O bond lengths resulting from extensive sub-
edge >OHo groups can form both inner- and outer-sphere sur- stitution of Mn(II) and Mn(III) for Mn(IV). Thus, there exists
face complexes with metal cations and oxyanions depending on a continuous series of stable and metastable compositions from
17-4 Properties and Processes

MnO to MnO2 forming a large variety of minerals. Among the TABLE 17.1  Published Examples for Chemical Representations
more common Mn oxohydroxides are pyrolusite (β-MnO2), the of Reactive Surface Sites Used in Development of Surface
hollandite–cryptomelane family (α-MnO2), todorokite, and Complexation Models to Describe Protonation–Deprotonation
birnessite (δ-MnO2). Reactions for Variably Charged Solids
The reactive surface functional group for all of the metal- Chemical Representations of Reactive Surface Sites
oxohydroxide phases is the inorganic >OHo moiety exposed on Chemical System Protonation–Deprotonation Reactions
the outer periphery of these minerals. The reactivity of a spe-
CaCO3 (calcite)–H2O–CO2 >CaOHo + H+ = >CaOH2+
cific metal oxohydroxide is dependent on the surface area (SA),
(Martin-Garin et al., 2003; >CaOHo = >CaO− + H+
surface-site density (NS), the degree of coordination of the >OHo
Gaskova et al., 2009) >CaOHo + CO32− + 2H+ = >CaHCO3o + H2O
group to the bulk structure, and the point of zero charge (PZC). >CaOHo + CO32− + H+ = >CaCO3− + H2O
The charge on the mineral surface may impose either attractive >CO3Ho = >CO3− + H+
or repulsive contributions to the overall adsorption reaction, >CO3Ho + Ca2+ = >CO3Ca+ + H+
depending on the type of charge possessed by the adsorbate. FeS (mackinawite)–H2O >FeSHo + H+ = >FeSH2+
The surface charge of oxohydroxide minerals and edge sites on (Wolthers et al., 2005) >FeSHo = >FeS− + H+
phyllosilicates is derived from the protonation and ionization of >Fe3SHo + H+ = >Fe3SH2+
exposed surface hydroxyl groups, represented by >OHo, where >Fe3SHo = >Fe3S− + H+
“>” represents the bond to structural elements within the solid Lignocellulosic >S1OH = >S1O− + H+ (carboxylic sites)
(e.g., Fe, Al, Mn). As a function of pH, the surface functional substrate–H2O >S2OH = >S2O− + H+ (phenolic sites)
groups can be generally described with the following ideal- (Ravat et al., 2000)
ized nomenclature: >OH 2+, >OHo, and >O−, which illustrates
the pH-dependent charging behavior in the absence of other COOH
potential-determining ions in solution. The exact charge asso-
ciated with the various surface functional groups is difficult to
measure, so the main purpose of employing this nomenclature is O O
O
to illustrate that surface charge varies as a function of soil solu-
tion chemistry. Discussions of surface-charging behavior and OH
Phenolic groups HOOC
surface-coordination reactions for a range of common soil min- HO O OH Alcohol groups
erals is provided elsewhere (e.g., Stumm, 1992; Sparks, 2003).
The properties of the adsorbent that impact surface complex- HOOC COOH
ation are controlled by both the grain size and specific chemical
structure of the solid phase. S O O
While the surfaces of oxohydroxide minerals constitute
NH
a significant fraction of sites that participate in chemisorp- COOH
tion reactions, they are not the only type of surface sites pres- HOOC
COOH Carboxylic groups
ent. Depending on soil type and mineralogy, other sources of
reactive surfaces may include carbonates, sulfides, and soil FIGURE 17.2  Hypothetical structural model of a soil organic mat-
organic matter. For these solids, the same conceptual conven- ter structural fragment illustrating types of reactive functional groups.
tion can be employed to identify the reactive chemical surface Protonation–deprotonation reactions occurring during acid titration
moiety for the purpose of describing chemisorption reactions are generally attributed to carboxylic and phenolic moieties.
based on chemical and electrostatic properties. There are sev-
eral published examples that illustrate application of the surface (e.g., Kelleher and Simpson, 2006; Simpson et al., 2007a, 2007b;
complexation model (SCM) concept to describe ion chemisorp- Smejkalova and Piccolo, 2008). A variety of functional groups are
tion to the surface of carbonates (Villegas-Jimenez et al., 2009), present in humic substances, and, like >OHo functional groups
sulfides (Wolthers et al., 2005), and components of soil organic of the inorganic metal oxohydroxides, these also are charac-
matter (Westall et  al., 1995; Cabaniss, 2008; Cabaniss, 2009). terized by pH-dependent charging mechanisms. The primary
Summarized in Table 17.1 is a listing of the types of chemical functional groups associated with humic substances in terms of
nomenclature used to represent the reactive surface sites for surface charge are typically represented as carboxyl and pheno-
these solid components. lic groups (Figure 17.2); however, less abundant amino, imidaz-
Soil organic matter, or humus, is derived from the physical, ole, sulfhydryl, or other potential structural groups may play an
chemical, and biological breakdown of vegetation and fauna important role in protonation–deprotonation and chemisorp-
originating from above and below the soil surface (e.g., Wershaw, tion reactions of some ions when present at trace levels (e.g.,
1994; Zech et al., 1997; Ponge, 2003; Sutton and Sposito, 2005). Schaumann, 2006; Niederer et  al., 2007; Matynia et  al., 2010).
The recalcitrant soil organic matter thus produced is com- Degradation of natural organic matter in soils leads to a change
prised of complex polymers called humic substances, which in the relative distribution of the chemical structures within the
constitute another very important reactive phase in soil solids complex suite of macromolecular compounds that constitute
Chemisorption and Precipitation Reactions 17-5

soil organic matter. As an example, Lorenz et al. (2007) illustrate occurs on the surfaces of organic or mineral particles.
a general scheme for the evolution of the chemical makeup of Heterogeneous nucleation is thought to be more impor-
terrestrial biomass during weathering resulting in the depletion tant in natural systems that are rich in reactive inorganic
of oxygenated-alkyl carbon structures and the enhancement of and biological surfaces. Precipitation may result in the
alkyl carbon structures. As illustrated in the review by Chefetz formation of sparingly soluble oxohydroxides, carbonates,
and Xing (2009), changes in the relative proportion of structural and, in anoxic systems, sulfides. Many precipitation reac-
components in soil organic matter may influence the reactivity tions have a strong dependence on pH.
of this adsorbent pool within soils, since these structural com- • Coprecipitation: Incorporation of an element as a trace
ponents comprise the reactive moieties in soil organic matter or minor constituent within a precipitating phase. In this
that are binding sites for dissolved inorganic and organic com- case, the ion substitutes for a more concentrated compo-
pounds in the soil solution. nent in the crystal lattice (isomorphous substitution). This
As illustrated by the previous discussion, chemical bond- process is distinct from adsorption due to incorporation
ing between solutes in the soil solution and the surfaces of soil of the ion within the bulk structure of the major min-
solids will exert control over solute concentrations. Typically, eral phase. Examples of coprecipitation include Cr(III)
these reactions dominate solid-water partitioning at low sol- in hydrous ferric oxide, Cd(II) in calcium carbonate, and
ute concentrations or in systems where there is minimal active As(III) in iron sulfide.
precipitation of new soil minerals. However, some soil systems • Surface precipitation: A precipitation process intermedi-
will be characterized by large fluxes of ions through the soil ate between surface complexation and precipitation from
pore water either due to infiltration from external water sources bulk solution. Surface precipitation represents the contin-
or internal instability of the mineral matrix as a function of uous growth of particles formed via heterogeneous nucle-
soil age (e.g., Huggett, 1998; Lilienfein et  al., 2003) or micro- ation. Macroscopic studies of adsorption of some solutes,
bial activity (e.g., Wiederhold et  al., 2007). In these systems, particularly divalent and trivalent cations, suggest that
active precipitation of new solid phases may dominate over precipitation occurs at surfaces under conditions where
chemisorption reactions to control solute concentrations in the the solid is apparently undersaturated based on solution
soil solution. concentrations (Dzombak and Morel, 1990).
• Mineral transformation: Adsorbed ions can become
incorporated into minerals that form as a result of recrys-
17.2.2  Precipitation and Coprecipitation tallization or mineral transformation processes in soils.
Transformation reactions may be accelerated or retarded
Mineral–water reactions occur during movement of water
by the ion, and in some cases mineral transformation may
through soil pores. These reactions may result in the release of
result in the exclusion of the solute from the solid phase.
structural components from soil solids due to mineral dissolu-
Examples include incorporation of anions, such as As(V)
tion or result in the buildup to oversaturation and consequent
and U(VI), into metastable hydrous ferric oxide (poorly
precipitation of secondary minerals. As an outcome of mineral–
crystalline ferrihydrite) and transformation to more crys-
water reactions along a flow path, fluid compositions and the
talline Fe oxohydroxides (e.g., Ford, 2002; Nico et  al.,
mineralogical makeup of the soil matrix will continuously
2009), coprecipitation of metals with iron monosulfide and
evolve toward a stable state or an equilibrium state. Mineral pre-
transformation to iron disulfide (e.g., Lowers et al., 2007),
cipitation processes in soil systems may govern the concentra-
and incorporation of metals into layered double hydrox-
tions of major and trace elements in the soil solution.
ides (LDHs; typically with Al) as intermediates between
Full treatment of precipitation processes, including cover-
adsorbed/surface precipitated metal ions like Ni and Zn
age of relevant thermodynamic and kinetic concepts, is outside
and metal-ion-containing phyllosilicates.
the scope of this document. The reader is referred to numerous
standard textbooks in geochemistry, soil science, and aquatic The relative importance of these processes will be determined
chemistry (e.g., Lindsay, 1979; Drever, 1982; Stumm, 1992; by solute characteristics as well as characteristics of soil solution
McBride, 1994; Stumm and Morgan, 1996; Langmuir, 1997; and solids within a given system. These individual processes are
Lasaga, 1999; Sparks, 2003; Sposito, 2008). The purpose of this discussed in more detail in the following sections.
section is to introduce key concepts and issues regarding the
potential impact precipitation reactions may exert on solute par- 17.2.2.1  Precipitation from Solution
titioning in soils. In general, mineral precipitation in relation to
Solution precipitation or crystallization can be divided into
the solid-phase partitioning of soil solutes can be discussed in
two main processes: nucleation and crystal growth. Nucleation
the context of four widely studied processes:
occurs prior to growth of a mineral crystal. Both nucleation and
• Precipitation from solution: Nucleation and growth of growth processes require a system to be oversaturated in the
a solid phase exhibiting a molecular unit that repeats new phase. The probability that nucleation will occur increases
itself in three dimensions. Homogeneous nucleation exponentially as a function of the degree of oversaturation.
occurs from bulk solution and heterogeneous nucleation Nucleation of a new phase is often facilitated in the presence of
17-6 Properties and Processes

a surface (heterogeneous nucleation) rather than in bulk solu- Characterization of metal partitioning in soils developed
tion (homogeneous nucleation). Because nucleation and growth under a variety of conditions have confirmed the importance of
are processes that compete for dissolved solutes, at high degrees the interfacial precipitation products identified in simple experi-
of oversaturation, the rate of nucleation may be so fast that all mental systems (e.g., Manceau et al., 2000; Jacquat et al., 2008).
excess solute is partitioned into crystal nuclei. In contrast, lower However, it is unclear if these phases were formed via homoge-
levels of oversaturation can result in the growth of existing crys- neous or heterogeneous reactions in the observed soil systems.
tals without nucleation. Well-formed or euhedral crystals typi- With improvements in the availability of solubility and ther-
cally develop slowly via growth from solution at low degrees of mochemical data for solids that were previously unidentified in
oversaturation. During crystal growth, various chemical reac- soil systems, it may become apparent that their formation can
tions can occur at the surface of the growing mineral, such as be assumed as a more common feature of solute partitioning. It
adsorption, ion exchange, diffusion, and formation of surface should be noted, however, that solid surfaces do play significant
precipitates. In general, the rate of crystal growth is controlled roles as collectors of solutes into a more confined reaction volume
either by transport of solutes to the growing surface (i.e., trans- and they often serve as the primary source of soluble components
port controlled), by reactions at the surface (i.e., surface con- that combine with solutes to form precipitation products.
trolled), or a combination of these factors.
For the most abundant cations present in soils, such as Al,
Si, Fe, Mn, Ca, and Mg, precipitation of mineral forms is com- 17.3  Influence of Abiotic and Biotic
mon and will in many cases control concentrations observed in Processes
solution (e.g., see Chapter 5 in Sposito, 2008). Concentrations
of trace solutes are typically several orders of magnitude below The chemical characteristics of the soil solution and properties
the concentrations of the major ions in soil solutions. At low of soil mineral components are, in part, influenced by micro-
concentrations, adsorption, surface precipitation, or formation bial reactions (e.g., Brown et al., 1999; Chadwick and Chorover,
of a dilute solid solution (coprecipitation; e.g., Shao et al., 2009) 2001; Birkham et  al., 2007). Microbial activity within the soil
may be the more probable removal processes for trace solutes system may also play a more direct role in controlling ion spe-
(McBride, 1994). ciation and mobility via direct respiration of solutes in soil pore
water or adsorbed to mineral surfaces (e.g., Lloyd et al., 2003).
17.2.2.2  Continuum from Surface Complexation The influence of microbial reactions may be more pronounced
to Precipitation in soils with large pools of degradable organic carbon and sup-
Experimental studies examining chemisorption at high solute porting nutrient fluxes. For microbially productive soil systems,
concentrations have been used to illustrate that surface loadings soil-solution chemical parameters such as pH, alkalinity, and
can exceed monolayer coverages (Dzombak and Morel, 1990). the concentrations of iron, manganese, and sulfur species may
Surface precipitation may result when adsorption leads to high be regulated, in part, by microbial respiration. As an example,
sorbate coverage at the mineral–water interface. Surface precipi- microbial respiration within the rhizosphere impacts the level of
tation can be thought of as an intermediate stage between surface CO2 in the soil solution, with resultant CO2 partial pressure
complexation and bulk precipitation of the sorbing ion in solu- 10- to 100-fold higher than that of the atmosphere (Hinsinger
tion (Farley et  al., 1985; Katz and Hayes, 1995; Lützenkirchen et  al., 2009). Ultimately, the soil solution chemistry will be
and Behra, 1995). At low concentrations of the sorbing metal at governed by the dynamic interaction between these biotic pro-
the mineral surface, surface complexation is the dominant pro- cesses and concurrent chemical weathering of solid components
cess. As the concentration of the sorbate increases, the surface within the soil. In order to provide perspective on the potential
complexation concentration increases to the point where nucle- influence of the subsurface microbiology, the following discus-
ation and growth of a surface precipitate occurs. Surface precipi- sion provides an overview of general characteristics of subsur-
tation can be viewed as a special case of coprecipitation, where face microbiology and the influence of microbial activity on the
the mineral interface is a mixing zone for ions incorporated into redox state within soil pore water.
the surface precipitate and those from the underlying substrate Since microorganisms chemically transform soil constitu-
(e.g., Thompson et  al., 1999; Schlegel et  al., 2001; Román-Ross ents such as dissolved oxygen, iron (aqueous and solid forms of
et al., 2006; Schlegel and Manceau, 2006). It is generally believed Fe(III) and Fe(II)), and sulfur (aqueous species such as sulfate
that surface precipitation can occur from solutions that would and dissolved sulfide), their metabolic reactions may exert sig-
appear to be undersaturated relative to precipitate formation nificant influence on the redox chemistry within soil pore water.
based on considering solution saturation indices. The reasons As previously discussed, redox conditions within the soil may
for this may be due, in part, to incomplete consideration of all govern precipitation–dissolution reactions that control pre-
possible precipitate phases with lower solubility that could form cipitation or coprecipitation of solutes, as well as the types and
under system conditions or to the way component activities at concentration of soil solids that may serve as adsorbents. From
the mineral–water interface are modeled (Kulik, 2002a, 2002b; this perspective, some knowledge about the microbial popula-
Sverjensky, 2003). tions that a function within the soil system may be necessary
Chemisorption and Precipitation Reactions 17-7

to understand the existing redox status and make projections • Manganese-reducing to iron-reducing conditions: When
about how it may evolve. For heterotrophic microorganisms, manganese oxide becomes limiting, iron reduction
the electrons or reducing equivalents (hydrogen or electron- becomes the predominant reaction mechanism. Available
transferring molecules) produced during degradation of organic evidence suggests that iron reduction does not occur until
compounds must be transferred to a terminal electron acceptor all Mn(IV) oxides are depleted. In addition, bacterial
(TEA). Observations of microbial systems have led to the devel- Mn(IV) respiration appears to be restricted to areas where
opment of a classification system that groups microorganisms sulfate is nearly or completely absent.
into three categories, according to predominant TEAs (Chapelle • Iron-reducing to sulfate-reducing conditions: Iron reduc-
et al., 2002; Salminen et al., 2006): tion continues until substrate or carbon limitations allow
sulfate-reducing bacteria (SRB) to become active. SRB
• Aerobic bacteria: Bacteria that can only utilize molecular then dominate until usable carbon or sulfate limitations
oxygen as a TEA. Without molecular oxygen, these bacte- impede their activity.
ria are not capable of degradation. • Sulfate-reducing to methanogenic conditions: Once usable
• Facultative aerobes/anaerobes: Bacteria that can utilize carbon or sulfate limitations occur, methanogenic bacte-
molecular oxygen or when oxygen concentrations are low ria are able to dominate.
or nonexistent, may switch to nitrate, manganese oxides,
or iron oxides as electron acceptors. Ultimately, these processes may govern both the chemical spe-
• Anaerobes: Bacteria that cannot utilize oxygen as an ciation of solutes in soil solutions and the solid-phase partition-
electron acceptor and for which oxygen is toxic. Though ing reactions that control aqueous solute concentrations. For the
members may utilize nitrate or other electron acceptors, latter, biotic controls on solution chemistry could potentially
it can be said that they generally utilize sulfate or carbon dictate the types of adsorbent surfaces or the saturation state of
dioxide as electron acceptors. the soil solution relative to solute precipitation reactions.
In any environment in which microbial activity occurs, there is As a unique example of the biogeochemical complexity of soil
a progression from aerobic to anaerobic conditions (ultimately systems, it is worth examining the volume of soil immediately
methanogenic) with an associated change in the redox status adjacent to living roots that project down from plants located
of the system. There is generally a definite sequence of electron at the soil surface. This zone within the soil system is referred to
acceptors used in this progression through distinctly different as the rhizosphere, which encompasses a unique setting relative
redox states. The rate, type of active microbial population, and to the fluxes of chemical constituents that are governed by inter-
level of activity under each of these environments are controlled actions among plant physiological processes, soil microorgan-
by several factors. These include the concentration of the elec- isms, soil mineral components, and the transport of soil water
tron acceptors, substrates that can be utilized by the bacteria, and gases (e.g., Belnap et al., 2003; Hinsinger et al., 2009). Within
and specific microbial populations active within the soil system. the rhizosphere, plants mediate the chemical composition of the
This results in a loss of organic carbon and various electron soil solution via release of low-molecular-weight organic acids
acceptors from the system as well as a progression in the types such as malate, citrate, and oxalate (Jones, 1998; Bais et al., 2006).
and physiological activity of the indigenous bacteria. These organic acids may form complexes with ions in solution,
If microbial activity is high, the soil system would be expected form surface complexes with soil minerals, or may be oxidized
to progress rapidly through these conditions. The following sce- to forms of inorganic carbon via microbial degradation (along
nario outlines a general sequence of events in which aerobic with new biomass). Depending on the relative concentration
metabolism of preferential carbon sources would occur first. The of these low-molecular-weight organic acids to ions and sorp-
carbon source may be from anthropogenic organic sources or tion sites, complexation reactions that occur in these ternary
other more readily degradable forms of natural organic carbon, systems may lead to decreased (Kraemer et al., 1999; Neubauer
which has entered the system previously or simultaneously with et al., 2000) or increased (Neubauer et al., 2000) ion adsorption
surface infiltration. onto mineral surfaces. More complex organic molecules, such
as siderophores and other hydroxamic acids that are secreted by
• Oxygen-reducing to nitrate-reducing conditions: Once plants and microorganisms (Kraemer et al., 2006; Crumbliss and
available oxygen is consumed, active aerobic populations Harrington, 2009), present a more specialized class of organic
begin to shift to nitrate respiration. Denitrification will molecules that can form polydentate complexes with ions in solu-
continue until available nitrate is depleted or usable car- tion. These organic molecules may possess specific functional
bon sources become limiting. roles such as increasing the availability of nutritional forms of
• Nitrate-reducing to manganese-reducing conditions: Once iron (e.g., Crumbliss and Harrington, 2009) or detoxifying metal
nitrate is depleted, populations that reduce manganese ions present in the soil solution (e.g., Gilis et al., 1998; Dimkpa
may dominate. Bacterial metabolism of substrates utilized et al., 2008). Interactions of ions with these organic molecules in
by manganese-reducing populations will continue until the soil solution exert direct influence on the potential for che-
the concentration of manganese oxide becomes limiting. misorption or precipitation reactions to occur.
17-8 Properties and Processes

17.4  Quantitative Descriptions modeled. The heterogeneity of soil systems hampers selection
of appropriate reactive surfaces and adsorption site densities
of Chemisorption and to be explicitly represented in an SCM. Two proposed model-
Precipitation Reactions ing strategies to address this difficulty include the component
additivity (CA) and general composite (GC) approaches. The
Reviews of mathematical models for describing chemisorption
CA approach is based on the summed contribution of individ-
reactions and their practical application for depicting solute
ual adsorbent phases, and, thus, makes use of individual reac-
complexation to solid surfaces in natural systems is provided in
tion expressions developed for each solute–adsorbent pair from
Zachara and Westall (1999) and Goldberg et al. (2007 and refer-
model experimental systems. The predictive capability of the CA
ences therein). In general, these models can be grouped into two
approach will be highly dependent on knowledge of the specific
categories that project solute partitioning using semiempirical
adsorbents active in solute chemisorption for a particular soil.
relationships or through the development of chemical reaction
The GC approach is based on the assumption that the assem-
expressions that depict chemisorption as the formation of chemi-
blage of adsorbent phases within the soil can be represented
cal bonds between the solute and surface sites representing the
by “generic” surface functional groups with reaction stoichi-
termination of the adsorbent structure. The second category of
ometries and formation constants derived from experimental
models is commonly referred to as SCMs. Their use for describing
adsorption data for individual soil samples. The utility of the GC
chemisorption reactions has become standard since they provide
approach over purely empirical partitioning coefficients is that
the following: (1) the means to rationalize observed patterns in
the chemisorption model can be coupled to equilibrium models
solute binding to solid surfaces due to electrostatic and chemi-
of aqueous solute speciation and solubility. Thus, chemisorp-
cal properties of the reactants and (2) a mathematical framework
tion model projections will be sensitive to changes in aque-
consistent with thermodynamic descriptions of aqueous com-
ous solute speciation and/or solution saturation state relative
plexation and precipitation reactions. The utility and chemical
to homogeneous precipitation of the solute. In addition, the GC
sensibility of this modeling framework has resulted in the devel-
approach allows for explicit accounting of electrostatic interac-
opment of computer software applications and supporting data
tions across the surface (based on laboratory measurements of
compilations of chemisorption reactions for cations and anions
surface-charging behavior) or incorporation of these interac-
on soil mineral phases (e.g., Dzombak and Morel, 1990; Tonkin
tions implicitly within the optimized surface complexation con-
et al., 2004). Detailed descriptions of the chemical basis and devel-
stant determined for a given system.
opment of SCMs is available in a number of sources (e.g., Sposito,
Another limitation of SCMs has been the standard state used
1984; Davis and Kent, 1990; Stumm and Morgan, 1996). Brown
to express the activities of surface sites and surface species. Kulik
(2009) presents an alternative framework in which to evaluate
(2002a, 2002b) and Sverjensky (2003) have illustrated that the
thermodynamic properties of chemisorption reactions. In this
hypothetical standard state employed in current model formula-
approach, the bond valence model is invoked to assess constraints
tions results in equilibrium constants that are directly depen-
on the types of surface bonds that can form. A primary constraint
dent on properties of the adsorbent such as the site density and
that is applied in this framework is the valence sum rule, which
surface area. Thus, surface protonation and stability constants
states that the sum of bond valences around any atom should be
for solute adsorption developed for a particular mineral speci-
equal to the atomic valence. In contrast to the common formalism
men, for example, goethite, at a given solid:solution ratio may
within most SCMs of providing explicit descriptions and account-
not be directly transferable to modeling adsorption of another
ing of electrostatic interactions across the surface, the bond
goethite specimen with different specific surface area and/or
valence model incorporates all electrostatic effects into the bonds
solid:solution ratio. Both authors have proposed an alternative
that are formed. The extent of adhesion between atoms in the
standard state that can be used to develop surface protonation
solid and solution (i.e., surface complex formation) is evaluated by
and complex stability constants that are independent of individ-
ensuring that the valence sum rule is obeyed around each atom in
ual adsorbent properties and experimental conditions. The new
the system. Although the bond valence model provides a way to
standard-state convention can be used to convert conditional
evaluate the chemical suitability of proposed bonding structures,
stability constants derived using law-of-mass action (LMA)
this approach is not currently implemented in a mathematical
algorithms (Sverjensky, 2003) or the Gibbs energy minimiza-
framework that can be merged with existing thermodynamic for-
tion (GEM) approach (Kulik, 2002b). As illustrated by Kulik
malisms for calculating solution complexation and precipitation
(2002a), surface complexation constants derived using the LMA
reactions. Until this occurs, the formalisms employed for describ-
convention can be converted to the GEM convention using the
ing surface bond formation in current SCMs will likely continue
newly proposed standard state for surface species. In addition,
to be employed.
Kulik (2002b) illustrates that the GEM approach also allows
Goldberg et al. (2007) and Goldberg and Criscenti (2008) have
one to factor in which adsorbents are stable or metastable, and
highlighted potential limitations for the application of SCMs to
how the site types are distributed between the adsorbent sur-
project chemisorption reactions in soil systems. Reaction expres-
faces. Given our understanding that the suite of mineral com-
sions depicting chemisorption reactions presume knowledge of
ponents, and their inherent solubility and surface complexation
the types and availability of solid surfaces in the system being
properties, undergoes dynamic transitions in soil systems
Chemisorption and Precipitation Reactions 17-9

(e.g.,  Chadwick  and  Chorover, 2001), the GEM approach pres- will focus on illustrative examples of the types of chemical
ents an attractive alternative for modeling low-temperature factors that influence chemisorption–precipitation versus an
aqueous chemistry reactions. exhaustive review of the periodic properties of the elements. In
A final issue of concern for modeling solute adsorption onto order to illustrate the disparity in potential reaction paths for
mineral surfaces is development of approaches to represent ions in soil solutions, the controls on solid-water partitioning
the transition from surface loadings less than to greater than for nickel (Ni) and selenium (Se) are reviewed in the following
monolayer coverage. As discussed previously, the formation of sections. These elements illustrate both the range of chemisorption–
a mononuclear surface complex may represent an intermediate precipitation reactions that influence ion partitioning in soils
step to the development of a polynuclear species with 2D or 3D and the degree of complexity inherent in monitoring and pro-
order, commonly referred to as surface precipitates. The com- jecting these reactions in dynamic soil systems.
position of surface precipitates will be governed by the partici-
pating elements from the solution and the host mineral surface.
17.5.1  Nickel
Modeling strategies have been developed within the convention
of the LMA-SCM (Farley et  al., 1985; Katz and Hayes, 1995), Nickel is not commonly seen as a critical element in agricultural
and they have been employed to replicate sorption data for wide or environmental systems. However, as noted in a recent review
ranges of surface coverage assuming either the formation of by Hansch and Mendel (2009), it is considered to be an impor-
a pure solid or solid solution incorporating the solute species tant micronutrient, and, for specific plant species, deficiencies in
(e.g., Charlet and Manceau, 1992; Román-Ross et al., 2006). For nickel availability may limit plant growth for agricultural (Bais
these applications, assumptions are made about the fraction of et  al., 2006) or phytoremediation applications (Wood et  al.,
the adsorbent that participates in formation of binary or higher- 2006). At higher concentrations in soil solutions, nickel may
order solid solutions, as well as the ideality of the modeled solid also exert a toxic effect on plant species (e.g., Khan et al., 2006).
solutions relative to the endmember structures. Curti et  al. In ambient aqueous systems, nickel exists in the divalent oxida-
(2005) and Kulik (2006) have proposed alternative strategies tion state and is not subject to oxidation-state transformations
to represent and select the solid solutions that may realistically under typical conditions. Nickel predominantly exists as a cat-
form based on GEM. Significant model development and testing ionic species (Ni2+) or various hydrolysis species (e.g., NiOH+)
remains before much confidence can be placed on projections at near-neutral pH (Baes and Mesmer, 1986). However, nickel
of surface precipitation or surface solid–solution formation in may also form dissolved complexes in the presence of high con-
soil systems. centrations of inorganic ions such as carbonate/bicarbonate and
sulfate (Hummel and Curti, 2003; Chen et al., 2005) or organic
ligands such as natural/synthetic carboxylic acids and dissolved
17.5  Observations of Cation and Anion humic compounds (Bryce and Clark, 1996; Baeyens et al., 2003;
Solid-Phase Partitioning in Soils Strathmann and Myneni, 2004). It is anticipated that nickel may
form complexes with dissolved sulfide under sulfate-reducing
The distribution of cations and anions between the solid–water conditions, although the current state of knowledge is insuf-
interfaces present in soils is governed by chemical characteris- ficient to ascertain the relative importance of these species in
tics of the aqueous and solid species and the chemistry of the soil aqueous systems (Thoenen, 1999). The formation of solution
solution. The distribution between adsorbed and precipitated complexes, especially with organic ligands (e.g., Strobel, 2001;
forms of these constituents will also be influenced by the total Fröberg et al., 2006), may limit sorption of nickel to mineral sur-
concentrations of reactive species, as well as the influence of faces in soils (see Section 17.5.1.2).
biotic processes that govern the distributions of redox-sensitive The solid-solution partitioning of Ni is chosen as a point of
reactants within the soil. As stated earlier, properties of the soil reference for ions that are not subject to a change in valence
solution, adsorbate, and sorption sites will govern the types of state due to shifts in redox characteristics in the soil solution.
chemisorption reactions that may take place. The solution spe- However, redox chemistry may exert an indirect control on
ciation of cations/anions, as controlled by solution complexation Ni partitioning by governing the distribution of solid surfaces
reactions and the distribution of ion oxidation states will govern that may influence chemisorption reactions, as well as the dis-
the saturation state of the soil solution with respect to poten- tribution and concentrations of solution species that limit the
tial precipitates. As one would anticipate, it is difficult to proj- solubility of Ni-bearing precipitates that may form. Nickel also
ect what reactions may dominate solid-solution partitioning for provides an example of an ion that demonstrates a wide range of
ions without full knowledge of the solution chemistry and solid solid-solution partitioning behavior including adsorption, sur-
surface properties. For some ions, such as the alkali metals or face precipitation, and homogeneous precipitation.
halide anions, this task is simplified due to the predominance of
a single oxidation state in natural systems and the high solubility 17.5.1.1  Chemisorption
of potential precipitate phases. However, this simplicity rapidly Nickel displays the commonly observed chemisorption behav-
diminishes with departure from these bracketing groups within ior for cation adsorption onto soil minerals with uptake onto
the periodic table of elements. Thus, the remaining discussion solid surface increasing with pH. Typically, the increase in
17-10 Properties and Processes

adsorption occurs over a narrow pH range, and the resultant humic/fulvic compounds along with simple organic acids may
plot of adsorption data has been given the name “adsorption not significantly influence the extent of nickel sorption to oxide
edge” (e.g., Stumm, 1992; Sparks, 2003). Adsorption of nickel in surfaces. This behavior is predicated on the availability of sorp-
soil environments is dependent on pH, temperature, and type of tion sites at concentrations significantly greater than competing
adsorbent (minerals or organic matter), as well as the concen- ligands in solution.
tration of aqueous complexing agents, competition from other In contrast, the presence of ligands that form highly stable
adsorbing cations, and the ionic strength in the soil solution. or multidentate solution complexes may exert greater influence
Nickel has been shown to adsorb onto many solid components on the degree of nickel sorption to oxide surfaces. As shown in
encountered in soils, including iron/manganese oxides, clay Figure 17.3c, nickel sorption may be inhibited (or nickel desorp-
minerals (Dähn et al., 2003; Bradbury and Baeyens, 2005), and tion enhanced) through the formation of solution complexes
solid organic matter (Nachtegaal and Sparks, 2003). Sorption with some classes of organic ligands such as hydroxamate sider-
to iron/manganese oxides and clay minerals has been shown ophores (Dimkpa et al., 2008). Published stability constants are
to be of particular importance for controlling nickel mobility available for a commonly occurring hydroxamate siderophore,
in subsurface systems. The relative affinity of these individual desferrioxamine B (DFB; Farkas et al., 1999). In order to model
minerals for nickel uptake will depend on the mass distribu- the nickel speciation in Figure 17.3c, equilibrium expressions for
tion of the adsorbent minerals as well as the predominant geo- the protonation of DFB and its complexation with nickel were
chemical conditions (e.g., pH and Ni aqueous speciation). For derived from published conditional stability constants (Evers
example, the pH-dependent distribution of nickel between et al., 1989; Farkas et al., 1999; see Table 17.2). As discussed pre-
iron and manganese oxides (hydrous ferric oxide [HFO] and a viously, the production of siderophores provides a mechanism
birnessite-like mineral [nominally MnO2]) for a representative for plants/organisms to overcome the low solubility of met-
soil solution composition is shown in Figure 17.3. Based on the als such as nickel in soil systems where the abundance of solid
available compilations for surface complexation constants onto sorption sites is high. As shown in Figure 17.3, the stability of
these two solid phases (Dzombak and Morel, 1990; Tonkin et al., solution complexes with carboxylic acids (natural or synthetic)
2004), one would project the predominance of nickel sorption to and the relative availability of sites for chemisorption affect that
MnO2 at more acidic pH and the predominance of HFO (or fer- degree of competition. For the hypothetical conditions modeled
rihydrite) at more basic pH. With increasing mass of MnO2, the in Figure 17.3, only strong complexation with DFB significantly
solid-phase speciation of nickel will be progressively dominated inhibits Ni adsorption to surface of hydrous Fe/Mn oxides. This
by sorption to this phase. There are examples of the relative pref- behavior is similar to that observed in experimental systems for
erence of nickel sorption to manganese oxides over iron oxides the synthetic chelating agent, EDTA (e.g., Bryce and Clark, 1996;
for natural systems (e.g., Manceau et al., 2002; Kjoller et al., 2004; Nowack et al., 1997). The model calculations presented in Figure
Manceau et al., 2007). As shown in Figure 17.3b, the presence of 17.3 do not include the possible formation of ternary surface

1200 1200
Ni species concentration (μg/L)

1000 1000

800 800
Σ[Ni]aq-inorg
600 Σ[Ni]aq-org 600
Σ[Ni]sorbed,HFO
400 400
Σ[Ni]sorbed,MnO
2

200 [Ni]sorbed,total 200

0 0
4 5 6 7 8 9 10 11 4 5 6 7 8 9 10 11 4 5 6 7 8 9 10 11
(a) pH (b) pH (c) pH

FIGURE 17.3  (a) Nickel sorption as a function of pH in the presence of a hypothetical soil with iron and manganese oxides reflective of the
crustal abundance of these elements (Schulze, 2002; assumed 30% porosity with 185.0 g HFO L−1 and 1.66 g MnO2 L−1); no organic ligands. (b) Same
conditions as in (a) but with 20 mg L−1 dissolved organic carbon (DOC; humics and fulvics) and 25 μM each of citrate, malonate, and oxalate.
(c) Same conditions as in (a), but with 5 μM DFB added as the sole organic ligand. Nominal water composition: 0.005 mol L−1 NaCl, 0.001 mol L−1
K 2SO4, 0.001 mol L−1 MgNO3, 0.001 mol L−1 CaCO3, and 17 μM Ni (1 mg Ni L−1). Model predictions using Visual MINTEQ (2009) Version 2.61 with
available surface complexation parameters derived from Dzombak and Morel (1990) and Tonkin et al. (2004), and metal-DOC speciation using
default settings in the DOC (SHM) module (Gustafsson, 2001); kaolinite set as an “infinite” solid for pH titration. This model does not make use of
the alternate hypothetical reference states proposed by Kulik (2002a, 2002b) or Sverjensky (2003).
Chemisorption and Precipitation Reactions 17-11

TABLE 17.2  Complexation Reactions between Ni(II) and DFB, a Microbially Produced
Trihydroxamate Siderophore in the Soil Rhizosphere
Acid–Base Reactions
Stoichiometry Log K (25°C) Structure of DFB
H3DFB + H = H4DFB
+ + 8.32 O
H3DFB − H+ = H2DFB− −8.74
H3DFB − 2H+ = HDFB2− −17.84
N HN
H3DFB − 3H+ = DFB3− −27.95
O
Complexation Reactions O–
Ni2+ + H3DFB − 3H+ = NiDFB− −20.41 O NH
Ni2+ + H3DFB − 2H+ = NiHDFB −0.95 Hydroxamate –O

Ni2+ + H3DFB − H+ = NiH2DFB+ −1.89 groups

O N
Ni2+ + H3DFB = NiH3DFB2+ 3.90

O
N O–
CH3

H
N Amino
H
group

Equilibrium reaction expressions and associated constants for protonation and complexation with nickel were
derived from Evers et al. (1989) and Farkas et al. (1999), respectively. All constants have been recalculated to zero
ionic strength using the Davies equation for the estimation of single-ion activities (Stumm and Morgan, 1981,
p. 135). Reaction expressions from the referenced sources were converted to the reaction format required within
the Visual MINTEQ (2009) database using H+, Ni2+, and H3DFB as components (MINTEQA2/PRODEFA2, 1999).

complexes with DFB or other multidentate ligands that might and Morse, 1992; Ford et al., 1999a; Hoffmann and Stipp, 2001).
serve as a bridging ligand between Ni and an oxyhydroxide sur- Predicted nickel concentrations in the presence of sulfide for
face (e.g., Nowack and Sigg, 1996; Nowack, 2002). several potential pure nickel precipitates are shown in Figure
As previously noted, adsorption of nickel onto mineral sur- 17.4a. These data suggest that phyllosilicate and LDH precipitates
faces may serve as a precursory step to the formation of trace pre- (incorporating aluminum) may limit Ni solubility in soils. These
cipitates that reduce the potential for desorption with changes in data also point to the limited capability of pure nickel carbonates
soil solution chemistry. This may be realized through the nucle- and hydroxides in controlling dissolved nickel concentrations to
ation and growth of surface precipitates on clay mineral surfaces sufficiently low values except under very alkaline conditions.
due to continued uptake of nickel. Three categories of surface For LDH precipitates, calorimetric measurements have demon-
precipitation have been identified in experimental systems: (1) strated that the interlayer anion exerts significant influence on
heterogeneous nucleation of pure Ni-bearing phases such as the precipitate stability (Peltier et al., 2006). In the presence of
hydroxides (e.g., Scheinost et al., 1999), (2) coherent growth of dissolved sulfide, the precipitation of a nickel sulfide may plau-
Ni-bearing solid phases that mimic the structure of the adsor- sibly control the concentration of dissolved nickel. The influence
bent (e.g., Dähn et al., 2002), and (3) nucleation of mixed-metal of dissolved silicate on the stability of Ni-bearing precipitates is
precipitates within the solid–water interface (e.g., Scheckel and shown in Figure 17.4b. According to these data, nickel-bearing
Sparks, 2000, 2001; Scheckel et al., 2000; Dähn et al., 2006). This phyllosilicate and/or LDH precipitates possess large stability
type of process may compete with other adsorption processes, fields indicating their relative importance to controlling nickel
such as ion exchange, depending on the prevailing soil solution solubility under a range of conditions. These calculations point
chemistry and characteristics of the clay mineral (e.g., Elzinga to the importance of dissolved aluminum and silicon concentra-
and Sparks, 2001). tions in the soil solution relative to the potential sequestration of
nickel via precipitation (Ford et al., 1999b; Scheinost et al., 1999).
17.5.1.2  Precipitation As discussed in Section 17.5.1.1, the formation of these nickel-
Nickel may be immobilized within soils through formation of bearing precipitates may be facilitated through initial adsorp-
pure nickel precipitates such as hydroxides, silicates, or sul- tion onto clay minerals within the soil.
fides (Merlen et  al., 1995; Mattigod et  al., 1997; Scheidegger Attenuation of nickel may also occur via coprecipitation
et al., 1998; Thoenen, 1999; Scheinost and Sparks, 2000; Peltier during the formation of (hydr)oxides or sulfides of iron. These
et al., 2006) or through coprecipitation with other soil-forming minerals have been observed to form at the boundaries between
minerals such as silicates, iron oxides/sulfides, or carbonates oxidizing and reducing zones within soil systems. There are
(Manceau et al., 1985; Manceau and Calas, 1986; Huerta-Diaz numerous laboratory and field observations that demonstrate
17-12 Properties and Processes

1.0 1.0

O2 Ni(NO3)2(aq) O2
Ni(NO3)2(aq)
H2O H 2O
0.5 0.5
2+
Ni

Eh (V)
Eh (V)

Ni0.63Al0.33(OH)2(SO4)0.125(s) Ni3Si4O10(OH)2(s)
0.0 0.0
H2O H2 O
NiS2(s) NiS2(s)
H2 H2

–0.5 –0.5

4 6 8 10 4 6 8 10
(a) pH (b) pH

FIGURE 17.4  Eh–pH diagrams for nickel at 25°C. (a) System Ni–H2O–Ca–Al–NO3–HCO3–SO4 (2 mg Ni L−1; 40 mg Ca L−1; 3 mg Al L−1; 6 mg NO3
L−1; 60 mg HCO3 L−1; 100 mg SO4 L−1). Stability fields for solids are shaded gray (Vaesite = NiS2). (b) Same system plus 3 mg Si L−1. Thermodynamic
data for Ni3Si4O10(OH)2 and Ni0.63Al0.33(OH)2(SO4)0.125 are from Peltier et al. (2006). (Note that the solubility of the Ni–Al–SO4 LDH was adjusted to
correct for charge imbalance for the chemical structure published in Peltier et al. [2006].)

the capacity of these precipitates for nickel uptake (Schultz et al.,

1987; Huerta-Diaz and Morse, 1992; Coughlin and Stone, 1995;
Ford et al., 1997, 1999a). Under these circumstances, the solubil- 1.0
ity of nickel will depend on the stability of the host precipitate
phase. For example, iron oxide precipitates may alternatively O2
transform to more stable forms (Ford et  al., 1997), stabilizing SeO42–
0.5 H2O
coprecipitated nickel over the long term, or these precipitates
HSeO3–
may dissolve concurrently with changes in soil solution redox
Eh (V)

chemistry (e.g., Zachara et al., 2001).

SeO32–
0.0
17.5.2  Selenium Se(0)(s)

Selenium provides an example of an element that is subject to

significant changes in solution and solid speciation as influenced
H2Se(aq) HSe–
by changes in system redox. Selenium is a metalloid exhibiting –0.5 H2O
physical and chemical properties between that of metals and H2
nonmetals. It chemically resembles sulfur and exists in organic
4 6 8 10
and inorganic chemical forms. Inorganic species include sele- pH
nide [Se(−II)], elemental selenium [Se(0)], selenite [Se(IV)], and
selenate [Se(VI)] (e.g., Fernandez-Martınez and Charlet, 2009). FIGURE 17.5  Eh–pH diagram for selenium at 25°C using thermo-
Organic species include methylated compounds, selenoamino dynamic data from Seby et al. (2001). ΣSe = 10−5 M (790 μg L−1). Solid
acids, and selenoproteins and their derivatives. The speciation stability field for elemental selenium is shaded gray.
of selenium is greatly influenced by the pH and redox conditions
of the environment (Figure 17.5). For example, Se(−II) exists in a Various strains of bacteria have been identified to facilitate
reducing environment as hydrogen selenide (H2Se) and as metal selenate reduction in soil systems. Two microbial processes,
selenides. Reduction of selenate to selenite and Se(0) has been namely, methylation of selenium and reduction of both sel-
shown to decrease its mobility in saline, mildly alkaline water enate and selenite to Se(0), have a major influence on the fate
(White et al., 1991). When dissolved in water, H2Se can oxidize and mobility of this element in the environment (Dungan
to elemental selenium. Elemental selenium is stable in a reduced and Frankenberger, 1999; Dungan et  al., 2003). Methylation
environment, but it can be oxidized to selenite and to selenate of selenium, and subsequent selenium volatilization, leads to
by a variety of microorganisms (Sarathchandra and Watkinson, dissipation of soil selenium to the atmosphere. Environmental
1981; Dowdle and Oremland, 1998). factors such as the existing microbial community, pH,
Chemisorption and Precipitation Reactions 17-13

temperature, moisture, and organic amendments control States has been documented (Neal et al., 1987; Neal and Sposito,
the rate of selenium volatilization from seleniferous soils 1989; Zachara et  al., 1994). This research demonstrated the
(Frankenberger and Karlson, 1989; Zhang and Frankenburger, importance of Fe- and Al-oxide surfaces for selenium adsorp-
1999). Under flooding conditions, part of the methylated sele- tion onto soils and highlighted the dependence of the extent
nium may be transported in water, thus decreasing selenium of adsorption on the pH of soil solution and the presence of
volatilization to the atmosphere (Zhang and Frankenburger, anions that compete for adsorption sites. Additional review of
1999). The addition of organic amendments to soils has been the published literature is provided in the following.
reported to stimulate indigenous microbes to methylate sele- Selenate has been shown to behave like sulfate with minimal
nium (Abu-Erreish et  al., 1968; Frankenberger and Karlson, adsorption and high mobility (Goldberg and Glaubig, 1988;
1989); whereas, organic substrates added to ponded sediments Neal and Sposito, 1989); whereas, selenite behaves analogously
(submerged soils) have been found to accelerate the reduction to phosphate, with greater adsorption than selenate (Neal et al.,
of selenate and selenite to Se(0) (Tokunaga et  al., 1996) and 1987; Barrow and Whelan, 1989a; Zhang and Sparks, 1990).
similar effects were reported in laboratory batch experiments Strawn et al. (2002) have observed selenite and selenate associ-
(Zhang et al., 2003). ated with iron-bearing minerals in acid-sulfate soils. In these
Mechanisms for selenium reduction by microbes are com- soils, selenite was predominantly associated with iron oxyhy-
plex as it occurs under both aerobic (Lortie et al., 1992) and droxides and selenate was associated with jarosite, presumably
anaerobic conditions (Oremland et  al., 1989, 1990; Tomei in a coprecipitated form. Adsorption of selenite on goethite
et  al., 1992). Both dissimilatory and detoxification mecha- decreases with increasing pH, with decreasing selenite concen-
nisms are possible (Oremland, 1994). The occurrence of tration, and with competing anions such as phosphate, silicate,
sequential reduction of selenate to selenite and then to Se(0) citrate, molybdate, carbonate, oxalate, and fluoride (Balistrieri
is suggested after amendment of contaminated soils with bar- and Chao, 1987). More selenite is adsorbed onto montmorillon-
ley straw under field capacity moisture conditions (Camps ite than on kaolinite (Frost and Griffin, 1977). Selenite adsorp-
Arbestain, 1998). The rate of selenate to selenite reduction in tion in seleniferous soils is decreased in the presence of sulfate,
wastewaters is proportional to their respective concentrations nitrate, and phosphate (Pareek et al., 2000). Selenite adsorption
in solution and also to the amount of the microbial biomass by aluminum hydroxides is adversely affected by organic acids
(Rege et al., 1999). A recent study has documented the occur- (Dynes and Huang, 1997). Desorption of selenate is faster and
rence of both intracellular and extracellular Se(0) granules in more nearly complete than selenite after adsorption and incuba-
three phylogenetically and physiologically distinct bacteria tion in soil (Barrow and Whelan, 1989b). Differences in the sta-
that are able to respire selenium oxyanions, suggesting that bility of selenate and selenite chemisorption to ferrihydrite are
this phenomenon appears to be widespread among such bac- illustrated in Figure 17.6. Selenite adsorption predominates for
teria (Oremland et al., 2004). The metal sites of selenate reduc- most of the modeled pH range, but there is a small stability field
tase from Thauera selenatis have been characterized (Maher for selenate adsorption in the pH range 7 < pH < 9, in part, due to
et al., 2004); the enzyme was found to contain Se in a reduced the pH-dependent distribution of selenium oxyanion oxidation
form (probably organic) and the Se is coordinated to both a state. As shown, model predictions indicate limited competition
metal (probably Fe) and carbon. Assessment of Se(IV) and from competing oxyanions common to soil solutions (e.g., car-
Se(0) reduction in anaerobic microcosms demonstrated the bonate, silicate, and sulfate) when available surface-site densities
sequential formation of Se(0) and ultimately Se(−II) during are far from saturation.
incubation with elemental selenium and/or lactate as electron Selenite selectively adsorbs at the carbonate (CO32−) site on
donors for microbial reduction (Herbel et al., 2003). Dissolved calcite (CaCO3) via ionic exchange, forming a two-dimensional
Se(−II) did not accumulate in pore water during incubation solid solution of the form Ca(SeO3)x(CO3)1−x at the interface;
due to precipitation with ferrous iron to form FeSe(s), which under identical chemical conditions, selenate adsorption is
was determined via solid-phase characterization using x-ray inhibited (Cheng et al., 1997). An earlier study showed selenate
absorption spectroscopy. substitution in calcite may also be supported under appropriate
conditions (Reeder et al., 1994).
17.5.2.1  Chemisorption Mechanisms of selenium adsorption have been studied
As noted above, the most common species of selenium in soil from both macroscale batch and microscale spectroscopic
solution are in the form of oxyanions. Thus, selenium adsorp- approaches. The presence of either selenate or selenite lowers the
tion onto soil minerals tends to be greatest under acidic pH electrophoretic mobility and decreases the PZC of ferrihydrite
with a gradual decrease as pH increases. In contrast to cation and goethite, suggesting inner-sphere complexation for both sel-
adsorption, the decrease in anion adsorption with increasing enate and selenite species (Su and Suarez, 2000). Both in situ attenu-
pH is more gradual, and the resultant plot of these adsorp- ated total reflectance–Fourier transform infrared (ATR–FTIR)
tion data has been given the name “adsorption envelope” (e.g., and diffuse reflectance infrared Fourier transform (DRIFT)
Stumm, 1992; Sparks, 2003). Selenate and selenite adsorption spectra indicated formation of bidentate complexes of selenate
behavior on individual soil minerals (Fe, Al, and Mn oxides, with ferrihydrite, and the DRIFT spectra of selenite on goethite
kaolinite, and calcite) and whole soils throughout the United indicated formation of bridging bidentate complex of selenite.
17-14 Properties and Processes

60
1.0
50
concentration (μg/L)
Selenium species

40 [Se(VI)]sorbed O2
[Se(IV)]sorbed SeO42– H2O
30 0.5
Total [Se]sorbed HSeO3–

Eh (V)
20 Total [Se]aq
CaSeO3 . H2O(s)
10 Se(0)(s)
0.0
(a) 0

FeSe(s)
10–1

Adsorbed components (M)

–0.5
H2O
10–3
H2

10–5 4 6 8 10
pH
10–7
FIGURE 17.7  Eh–pH diagram for selenium at 25°C using thermo-
Free sites Carbonate
dynamic data from Seby et  al. (2001). System Se–H 2O–Fe–Ca, with
Ca and Mg Sulfate 10–9
Selenium Silicate ΣSe = 10−5 M (790 μg L−1), ΣFe = 10−4 M (5.6 mg L−1), and ΣCa = 10 −2 M
(400 mg L−1). Solid stability fields for elemental selenium, hydrous
10–11 calcium selenite, and ferrous selenide are shaded gray. FeSe2 was
4 5 6 7 8 9 10 11
(b) pH suppressed (data not available in the Seby et al., 2001); however, the
stability field of the diselenide would be intermediate between ele-
FIGURE 17.6  (a) Selenium species adsorption as a function of pH in the mental selenium and FeSe.
presence of a hypothetical soil with iron oxide content reflective of
the crustal abundance (Schulze, 2002; assumed 30% porosity with 185.0 g
HFO L−1). (b) Total component adsorption for modeled water composi-
soils (Rai et al., 1995; Sharmasarkar et al., 1996). These phases
tion. Nominal water composition: 0.005 M NaCl, 0.001 M K2SO4, 0.001 M
are anticipated to primarily be significant in situations where
MgNO3, 0.001 M CaCO3, and 0.7 μM Se (55.2 μg Se L−1). Model predic-
tions using Visual MINTEQ (2009) Version 2.61 with available surface selenium concentrations are highly elevated. Reduction to
complexation parameters derived from Dzombak and Morel (1990) at a form elemental selenium [Se(0)] can result in very low concen-
fixed Eh = 500 mV; kaolinite set as an “infinite” solid for pH titration. This trations of dissolved selenium. In general, it has been observed
model does not make use of the alternate hypothetical reference states that selenium reduction to insoluble Se(0) results in immo-
proposed by Kulik (2002a, 2002b) or Sverjensky (2003). bilization and stabilization of this element in the soil matrix,
since the reoxidation reaction of Se(0) to soluble selenate and
These results are consistent with an earlier in situ extended selenite is relatively slow (Tokunaga et  al., 1994; Zawislanski
x-ray absorption fine structure (EXAFS) spectroscopic study and Zavarin, 1996; Dowdle and Oremland, 1998; Losi and
(Manceau and Charlet, 1994) that shows that selenate forms an Frankenberger, 1998). Abiotic reduction of selenite to Se(0)
inner-sphere binuclear bridging surface complex on hydrous was also suggested in SRB biofilms (Hockin and Gadd, 2003).
ferric oxide and goethite. On the contrary, an earlier EXAFS Further reduction to selenide [Se(−II)] can lead to precipita-
study (Hayes et al., 1987) concluded that selenate forms an outer- tion of metal selenides, including ferrous iron and manganese
sphere surface complex on goethite. A recent combined data set selenides, similar to the formation of metal sulfides under
of Raman and ATR–FTIR spectra indicate that both inner- and sulfate-reducing conditions. As demonstrated by Scheinost
outer-sphere surface complexes of selenate occur on goethite, as and Charlet (2008a) and Scheinost et al. (2008b), selenite may
predominantly monodentate inner-sphere surface complexes be reduced and precipitated via abiotic reactions with Fe(II)-
at pH < 6, and as predominantly outer-sphere surface complexes at bearing minerals in soils. The propensity to form elemental
pH > 6 (Wijnja and Schulthess, 2000). selenium versus ferrous-selenide precipitates will likely be gov-
erned by pH, major ion composition of the soil solution, and
17.5.2.2  Precipitation the solubility of ferrous iron.
Selenium has the potential of forming precipitates for all of its While not commonly observed, it is anticipated that many
oxidation states (Seby et al., 2001; see Figure 17.7). For selenate suboxic soil environments (e.g., redoximorphic soils) contain
and selenite, this includes precipitates with common major cat- green rust, which is a mixed ferrous, ferric hydroxide that also
ions in soil solutions (Ca, Mg) as well as transition metals (Fe, contains interlayer anions such as sulfate and carbonate in its
Mn) or heavy metals that may be anticipated in contaminated structure (Feder et al., 2005). Identification of green rusts in soils
Chemisorption and Precipitation Reactions 17-15

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 18
Role of Abiotic Catalysis
in the Transformation of
Organics, Metals, Metalloids,
and Other Inorganics
18.1 Introduction............................................................................................................................18-1
18.2 Fundamentals of Catalysis....................................................................................................18-2
Definition of Catalysis  •  Homogeneous and Heterogeneous Catalysis  • 
Proton and Electron Transfer Catalysis
18.3 Abiotic Catalysis of Natural and Anthropogenic Organic Compounds.......................18-3
Oxidative Transformation of Phenolic and Other Organic Compounds  •  Polycondensation
of Phenolic Compounds and Amino Acids  •  The Maillard Reaction and Integrated
Polyphenol–Maillard Reactions  •  Surface Brønsted and Lewis Acidity and Hydrolysis
of Organic Compounds  •  Reductive Transformation of Organic Compounds  • 
Genotoxicity and Bioavailability of Xenobiotics as Influenced by Mineral Catalysis
18.4 Abiotic Catalysis in the Transformation of Metals, Metalloids,
and Other Inorganics...........................................................................................................18-19
Pan Ming Huang Transformation of Metals and Metalloids  •  Transformation of Other Inorganics
(Deceased) 18.5 Role of Nanoparticles in Abiotic Catalysis.......................................................................18-27
University of Saskatchewan
18.6 Conclusions...........................................................................................................................18-28
A.G. Hardie Acknowledgment..............................................................................................................................18-29
Stellenbosch University References..........................................................................................................................................18-29

18.1  Introduction catalysis (Furukawa and Brindley, 1973; McBride, 1979; Jauregui
and Reisenauer, 1982; Stone and Morgan, 1984b).
Abiotic catalysis plays a vital role in many physicochemical pro- Abiotic catalytic reactions are also important in the transfor-
cesses in soil and related environments. Clay minerals, metal mations of anthropogenic organic compounds such as pesticides,
(oxy)hydroxides and oxides, and dissolved metals often dem- antibiotics, explosives, and dyes (Theng, 1974, 1979; Cheng, 1991;
onstrate their ability to catalyze the transformations of natural Stone and Torrents, 1995; Smolen and Stone, 1998; Wang and
organic and anthropogenic organic compounds, metals, metal- Arnold, 2003; Szecsody et al., 2004; Barrett and McBride, 2005;
loids, and other inorganics. Baldrian et al., 2006; Hofstetter et al., 2006; Kang et al., 2006;
Metal (oxy)hydroxides and oxides and clay minerals have the Rubert and Pedersen, 2006; Fimmen et al., 2007; Cheng et  al.,
ability to catalyze the transformation of biomolecules and the 2008; Zhang et al., 2008). Soils and sediments contain a series
resultant formation of humic substances (Huang and Hardie, of solid surfaces and dissolved constituents. These components
2009). Iron (oxy)hydroxides and oxides (Scheffer et al., 1959; can catalyze the transformation reactions through Brønsted and
Shindo and Huang, 1984a; Wang and Huang, 2000a, 2000b; Lewis acidity, hydrolysis, and oxidative or reductive processes,
Gonzalez and Laird, 2004) and especially Mn oxides (Shindo which can result in the alteration of transformation pathways
and Huang, 1982, 1984a, 1984b; Kung and McBride, 1988; and kinetics, thereby influencing the toxicity and environmental
Wang and Huang, 1992, 2000a,b; Jokic et al., 2001a, 2001b, fate of these organic compounds.
2004a, 2004b; Hardie et al., 2007) are most reactive in mediat- Manganese oxides and Fe-bearing minerals have the abil-
ing the transformations of phenolic compounds, amino acids, ity to catalyze the transformations of metals, metalloids, and/or
and sugars. Other organic compounds such as aromatic amines other inorganics. Manganese oxides are effective catalysts in
and organic acids can also be oxidatively transformed by abiotic promoting many reactions such as the transformation of As(III)

18-1
18-2 Properties and Processes

to As(V) (Oscarson et al., 1981a; Chiu and Hering, 2000; Power in the reaction. In certain circumstances, very small quantities
et al., 2005; Feng et al., 2006b), Fe(II) to Fe(III) (Krishnamurti of catalyst can speed up very large reactions. Some catalysts are
and Huang, 1987, 1988), Pu(III/IV) (Cleveland, 1970; Amacher also highly specific in the type of reaction they catalyze, particu-
and Baker, 1982; Morgenstern and Choppin, 2002) and Pu(V) larly in biochemical reactions.
(Keeneykennicutt and Morse, 1985; Duff et al., 1999) to Pu(VI),
as well as Cr(III) to the more toxic and mobile Cr(VI) (Bartlett 18.2.2  Homogeneous and Heterogeneous
and James, 1979; Amacher and Baker, 1982; Stepniewska et al., Catalysis
2004; Negra et al., 2005; Feng et al., 2007). Manganese(IV)
oxides also catalyze the oxidation of nitrite to nitrate (Bartlett, The process of changing the rate of a chemical reaction by the
1981; Luther and Popp, 2002), and NH3 and organic N to N2 use of a catalyst that has the same phase as the reactant is homo-
(Luther et al., 1997). Heterogeneous oxidation/reduction reac- geneous catalysis (e.g., dissolved metals in catalyzing organic
tions involving electron transfer between metals/metalloids reactions or enzymes in biochemical reactions) (Daintith, 1990).
and Fe-bearing minerals have been demonstrated (Wehrli and A process driven by a catalyst that has a phase different from the
Stumm, 1989; Ilton and Veblen, 1994; Peterson et al., 1996; reactant is heterogeneous catalysis (e.g., metal oxides in catalyz-
White and Peterson, 1996; Myneni et al., 1997; Powell et al., ing organic and inorganic reactions). In heterogeneous cataly-
2004; Jeon et al., 2005; Jung et al., 2007; Jang and Dempsey, 2008; sis, the catalyzed reaction steps take place at or very close to the
Scheinost and Charlet, 2008; Su and Puls, 2008). Further, it has solid surface. These steps may be between molecules adsorbed
been suggested that reduced Fe and Mn minerals are respon- on the catalyst surface or may involve the topmost atomic lay-
sible for catalyzing nitrate immobilization into dissolved and ers of the catalysts (Twigg, 1989). The sequence of stages for a
humic N fractions in soils and sediments (Davidson et al., 2003; heterogeneous catalytic reaction is shown in Table 18.1. Any
Huygens et al., 2008). of these stages, if slow, may limit the overall rate of a catalytic
Therefore, abiotic catalysis plays an important role in the reaction. Distinctions are often drawn between catalysts that
transformation of organics, metals, metalloids, and other inor- are film-diffusion controlled (i.e., limited by stages 1 and/or 7),
ganics in soil and related environments. The impact of abiotic pore-diffusion controlled (i.e., limited by stages 2 and/or 6), and
catalysis on environmental quality and ecosystem integrity reaction controlled (i.e., limited by stages 3, 4, and/or 5). There is
deserves increasing attention. a complex interaction between the relative importance of these
different stages and the resulting catalytic effect on organic and
inorganic reactions.
18.2  Fundamentals of Catalysis Advances in surface science and catalysis are presented in a
treatise edited by Hightower et al. (1996). Both homogeneous
18.2.1  Definition of Catalysis and heterogeneous catalytic reactions are significant in soil and
The process of changing the rate of a chemical reaction by the environmental sciences (Bartlett, 1986; Huang, 1990, 1991b;
use of a catalyst is termed catalysis, coined by Berzelius in 1836 Stumm, 1992; Stone and Torrents, 1995; Smolen and Stone, 1998;
to describe some enhanced chemical reactions (Williams, 1965). Davidson et al., 2003; Livens et al., 2004; Stepniewska et al., 2004;
The accepted definition of a catalyst, due to Oswald, is that it is a Barrett and McBride, 2005; Hofstetter et al., 2006; Cheng et al.,
substance that changes the speed of a chemical reaction without 2008; Scheinost and Charlet, 2008; Zhang et al., 2008).
itself undergoing any permanent chemical change. Since a reac- TABLE 18.1  Sequence of Stages in the Catalysis of
tant or a product may also be a catalyst, Bell (1941) suggests the a Reaction by a Heterogeneous Catalysta
definition, “A catalyst is a substance which appears in the rate
1. Transport of reactants through the liquid or gas phase to the
expression to a power higher than that to which it appears in the exterior of  the catalyst
stoichiometric equation.” Actually many substances classified as 2. Transport of reactants through the pore system of the catalyst to a
catalysts are destroyed either as a result of the process that gives catalytically active site
them their catalytic activity or because of subsequent combina- 3. Adsorption of reactants at the catalytically active site
tion with the products (Moore and Pearson, 1981). From a prac- 4. Chemical reactions between reactants at the catalytically active site
tical point of view, a catalyst is a substance that changes the rate (frequently several steps)
of a desired reaction, regardless of the fate of the catalyst itself. 5. Desorption of products from the catalytically active site
An important criterion of a catalyst is that it changes the 6. Transport of products through the catalyst pore system from the
mechanism of the parent reaction (Moore and Pearson, 1981). catalytically active site to the exterior of the catalyst
Without this change in mechanism, the observed change in rate 7. Transport of products into the liquid or gas phase from the exterior
of the catalyst
could not occur. Since catalysts increase the rate of reaction, the
mechanism must change to one that is easier for the system to Source: Modified from Twigg, M.V. 1989. Catalyst handbook. Wolfe
follow, involving, in general, a lower energy barrier. Therefore, Publishing Ltd., London, U.K. Copyright Wolfe Publishing Ltd., with
permission.
the catalyst provides an alternative pathway by which the reac- a Several different catalytically active sites may be involved. Adsorption,

tion comes to equilibrium, although it does not alter the position possibly followed by reaction, may occur at one site, followed by trans-
of the equilibrium (Daintith, 1990). The catalyst itself takes part port of an intermediate product to a different site for further reactions.
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-3

18.2.3  Proton and Electron Transfer Catalysis Presumably a metal-organic complex is formed that reduces the
negative charge and increases the electron transfer. The catalytic
Brønsted acid–base catalysis is effective because proton trans- efficiency of a metal ion depends both on its positive charge and
fers are generally rapid compared with the making and breaking on its ability to form a stable complex and chelate the reactant.
of other chemical bonds. Therefore, reactions involving proton In such reactions, the metal ions are acting as generalized acids.
transfer in a typical acid or base catalysis are rapid compared However, metal ions have some significant advantages over pro-
with similar reactions of comparable free energy. The rate of a tons. They can have greater charges, which lead to greater polar-
chemical reaction is related to the steric hindrance involved. ization of the reactant molecules. Unlike the proton, metal ions
Steric hindrance, which is the repulsion of nonbonded atoms can be stabilized by other ligands and, thus, can exist in neutral
in an activated complex, is the most important factor in deter- or even basic solutions. The high coordination numbers of metal
mining the activation energy of a reaction (Moore and Pearson, ions permit the binding of a substrate at more than one site. This
1981). Since a proton lacks the filled inner electron shells usu- advantage helps to make metal ions very efficient catalysts for the
ally responsible for repulsion and is not surrounded by other hydrolysis of many organic compounds (Kroll, 1952). Further,
groups, it is quite free from steric hindrance effects. Proton some metal ions have the ability to simultaneously bind both a
transfers involving oxygen–hydrogen bonds are generally rapid substrate and a reagent. This can have the effect of a template, in
but they are not instantaneous. For instance, in the ionization which the two reactants are assembled (brought into close prox-
of water, the activation energy is at least 57 kJ mol−1 (the heat of imity) prior to combination (Basolo and Pearson, 1968).
the reverse reaction) and the entropy of activation is negative; Many metal ions, especially of the transition series, have sev-
therefore, the rate constant (5 × 10−7 mol L−1 s−1) is small (Moore eral stable oxidation states, which enables them to act as cata-
and Pearson, 1981). This example demonstrates that an unfa- lysts in certain redox reactions. Transition metals are the best
vorable equilibrium constant must necessarily make a reaction catalysts, in most cases, for catalyzing reactions that are slow for
slow, even if other factors are quite favorable. Given a favorable symmetry reasons (Pearson, 1976). In addition to the slow three-
equilibrium, proton transfers involving O and N bonds to H are body reactions, a second class of slow reactions is forbidden by
almost always very fast, approaching diffusion control in many orbital symmetry (Moore and Pearson, 1981). Even when the
cases. Exceptions can occur if the proton is in a well-shielded reaction is thermodynamically favorable, a large energy barrier
position (Kresge, 1975). can exist. Such reactions are prime candidates for catalysis. The
Catalysis by proton transfer is by far the most common in reason why transition metals are often the best catalysts is due
homogeneous reactions. For those reactions that are subject to their partly filled d orbitals, which have symmetry proper-
to proton transfer catalysis, an expected relationship exists ties that are different from those of s and p orbitals. Because of
between the strength of the acid or base, as determined by its the special properties of metal ions, particularly transition metal
ionization constant, and its efficiency as a catalyst, determined ions, they can catalyze a wide variety of organic and inorganic
by the observed rate constant. This relationship is best shown by reactions in soil and related ecosystems.
the Brønsted catalysis law (Brønsted, 1928):

ka = CA K aα kb = CB K bβ , (18.1) 18.3  Abiotic Catalysis of Natural
and Anthropogenic Organic
where
ka and k b are the rate constants (also termed the catalytic con-
Compounds
stants) for acid and base catalytic reactions, respectively 18.3.1  Oxidative Transformation of Phenolic
Ka and Kb are the acid and base ionization constants and Other Organic Compounds
CA, CB, α, and β are constants characteristic of the reaction,
the solvent, and the temperature 18.3.1.1  Phenolics
Phenolics are the most widely distributed class of plant second-
Normally, α and β are positive and have values between 0 and 1. ary metabolites and play an important role in regulating nutri-
In the Brønsted equation, a low value of α and β signifies a low ent cycling in the terrestrial environment (Hättenschwiler and
sensitivity of the catalytic constant to the strength of the catalyz- Vitousek, 2000). Phenolics may be released from natural sources,
ing acid or base, and vice versa. Proton transfer catalysis is of sig- industrial activities, or agricultural practices; and they can harm
nificance in soils and associated environments (Theng, 1974, 1979; the environment, especially in the form of pesticides (e.g., chlo-
Cheng, 1991; Nannipieri and Gianfreda, 1998) as discussed later. rophenols), nitrophenols, hormones, and azo dyes (Gianfreda
In acid catalysis of reactions involving negatively charged et al., 2006). The oxidative transformation of phenolics can be
organic molecules, adsorption of a proton reduces their negative accelerated enzymatically and nonenzymatically (Huang, 1990;
charge and, thus, facilitates the transfer of electrons (Steinberger Bollag et al., 1995; Naidja et al., 2000; Gianfreda et al., 2006). Soil
and Westheimer, 1949, 1951). In agreement with this explanation, minerals, in particular (SRO) Fe(III) and Mn(IV) oxides, play an
a number of multiply charged cations act as catalysts in the trans- important role in catalyzing the abiotic oxidative polymerization
formation of organic compounds (Stone and Torrents, 1995). of phenolic compounds and the subsequent formation of humic
18-4 Properties and Processes

substances (Wang et al., 1986; Pal et al., 1994; Bollag et al., 1998; oxide. This also explains the stronger catalytic ability of the
Huang, 2004; Huang et al., 2005). The surfaces of soil mineral Mn oxide than Fe, Al, and Si oxides in accelerating catechol oxi-
colloids promote oxidative polymerization reactions by acting as dation. In addition, the lower point of zero salt effect (PZSE) and
electron acceptors. The rate-determining step in the formation more negative charges of the Mn oxide than the Fe and Al oxides
of humic acids (HAs) from polyphenols is apparently the forma- could also enhance the oxidation of catechol (Liu and Huang,
tion of a semiquinone-free radical involving a single electron 2001). A more negatively charged mineral surface may favor
transfer reaction (Schnitzer, 1982). Semiquinones couple with the binding of protons released from catechol and subsequently
each other to form a stable HA polymer. The coupling of free increase the catalytic reaction rate. Therefore, the catalytic abil-
radicals requires little activation energy, in contrast to electron ity of a metal oxide in polyphenol transformation depends on
transfer reactions (Chang and Allen, 1971). Therefore, coupling the E° value of the overall redox reaction and the ability of the
of semiquinones rather than the formation of quinones should metal ions to complex with ligands, to shift electron density and
be kinetically the preferred reaction pathway in the transforma- molecular confrontation in the way conducive to the reaction,
tion of polyphenols to humic macromolecules. and to favor the binding of protons to the metal oxide.
Manganese(IV) oxides, such as birnessite (δ-MnO2), cryp- Birnessite strongly promotes the formation of humic mac-
tomelane (α-MnO2), and pyrolusite (β-MnO2), which com- romolecules from pyrogallol (1,2,3-trihydroxybenzene) under
monly occur in soils and sediments (McKenzie, 1989), are environmentally relevant conditions; total yields of humic sub-
powerful catalysts of the abiotic oxidation of polyphenols, such stances were 10.5-fold higher than in pyrogallol reacted in the
as catechol (1,2-dihydroxybenzene), compared with Fe, Al, and absence of birnessite (Wang and Huang, 1992). Manganese(IV)
Si oxides (Shindo and Huang, 1982, 1984a; Shindo, 1992; Liu and oxide has also been effectively used to treat polyphenol-polluted
Huang, 2001; Colarieti et al., 2006). This is partially attributable olive mill wastewater by enhancing humification (polymeriza-
to the lower electronegativity of Mn (Liu and Huang, 2001). The tion) (Brunetti et al., 2007). The Mn oxide-treated wastewater was
electronegativity values of Mn, Fe, Al, Si, H, and O are, respec- found to enhance the humified C content of amended soils and
tively, 1.55, 1.83, 1.61, 1.90, 2.20, and 3.44 (Porterfield, 1983). increased the overall fertility of the soil (Brunetti et al., 2007).
Catechol acts as a hard Lewis base, and Mn, Fe, Al, and Si are During the abiotic catalytic transformation of pyrogallol to
hard Lewis acids. When Mn, Fe, Al, or Si replace H in catechol to HA, Mn(IV), Fe(III), Al, and Si oxides also promote the abiotic
form metal–catechol complexes, the electron cloud delocalizes generation of CO2 through their ability to cleave the ring struc-
from the phenolic oxygen into the π-orbital formed from over- ture of pyrogallol (Wang and Huang, 1992, 2000b). The order of
lap of the 2p orbitals of the aromatic C atoms, thus accelerating CO2 release from the oxide-catalyzed pyrogallol reaction systems
the formation of semiquinone-free radicals and their polymer- was Mn(IV) oxide >>> Fe(III) oxide > Al oxide > Si oxide (Wang
ization. The electron cloud around the Mn–O bond in the Mn and Huang, 2000b). The release of CO2 was related to the devel-
oxide–phenolic complex should be more delocalized than that opment of carboxylic group contents in the HA fraction. Wang
around the Al–O bond in the Al–catechol complex and espe- and Huang (2000a) showed that the infrared spectrum of the
cially the Si–O or Fe–O bond in the Si or Fe oxide–phenolic fulvic acid (FA) fraction from the Mn oxide–pyrogallol system
complex due to the lower electronegativity of Mn than those of closely resembles that of the FA fraction extracted from a natural
Al, Fe, and Si. This provides a partial explanation for the greater Borosaprist soil. The abiotic ring cleavage of polyphenols by soil
accelerating effect of Mn oxide on the humification of catechol inorganic components may partially account for the findings of
than Fe, Al, or Si oxides. Naturally, redox reactions also play an the high aliphaticity of natural humic substances (Wilson and
important role in many abiotic catalytic reactions. Aluminum Goh, 1977; Hatcher et al., 1981). Lee and Huang (1995) showed
and silicon oxides are not subject to redox reaction. The stan- that the abiotic release of CO2 in the birnessite–polyphenol and
dard electrode potential (E°) values of the overall redox reac- polyphenol systems increases with light intensity, a consequence
tion of the Fe(III) oxide–catechol and Mn(IV) oxide–­catechol of a photofragmentation of polyphenolics catalyzed by birnes-
systems are +0.071 V and +0.509 V, respectively, as indicated by site. These findings imply that the pathways of C turnover in the
the following reactions (Shindo and Huang, 1984a): photic zones of soils and aquatic environments may differ from
those in their subsurface and submerged layers.
Fe3+ + e − = Fe2+ E° = 0.770 V, (18.2) Shindo and Huang (1992) compared the catalytic effects of Mn
oxide and the oxidoreductase enzyme, tyrosinase, on the oxida-
tive polymerization of diphenols over the pH range common in
MnO2 + 4H+ + 2e − = Mn2+ + 2H2O E° = 1.208 V, (18.3) soil environments. Manganese oxide influences the oxidative

polymerization of hydroquinone and resorcinol to a larger extent
than does tyrosinase, whereas the reverse is true for catechol. The
C 6H 4 (OH)2 = C 6H 4O2 + 2H+ + 2e − E° = 0.6992V. (18.4)
yields of HAs are significantly influenced by the kind of catalyst
and polyphenol. In the Mn oxide system, the yield of HAs is in
The positive E° values of the overall redox reactions indicate that the order hydroquinone > catechol > resorcinol. In the tyrosi-
the reactions are thermodynamically feasible, and catechol oxi- nase system, catechol produces the highest yield of HA, followed
dation can thus be accelerated by Fe oxide and especially Mn by hydroquinone and resorcinol. These findings indicate that the
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-5

relative catalytic effects of Mn(IV) oxides and enzymes such as conditions (Pizzigallo et al., 2004). Pyrolusite is able to oxida-
tyrosinase would vary with the type of polyphenols in soils. HAs tively degrade the carcinogenic pesticide and antiseptic agent
formed by mineral catalysis have a better defined chemical struc- TCP (2,4,6-trichlorophenol) under near-dry conditions; how-
ture than those formed by enzymatic oxidative polymerization, ever, the transformation products may actually be more toxic
favoring the formation of components with lower degrees of aro- and persistent than the parent compound (Smith et al., 2006).
matic ring condensation and lower molecular weights compared Methoxylyated phenols have been used to mediate the oxida-
with those generated in the presence of tyrosinase (Naidja et al., tive polymerization of the nonphenolic fungicide, cyprodinil
1998). Ahn et al. (2006) showed that the presence of the abiotic (4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine), in the
catalyst birnessite actually inhibits the catechol oxidative polym- presence of birnessite (Kang et al., 2004). Birnessite-induced oxi-
erization activity of the enzyme laccase, which was attributed to dative coupling also results in the decarboxylation, demethoxyl-
the Mn2+ released during the reduction of birnessite by catechol, ation, and dehalogenation of substituted phenolic subtrates (Dec
which binds to the enzyme and alters its active site. et al., 2001, 2003). Electron-withdrawing substituents, such as
Phenolic acids have been shown to be oxidized rapidly in –COOH and –Cl, are more susceptible to release than electron-
the presence of MnO2 to form a number of soluble products donating ones, such as –OCH3 and –CH3 (Dec et al., 2003).
(Lehmann and Cheng, 1988). Mass spectrometric data show The catalytic ability of Fe oxides in the rapid oxidative polym-
that some of the soluble products of the reaction have somewhat erization of polyphenols (Scheffer et al., 1959) increases in the
higher molecular weights than the parent compounds. However, following order: ferrihydrite > goethite > maghemite > lepido-
the soluble products of the reaction of ferulic acid and MnO2 do crocite > hematite. Ferrihydrite, which is SRO Fe oxide with
not contain any ferulic acid hexamers (Liu et  al., 1981; Bollag high surface area, is most reactive in catalyzing the oxidative
et al., 1982). The oxidized products of ferulic acids are apparently polymerization reaction. Besides the nature of Fe oxides, the
rapidly sorbed on the surfaces of MnO2. Polyhydroxyphenolic catalytic ability of Fe is related to structure and functionality of
acids with p- and o-OH groups are rapidly oxidized by Mn phenolic compounds (Shindo and Huang, 1984a; Shindo, 1992;
oxides (Pohlman and McColl, 1989) (Table 18.2) to polymeric Pracht et al., 2001).
humic products in both soil and Mn suspensions. On the other The oxidative polymerization of polyphenols is substantially
hand, m-polyhydroxyphenolic acids are not readily oxidized. influenced by the catalysis of Al hydroxides (Wang et al., 1983).
Monophenolic compounds, such as phenol (Jung et al., 2008b), Soluble silicic acid in aqueous solution and precipitated short-
and particularly those containing electron-donating substituent range order silica can catalyze the oxidation of polyphenols
groups on the aromatic ring, can be oxidatively transformed by (Ziechmann, 1959). Liu and Huang (2000) reported that silicic
Mn(IV) oxides (Lehmann et al., 1987; Stone, 1987; Ulrich and acid and especially hydroxyl Al ions substantially enhance
Stone, 1989; Zhao et al., 2006). Manganese(IV) oxide has been oxidative polymerization of catechol. Liu and Huang (2002)
found to be an effective abiotic catalyst of the oxidative transfor- showed that hydroxy-aluminosilicate ions, which are precur-
mation of highly toxic and recalcitrant compound, pentachlo- sors to noncrystalline aluminosilicates, are also effective in
rophenol (PCP), under aquifer (Petrie et al., 2002) and near-dry promoting the oxidative polymerization of catechol. The sur-
face of ground quartz has a disturbed layer, which is SRO in
nature (Iler, 1979). Similar disturbed surface layers are present
TABLE 18.2  Kinetic Constants for Polyhydroxyphenolic Acid
Oxidation by Soil and Manganese Oxide Suspensiona on quartz grains in soils (Ribault, 1971). Oxidative polymeriza-
tion of polyphenols may be catalyzed by the disturbed surface
Rate Constants (L mol−1 s−1)
of quartz in soils.
Compound Challenge A Horizon MnO2 Besides metal oxides, clay size layer silicates have the ability
2,3-Dihydroxybenzoic acid ND b 0.03 to catalyze the oxidative transformation of polyphenols. Before
2,5-Dihydroxybenzoic acid 0.06 0.04 the pioneering work on the catalytic role of clay size layer sili-
2,6-Dihydroxybenzoic acid 0.00c ND cates in oxidative polymerization of phenolic compounds and
3,4-Dihydroxybenzoic acid 0.10 0.04 the subsequent formation of humic substances (Kumada and
3,5-Dihydroxybenzoic acid 0.00 0.00 Kato, 1970; Filip et al., 1977; Wang and Li, 1977), the conver-
Gallic acid 0.25 0.05 sion of many aromatic amines into their color derivatives by clay
Syringic acid ND 0.01 minerals and clays had been investigated (Faust, 1940; Hauser
Vanillic acid ND 0.00 and Legget, 1940). Solomon (1968) reported that, except for talc,
Source: From Pohlman, A.A., and J.G. McColl. 1989. Organic oxi-
a large number of representative minerals produce a blue color
dation and manganese and aluminum mobilization in forest soils. Soil of varying intensity when brought into contact with a saturated
Sci. Soc. Am. J. 53:686–690. With permission of the Soil Science solution of benzidine hydrochloride. The active sites for the
Society of America. oxidation of benzidine are located on the crystal edges and on
a Oxidations were run using 10 g L−1 soil and 2.5 × 10−4 mol L−1 phe-
transition metal atoms in the higher oxidation state that occupy
nolic acid or 0.19 g L−1 MnO2 and 5.0 × 10−4 mol L−1 phenolic acid at pH
4.5 and 30°C.
octahedral sites in the silicate layers. Thompson and Moll (1973)
b ND, not determined. measured the oxidative power of smectites by oxidation of hydro-
c No oxidation of phenolic acid within 120 min of reaction. quinone to p-benezoquinone in a clay slurry. Oxidation occurs
18-6 Properties and Processes

in the presence of O2 (air), but not N2 unless Fe3+ or Cu2+ are the catechol. The resultant carboxyl group-containing intermediates
exchangeable cations. Adsorbed O2 molecules or radicals on the are further oxidized to form CO2 and aliphatic fragments. In the
clay surface are apparently partially responsible for the oxidation. reaction systems, intermediate products and aliphatic fragments
Pinnavais et al. (1974) reported aromatic radical cation for- may form polycondensates. The structure and functionality of
mation on the intracrystal surfaces of transition metal-saturated polyphenols thus have an important role in influencing the extent
layer silicates. Aromatic molecules, when reacted under very of catalytic transformations by nontronite.
moderated conditions with Cu(II) or Fe(II) ions, may donate Primary minerals, which are commonly present in soil envi-
electrons to the metal cations, leading to the formation of poly- ronments (Dixon and Weed, 1989), can catalyze the oxidative
mers (Mortland and Halloran, 1976). Montmorillonite, ver- polymerization of polyphenols (Shindo and Huang, 1985b). The
miculite, illite, and kaolinite accelerate the formation of HAs degree of acceleration of the oxidative polymerization of hydro-
to varying degrees (Shindo and Huang, 1985a). The promoting quinone is greatest in the tephroite system, which increases the
effect of 2:1 layer silicates is higher than that of 1:1 layer silicates total HA yields more than ninefold because (1) tephroite (ideal
because of the larger specific surface and lattice imperfections, chemical formula, MnSiO4) is a Mn-bearing silicate, (2) part
which favor adsorption of O2 molecules or radicals. of the Mn in tephroite is present in the higher valence states,
One of the well-identified precursors (Flaig et al., 1975; Hayes and (3) the oxidation of diphenols [C6H4(OH)2] by Mn(III) and
and Swift, 1978) for the formation of humic substances, hydro- Mn(IV) is thermodynamically favorable (Lide, 2008).
quinone, can be transformed in aqueous solution at near-neutral The hydroquinone-derived polymers with molecular weights
pH (6.5) to humic macromolecules and deposited in the interlay- of approximately 3500 and higher formed in the presence of
ers of nontronite saturated with Ca, which is the most common the tephroite system (Shindo and Huang, 1985b) have similar
and most abundant exchangeable cation in soils and sediments IR absorption bands to those of humic substances (Schnitzer,
(Wang and Huang, 1986). Most of the interlayer humic macro- 1978). The surface features of these polymers (Figure 18.1) are
molecules are highly resistant to alkali extraction and may, thus, similar to those of soil HA and FA (Stevenson and Schnitzer,
be humin-type materials. Therefore, besides Al interlayers in 1982) with the smallest discrete particles being spheroids with
2:1 expansible layer silicates, the formation of humic substance diameters of 0.1–0.2 μm (Figure 18.1a) and some aggregation
interlayers in 2:1 expansible layer silicates, through polymeriza- of individual spheroids (Figure 18.1b and c). Small aggregates
tion of phenol monomers and the associated reactions in soils (Figure 18.1c) resemble moss while the large aggregates are nod-
and sediments, deserves close attention. ule like (1–5 μm diameter) and doughnut like (6–8 μm diam-
The ability of nontronite to promote the oxidation of poly- eter) (Figure 18.1a and b). The polymers do not appear to be
phenols is related to the structure and functionality of the poly- associated with the surfaces of tephroite particles (Figure 18.1d).
phenols, and part of the reaction process may proceed as shown Consequently, the role of primary minerals in the oxidative
below (Wang and Huang, 1994): polymerization of polyphenols and the subsequent formation of
humic substances in soils should not be overlooked (Shindo and
OH OH Huang, 1985b).
OH
Nontronite COOH SRO aluminosilicates, such as allophone, are known to act as
CO2 + Aliphatic fragments
COOH catalysts in the oxidative degradation of polyphenols (Kyuma
OH
and Kawaguchi, 1964; Kumada and Kato, 1970). Hydroxy-
Pyrogallol
aluminosilicate ions (proto-imogolite sol) also have the ability
(18.5)
to catalyze polyphenol humification (Liu and Huang, 2002).
OH However, the role of other SRO aluminosilicates remains
Nontronite COOH CO2 + Aliphatic fragments obscure. On the other hand, the formation of SRO alumino-
OH COOH silicates is significantly affected by inorganic ligands, low-
Catechol molecular-weight organic acids, humic substances, metallic
(18.6) cations, and expansible layer silicates (Huang, 1991a), resulting
in the formation of ill-defined aluminosilicate complexes and
OH hydroxyaluminosilicate-intercalated layer silicates. The cata-
lytic ability of these SRO mineral colloids in the transformation
Nontronite of polyphenols and other organic compounds in soils has yet to
CO2 + Aliphatic fragments (18.7)
be investigated.

OH 18.3.1.2  Other Organic Compounds

Hydroquinone Many naturally occurring organic acids, including salicylic,
pyruvic, oxalic, and malic acids, are degraded by mineral col-
Catechol with two o-OHs is evidently more easily cleaved than loids such as Mn oxides by electron transfer reactions (Stone
hydroquinone with two p-OHs while pyrogallol with three and Morgan, 1984a, 1984b). A wide range of nonphenolic xeno-
hydroxyls in adjacent positions is even more easily cleaved than biotic compounds, including pesticides, antibiotics, dyes, and
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-7

(a) (b)

(c) (d)

FIGURE 18.1  SEM micrographs of hydroquinone polymers in the supernatant and mineral particles settled in the tephroite system at the ratio
of mineral to hydroquinone solution of 0.01 at the initial pH of 6.0 at the end of 7 days. (a, b, c) Hydroquinone polymers; (d) tephroite particles after
reaction with hydroquinone. Bar in (a) equals 10 μm; bars in (b)–(d) equals 2 μm. (Reprinted from Shindo, H., and P.M. Huang. 1985b. Catalytic
polymerization of hydroquinone by primary minerals. Soil Sci. 139:505–511.)

explosives, are subject to abiotic soil mineral-catalyzed oxida- decarboxylation mechanisms (Shin et al., 2000). The removal of
tive transformation. Abiotic degradation pathways of biocides 4-chloroaniline and PCP by a mechanochemical procedure was
(pesticides and antibiotics) are particularly important in the far more effective than by batch contact (solution) in the pres-
environment as the toxicity of these substances can limit their ence of birnessite and ferrihydrite (Pizzigallo et al., 2004). The
biotic degradation. mechanochemical contact of polychlorinated biphenyls (PCBs)
and birnessite produced a removal of pollutant that was a func-
tion of the number of chlorine atoms, that is, the more the chlo-
18.3.1.2.1  Pesticides rine atoms the less effective the oxidative degradation (Pizzigallo
Manganese(IV) oxides are able to catalyze the oxidative polym- et al., 2004). Possible contributions of solid-state degradation to
erization of toxic anilines, chloroanilines, and other aromatic herbicide breakdown by abiotic catalysis should be considered in
amines, which originate from pesticides, as well as from chemi- modeling herbicide breakdown or when designing experiments
cal manufacturing residues (Laha and Luthy, 1990; Pizzigallo for soil remediation.
et al., 1998; Li et al., 2003). Birnessite is an effective solid-state Birnessite is able to oxidatively degrade glyphosphate
catalyst of the breakdown of organic pollutants such as the her- (N-phosphonomethyl-glycine), which is the most commonly
bicide 2,4-D (2,4-dichlorophenoxyacetic acid) and diethyl ether, used pesticide worldwide (Barrett and McBride, 2005). The
which are adsorbed on birnessite and rapidly oxidized (Cheney abiotic degradation mechanism involves C–P and C–N bond
et al., 1996), both producing CO2 as a major product, but by cleavage of glyphosphate and its degradation product, sarco-
somewhat different mechanisms. Nasser et al. (2000) demon- sine, due to electron transfer reactions at the Mn oxide surface
strated a dry mechanochemical technique for quickly and com- (Figure 18.2; Barrett and McBride, 2005). Pyrolusite is able to
pletely degrading 2,4-D by lightly grinding it with birnessite, effectively oxidatively degrade the widely found organic pollut-
thus eliminating the need for organic solvents such as diethyl ant 2-mercaptobenzothiazole (a biocide and compound used in
ether. The widely used herbicide atrazine (2-chloro-4-ethylamino- manufacture of rubber) into SO4 2− and NO3 −; however, the pres-
6-isopropylamino-s-triazine) is also partially degraded by ence of organic acids, carboxylic acids (oxalic, citric, tartaric,
mechanochemical contact with Mn(IV) oxides (birnessite, cryp- and malic acids), or metal ions (Ni 2+, Ca 2+, Mn2+, and Cr3+) has
tomelane, and pyrolusite) via N-dealkylation and subsequent an inhibiting effect on the rate of degradation (Li et al., 2008).
18-8 Properties and Processes

O O 18.3.1.2.2  Antibiotics
Mn3+ O P CH2 +
NH2 CH2 C Manganese(IV) oxides are able to oxidatively degrade many of
OH the leading groups of antibacterial agents used in the treatment
OH
of humans and animals, in livestock feed additives, or in active
Electron transfer ingredients in personal care products (Zhang et al., 2008).
Manganese(IV) oxide is able to catalyze the oxidative degra-
O O dation of the popular and potent fluoroquinolone (FQ) antibi-
+ •O + otic agents under environmental conditions (Zhang and Huang,
Mn2+ P CH2 NH2 CH2 C
2005a). The oxidative degradation mechanism (Figure 18.4)
OH Glyphosate OH
involves a surface reaction mechanism that likely begins with
the formation of a surface complex between FQ and the sur-
face-bound Mn(IV), followed by oxidation at the aromatic N1
atom of FQ’s piperazine moiety to generate an anilinyl radical
O O O
• intermediate. The radical intermediates subsequently undergo
P + H2C NH+2 CH2 C
N-dealkylation, C-hydroxylation, and possibly coupling to yield
OH OH a range of products. The δ-MnO2 exhibited reactivity to the FQ
antibiotics in the order of ciprofloxacin ≈ enrofloxacin ≈ norflox-
acin ≈ ofloxacin > lomefloxacin > pipemidic acid >> flumequine
O (Zhang and Huang, 2005a). The veterinary N-oxide antibiot-
O
ics, carbadox, olaquindox, quinoline N-oxide, and quindoxin
P OH + H3C NH CH2 C also exhibit high oxidation reactivity toward MnO2 (Zhang and
OH OH Sarcosine OH Huang, 2005b). The transformation mechanism involves the for-
mation of an N-oxide radical intermediate and the generation of
Mn(II) (Zhang and Huang, 2005b).
Manganese(IV) oxides are also able to promote the apprecia-
O ble degradation of tetracycline antibiotics (Rubert and Pedersen,
NH+3 CH2 C + HCOOH 2006). Reactivity of tetracycline antibiotics toward MnO2
Glycine OH increases in the following order: rolitetracyline ≈ oxytetracy-
cline ≤ tetracycline ≈ meclocycline < chlortetracycline. Abiotic
FIGURE 18.2  A possible degradation reaction scheme for glyphos- degradation of the veterinary ionophore and macroclide antibi-
phate adsorbed on Mn oxide. (Reprinted with permission from Barrett, otics, monensin and tylosin, does take place in soil, however at a
K.A., and M.B. McBride. 2005. Oxidative degradation of glyphosate and much slower rate than by microbial degradation in soil (Sassman
­aminomethylphosphonate by manganese oxide. Environ. Sci. Technol. and Lee, 2007; Sassman et al., 2007).
39:9223–9228. Copyright 2005 American Chemical Society.)

18.3.1.2.3  Explosives and Dyes

O
Clay O The explosive CL-20 (hexanitrohexaazaisowurtzitane) was
R O R O found to be quickly (in minutes) abiotically, and oxidatively
NH Room
NH
temperature degraded in the presence of 2:1 layer silicates (montmorillon-
O2N
ite, hectorite, and nontronite), micas (biotite and illite), and
FIGURE 18.3  Chemical structure of carbamates and their nitro birnessite (Szecsody et al., 2004). The exact mechanism remains
derivatives in clay-catalyzed nitration. (Reprinted with permission from unclear, but it is known that the cage structure of CL-20 is bro-
Kodaka, R., T. Sugano, T. Katagi, and Y. Takimoto. 2003. Clay-catalyzed ken and that cleavage of C–C and C–N bonds occurs due to the
nitration of a carbamate fungicide diethofencarb. J. Agric. Food Chem. formation of nitrite and formate anions (Szecsody et al., 2004).
51:7730–7737. Copyright 2003 American Chemical Society.) Birnessite has also been found to effectively catalyze the complete
abiotic transformation of the Fe0-induced reduction products of
Clay minerals, kaolinite and montmorillonite, are able to the explosive 2,4,6-trinitrotoluene (TNT) via oxidative-coupling
catalyze the nitration of the carbamate fungicide, diethofencarb reactions (Kang et al., 2006).
(isopropyl 3,4-diethoxycarbanilate), which most likely proceeds Magnetite and other mixed metal (Co, Cu, and Mn)-ferrite
through the formation of NO2• radicals on the surface of the clay oxides are able to efficiently catalyze the oxidative degradation
(Figure 18.3). The similar nitration of the phenyl ring of the pes- and decolorization of various dyes (bromophenol blue, Chicago
ticide, famoxadone (3-anilino-5-methyl-5- (4-phenoxyphenyl)- sky blue, Cu-phthalocyanine, eosin yellowish, Evans blue, naph-
1,3-oxazolidine-2,4-dione), has been reported (Jernberg and thol blue black, phenol red, poly B-411, and reactive orange 16)
Philip, 1999). Nitration of pesticides is only known as a clay- in the presence of hydrogen peroxide by generating hydroxyl-
catalyzed reaction (Nikalje et al., 2000). free radicals (Baldrian et al., 2006). The metal oxide catalysts are
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-9

>MnIVOH >MnIII
Further reduced to MnII
+ ·
Ar a N NH Ar N NH I Dimerization
–e–
II
C-hydroxylation
III
N-dealkylation
+ IV
X · N NH Others
O H
H+ HO OH Ar N NH2
O HH O
+ –2e– + + H2O
II: Ar N NH Ar N NH Ar N NH Ar N NH + H O
–e–
Ar NH NH

H+
+ H2O –2e– –2e– + H2O
III: Ar N NH Ar NH NH2 Ar NH NH2 Ar NH2
–e– H2O

a Ar = aromatic ring Dimerization or potential polymerization

FIGURE 18.4  Proposed reaction scheme for oxidation of fluoroquinolone antibiotics by δ-MnO2. (Reprinted with permission from Zhang, H.C.,
and C.H. Huang. 2005a. Oxidative transformation of fluoroquinolone antibacterial agents and structurally related amines by manganese oxide.
Environ. Sci. Technol. 39:4474–4483. Copyright 2005 American Chemical Society.)

able to retain their activity even after repeated catalytic cycles with the formation of NH3–N and nitrogenous polymers (Table
and over a broad pH range unlike enzymatic catalysts such as 18.3). The proposed processes are as follows: (1) the Mn oxide
laccase (Baldrian et al., 2006). The ferric iron species in layer sili- acts as Lewis acid by accepting electrons from hydroquinone,
cate clays are also able to catalyze the oxidative degradation of which is thus oxidized and subsequently polymerized; (2) the
the organic dye, malachite green, in the presence of hydrogen products of the reaction of glycine with hydroquinone polymer-
peroxide (Cheng et al., 2008). The exchangeable interlayer Fe(III) ize to form nitrogenous polymers, thereby incorporating glycine
ions exhibit a much higher reactivity than structural Fe(III) in into the polymers during the oxidative polymerization of hydro-
the octahedral sheet. The Fe-containing clays are chemically and quinone; and (3) a partial deamination of glycine occurs during
mechanically stable, and no loss of activity was observed after 14 the second process.
recycles (Cheng et al., 2008). Birnessite also catalyzes the polycondensation of glycine and
pyrogallol and deamination and decarboxylation of glycine espe-
cially in the presence of pyrogallol (Wang and Huang, 1987). The
18.3.2  Polycondensation of Phenolic
formation of HA and FA is not evident in the presence of glycine
Compounds and Amino Acids
alone. In a N2 atmosphere, CO2 release in the birnessite–glycine–
The transformation of colorless amino acids and polyphenols pyrogallol system is drastically reduced. Birnessite also greatly
by quinone–amino acid polycondensation reactions into darkly enhances the formation of N-containing humic polymers. Most
colored polymers is a significant browning reaction in nature of the released NH3 can be attributed to the deamination of gly-
(Bittner, 2006). Birnessite efficiently catalyzes the polycondensa- cine by pyrogallol-derived free radicals as catalyzed by birnessite
tion of phenolic compounds and amino acids such as in hydro- but an appreciable amount can also be directly derived from the
quinone–glycine systems in the common pH range (4–8) of soils deamination of glycine by birnessite.

TABLE 18.3  Formation of NH3–N and Polymer–N (in mg kg−1) in the Hydroquinone–Glycine System Both in the Absence and Presence
of Mn Oxide at Different pH Values at the End of 24 h
Initial pH of 4.0 Initial pH of 6.0 Initial pH of 7.3
Final pH NH3–N Polymer–N Sum-N Final pH NH3–N Polymer–N Sum-N Final pH NH3–N Polymer–N Sum-N
Hydroquinone– 4.1 4.4 3.0 7.4 6.1 6.0 2.0 8.0 6.9 11.7 3.4 15.1
glycine
Mn oxide 4.1 30.5 12.6 43.1 7.6 30.2 40.1 70.3 7.9 34.1 41.2 75.3
hydroquinone–
glycine
Source: Shindo, H., and P.M. Huang. 1984b. Significance of Mn(IV) oxide in abiotic formation of organic nitrogen complexes in natural environments.
Nature 308:57–58. With permission of Macmillan, London.
18-10 Properties and Processes

Carbon-14 labeling of glycine was used to measure the extent sugars and amino acids, and reaction intermediates, known as
of incorporation of carboxyl C and alkyl C into the polycon- Amadori and Heyns compounds (Yaylayan, 1997).
densates of pyrogallol and glycine (Wang and Huang, 1997). The initial reaction in the Maillard reaction involves con-
Birnessite promotes the incorporation of carboxyl and especially densation between the α-hydroxy carbonyl group of a reducing
alkyl C of glycine into the polycondensates formed in the pres- sugar and the amino group from an amino acid with the forma-
ence of pyrogallol (Wang and Huang, 1997, 2005). The results tion of a Schiff base, which rearranges to form either Amadori
indicate that the formation of the C–C bond is more prevalent or Heyns compounds. Aldohexoses generate Amadori com-
than that of the C–O bond in the polycondensation of glycine pounds while ketohexoses generate Heyns products (Yaylayan,
and pyrogallol catalyzed by birnessite. 1997). These compounds can undergo retroaldolization reac-
Besides birnessite, clay size layer silicates also have the abil- tions forming α-dicarbonyl and α-hydroxyketone compounds.
ity to catalyze the polycondensation of phenolic compounds All these compounds are highly reactive and readily polymer-
and amino acids. Wang et al. (1985) show the catalytic effect of ize in the presence of amino compounds to form brown-colored
Ca-illite on the formation of N-containing HAs in the systems melanoidins. Amino acids can react with the α-dicarbonyl com-
containing phenolic compounds and amino acids at neutral pH. pounds, undergoing the Strecker degradation and then form-
The yields and N contents of the synthesized HAs depend on the ing α-amino ketones. The α-amino ketones may then condense
nature of amino acids. resulting in the formation of pyrazines (Ho, 1996; Yaylayan,
Nontronite in which structural Fe(III) acts as an electron 1997). In addition, the Maillard reaction can result in the forma-
acceptor analogous to Mn(IV) in MnO2 (Solomon, 1968; tion of polyphenols, such as catechol, resorcinol, hydroquinone,
Theng, 1974) also catalyzes the polycondensation of glycine and pyrogallol, which can enhance the degree of browning dur-
and pyrogallol (Wang and Huang, 1991). The IR and elec- ing the Maillard reaction by affecting the redox potential of the
tron spin resonance (ESR) spectra of the HA and FA formed, system (Haffenden and Yaylayan, 2005) and undergoing polym-
which show the presence of a stabilized organic free radical erization and polycondensation (Wang and Huang, 2005).
(semiquinone), are similar to those of natural soil HA and FA Commonly found soil metal oxides, birnessite (Jokic et al.,
(Schnitzer, 1977; Senesi and Schnitzer, 1977; Schnitzer and 2001b), goethite (Gonzalez and Laird, 2004), and smectite clays
Levesque, 1979; Hatcher et  al., 1980; Schnitzer and Ghosh, (Gonzalez and Laird, 2004), have been shown to catalyze the
1982). The formation of semiquinone-free radicals appears to Maillard reaction under typical pH and temperature ranges
proceed through electron transfer from pyrogallol to Fe(III) found in the natural environment. Jokic et al. (2001b) were
or other variable-valence transition metal ions on the edges the first to report that birnessite catalyzes the Maillard reac-
or in the nontronite structure (Solomon, 1968). Electrons dif- tion between glucose and glycine. Their data showed that the
fuse or tunnel to octahedral sites from layer edges or basal presence of a redox-reactive mineral, namely, birnessite, sig-
surfaces (Tennakoon et al., 1974). The strong oxidation power nificantly accelerates the reaction by one to two orders of mag-
of chemisorbed O2 on silicates (Solomon and Hawthorne, nitude under environmentally relevant temperatures (25°C
1983) such as nontronite seems to cause the ring cleavage of and 45°C) and a neutral pH (7.00). This reaction is kinetically
pyrogallol and the decarboxylation and deamination of gly- sluggish under ambient temperatures (Jokic et al., 2001c) but
cine (Wang and Huang, 1991). Semiquinone-free radicals, the presence of birnessite significantly catalyzes the reaction
aliphatic fragments, and glycine apparently undergo polycon- by decreasing the activation energy required. Other groups
densation to form humic polymers. (Bosetto et al., 1995, 1997; Arafaioli et al., 1997, 1999) have also
Natural soil clays, from temperate and tropical environments, investigated the clay mineral catalysis of the Maillard reaction
have been shown to catalyze the polycondensation of pyrogallol between various amino acids and glucose at relatively high
and glycine, the ring cleavage of pyrogallol, its polymerization, temperatures (at 70°C).
and the deamination of glycine (Wang and Huang, 2003). The Light enhances birnessite catalysis of the Maillard reaction,
reactivity of the mollisol and oxisol clays was attributed to the but the reaction still proceeds in the absence of light (Jokic
catalysis of the layer silicates and oxides of Fe, Al, and Mn pres- et al., 2001a). This means that the reaction could readily occur
ent in the natural soil clays (Wang and Huang, 2003). in the subsoil in the presence of a mineral catalyst such as
birnessite. The Maillard reaction between glucose and glycine
as catalyzed by birnessite results in the formation of humic sub-
18.3.3  The Maillard Reaction and Integrated
stances that contain significant amounts of (1) amides, which
Polyphenol–Maillard Reactions
are the dominant N types in humic substances, soils, and
The Maillard reaction (Maillard, 1913), involving condensa- sediments, and (2) heterocyclic N compounds, which are often
tion reactions between reducing sugars and amino acids, is referred to as unknown N (Jokic et al., 2004a) (Figure 18.5). The
considered to be an important pathway in natural humification mineral-catalyzed Maillard reaction provides a possible expla-
(Ikan et al., 1996). Sugars and amino acids are among the most nation for one of the pathways for the formation of heterocyclic
abundant constituents of terrestrial and aquatic environments and amide N found in humic substances in the environment
(Anderson et al., 1989). The Maillard reaction involves numer- (Jokic et al., 2004a). The action of birnessite on glucose should
ous reactions between the degradation products of the precursor promote the autoxidation of glucose, which results in the
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-11

1. Oxidation of carbohydrate or Strecker aldehyde by δ-MnO2 to

N 1s
form carboxylic acid, or formation of carboxylic acid during
Pyridone Strecker degradation
Amide
Pyrrolic 2. Deamination of amino acid by δ-MnO2

R
Pyridinic
δ-MnO2 –
R C COOH CO2 + NH3 + other products

NH2
(a) 3. Amide formation

RCOH + NH3 RCNH2 + H2O

O O

FIGURE 18.6  Possible amide formation pathway including the key

role of MnO2. (Reprinted from Jokic, A., H.-R. Schulten, J.N. Cutler,
M. Schnitzer, and P.M. Huang. 2005. Catalysis of the Maillard reaction
by δ-MnO2: A significant abiotic sorptive condensation pathway for the
(b) formation of refractory N-containing biogeomacromolecules in nature,
p. 127–152. In P.M. Huang, A. Violante, J.-M. Bollag, and P. Vityakon
(eds.) Soil abiotic and biotic interactions and impact on the ecosystem
395 400 405 410 415 and human welfare. Science Publishers Inc., Enfield, NH. Copyright
Photon energy (eV) Science Publishers Inc. With permission.)

FIGURE 18.5  N 1s XANES spectra of (a) fulvic acid isolated from a

glucose–glycine–δ-MnO2 system and (b) the lyophilized solid phase. Jokic et al. (2004b) were the first to study an integrated
The peaks are assigned to pyridinic (398.6 eV), pyridone (400.7 eV), Maillard reaction and polyphenol (glucose, glycine, and cat-
amide (401.3 eV), and pyrrolic (402.0 eV) moieties. (Reprinted from echol) pathway of humification, using birnessite as catalyst.
Jokic, A., H.-R. Schulten, J.N. Cutler, M. Schnitzer, and P.M. Huang. Their data showed that birnessite significantly accelerates
2004a. A significant abiotic pathway for the formation of unknown humification processes in an integrated polyphenol–Maillard
nitrogen in nature. Geophys. Res. Lett. 31:L05502. With permission of reaction system under ambient conditions (25°C and 45°C). In
the American Geophysical Union.) nature, it is likely that the Maillard reaction and polyphenol
pathways interact closely, since sugars, amino acids, and poly-
generation of reactive dicarbonyl compounds, hydrogen per- phenols coexist in soil solutions and natural waters. Jokic et al.
oxide, and hydroxylating agents (Wolff, 1996). These reactive (2004b) also showed that the integrated polyphenol–Maillard
dicarbonyl compounds would then react with ammonia formed reaction system is more effective in generating humic polymers
by the known deamination of glycine catalyzed by birnessite than the Maillard reaction alone. The type of polyphenol and
(Wang and Huang, 1987), as proposed by Vairavamurthy and the molar ratio of polyphenol to Maillard reagents in the poly-
Wang (2002) or with glycine (undergoing the Strecker degra- phenol–Maillard reaction system significantly affect not only
dation), resulting in either case in the formation of heterocy- the humification processes but also the biomolecule-induced
clic N compounds (Wong and Shibamoto, 1996). Ammonium formation of inorganic C, namely, rhodochrosite (MnCO3)
ions are known to react with compounds containing reactive (Hardie et al., 2009). Increasing the molar ratio of polyphenols
carboxyl groups to form pyridinic structures (Steelink, 1994). to Maillard reagents results in a significant enhancement of
Carboxylic acids are produced during the Strecker degradation humification in the polyphenol–Maillard reaction in the pres-
of amino acids (Wong and Shibamoto, 1996) or by the action of ence of birnessite. Polyphenols with ortho-OH groups (pyro-
manganese dioxides on simple carbohydrates (Bose et al., 1959; gallol) participate in direct electron transfer reactions with
Gonzalez and Laird, 2006). When heated, carboxylic acids react birnessite more readily than polyphenols with meta-OH groups
with ammonia to form amides (Smith and March, 2001). The (resorcinol), and subsequently undergo oxidative polymeriza-
scheme for possible amide formation is shown in Figure 18.6. tion and ring-cleavage reactions to a greater extent. Thus, the
Gonzalez and Laird (2004) showed that four different smectites humic polymers formed in the pyrogallol–Maillard system are
saturated with various metal cations (Ca, Na, Cu(II), and Al) could significantly more aliphatic in character than those formed in
catalyze the Maillard reaction between arginine and glucose at the resorcinol–Maillard system. Furthermore, the greater extent
an environmentally relevant temperature (37°C). They found that of polymerization reactions in the birnessite-catalyzed pyrogal-
only saturation with Cu(II) significantly altered the amount of lol–Maillard system results in the suppression of MnCO3 forma-
humic substances produced. They also observed that some of the tion. Hardie et al. (2007) also compared the HA fraction formed
adsorbed humic substances were intercalated into the smectites. in the presence of birnessite from the Maillard reaction and two
18-12 Properties and Processes

­ olyphenol–Maillard reaction systems with natural soil and

p sterilized soil to atrazine solution increased the hydrolysis rate of
peat HA using C K-edge NEXAFS and found that these HAs are atrazine 10-fold. Soil catalytic degradation of atrazine through
basically similar, especially the HA from the Maillard reaction hydrolysis is an important pathway. Mineral surface acidity also
and ­pyrogallol–Maillard systems. catalyzes hydrolysis of the chloro-s-triazine herbicides to the
nonphytotoxic 2-hydroxy-s-triazines (Russell et al., 1968b) and
may be of significance in a wide range of other organic com-
18.3.4  Surface Brønsted and Lewis Acidity pounds (McBride, 1994).
and Hydrolysis of Organic Compounds Besides the Brønsted acid, the Lewis acid properties of met-
Mineral colloids may detoxify adsorbed pesticides by catalyzing als appear to be of significance in mineral-catalyzed hydrolysis
their decompositions through the ability of mineral colloids to reactions. The oxides of Fe and Al in water, and especially in
behave as Brønsted acids and donate protons or to act as Lewis the dry state, have some catalytic function in organic hydrolysis
acids and accept electron pairs. Brønsted acidity derives essen- reactions, at least for those that are known to be hydroxyl ion
tially from the dissociation of water molecules coordinated to catalyzed (Hoffmann, 1990). Those hydrolyzable organics that
surface-bound cations, resulting in the formation of active pro- have a suitable structure to chelate with the surface metal cat-
tons. This acidity is, thus, strongly influenced by the hydration ions are, in general, the most susceptible to mineral-catalyzed
status and polarizing power of surface-bound and structural degradation.
cations on mineral colloids (Mortland, 1970, 1986). Low water Dissolved metals and metal-containing surfaces play an
contents and highly polarizing cations (small, high charge) pro- important role in catalyzing the hydrolysis of organic pollut-
mote Brønsted acidity. Lewis acidity arises from constituent ions ants. The catalytic effectiveness of a metal ion depends on its
such as Al and Fe ions exposed at the edges of mineral colloids ability to complex reactant molecules (e.g., ester linkage, leaving
(Sposito, 1984; McBride, 1994). group, and attacking nucleophile) and shift electron density and
Many uncharged organic molecules that require extremely acid conformation in ways favorable to reaction (Hoffmann, 1980).
conditions to accept a H+ ion in solution can be protonated on the Metals vary in their complex formation constants, which reflect
surface of mineral colloids (Huang, 1990; McBride, 1994). The difference in metal–ligand bond strengths and solvation forces.
Brønsted acid strength and the degree of protonation are related The following rules can explain the general features: (1) complex
to the electronegativity and polarizing power of the exchange- formation constants generally increase as the charge to radius
able and structural metal cations in the following order (McBride, ratio of the metal ion is increased, because the electrostatic con-
1994): H+ > Al3+, Fe3+ > Mg2+ > Ca2+ > Na+ > K+. As clay surfaces tribution to bond formation is increased; (2) polarizable metals
become drier, the Brønsted acidity increases and protons are con- and ligands gain additional complex stability through cova-
centrated in a smaller volume of water resulting in more extreme lent bond formation; and (3) as complex formation constants
surface acidity. Even very weak bases, that is, poor proton accep- increase, competition for the metal among available ligands
tors can be protonated on the surfaces of such mineral colloids. (including OH− and other inorganic constituents) becomes
The degradation of certain pesticides is catalyzed as the result more pronounced. Trivalent metals such as Al and Fe(III) and
of their adsorption on mineral colloids, which was first observed tetravalent metals such as Ti(IV) are classic hard metals, which
by formulation chemists who used clays as carriers and diluents form strong complexes with classic hard ligands (Pearson, 1966).
(Fowkes et al., 1960). Surface-catalyzed degradation of pesticides Organic compounds possessing O and N donor atoms are clas-
on clays was later demonstrated for several organophosphate sified as hard ligands, whereas those possessing S donor atoms
and s-triazine pesticides and has been attributed to the surface are classified as soft ligands. Oxygen donor organic ligands form
acidity of clay minerals (Brown and White, 1969; Salztman et al., strong complexes with metals such as Al, Fe(III), and Ti(IV).
1974; Minglegrin et al., 1977). Minglegrin and Salztman (1979) However, they compete with hydroxo (OH−) and oxo (O2−) spe-
demonstrated that the nature of the clay, its saturating cation, cies that limit metal solubility near-neutral pH values. Although
and hydration status determine the rate and mechanism of deg- Ca 2+ and Mg2+ are also classified as “hard” metals, their s and p
radation of parathion. The adsorption-catalyzed degradation of orbitals form bonds that are primarily ionic in nature (Stone and
parathion is a hydrolysis reaction that proceeds either directly or Torrents, 1995).
through a rearrangement step. Complex formation constants of metals with a ligand primar-
Magnesium-saturated montmorillonite converts the amino ily vary with the ionic radius of metals, although increases in
form of 3-aminotriazole to the imino form (Russell et al., 1968a) polarizability with increasing atomic number are also important
as shown below: (Houghton, 1979). Even if differences in metal–ligand complex
formation constants are taken into consideration, differences in
HN N HN NH + electronic structure cause some metals to emerge as particularly
H+
(18.8) effective catalysts.
N NH2 N NH2 Metals can form a series of metal hydroxo complexes (Bases

and Mesmer, 1986). Although metal hydroxo complexes are less
Triazine compounds can also be protonated on dry mineral reactive nucleophiles than hydroxide ions, their concentrations
colloids. Armstrong et al. (1967) showed that the addition of can be substantially higher, especially in the neutral to acidic
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-13

pH range. Because the pK1 values for strong Lewis acid met- TABLE 18.4  Mechanisms of Metal Catalysis
als are low, they generate hydroxo species across a wider pH Type 1 The metal coordinates the electrophile, shifting the electronic
range. The nucleophiles of various metal hydroxo complexes are distribution in the molecule in a way that enhances its reactivity
governed by pK1 and the polarizability of the metal (Stone and Type 2 The metal coordinates to the leaving group, increasing its leaving
Torrents, 1995). ability
The reactivity of hydrolyzable organic pollutants arises from Type 3 The metal acts as a center for simultaneous attachment of both
the presence of electrophilic (electron deficient) sites within the the electrophile and attacking nucleophile (template effect)
molecules (Stone and Torrents, 1995). The SN2 mechanism (neu- Type 4 The metal coordinates the nucleophile and induces deprotonation
(which increases the reactivity of the nucleophile)
cleophilic substitution) involves attack of the electrophilic sites
Type 5 Coordination of the substrate with the metal induces
by OH− or H2O, generation of a higher coordination number confirmation changes that facilitate reaction
intermediate, subsequent elimination of the leaving group, and Type 6 Coordination of the substrate with the metal makes the molecule
the formation of a hydrolysis product: more positive, lessening unfavorable electrostatic interaction
with the nucleophile
SN2 Type 7 Coordination with the metal blocks inhibitory reverse reaction
paths, such as (1) loss of OH− from a tetrahedral intermediate
OH instead of loss of the leaving group X− or (2) nucleophilic
:OH– –X:–
R C X R C X R C OH (18.9) attack by X−

Y Y– Y Source: From Stone, A.T., and A. Torrents. 1995. The role of dissolved met-

als and metal-containing surfaces in catalyzing the hydrolysis of organic pol-
lutants, p. 275–298. In P.M. Huang, J. Berthelin, J.-M. Bollag, W.B. McGill, and
In the case of the SN1 mechanism (nucleophilic substitution A.L. Page (eds.) Environmental impact of soil component interactions, Vol. 1.
monomolecular), the reaction proceeds with the loss of the leav- Natural and anthropogenic organics. CRC Press/Lewis Publishers, Boca
Raton, FL. With permission.
ing group to generate a lower coordination number intermedi-
ate and then followed by generation of the hydrolysis product by
(Stone and Torrents, 1995). In the mid-1950s, the catalytic abil-
nucleophilic addition as shown below:
ity of metals in hydrolysis of thionophosphate pesticides such as
SN1 parathion and EPN (thionobenzene phosphoric acid O-ethyl-O-
OH
p-nitrophenyl ester) was recognized (Ketelaar et al., 1956). Rate
X
–X:– R Y :OH– enhancements arising from the addition of 1.0 × 10−4 mol L−1
R P Y P+ R P Y Cu2+ are as high as 20-fold for parathion at pH 8.5 and 48-fold
for EPN at pH 8.2. Coordination of the S donor group by Cu 2+
Z Z Z activates the P center to nucleophilic attack (type 1 catalysis).
(18.10) Chlorpyrifos, a phosphorothionate pesticide, contains a pyridyl
N capable of forming a six-membered chelate ring with the Cu2+
It is generally accepted that metal ions can catalyze hydrolysis in ion (Blanchet and St.-George, 1982).
a way similar to acid catalysis. Metal ions and protons coordinate Metal ion catalysis arises from the increased electrophilicity
to the pollutants so that electron density is shifted away from of the P atoms in the chelate ring (type 1 catalysis) (Blanchet
the site of nucleophilic attack to facilitate the reaction. Because and St.-George, 1982) and from possible leaving group effects
protons have an extremely high charge density and great polar- (type 2 catalysis). Copper(II) is by far the most reactive cata-
izing power, metal catalysis is insignificant in acidic solutions. lyst among a number of metals [including Mg(II) and Al(III)],
However, metal ions can readily coordinate two or more ligand which have been observed to catalyze chlorpyrifos hydrolysis.
donor sites on a molecule and can greatly outnumber protons However, Cu2+ concentration would have to exceed 10−5 mol L−1,
in neutral and alkaline conditions (Plastourgou and Hoffmann, which seldom occurs in soil solutions and other natural waters,
1984). A list of metal catalysis mechanisms is given in Table 18.4. in order for the metal-catalyzed pathway to surpass the rate of
The hydrolysis of compounds possessing good leaving groups the uncatalyzed hydrolysis pathway (Mill and Mabey, 1988).
is limited by the rate of nucleophilic attack. These compounds are Many metals, which are potentially catalytic, form low-
susceptible to types 1, 3, 4, 6, and possibly 5 of metal catalysis. The solubility inorganic solids within the pH domain of soils and
hydrolysis of compounds possessing poor leaving groups is lim- associated environments. Therefore, surface-bound metals
ited by the breakdown of the tetragonal intermediate; therefore, must be accessible to reactants in order for a metal-catalyzed
types 2, 7, and possibly 5 are important. A number of pesticides effect to be observed. Since the mid-1950s, research has estab-
and other pollutants are in the intermediate region, where metal lished that metal oxide/hydroxide precipitates act as hydrolysis
catalysis may shift the rate-limiting step from nucleophilic attack catalysts for phosphate esters (Butcher and Westheimer, 1955;
to breakdown of the tetrahedral intermediate or vice versa. Wilkins, 1991). Much has been subsequently learned about the
Many organic compounds are susceptible to metal ion catal- chemical properties and reactivities of naturally occurring
ysis. These include carboxylic acid esters, amides, anilides, solids such as oxides, carbonates, sulfides, and aluminosili-
phosphate-containing esters, and other hydrolyzable compounds cates (Stone and Torrents, 1995; Smolen and Stone, 1998).
18-14 Properties and Processes

Complex formation equilibria among dissolved and The hydrolysis of phenyl picolinate (PHP) is catalyzed by
s­ urface-bound metal species are similar in many aspects. both surface-bound and homogeneous solution metal ions (type
Surface complex formation constants for the metal ions and 1 catalysis; Fife and Przystas, 1985; Torrents and Stone, 1991).
organic ligands increase in magnitude as the formation con- Appropriate metal ions chelate the heterocyclic N and carbonyl
stants of analogous complexes in solution are increased O of PHP and increase the partial positive charge at the carbonyl
(Kummert and Stumm, 1980; Stumm et al., 1980; Davis and C, thus facilitating nucleophilic attack and increasing its suscep-
Hayes, 1986). Attempts have been made to compare reactivities tibility to hydrolysis. Suspensions containing FeOOH or TiO2
of dissolved and surface-bound metal species (Wehrli, 1990; dramatically accelerate PHP hydrolysis rate, while in particle-
Wehrli et al., 1990). To compare the catalytic reactivity of dis- free solution and suspensions containing Al2O3 or SiO2, hydro-
solved and surface-bound metals, any unusual or unique char- lysis is negligible (Figure 18.7). Similar results are obtained with
acteristic of the mineral/water interface must be investigated. methyl picolinate (MEP; Stone and Torrents, 1995). Catalysis
The high Lewis and Brønsted acidity of unoccupied coordina- arises from reaction at the oxide surface and not from release of
tive sites is responsible for the well-known hydrolytic reactiv- soluble metals, since removal of particles by filtration causes an
ity of dehydrated and partially dehydrated mineral surfaces immediate halt to any catalytic activity.
(Theng, 1982; Voudrias and Reinhard, 1986). Although the The susceptibility of hydrolyzable compounds to metal catal-
catalysis by surface-bound metals is influenced by hydration, ysis depends on the nature of the auxiliary donor group. The
dramatic effects of solid surfaces on hydrolysis rates in aque- pyridyl N of PHP and MEP encourages chelate formation with
ous suspensions have been demonstrated (Sanchez-Camazano Ti(IV) and Fe(III) in preference to less polarizable Al. Therefore,
and Sanchez-Martin, 1983). TiO2 and FeOOH are effective hydrolysis catalysts and Al 2O3 is
The catalysis by surface-bound metals is observed when all not. In contrast, O donor groups, such as the phenolic group in
participating reactants are adsorbed to a significant extent and phenyl salicylate and the O heteroatom of methyl furanoate, are
when rate constants for the reactions at the mineral–water sur- harder and thus more favorable to Al chelate formation (Stone
face are comparable to or exceed rate constants for the reaction and Torrents, 1995). Hydrolysis of PHP in the presence of TiO2 is
in homogeneous solution. Although adsorption phenomena virtually pH independent and in the presence of FeOOH exhib-
have accounted for catalysis, relatively little is known about the its only a slight pH dependence. In particle-free solution, PHP
conformation and stoichiometry of adsorbed species. This ham- exhibits classic base-catalyzed hydrolysis behavior; the reaction
pers our understanding of surface catalysis on a fundamental rate of the hydrolysis increases by an order of magnitude for
level. However, based on the existing literature, two generali- every unit increase in pH. Activation of the ester linkage through
ties can be made: (1) auxiliary donor groups that facilitate metal chelate formation with a surface-bound metal ion is apparently
catalysis by metal ions in solution should also facilitate surface strong enough to react with the weak nucleophile H2O, which
catalysis and (2) phenomena of only secondary importance in dominates over the pH-dependent reaction with OH−.
reactions of dissolved complexes, for example, electrostatic and Positively charged surfaces such as Al2O3 (below pH 8.6) and
hydrophobic interactions may play a much greater role in sur- TiO2 (below pH 6.4) accelerate the hydrolysis of monophenyl
face catalysis (Stone and Torrents, 1995). The nature and poten- terephthalate (MPT) by an order of magnitude or more (Stone
tial significance of surface catalysis are summarized later. and Torrents, 1995). Hydrolysis of MPT catalyzed by Al 2O3

1E–4
(PHP)aq (M)

Particle-free solution
1E–5
Al2O3
SiO2
Fe2O3
FeOOH(2)
FeOOH(1)
TiO2
1E–6
0 20 40 60 80 100
Time (h)

FIGURE 18.7  Effect of various metal oxides on the loss of phenyl picolinate (PHP) from solution via hydrolysis. All suspensions contained 10 g L−1
oxide, 1.0 m mol L−1 acetate buffer (pH 5.0), and 50 mM NaCl. (Reprinted with permission from Torrents, A., and A.T. Stone. 1991. Hydrolysis of
phenyl picolinate at the mineral/water interface. Environ. Sci. Technol. 25:143–149. Copyright 1991 American Chemical Society.)
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-15

and TiO2 exhibits elements of both type 3 and type 6 catalyses. hydrolysis reactions, the nature and relative significance of
Positive oxide surfaces serve as the template to accumulate both type 4 catalysis are poorly understood and, thus, merit closer
anionic reactants, OH− and MPT ions, increasing their encoun- attention.
ter frequency. Type 6 catalysis (electrostatic interactions favor- Among the clay minerals, montmorillonite, beidellite, illite,
ing encounter between like-charge species) is more important and vermiculite, only montmorillonite is able to enhance the
for surface chemical reactions than for solution reactions due hydrolysis of the carbamate pesticides, carbosulfan, and aldi-
to the additive electrostatic effect arising from neighboring carb, probably due to its stronger surface acidity and chelating
charged groups. Type 3 catalysis (simultaneous attachment of ability compared to the other clay minerals (Wei et al., 2001).
substrate and nucleophile) is also typical of surface chemical Suspensions of sea sand, TiO2, α-Fe2O3, α-FeO(OH), laponite
reactions. (smectite clay), and SiO2 are able to catalyze the hydrolysis of
Many pesticides are susceptible to surface-catalyzed hydro- the cyclodiene pesticide, endosulfan to the less toxic endosulfan
lysis (Torrents, 1992). For example, catalysis of chlorpyrifos diol (Walse et al., 2002). The rates of endosulfan hydrolysis over
hydrolysis by TiO2, FeOOH, and Al2O3 apparently involves che- the different surfaces correspond to their tritium-exchange site-
late formation between the surface-bound metal ion, the thion- density and suggest a mechanism involving surface coordina-
ate S, and pyridinyl N. tion prior to nucleophilic attack (Walse et al., 2002).
A surface-catalyzed reaction following type 4 catalysis has Birnessite is able to catalyze the hydrolysis of the herbicide
been postulated for the degradation of the fungicide oxycar- atrazine (2-chloro-4-(ethylamino)-6-(isopropylamino)-1,3,5-
boxin stored in borosilicate glass (Stanton, 1987). Because of triazine) by acting as a Lewis acid activator and a source of
low hydroxide ion concentration in neutral and acidic pH, metal-bound hydroxide as a nucleophile (Figure 18.8) (Shin and
hydrolytic ring cleavage is not observed in the absence of a Cheney, 2004, 2005). Furthermore, birnessite is also able to cata-
catalyst. The glass exerts its catalytic effect by providing suf- lyze the N-dealkylation of atrazine via a nonoxidative mecha-
ficiently strong nucleophiles (surface-bound OH− and O22−) for nism involving proton transfer to Mn(IV)-stabilized oxo and
attacking the oxathiin ring. Quartz and aluminosilicate sur- imido bonds (Wang et al., 1999; Shin and Cheney, 2005).
faces present in soils and associated environments could also Recently, it has been shown that dissolved HAs are able to cat-
catalyze oxycarboxin hydrolysis. It has been reported that metal alyze the abiotic hydrolysis of phenylurea herbicides by acting as
oxides catalyze the hydrolysis of p-nitrophenyl acetate by this bifunctional buffers, similar to HCO3−/CO32− or H2PO4−/HPO42−.
mechanism (Hoffmann, 1990). However, in surface-catalyzed The hydrolysis reaction rate increases with the carboxyl group

Cl Cl
N N N N
CH3 C2H5 CH3 + C2H5
1. Delocalization CH CH
N N N N N N
CH3 CH3
H H H H
Cl
Cl
N N
N N +H+ CH3 C2H5
2. Protonation CH3 + C2H5 CH +
CH N N N
N N N CH3 H
CH3 pK2 = 1.60 H H
H H

Cl .. ..
3. Hydrolysis O H O H
N N
CH3 + C2H5
CH N + –Mn(IV)-O-Mn(IV)–
CH3 N N
H
H H

OH

N N
+ Cl–
(CH3)2CHHN N NHC2H5

FIGURE 18.8  Hypothesized hydroxyatrazine formation pathway from the reaction of atrazine with birnessite (δ-MnO2) at pH 4.3 and 20°C.
(From Shin, J.Y., and M.A. Cheney. 2005. Abiotic dealkylation and hydrolysis of atrazine by birnessite. Environ. Toxicol. Chem. 24:1353–1360.
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)
18-16 Properties and Processes

content of the HAs, indicating that the carboxyl groups are respon- 11 1.00
sible for the catalysis (Salvestrini et al., 2008).
10

Adsorption Fe(II) (%)

0.75
9
18.3.5  Reductive Transformation

kobs (min–1)
8
of Organic Compounds 0.50
7
In anoxic groundwater and surficial water, biogeochemical
processes provide a variety of potential reductants for abiotic 6
0.25
contaminant transformation. Persistent xenobiotics, such as 5
polyhalogenated alkanes and alkenes, aromatic nitro and azo
compounds, may be transformed to reaction products that can 4 0.00
6.3 6.6 6.9 7.2 7.5 7.8
be further microbially degraded or to products that can be more
pH
toxic than the parent compounds (Hofstetter et al., 2006).
FIGURE 18.9  Role of pH on the sorbed Fe(II) (○) and observed
pseudo-first-order rate constants (⬤) for the reduction of trifluralin
18.3.5.1  Ferrous Iron as Catalyst
with 1 mmol L−1 Fe(II) in a suspension of 7.2 m2 L−1 (0.65 mg mL−1) goe-
Soluble Fe(II) is an important reductant in anaerobic aqueous thite. The kobs value (▪) at pH 7.8 was extrapolated from a regression of
environments; however, its availability is limited in neutral and log kobs versus pH. (Reprinted from Wang, S., and W.A. Arnold. 2003.
alkaline pH ranges by the precipitation of FeS, Fe3(PO4)2, FeCO3, Abiotic reduction of dinitroaniline herbicides. Water Res. 37:4191–4201.
and other Fe(II)-rich minerals (Charlet et al., 1998). Ferrous Copyright 2003, With permission from Elsevier.)
iron present within or sorbed on iron oxide mineral particles is
highly reactive even at high pH conditions (Charlet et al., 1998). are readily reduced by soluble Fe(II) and Fe(II)-treated goe-
Reduction of nitrite ions to N2O by Fe(II) sorbed on lepidocroc- thite suspensions, especially if there are electron-withdraw-
ite at a pH range of 6.0–8.5 was demonstrated by Sorensen and ing substituents in the para position (Colon et al., 2006b).
Thorling (1991). Above pH 5.5, Fe2+ starts to be adsorbed onto par- However,  N-hydroxylanilines,  the  second intermediates, are
ticles, and this adsorption is completed on most mineral phases only reduced in the presence of Fe(II)-treated goethite suspen-
around pH 7.5, that is, before the onset of precipitation. Above sions, and in contrast to nitrobenzenes, electron-withdrawing
pH 6.5, a significant part of sorbed Fe(II) is present as a highly substituents in the para position decrease the rate of reduc-
reactive hydroxylated surface complex, =Fe(III)–O– Fe(II)–OH tion (Colon et  al., 2006b). The rate of reduction of p-cyano-
(Charlet et al., 1998). This hydrolyzed surface species is a very N-hydroxylaniline showed a linear relationship against the
effective reductant toward many persistent xenobiotics, such as concentration of mineral surface-associated Fe(II) in hematite,
4-chloronitrobenzene (Charlet et al., 1998). goethite, and lepidocrocite suspensions (Colon et al., 2006b). The
Mossbauer spectra of Fe(II) adsorbed to rutile (TiO2) and alu- reactivity of mineral surface-associated Fe(II) toward the reduc-
minum oxide (Al2O3) show only Fe(II) species, whereas spectra of tion of p-cyano-nitrobenzene decreases in the order ­hematite >
Fe(II) reacted with the iron oxides, goethite, hematite, and ferri- goethite > ­lepidocrocite > ferrihydrite, and interestingly, the sur-
hydrite demonstrate electron transfer between the adsorbed Fe(II) face density of surface-bound Fe(II) does not play a major role in
and the underlying iron(III) oxide (Williams and Scherer, 2004). determining the observed reactivity trend (Colon et al., 2006a).
The electron transfer reactions that occur during the reduction Ferrous iron in the presence of goethite and magnetite abi-
of nitrobenzene induce growth of an Fe(III) layer on the oxide otically catalyzes the degradation of trichloronitromethane
surface that is similar to the bulk oxide (Williams and Scherer, via reduction, while trichloroacetonitrile, 1,1,1-trichloropropa-
2004). Similarly, it has been shown that the reductive degradation none, and trichloroacetaldyde hydrate are transformed via both
of 4-chloronitrobenzene and trichloronitromethane in the pres- hydrolysis and reduction reactions (Chun et al., 2005). The Fe(II)
ence of Fe(II) and goethite results in the growth of goethite in the bound to the iron minerals has a greater reactivity than either
c-direction; however, the newly formed goethite is progressively aqueous Fe(II) or structural Fe(II) present in magnetite (Chun
less reactive than the original goethite (Chun et al., 2006). et al., 2005). Ferrous iron bound to magnetite is an effective
Ferrous iron in the presence of goethite can catalyze the abi- catalyst for the degradation of the high-energy explosive RDX
otic reductive degradation of the widely used dinitroaniline (hexahydro-1,3,5-trinitro-1,3,5-triazine), ultimately breaking it
herbicides (trifluralin, pendimethalin, nitralin, and isopropalin) down into NH 4+, N2O, and formaldehyde (Gregory et al., 2004).
at neutral solution pH (Klupinski and Chin, 2003; Wang and Ferrous iron sorbed on the surface of goethite is able to cata-
Arnold, 2003). Increasing the solution pH results in increased lyze the abiotic reductive dehalogenation of carbon tetrachlo-
rate constants due to the increase in Fe(II) sorbed and cre- ride (CCl4) to form the even more toxic compound, chloroform
ation of highly reactive species on the surface of the goethite (CHCl3) (Amonette et al., 2000). The reductive dehalogenation
(Figure 18.9) (Wang and Arnold, 2003). Nitrobenzenes and of carbon tetrachloride did not occur in the presence of soluble
N-hydroxylanilines are reaction intermediates of the reduc- Fe(II) without goethite (Amonette et al., 2000). Reduction of
tion of nitroaromatics. Nitrobenzenes, the first intermediates, CCl4 by surface-associated Fe(II) on goethite occurs in a single
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-17

electron transfer reaction and results in the cleavage of one C–Cl biotite, vermiculite, and montmorillonite on chlorinated ethyl-
bond and the generation of unstable trichloromethyl radicals, as enes (tetrachloroethylene, trichloroethylene, cis-dichloroethyl-
shown below (Elsner et al., 2004a): ene, and vinyl chloride) with or without the addition of Fe(II)
was investigated by Lee and Batchelor (2004). Biotite had the
O2 greatest rate constant among the phyllosilicates, both with and
(O CCI2), CO2 without Fe(II) addition (Figure 18.10), which is attributed to the
R-S–
Sulfur adducts higher content of Fe(II) sites on biotite. The Fe(II) content of bio-
+1 e– •
CCI4 CCI3 e– (18.11) tite is 8 and 97.5 times higher than that of vermiculite and mont-
–1 CI– :CCI3– morillonite, respectively (Lee and Batchelor, 2003). The addition
R-H of Fe(II) to the mineral suspensions increased the rate constants
CHCI3 of the dechlorination reactions, which is attributed to the regen-
eration of active sites on the phyllosilicates resulting from redox
The presence of oxygen and sulfur species can thus lead to reaction with Fe(II) or due to the reactivity of Fe(II) that binds to
completely dehalogenated reaction products in radical reac- the phyllosilicate surfaces (Lee and Batchelor, 2004).
tions. However, the presence of H radical donors, such as trace Ferruginous smectite, chemically reduced with dithionite is
amounts of natural organic matter, promotes the formation of able to reduce and dechlorinate trichloroacetonitrile and chloro-
toxic chloroform (Elsner et al., 2004a). Ferrous iron bound to picrin (Cervini-Silva et al., 2001). Similarly, chemically reduced
the surface of iron oxides (goethite, hematite, lepidocrocite, and montmorillonite and ferruginous smectite are able to catalyze
magnetite) is capable of reducing a variety of other polyhalo- the abiotic reduction of nitrobenzene to aniline, and as much
genated methanes under aquifer conditions, and the pseudo- as 40% of the structural Fe(II) in the reduced smectite was
first-order reaction rate constants, kobs, of the polyhalogenated oxidized to Fe(III) during the reaction (Yan and Bailey, 2001).
methanes increased in the order CHBrCl2 < CHBr2Cl < CHBr3 < Hofstetter et al. (2006) investigated the reactivity of Fe(II) spe-
CCl4 < CFBr3 < CBrCl3 < CBr2Cl2 (Pecher et al., 2002). cies in suspensions of chemically reduced montmorillonite, with
Reactive Fe(II) does form not only on the surface of oxides but a low structural iron content, and reduced iron-rich nontronite
also on the surfaces of other iron minerals such as iron sulfide
(FeS), pyrite (FeS2), and siderite (FeCO3) (Elsner et al., 2004b). 1
Elsner et al. (2004b) compared the 4-chloronitrobenzene,
4-­chlorophenyl hydroxylamine, and hexachloroethane-reducing
reactivity of Fe(II) aqueous suspensions in the presence of sid-
erite, hematite, lepidocrocite, goethite, magnetite, sulfate green
rust, pyrite, and mackinawite. The surface area-normalized 0.9
reaction rates generally increase in the order Fe(II) + siderite <
c/c0,chlorine

Fe(II) + iron oxides < Fe(II) + iron sulfides (Elsner et al., 2004b).
Ferrous iron-bearing minerals are also important environ-
mental abiotic reductants. Magnetite, pyrite, and green rust 0.8
are able to catalyze the abiotic reductive dechlorination of
chlorinated ethylenes (Kriegman-King and Reinhard, 1994;
Butler and Hayes, 1998; Lee and Batchelor, 2002a, 2002b).
Surface area-­normalized pseudo-first-order initial rate con-
stants for the reduction of chlorinated ethylenes (tetrachlo- 0.7
roethylene, trichloroethylene, cis-dichloroethylene, and vinyl 0 20 40 60 80 100
chloride) by green rust were found to be 3.4–8.2 times greater Time (day)
than those by pyrite (Lee and Batchelor, 2002b), and the rate pH = 7
constants by pyrite were found to be 23.5–40.3 times greater Biotite Biotite w/Fe(II)
than those by magnetite (Lee and Batchelor, 2002a). Vermiculite Vermiculite w/Fe(II)
Montmorillonite Montmorillonite w/Fe(II)
In clay minerals, Fe(II) may be present as (1) structural Fe(II),
Control Control w/Fe(II)
(2) Fe(II) complexed by surface hydroxyl groups, and (3) Fe(II)
bound by ion exchange. Hofstetter et al. (2003) investigated the
FIGURE 18.10  Reductive dechlorination of chlorinated ethylenes
accessibility and reactivity of these three types of Fe(II) species
(0.19 mM) in iron-bearing phyllosilicate suspensions (0.085 g g−1) with
in suspensions of ferrous iron-bearing nontronite or iron-free
and without Fe(II) addition (4.28 mM). (Reprinted from Lee, W.J., and
hectorite. They found that both structural Fe(II) and Fe(II) B. Batchelor. 2004. Abiotic reductive dechlorination of chlorinated
complexed by surface hydroxyl groups of nontronite reduced ethylenes by iron-bearing phyllosilicates. Chemosphere 56:999–1009.
the nitroaromatic compounds to anilines. Fe(II) bound by ion Copyright 2004, with permission from Elsevier.) C 0 and C stand for the
exchange did not contribute to the observed reduction of the concentration (mM) of the organic chlorine compound at time 0 and
nitroaromatic compounds. The abiotic reductive reactivity of the sampling time.
18-18 Properties and Processes

using acetylnitrobenzene compounds. Their results indicate (Bussan and Strathmann, 2007). Iron(II)–tiron complexes are
that Fe(II) bound in the octahedral sheet of reduced smectites able to quantitatively reduce trichloroethane to acetaldehyde, a
is the predominant reductant, and that electron transfer pre- product previously only reported for reactions with Cr(II), but
sumably occurs via basal siloxane planes. Nonreactive electron not with Fe-based reductants (Bussan and Strathmann, 2007).
donor–acceptor complexation of the nitroaromatic compounds The explosive RDX is rapidly reductively degraded in the
occurred at the basal smectite surfaces of the reduced montmo- presence of black carbon (BC) and sulfide to low-molecular-
rillonite but was not observed in suspensions of reduced iron- weight ring-cleavage products (Kemper et al., 2008). RDX was
rich nontronite. not degraded in the presence of BC-only or sulfide-only suspen-
Reduced aquifer sediments from the perched Pantex aquifer sions. Due to the heterogeneous nature of BC, it remains unclear
(Amarillo, TX) were found to efficiently, abiotically degrade the whether the quinone material in the BC or the ability of BC to
explosives RDX, HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7- sorb the hydrophobic RDX facilitated the reductive degradation
tetrazocine), and TNT (Boparai et al., 2008). When Fe(II) was (Kemper et al., 2008).
partially removed from the reduced sediments by washing On the other hand, natural organic matter can decrease the
(citrate-bicarbonate buffer), RDX degradation was suppressed, reductive potential of Fe(II) by competing for reactive sites on
but the addition of Fe(II) restored the degradation efficiency of Fe(II)-mineral surfaces. Hakala et al. (2007) found that dis-
the sediment (Boparai et al., 2008). solved organic matter only enhances the reductive capacity
of Fe(II) toward nitroaromatic compounds in the absence of
18.3.5.2  Natural Organic Matter as Catalyst iron oxide colloids. Colon et al. (2008) found that Suwannee
and Redox Mediator/Inhibitor River HA decreases the reduction capacity of Fe(II)-treated
Humus plays a significant role in the anaerobic degradation of goethite toward nitrobenzene, by complexing the surface-­
xenobiotics by shuttling electrons. Humic functional groups, associated Fe(II) species or hindering access of nitrobenzenes
in particular quinones, can act as redox mediators and elec- to the Fe(II) sites.
tron donors for accelerating abiotic reductive transformation
processes (Field et al., 2000; Doong and Chiang, 2005; Fimmen
18.3.6  Genotoxicity and Bioavailability
et  al., 2007; Ratasuk and Nanny, 2007). Electrochemically
of Xenobiotics as Influenced
reduced soil and aquatic HAs are able to reduce hexachloroeth-
by Mineral Catalysis
ane at appreciable rates, which indicates that HA could play an
important role in the reductive transformation of xenobiotics in Much is known about the toxicity of xenobiotic parent com-
anoxic environments (Kappler and Haderlein, 2003). pounds, whereas, relatively little work has been carried out on
Natural organic matter can act as an electron transfer medi- investigating the toxicity of the degradation products of xenobi-
ator in the presence of a bulk electron donor such a Fe(II) or otics (Sinclair and Boxall, 2003). In some cases, the transforma-
HS− and thus significantly enhances the rate of reduction of tion products of xenobiotics, such as commonly used pesticides
halogenated hydrocarbons, such as carbon tetrachloride or bro- and herbicides, can be even more toxic than the parent com-
moform (Curtis and Reinhard, 1994) or substituted nitroben- pound (Osano et al., 2002; Sinclair and Boxall, 2003). To date,
zenes (Dunnivant et al., 1992). Strathmann and Stone (2002) very little research has been carried out on investigating the bio-
demonstrated that natural organic matter from the Great Dismal availability and toxicity of xenobiotics after reaction with abiotic
Swamp facilitates oxime carbamate pesticide reduction by Fe(II) catalysts, such as metal oxides or clay minerals.
in the same manner as individual organic ligands, carboxylate, The oxidative coupling of the polycyclic aromatic hydro-
and aminocarboxylate. carbon, phenanthrene, with catechol as catalyzed by birness-
Complexation of Fe(II) by catechol and organothiol ligands, ite significantly reduces the bioavailability of phenanthrene to
which are similar to the functional groups found in natural humic microorganisms (Russo et al., 2005). The oxidative coupling of
substances, leads to the formation of highly reactive aqueous spe- phenol induced by birnessite or soil significantly decreases the
cies that are capable of reducing substituted nitroaromatic com- toxicity of the compound as determined with a Microtox System
pounds (Naka et al., 2006, 2008). The nitroaromatic compounds (Jung et al., 2008b).
are not reduced in Fe(II)-only or ligand-only solutions (Naka The pesticides, oxamyl (carbamate family) and alachlor (chlo-
et al., 2006, 2008). The high reactivity of these Fe(II)–organic roacetanilide family), reacted with reduced nontronite clay (fer-
ligand complexes is attributed to a lowering of standard one- ruginous smectite) show a significant decrease in their overall
electron reduction potential of the Fe(III)/Fe(II) redox couple on mammalian cell cytotoxic (toxicity to cells) potential, whereas
complexation by the ligands. The organothiol ligands are also the pesticide 2,4-D (phenoxy family) shows no difference in
able to re-reduce the Fe(III) that forms when Fe(II) complexes toxicity after treatment with the reduced clay (Sorensen et al.,
are oxidized by reactions with the nitroaromatic compounds 2004). The pesticide, dicamba (benzoic acid family), reacted
(Naka et al., 2008). Ferrous iron–catechol and ferrous iron– with reduced nontronite clay actually generates products, which
organothiol complexes are also able to completely reductively are more cytotoxic than the parent compound (Sorensen et al.,
degrade the explosive RDX (Kim and Strathmann, 2007) and to 2004). Oxidized nontronite had no effect on the cytotoxicity of
catalyze the reductive degradation of polyhalogenated alkanes any of the aforementioned pesticides, which indicates reduced
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-19

Fe in smectites plays an important role in altering the cytotoxic- 6.0 (a)

ity of pesticides and should thus be taken into account in pesti-
5.0
cide management programs (Sorensen et al., 2004).

μg mL–1As(III) in solution
The genotoxic potency (potential damaging effect on DNA) of 4.0
most pesticides in mammalian cells is unknown, let alone their
Buffalo pound
abiotic transformation products. Sorensen et al. (2005) were the 3.0 Pasqua
first group to investigate the effect of reduced ferruginous smec- Echo
tite on the genotoxicity of the pesticides 2,4-D, dicamba and 2.0 Mission
Katepwa
oxamyl. Neither 2,4-D alone nor its transformation products
1.0
after reaction with the reduced clay were found to be genotoxic.
The genotoxicity of oxamyl actually decreased after reaction 0

μg mL–1As(V) in solution
2.5
with the reduced clay. Dicamba alone was not genotoxic but (b)
became genotoxic after reaction with the reduced clay. 2.0
1.5
18.4  Abiotic Catalysis in the 1.0
Transformation of Metals, 0.5
Metalloids, and Other Inorganics 0
1.0 (c)
18.4.1  Transformation of Metals and Metalloids

As(III)/As(III) + As(V)
0.8
18.4.1.1  A rsenic
0.6
Arsenic bioavailability and toxicology depend on its chemical
state (Huang and Fujii, 1996) with As(III) (arsenite) being much 0.4
more toxic than As(V) (arsenate). Manganese(IV) oxides, such
as birnessite (Table 18.5), are very effective oxidants of As(III) 0.2
48 h 72 h
(Oscarson et al., 1981a, 1981c, 1983b; Feng et al., 2006b). In the
0
control experiment, no detectable As(III) is oxidized in the 10 20 30 40 50 60 70
absence of Mn(IV) oxide (Table 18.5). Arsenic(III) oxidation by
Time (h)
birnessite proceeds through two single electron transfer steps
with the formation of Mn(III) as intermediate (MnOOH), as fol- FIGURE 18.11  Oxidation of As(III) to As(V) and the sorption of As
lows (Nesbitt et al., 1998; Tournassat et al., 2002): by lake sediments as a function of time. (a) Concentration of As(III) in
solution, (b) concentration of As(V) in solution, and (c) As(III)/As(III) +
As(V). Ten μg mL−1 of As(III) were added initially. During the reaction
2MnO2 + H3AsO3 = 2MnOOH + H3AsO4 , (18.12)
period, the pH of the As-sediment suspension ranged from 8.0 to 8.2 for
the Buffalo Pound sediment and from 7.3 to 7.6 for the other four sedi-
2MnOOH + H3AsO3 = 2MnO + H3AsO4 + H2O. (18.13) ments. (Reprinted from Oscarson, D.W., P.M. Huang, and W.K. Liaw.
1980. The oxidation of arsenite by aquatic sediments. J. Environ. Qual.
9:700–703. With permission of the American Society of Agronomy.)
Poorly crystalline Fe(III) oxyhydroxides (Devitre et al., 1991;
Nicholas et al., 2003; Jang and Dempsey, 2008) and the surfaces of the clay minerals illite and kaolinite (Manning and Goldberg,
1997) are also able to catalyze the oxidation of As(III).
TABLE 18.5  Oxidation of As(III) and Sorption of As by Mn(IV) Although As(V) is a thermodynamically stable species in oxy-
Oxide (in μg mL−1 in Solution) genated water at common pH values (Penrose, 1974), the kinet-
ics of oxidation of As(III) with O2 is very slow at near-neutral
As(III) or As(V)
Added (μg mL−1) As(III) As(V) Mn Final pH pH values (Kolthoff, 1921). Lake sediments from Saskatchewan,
Canada, can oxidize As(III) (700 μg As) to As(V) within 48 h
100 As(III) NDa 83.5 ± 1.4b 0.41 ± 0.12 7.1
(Figure 18.11). The oxidation of As(III) is not detectable within
300 As(III) 63.2 ± 7.0 186 ± 5 8.08 ± 0.36 7.1
72 h in the absence of sediment. The oxidation of As(III) to
500 As(III) 213 ± 4 205 ± 1 6.06 ± 0.60 7.3
As(V) is not affected by flushing N2 or air through the sediment
1000 As(III) 665 ± 5 216 ± 4 4.16 ± 0.86 7.5
suspensions, nor does the addition of HgCl2 to the system elimi-
300 As(V) ND 298 ± 1 0.06 ± 0.02 7.5
nate the conversion of As(III) to As(V). This indicates that the
Source: Oscarson, D.W., P.M. Huang, C. Defosse, and A. Herbillon. oxidation of As(III) to As(V) is an abiotic process.
1981a. Oxidative power of Mn(IV) and Fe(III) oxides with respect to When the lake sediments are treated with hydroxylamine
As(III) in terrestrial and aquatic environments. Nature 291:50–51. With
­permission of Macmillan, London.
hydrochloride or sodium acetate, which are effective extractants
a ND, not detectable. for Mn, the oxidation of As(III) to As(V) by the treated sedi-
b Mean ± SD; n = 3. ments is greatly decreased relative to the untreated sediments
18-20 Properties and Processes

(Oscarson et al., 1981c). Hydroxylamine hydrochloride treat- of cryptomelane. Consequently, the rate of depletion of As(III)
ment also removes Fe oxide; however, the evidence obtained from solution is greater for birnessite than for cryptomelane.
from colorimetry and x-ray photoelectron spectroscopy shows The structure and composition of Mn oxides, as well as the
that a redox reaction between Fe oxide and As(III) does not solution pH, ionic strength, and presence of organic ligands
occur within 72 h, indicating that the redox reaction between all affect the rate of As(III) oxidation by Mn oxides. Tunnel-
As(III) and Fe(III) is kinetically slow (Oscarson et al., 1981a). structured cryptomelane has the strongest As(III) oxidation
This supports the evidence that Mn oxide is the primary com- ability (842.2 mmol kg−1), compared with layered–structured
ponent responsible for catalyzing the conversion of As(III) to birnessite (480.4 mmol kg−1), and Mn(II/III)-bearing hausmannite
As(V). The rate constant increases with increasing temperature (117.9 mmol kg−1) (Feng et al., 2006b). Increasing the reaction sys-
from 278 to 298 K; the heat of activation for the process varies tem pH from 3.0 to 6.5 results in a significant increase in the rate
from 13.8 to 35.6 kJ mol−1, indicating that the depletion of As(III) of oxidation of As(III) by the three Mn oxides, whereas increasing
is predominantly a diffusion-controlled process (Oscarson et al., the ionic strength results in a decrease in the oxidation of As(III)
1981b). Other recent studies have also suggested that Mn oxides by birnessite and cryptomelane, while hausmannite is unaffected
are largely responsible for the oxidation of As(III) in aquifer sed- (Feng et al., 2006b). The presence of tartaric acid at a concentra-
iments from Maine, USA (Amirbahman et al., 2006) and Dhaka, tion below 4 mol L−1 promotes oxidation of As(III) by birnessite,
Bangladesh (Stollenwerk et al., 2007). cryptomelane, and hausmannite, whereas it decreases As(III) oxi-
The ability of Mn oxides to deplete As(III) from solution (oxi- dation by cryptomelane and hausmannite when the concentration
dation plus sorption) varies with their crystallinity and specific is increased above 4 mol L−1 (Feng et al., 2006b). The oxidation of
surface (Oscarson et al., 1983b). The depletion of As(III) by Mn As(III) by the Mn oxyhydroxide, manganite [MnO(OH)], occurs
oxides follows the first-order kinetics. Pyrolusite is highly ordered on the time scale of hours. The presence of competing anions such
and has a low specific surface; conversely, birnessite and cryp- as phosphate decreases the oxidation rate of As(III) to As(V) by
tomelane are poorly crystalline and have relatively high specific manganite (Chiu and Hering, 2000). The presence of a divalent
surfaces (Table 18.6). Because birnessite and cryptomelane have cation, Zn2+, significantly suppresses the oxidation of As(III) by
relatively high specific surface areas due to their porous nature birnessite, and this suppression is more pronounced when the
(Huang, 1991b), their rate constants for the depletion of As(III) Zn2+ is presorbed on the birnessite (Power et al., 2005).
are much higher than those for pyrolusite (Table 18.6). On the The surfaces of many soil Mn oxides are coated with various
other hand, the rate constants for the depletion of As(III) by chemical species (McKenzie, 1989). The rate constants for the
birnessite are significantly greater than those for cryptomelane, depletion (oxidation plus sorption) of As(III) are generally sub-
despite its higher specific surface. Birnessite has a greater nega- stantially smaller for the Mn oxides with higher levels of coat-
tive charge density than cryptomelane at pH 7 (McKenzie, 1981). ings of Fe and Al oxides and CaCO3 than those for the untreated
Because As(V) is also negatively charged at pH 7, the repulsive MnO2 or MnO2 with lower levels of coatings (Oscarson et al.,
interaction energy would be greater between birnessite than 1983a). HA coatings on natural Mn nodules also significantly
cryptomelane and As(V), which is why birnessite does not sorb a reduce the As(III) depletion capacity of the nodules (Chen
detectable amount of As(V) relative to cryptomelane (Oscarson et al., 2006). The electron-accepting sites on MnO2 are partially
et al., 1983b). Differences in the point of zero charge (p.z.c.) of masked by the oxides, CaCO3, and organic matter. There is evi-
birnessite and cryptomelane and their ability to sorb As(V) dence that shows that Fe(III) and Al oxides and CaCO3 do not
explain the greater As(III) depletion by birnessite than by cryp- oxidize As(III) to As(V) (Oscarson et al., 1981a, 1983a), and
tomelane even though cryptomelane has the greater surface area. thus, the oxidation of As(III) to As(V) on the coated MnO2 is
Little As(V) is sorbed from solution by birnessite upon oxidation solely attributed to MnO2 in this case.
of As(III), and less total As is sorbed by birnessite than by cryp- However, some studies have shown that Fe oxides and oxyhy-
tomelane; the electron-accepting sites on the surface of birnes- droxides can catalyze the oxidation of As(III) to As(IV). Devitre
site are, thus, blocked to a lesser extent than those on the surface et al. (1991) showed that As(III) is rapidly oxidized by diagenetic

TABLE 18.6  Specific Surface and Point of Zero Charge (p.z.c.) of the Mn Dioxides and
Rate Constants and Energies of Activation for the Depletion of As(III) by the Mn Dioxides
Specific Energies of
Rate Constant × 10−3 (h−1)
Surface Activation
Mineral (m2 g−1) p.z.c. 278 K 298 K 318 K (kJ mol−1)
Birnessite 277 ± 5a 2.3 ± 0.1 126 ± 13 267 ± 6 533 ± 38 26.0 ± 0.2
Cryptomelane 346 ± 4 2.8 ± 0.1 54 ± 10 189 ± 8 318 ± 22 32.3 ± 6.7
Pyrolusite 8±1 6.4 ± 0.3 0.12 ± 0.02 0.44 ± 0.03 0.58 ± 0.05 29.0 ± 9.8
Source: Oscarson, D.W., P.M. Huang, W.K. Liaw, and U.T. Hammer. 1983b. Kinetics of oxidation
of arsenite by various manganese dioxides. Soil Sci. Soc. Am. J. 47:644–648. With permission of the
Soil Science Society of America.
a Mean ± SE.
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-21

amorphous Fe(III) oxyhydroxides. The rapid oxidation of As(III)

is observed on the Fe oxyhydroxide, ferrihydrite, in the presence
of hydrogen peroxide (Nicholas et al., 2003). Jang and Dempsey
(2008) found that the oxidation of As(III) by Fe oxyhydroxides
is significant only in the presence of As(V). Magnetite (Fe3O4) is
able to catalyze the oxidation of As(III), which is attributed to
Cop.,
the presence of structural Fe(III) and possible Mn impurities in 63 h
the magnetite (Su and Puls, 2008).
The oxidation of As(III) by the Mn oxides, birnessite, todor- Cop.,
okite, and hausmannite, increases significantly in the presence 150 h

F/i0
of the Fe(III) oxide, goethite (Feng et al., 2006a). Goethite pro- Ads.,
motes As(III) oxidation on the Mn oxide minerals by adsorption 130 h
of the As(V) produced during the reaction, thus decreasing the
As(V) concentration in solution. Therefore, the combined effects Se(0)
of the Mn and Fe oxide minerals can lead to the rapid oxidation
and immobilization of As in soils (Deschamps et al., 2003; Feng
et al., 2006a). Se(IV)
The conversion of As(III) to As(V) by uncoated and coated
Mn oxides has important implications for the transport, fate,
Se(VI)
and toxicity of As in terrestrial and associated environments. In
some environments that have been contaminated with As(III), 12,650 12,660 12,670 12,680 12,690
the addition of reactive Mn oxides may alleviate the toxicity of
Photon energy (eV)
As(III) through their catalytic reactions.
FIGURE 18.12  In situ XANES spectra of Se(VI) reaction with green
18.4.1.2  Selenium rust as a function of sorption mechanisms (coprecipitation [Cop.] and
Selenium is an essential trace element in the human and animal adsorption [Ads]). The XANES spectra of Se models in different oxida-
nutrition; however, there is a very narrow optimal concentration tion states are shown for comparison. The vertical line in the center shows
the position of Se(VI). (Reprinted from Myneni, S.C.B., T.K. Tokunaga,
range between deficiency and toxicity (selenosis). The mobility
and G.E. Brown. 1997. Abiotic selenium redox transformations in the
and availability of Se are largely controlled by its redox state,
presence of Fe(II,III) oxides. Science 278:1106–1109. With permission of
which affects its sorption to mineral and organic matter surfaces the American Association for the Advancement of Science.)
(Masscheleyn et al., 1990; Charlet et al., 2007). Selenium(VI) is
the stable valence state in oxic environments and exists as the
and coprecipitation mechanisms (Figure 18.12) (Myneni et al.,
selenate (SeO42−) oxyanion. Selenium(IV) is the stable valence
1997). The reaction proceeds as follows; magnetite is produced
state under mildly reducing or anoxic conditions and exists
during the oxidation of the green rust:
as the selenite (SeO32−) oxyanion. Selenate is weakly sorbed by
minerals and is more soluble and bioavailable than selenite,
which binds strongly to the surfaces of metal oxides by inner- HSeO4 − + 4FeII4 Fe2III (OH)12 SO4 3H2O
sphere complexes. In reducing sediments, Se(VI) and Se(IV)
↔ HSe − + 8Fe3O4 + 4SO4 2 − + 8H+ + 32H2O. (18.14)
can be reduced to Se(0) and other reduced species (oxidation
states of −1 and −2), such as Se-pyrite or ferroselite. The for-
mation of elemental and pyritic Se is regarded as an important Similarly, zero-valent iron reacted with Se(VI) catalyzes the for-
mechanism for controlling the availability of Se in the environ- mation of Se(0) and produces a green rust layer on the exposed
ment (Belzile et al., 2000). The reduction of Se(VI) and Se(IV) surfaces of the iron(0) (Scheidegger et al., 2003).
may be facilitated by sorption of these species on the surfaces The reduction of selenite [Se(IV)] to solid Se(0) can be cata-
of Fe–Mn oxyhydroxides or Fe(II)-bearing minerals or by the lyzed by Fe(II)-bearing mineral, pyrite (FeS2), via the process
involvement of HS−, pyrite, and organic matter (Myneni et al., of adsorption on the surface of pyrite (Bruggeman et al., 2005;
1997; Belzile et al., 2000; Bruggeman et al., 2005; Charlet et al., Breynaert et al., 2008). The presence of illite-rich Boom clay
2007; Scheinost and Charlet, 2008). Previously it was thought sediments (Belgium) and natural humic substances decreases
that these reactions are principally mediated by microorganisms the rate of selenite reduction by pyrite due to the competitive
(Myneni et al., 1997). adsorption (Bruggeman et al., 2005). Troilite (FeS) is also able to
The abiotic reduction of Se(VI) and Se(IV) to Se(0) can be catalyze the reduction of selenite, however, through a different
catalyzed by Fe(II) either sorbed on the surfaces of clays or mechanism that involves reduction by dissolved sulfide and the
structurally present in Fe-bearing minerals. Green rust, an formation of Se(0) as an intermediate (Breynaert et al., 2008).
Fe(II/III) oxide commonly present in reduced sediments and The Se(0) is then further reduced to FeSex species, which precipi-
soils, is able to reduce Se(VI) to Se(IV) and Se(0) by adsorption tate on the surface of the troilite. Nanoparticulate Fe(II)-bearing
18-22 Properties and Processes

minerals mackinawite [(Fe, Ni)1+xSx] and magnetite (Fe3O4), and

O2
micrometer-sized siderite (FeCO3) are able to rapidly reduce
+1.0 H2O
selenite (Scheinost and Charlet, 2008). Mackinawite reduces sel-
enite to Se(0) at pH 6.3 and FeSe at pH 4, whereas magnetite
reduces selenite to FeSe and Fe7Se8 species at pH 5. Siderite is +0.8
weakest catalyst of three minerals and only partially reduces
selenite to Se(0) (Scheinost and Charlet, 2008).
+0.6
Montmorillonite equilibrated with Fe2+ is able to catalyze
MnO2
the slow reduction of selenite [Se(IV)] to nanoparticulate Se(0)
(Charlet et al., 2007). Mossbauer and XAS spectroscopy sug-

Eh (V)
+0.4
gest that the Se and Fe redox reactions are not directly coupled,
Mn2a +q MnOOH
but rather that a small amount of Fe(II) that is presorbed on the
montmorillonite is oxidized to Fe(III), and the electrons that +0.2
are produced during this reaction are stored by the formation
Mn3O4
of surface H2 species, which then later are able to reduce selenite 0
(Charlet et al., 2007). H2O
H2
–0.2
18.4.1.3  I ron
Manganese oxides, which have different structural and sur- Mn(OH)2
face properties, vary in their ability to catalyze the conversion –0.4
0 2 4 6 8 10 12
of Fe(II) to Fe(III) and the subsequent formation of Fe oxides pH
and oxyhydroxides (Krishnamurti and Huang, 1987, 1988). The
standard electrode potential (E°) of the redox pairs Fe2+–MnO2 FIGURE 18.13  Stability relations of different species of Mn at 25°C,
0.101 MPa, and a Mn2+ = 10−6 (Bricker 1965). The Eh and pH ranges of the
and Fe2+–Mn3O4 can be described by the following equations
systems during the formation of iron oxide precipitates in the presence
(Bricker, 1965):
of Mn oxides in the present study are shown as shaded region. (Reprinted
from Krishnamurti, G.S.R., and P.M. Huang. 1988. Influence of manga-
2Fe2+ + MnO2 + 4H+ = Mn2+ + 2Fe3+ + 2H2O E° = +0.438 V, nese oxide minerals on the formation of iron oxides. Clay. Clay Miner.

36:467–475. With permission of the Clay Minerals Society.)
(18.15)

Fe2+ under anoxic conditions at neutral pH (Park and Dempsey,

2Fe2+ + Mn3O4 + 8H+ = 3Mn2+ + 2Fe3+ + 4H2O E  = +1.04 V.
2005). During this reaction, the hydrous ferric oxide is partially
(18.16) converted to goethite. The reaction mechanism involves an anode/
cathode mechanism with O2 reduced at ­electron deficient sites
These E° values indicate that oxidation of Fe2+ by Mn oxides is with Fe(II) strongly sorbed, and Fe(II) is oxidized at ­electron-rich
thermodynamically feasible. The Eh–pH diagram (Figure 18.13) sites without sorbed Fe(II). Iron(III) has been found to play a dom-
indicates the feasibility of the conversion of Mn4+ and Mn3+ to inant role in pyrite (FeS2) oxidation in comparison with dissolved
Mn2+ in the Mn oxides in the Eh–pH ranges of the formation oxygen under acidic conditions (Mazumdar et al., 2008).
of Fe oxides and oxyhydroxides. Further, the ESR spectra of the
filtrates after the reaction of Fe2+ with Mn oxides show the pres- 18.4.1.4  Manganese
ence of a significant amount of Mn2+, demonstrating the reduc- Although oxidation of Mn in soils by atmospheric O2 is a ther-
tion of Mn(IV) and Mn(III) oxides to Mn2+ in the presence of modynamic possibility throughout the pe and pH range com-
Fe2+ in solution. Simultaneously, the oxidation of Fe2+ to Fe3+ mon in well-aerated soils, Mn is not readily oxidized in solutions
by Mn oxides leads to subsequent hydrolysis of Fe3+ to form a unless the pH is raised above pH 8.5 (Ross and Bartlett, 1981).
series of the precipitation products including lepidocrocite, aka- A catalytic mechanism of some sort is apparently necessary.
ganeite, feroxyhyte, and magnetite. Because various Mn oxides Oxidation of Mn in soil environments is generally assumed to be
differ in their ability to catalyze the formation of Fe oxides and microbially mediated (Tebo et al., 2005; Thompson et al., 2005).
oxyhydroxides, their role in the transformation of Fe deserves Oxidation of Mn(II) by soils has been shown to be propor-
attention. tional to the level of existing reactive Mn oxides (Ross and
At neutral pH conditions, structural Fe(III) in hematite is able Bartlett, 1981). Arrhenius plots of rates of the oxidation between
to catalyze the oxidation of sorbed Fe(II) to amorphous ferric 1°C and 35°C show that the oxidation of Mn(II) by soils has
oxide on the surface of hematite (Jeon et al., 2003). Solid-phase nonbiological characteristics. Generally, oxidation of Mn(II)
contact among hematite, amorphous ferric oxide, and structural is initially rapid with no lag period and may be related to the
Fe(II) eventually produces magnetite (Fe3O4) (Jeon et al., 2003). mechanism proposed for the accumulation of Co and Zn on
Hydrous ferric oxide is able to catalyze the abiotic oxidation of Mn oxide surfaces (Loganathan et al., 1977). The adsorption on
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-23

the oxide surfaces is specific and not a simple function of sur- (Shaughnessy et al., 2003). Surprisingly, it has also been shown
face charge. Above pH 5–6, this adsorption reverses the surface that pyrolusite (α-MnO2), a Mn(IV)-bearing oxide, can pro-
charge of the Mn oxides from negative to positive, as measured mote the reduction of Pu(VI) (Kersting et al., 1999; Powell et al.,
by electrophoretic mobility. A positively charged surface should 2006). Powell et al. (2006) attributed this to the observation that
result in a higher OH− concentration near the surface, which pyrolusite can initially oxidize Pu(IV) to Pu(VI); however, if the
could enable oxidation of adsorbed Mn(II) by atmospheric O2. oxidized species remains associated with the solid phase, the ini-
The mechanism of specific adsorption is not fully understood, tial oxidation step is followed by reduction to a stable hydrolyzed
but the preferential adsorption of transition metals by Mn oxides Pu(IV) species, which is not affected by the oxidizing surface,
is well documented (Jenne, 1977). The oxidation of Mn(II) by and over time becomes the predominant solid-phase Pu spe-
Mn oxides is theorized to be autocatalytic, involving specific cies. These findings are important when assessing the risk of the
adsorption of Mn(II) on existing Mn oxide surfaces (Ross and geological burying of nuclear waste in areas containing Mn(IV)-
Bartlett, 1981). bearing minerals, such as Yucca Mountain or the Hanford sites
The Fe(III) oxyhydroxide, akaganeite, promotes the formation (Powell et al., 2006).
of birnessite (δ-MnO2) by catalyzing the air oxidation of surface Iron(II)-bearing minerals can reduce highly mobile Np(V)
adsorbed Mn(II) (Cornell and Giovanoli, 1991). Hematite, espe- and Pu(V/VI) species, as well as, many other mobile higher
cially at a particle size below 4 nm, is able to promote the oxida- valency species of radionuclides such as uranium and techne-
tion Mn(II) in the presence of O2 by donating electron density to tium. Natural uranium is mildly radioactive and occurs in trace
adsorbed Mn2+, which promotes reaction with O2 (Madden and amounts in most rocks, soils, and water. The more strongly
Hochella, 2005). radioactive isotope, U-235, is selectively enriched and used for
nuclear weapons and for fuel for nuclear reactors. The U-235-
18.4.1.5  Radionuclides depleted uranium is used for making weapons and armor, and
Radionuclides are unstable isotopes of elements that are radio- has been used for counter weights in aircraft tails. All the above-
active. Most elements with an atomic number greater than 83 mentioned uses result in the release of U into the environment.
have an unstable nucleus and are thus radioactive, and there- Similar to Pu and Np, U has a variety of oxidation states with
fore, all of their isotopes are radionuclides. Many radionuclides uranyl U(VI)O22+ species being the most mobile. Technetium is
are man-made, for example, plutonium and technetium, and are an artificial element produced during nuclear fission and is com-
released into the environment as a result of nuclear waste, monly found in groundwater at sites where nuclear waste has
airborne emissions from nuclear reactors, nuclear weapons been processed or stored. It has a similar chemistry to Mn and
testing and processing, and infrequently due to incorrect disposal has several oxidation states. Under oxic conditions, it occurs
of medical or industrial radiation sources (Salbu et al., 2004; as a pertechnetate anion, Tc(VII)O4 −, which is poorly sorbed
USEPA, 2009). Most of the commonly encountered polluting across the environmental pH range. The lower valency Tc(IV)
radionuclides have multiple oxidation states, and thus, redox readily precipitates as insoluble hydrous oxides or is sorbed on
chemistry plays a dominant role in their environmental mobil- mineral surfaces.
ity and availability. Magnetite (Fe3O4) can reduce Pu(V) to strongly sorbed Pu(IV)
Plutonium and neptunium are the chief radionuclides of con- over a wide pH range (pH 3–8; Powell et al., 2004). Similarly,
cern for long-term storage of nuclear waste due to their long magnetite can reduce Tc(VII) to Tc(IV) (Cui and Eriksen, 1996),
half-lives (t1/2 = 2.14 × 106 years for 237Np and 2.41 × 104 years Np(V) to Np(IV) (Nakata et al., 2004), and U(VI) to U(IV)
for 239Pu), radiotoxicity, and chemotoxicity (Runde et al., 2002). (Scott et al., 2005; El Aamrani et al., 2007). Biotite, which con-
Plutonium exists in the III–VI oxidation states as Pu3+, Pu4+, tains significant amounts of Fe(II), is also able to reduce U(VI)
PuO2+, and PuO22+ in strong acid conditions. Plutonium(III/IV) on exposed edge sites over a broad pH range (Ilton et al., 2004).
cations are sorbed by soil constituents, and therefore, immobile Green rusts, which are mixed Fe(II/III) hydrous oxides, are
in most aqueous and soil environments, whereas, Pu(VI) cat- potent reducing agents in suboxic environments and can read-
ions are not sorbed by temperate soils and thus quite mobile and ily reduce U(VI) to U(IV) to precipitate nanoparticular UO2
bioavailable. Pu(V)O2+ can be sorbed onto soil surfaces from (O’Loughlin et al., 2003a) and reduce Tc(VII) pertechnetate
dilute solutions or seawater (Keeneykennicutt and Morse, 1985). anions to strongly surface-complexed Tc(IV) (Pepper et al.,
Neptunium tends to occur as highly mobile Np(V)O2+ oxida- 2003). Likewise, amorphous FeS can reduce U(VI) to U(V)
tion state under a wide range of environmental conditions (Wilk and U(IV) oxides (Hua and Deng, 2008). Mackinawite (FeS)
et al., 2005). is able to reduce Tc(VII) to form Tc(IV)S2 , U(VI) to U(V/IV)
Manganese(III/IV) oxides and oxyhydroxides can oxi- oxide phases, and Np(V) to Np(IV) surface complexes (Livens
dize Pu(III/IV) (Cleveland, 1970; Amacher and Baker, 1982; et al., 2004).
Morgenstern and Choppin, 2002) and Pu(V) (Keeneykennicutt Fe(II) sorbed to the surface of Fe(III)-containing oxides,
and Morse, 1985; Duff et al., 1999) to the more mobile and toxic forming the reactive surface species ≡FeIIIO–FeIIOH0, is also a
Pu(VI). Conversely, Mn(II)-bearing oxides, hausmannite and potent reducing agent of radionuclides. In contrast to the abiotic
manganite, can reduce Pu(VI) to Pu(IV), which then forms reduction of organics (e.g., nitrobenzenes) by Fe(II) sorbed to
strong inner-sphere complexes with the surface of the mineral hematite or magnetite, which is an outer-sphere mechanism, the
18-24 Properties and Processes

reduction of inorganics such as U(VI) involves an inner-sphere pH, Cr(III) hydroxy hydrate precipitates on the manganite sur-
electron transfer mechanism (Charlet et al., 1998; Liger et al., face, and the oxidation reactions are minimized (Weaver et al.,
1999). The first step is the adsorption of U(VI) ion by the reactive 2002). Feng et al. (2007) compared the Cr(III) oxidative power of
surface species and the formation of an inner-sphere complex, four different Mn oxides and found that order of reactivity was
followed by two reductive steps, which lead to the formation of a as follows (mmol Cr(III) kg−1 oxide): birnessite (1330.0) > cryp-
mixed U(IV)O2/Fe(OH)3 solid phase (Charlet et al., 1998; Liger tomelane (422.6) > todorokite (59.7)  > hausmannite (36.6).
et al., 1999). The reduction of U(VI) by Fe(II) sorbed to synthetic The Cr(III) oxidative ability of the Mn oxides depends on the
Fe oxides (magnetite, goethite, and hematite) and natural Fe(III) crystallinity, structure, composition, and surface properties of the
oxide-containing sediments has been demonstrated, and the minerals (Feng et al., 2007).
natural sediments are less efficient than the pure oxides due to The kinetics of Cr(III) oxidation on Mn(III/IV) oxides shows
their lower Fe(II) sorption capacity (Jeon et al., 2005). Iron(II) a trend similar to that observed for soils (Amacher and Baker,
sorbed to hematite and goethite is much more efficient Tc(VII)- 1982). Negra et al. (2005) demonstrated that greater Mn(IV)
reducing agent than Fe(II) sorbed to phyllosilicates (vermiculite, oxide abundance in soils enhances the Cr(III) oxidation poten-
illite, and muscovite) or structural Fe(II) in the phyllosilicates tial. It has also been shown that the oxidation state of Cr in soils
(Peretyazhko et al., 2008a). Iron(II) sorbed to Al oxyhydrox- in the long-term depends on balances between organic carbon
ide, disaspore, and Al oxide, corundum, is also able to reduce availability (enhances Cr reduction) and the Mn redox status
Tc(VII) to insoluble Tc(IV) (Peretyazhko et al., 2008b). [Mn(III)/(IV) oxides enhance oxidation] (Stepniewska et al.,
Natural humic substances and quinoid-enriched humic 2004; Tokunaga et al., 2007). Nonliving biomaterials, such as sea-
substances are able to catalyze the abiotic reduction of Pu(V) weed, dead fungi, sawdust and pine bark, and needles, are able to
to insoluble Pu(IV) over a wide pH range and under oxic and abiotically (nonenzymatically) catalyze the adsorption-coupled
anoxic conditions (Andre and Choppin, 2000; Shcherbina reduction of Cr(VI) to Cr(III) (Park et al., 2004, 2007, 2008b).
et al., 2007a). Humic substances are only able to reduce Np(V) The Cr(VI)-reducing capacity of pine bark is 8.7 times higher
to Np(IV) under acidic, anoxic conditions (Shcherbina et al., than that of a common chemical Cr(VI) reductant, FeSO4 · 7H2O.
2007a, 2007b). When Cr(VI) comes in contact with biomaterials, there are two
possible reduction mechanisms (Figure 18.14) (Park et al., 2005,
18.4.1.6  Other Trace Metals 2007). Mechanism I, the direct reduction mechanism, involves
In addition to oxidation of metalloids such as As(III) and metals the direct reduction of Cr(VI) to Cr(III) by contact with electron-
such as Fe(II), Mn(II), Mn oxides, and oxyhydroxides can cata- donor groups of the biomaterial, such as amino and carboxyl
lyze the oxidation of trace metals by disproportionation of Mn2+ groups (Figure 18.14). Mechanism II, the indirect reduction
and MnO2. The disproportionation facilitates electron transfer mechanism, involves three steps: (1) the binding of anionic
processes that can either greatly decrease or increase the equi- Cr(VI) to the positively charged groups present on the bioma-
librium solubility of certain metals (Hem, 1978). terial surface, (2) the reduction of Cr(VI) to Cr(III) by adjacent
Chromium and Pu are similar in chemical behavior in aque- electron-donor groups, and (3) the release of the reduced Cr(III)
ous environments (Rai and Serne, 1977; Bartlett and James, into the aqueous phase due to electronic repulsion between the
1979). Chromium occurs in the II, III, and VI oxidation states positively charged groups and the Cr(III), or the complexation of
in water. Chromium(II) is unstable. Chromium(III) has broad the reduced Cr(III) with adjacent groups (Figure 18.14). A lower
stability and exists as the cation Cr3+ and its hydrolysis prod- pH makes the biosurface more positively charged and acceler-
ucts or as the anion CrO2 −. Chromium(VI) exists under strongly ates redox reactions, which enhances Cr(VI) removal (Park et al.,
oxidizing conditions, occurs as dichromate Cr2O7 2−, or chromate 2007). The addition of soil slurry to nonliving biomaterials, such
HCrO 4 − and CrO4 2− anions. Chromium(III) cations are readily as pine bark, significantly enhances the Cr(VI)-reducing capabil-
sorbed to soil constituents, and therefore, immobile in most ity of the pine bark, by sorbing Cr(III) from solution (Park et al.,
aqueous and soil environments; however, Cr(VI) is not sorbed 2008a). Therefore, although Mn oxides can enhance the mobility
by temperate soils to any extent and is thus quite mobile in soils and toxicity of Cr in soils and related environments, the presence
and associated aqueous environments. Therefore, hexavalent Cr of organic matter decreases its oxidation potential.
is readily bioavailable and extremely toxic (Amacher and Baker, Manganese oxides and oxyhydroxides can also catalyze the
1982) and, thus, of concern in food-chain contamination and oxidation of other trace metals such as Co, Pb, Ni, Cu (Hem,
ecosystem health. Manganese(III/IV) oxides can oxidize Cr(III) 1978), and Sb (Belzile et al., 2001). The catalytic transformation
and are the only known oxidizers of Cr(III) in the soil environ- of these metal ions may be directly influenced by redox processes
ment (Stepniewska et al., 2004; Negra et al., 2005). coupled to disproportionation of Mn mixed valence oxide, to
The kinetics of Cr(III) oxidation by Mn oxide is very rapid with catalyzed oxidation by aqueous O2, or to other redox reactions
most of the conversion of Cr(III) to Cr(VI) occurring during the involving changes from one Mn oxide species to another. When
first hour (Amacher and Baker, 1982). The oxidation of Cr(III) the oxidized form of the element has a lower solubility than the
increases with increasing temperature. Manganite (γ-MnOOH) is reduced form, this effect can be of major significance.
also able to catalyze the oxidation of Cr(III), and the reaction rate X-ray photoelectron spectroscopy measurements of Co
increases under acidic conditions (Weaver et al., 2002). At higher adsorbed on MnO2 reveal strong evidence that Co(II) is oxidized
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-25

Mechanism II Mechanism I

HCrO4– Cr3+ HCrO4–

H+

H+
HCrO4– Cr3+

e– e–
+ +

Natural biomaterials

(1) Binding (2) Reduction by (3) Release by Reduction by

with positively adjacent electron electronic repulsion contact with
charged group donor group or complexation with electron donor group
Cr binding group

Positively Cr binding Electron

+ charged group group e– donor group

FIGURE 18.14  Proposed direct and indirect mechanisms for Cr(VI) biosorption and reduction by natural biomaterials. (Reprinted from Park, D.,
Y.S. Yun, and J.M. Park. 2005. Studies on hexavalent chromium biosorption by chemically-treated biomass of Ecklonia sp. Chemosphere 60:1356–1364.
Copyright 2005, with permission from Elsevier.)

to Co(III) in the presence of the strong electric field at the spectroscopy. Structural Fe(II) in magnetite and ilmenite het-
MnO2–solution interface (Murray and Dillard, 1979). Nickel(II), erogeneously reduces aqueous Cu(II), V(IV), and Cr(VI) ions at
however, cannot be oxidized at the interface except at very high the oxide surfaces over a pH range of 1–7 at 25°C (White and
concentrations. Strong experimental evidence for the oxidation Peterson, 1996). Calcium carbonate coatings on the surface of
of other trace metals catalyzed by Mn oxides still remains to be magnetite reduce or eliminate its ability to reduce Cr(VI) (Doyle
attained. Further, more information on the kinetics and mecha- et al., 2004). Siderite (FeCO3) is also able to reduce aqueous
nisms of redox reactions of these trace metals on the surfaces of Cr(VI), and its reactivity increases with addition of acid and
Mn oxides is needed. with increasing temperature (Erdem et al., 2004). Pyrite is also
Other than Mn oxides, heterogeneous oxidation/reduction an effective reductant of Cr(VI), and the reaction is about 100
reactions involving electron transfer between transition metals times faster than reduction by biotite, which is related to the
and Fe-containing minerals have been investigated in numerous relative amount and dissolution rate of Fe(II) from the miner-
studies. Vanadium(II) and V(IV) can be oxidized by Fe(III) oxy- als (Chon et al., 2006). Similarly, Lin and Huang (2008) investi-
hydroxides (Wehrli and Stumm, 1989). Amorphous Fe(III) oxyhy- gated the kinetics and effect of solution characteristics on Cr(VI)
droxides present in natural waters and sediments can also oxidize reduction by pyrite under dark and anaerobic conditions and
the more toxic Sb(III) into Sb(V) (Belzile et al., 2001). The oxida- found that the reduction is highly dependent on the solution
tion pseudo-first-order rate of Sb(III) by natural Fe oxyhydroxides pH, which influences the dissolution of Fe(II) and sulfide ions
is slower compared to synthetic Fe oxyhydroxides. This is attrib- from pyrite, which are responsible for the reduction of Cr(VI).
uted to the slight crystallinity of the natural oxides (compared Magnetite (within days) and mackinawite (within minutes) are
to amorphous synthetic compounds) and to their more complex able to reduce Sb(V) to the more toxic Sb(III) form (Kirsch et al.,
chemical composition, which can include adsorbed ions and 2008). The Sb(V) reduction by mackinawite proceeds solely by
organic matter (Belzile et al., 2001). Goethite has also been shown oxidation of surface Fe(II), while the oxidation state of sulfide is
to catalyze the oxidation of Sb(III) to Sb(V) (Leuz et al., 2006). conserved, with the formation of amorphous or nanoparticulate
Iron(II)-bearing minerals are able to reduce a variety of trace SbS3-like solids (Kirsch et al., 2008).
metals. Reduction of Cr(VI) by biotite has been shown by Eary The Fe(II)-rich chlorite and corrensite clays are able to reduce
and Rai (1989) and Ilton and Veblen (1994). Magnetite and Cr(VI) under acidic conditions, and during the reaction, struc-
ilmenite are the most common Fe(II)-containing oxide miner- tural Fe(II) is oxidized to Fe(III) (Brigatti et al., 2000). Mixed
als in the earth’s crust and potentially important in controlling Fe(II)/Fe(III) hydroxides, known as green rusts, commonly
heterogeneous redox reactions involving aqueous transition found in suboxic environments are able to readily reduce a vari-
metals in soil environments. Direct evidence of Cr(VI) reduc- ety of trace metals, such as Ag(I), Au(III), Cu(II), and Hg(II) to
tion on magnetite surfaces has been documented by Peterson Ag(0), Au(0), Cu(0), and Hg(0) (O’Loughlin et al., 2003b). Sulfate
et al. (1996) using x-ray adsorption fine structure (EXAFS) green rusts are able to effectively reduce Cr(VI) to Cr(III), which
18-26 Properties and Processes

initially involves chromate anions replacing sulfate in the inter- 3

Log nitrate formed/exchangeable Mn(II)

layer of the green rust, and then the chromate is reduced by Fe(II)
(Skovbjerg et al., 2006). Even though the formation of sparing
soluble Cr(III) blocks further chromate entry, Cr(VI) reduction
continues at the green rust solid/solution interface due to electron 2
transfer from the center of the green rust crystals. During this
process, Cr-substituted goethite is formed, which is sparingly sol-
uble and thus essentially locks away the Cr, which has important r 2 = 0.99
implications for environmental remediation (Skovbjerg et  al., 1 Y = 0.072x – 0.006
2006). Sulfate green rust is also able to reduce the highly stable
Sb(V) to the more toxic Sb(III) (Mitsunobu et al., 2008).
Iron(II) sorbed to the surface of Fe oxides and clay miner-
als are also able to catalyze the reduction of Cr(VI) to Cr(III).
0 10 20 30 40
Buerge and Hug (1999) compared the Cr(VI) reduction reactiv-
MnO2/nitrite added
ity of Fe(II) in the presence of aluminum oxide, silicon diox-
ide, goethite, lepidocrocite, montmorillonite, and kaolinite and FIGURE 18.15  The logs of the ratios of nitrate formed from nitrite over
found that only Al2O3 did not accelerate the reduction reaction Mn reduced to the exchangeable form plotted against the MnO2/nitrite
in the presence of Fe(II). The order of reactivity was as follows ratios in the original suspensions. (Reprinted from Bartlett, R.J. 1981.
(Buerge and Hug, 1999): goethite ≈ lepidocrocite >> montmo- Nonmicrobial nitrite-to-nitrate transformation in soils. Soil Sci. Soc. Am.
rillonite > kaolinite ≈ SiO2 >> Al2O3. Similarly, Fe(II) added to J. 45:1054–1058. With permission of the Soil Science Society of America.)
magnetite significantly improves the Cr(VI) reductive ability of
magnetite (Jung et al., 2007). Such a process of substantial reduction of Mn in the solid phase
Organic complexes of Fe(II) also strongly affect the reduction relative to the release of exchangeable Mn(II) might be described
of Cr(VI) to Cr(III) (Buerge and Hug, 1998). Fe(III)-stabilizing better as the insertion of electrons into the overlapping elec-
ligands such as bi- and multidentate carboxylates and pheno- tronic orbitals of the solid, such that the electron excess is delo-
lates generally accelerate the reduction reaction, whereas Fe(II)- calized over the solid, rather than the reduction of one Mn4+
stabilizing ligands such as phenanthroline essentially stop the atom to Mn2+ at a particular surface site. The overlapping atomic
reaction. Natural dissolved organic matter from a forest soil orbitals form bands of many energy levels rather than a single
shows quantitatively the same accelerating behavior as the inves- energy level.
tigated Fe(II)-carboxylate complexes (Buerge and Hug, 1998). Luther and Popp (2002) studied the kinetics of nitrite oxi-
dation by polymeric Mn(IV) oxides, which are highly reactive
Mn oxide phases. The energy of activation and the entropy of
18.4.2  Transformation of Other Inorganics
activation show the oxidation reaction to be associative and dif-
Nitrate formation in soils from NO2 − is related to soil level of fusion controlled, occurring via an inner-sphere mechanism,
reactive Mn oxides, which catalyze the oxidation (Bartlett, likely with O atom transfer from MnO2 to HNO2. The reaction
1981). Nitrite oxidation, NO3 − formation, and MnO2 reduction requires protons and slows down at a pH above 5.5, where NO2 −
are stoichiometrically related reactions both in the presence and and MnO2 (negatively charged) become the dominant species
the absence of atmospheric O2. The relationship shown in Figure (Luther and Popp, 2002).
18.15 suggests that at high ratios of MnO2 /NO2 − , most of the Manganese(IV) oxide is also able to catalyze the oxidation of
Mn(IV) is reduced only to nonexchangeable solid Mn(III) oxide NH3 and organic N to N2, which has traditionally been assumed
rather than to exchangeable Mn(II) ions. When the MnO2 /NO2 − to be a microbially mediated process in sediments (Luther et al.,
ratio is high, little Mn(II) becomes exchangeable relative to the 1997). The MnO2-catalyzed formation of NO32− from NH3 can
NO3 − formed, as indicated by high values of NO3 − /Mn(II). At also occur, but the formation of N2 from NH3 is more favorable
low MnO2 /NO2 − ratios, more exchangeable Mn(II) relative to (Luther et al., 1997). Luther et al. also observed the reduction
NO3 − is formed. Therefore, the more MnO2 relative to NO2 −, NO32− to N2 by dissolved Mn2+. These oxidation and reduction
the greater is the efficiency of the NO2 − to NO3 − transformation reactions can occur in the presence or absence of O2. Hulth et al.
and the less exchangeable Mn(II) formed relative to NO3 −. High (1999) found that introduction of Mn oxides from oxidized sur-
MnO2 /NO2 − ratios likely prevail in many soils. Equation 18.17, face sediments into anoxic sediments results in anoxic nitrifi-
which does not involve a pH change, may describe the NO2 − cation and the net production of NO3 − and NO2 −. They found
to NO3 − transformation in high Mn oxide soils better than that the anoxic nitrification rates were directly related to the Mn
Equation 18.18: oxide content of the sediment.
Iron(II)-bearing minerals can catalyze the abiotic reduction
NO2 − + 2MnO2 = Mn2O3 + NO3 − , (18.17) of nitrate and nitrite. Some field studies have suggested that
structural Fe(II) in clay minerals catalyzes the reduction of NO3 −
NO2 − + MnO2 + 2H+ = Mn2+ + NO3 − + H2O. (18.18) to NO2 −, as indicated by significant negative correlations in the
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-27

NO3 − and Fe(II) content in minerals in clayey till and catchment Mineral nanoparticles exhibit considerably different chemical
sediments (Ernstsen and Morup, 1992; Ernstsen, 1996). Chloride and physical properties than their larger counterparts, due to
and sulfate intercalated green rusts (mixed Fe(II/III) hydrous the fact that a large percentage of their atoms are on the surface
oxides), which commonly occurs in anaerobic soils and sedi- (e.g., for a particle with a diameter of 4 nm approximately 50%
ments, are able to rapidly reduce NO3 − to NH 4+ NH4+, with the of its atoms are on the surface) (Grassian, 2008; Hochella et al.,
formation of magnetite (Fe3O4) (Hansen et al., 1996; Hansen and 2008). This can result in surface strain or reconstruction (relax-
Koch, 1998; Hansen et al., 2001). Wustite (FeO) is able to cata- ation), structural disorder, and variations in surface topogra-
lyze the rapid reduction of NO32− to NO2 − and ultimately NH 4+ phy and crystallographic structure that is exposed. Although
(Rakshit et al., 2005). During this reaction, an Fe(II/III) oxide, nanoparticles are highly reactive, which is attributable to their
magnetite (Fe3O4), is formed. Siderite (FeCO3) is able to catalyze very high specific surface area, it has become clear that their
the abiotic reduction of NO2 − to N2O, during which siderite is increased reactivity cannot be solely attributed to this character-
transformed to lepidocrocite (γ-FeOOH) (Rakshit et al., 2008). istic. Surface area-normalized studies have reported enhanced
Nitrate immobilization into dissolved and humic organic nanoparticle reactivity such as cation adsorption and redox
N fractions can be abiotically catalyzed in soils and sediments reactions, which could only be attributed to a greater density of
(Dail et al., 2001; Davidson et al., 2003; Huygens et al., 2008; reactive sites per surface area unit or a greater inherent reactivity
Torres-Canabate et al., 2008). It has been suggested that anaer- of nanoparticle surface sites (Waychunas et al., 2005; Grassian,
obic microsites in soils that contain reduced Fe and Mn miner- 2008; Hochella et al., 2008).
als are responsible for catalyzing the reactions (Davidson et al., Several studies have shown that the reactivity of Fe oxides
2003; Torres-Canabate et al., 2008). The mechanism is thought to and oxyhydroxides, which commonly occur as nanoparticles
involve the abiotic reduction of NO32− by Fe(II) (present in anaero- (3–10 nm range), is strongly dependent on particle size. The sur-
bic microsites) to NO2 −, which then rapidly abiotically reacts with face area-normalized reductive dissolution of 4 nm particles of
existing organic matter via nitrosation (Thorn and Mikita, 2000) ferrihydrite by hydroquinone is 20 times faster than that of 6 nm
and thus is incorporated into the organic N fraction (Davidson particles (Anschutz and Penn, 2005). Similarly, Erbs et al. (2008)
et al., 2003). Further research is required to elucidate the exact investigated the effect of particle size on reductive dissolution
mechanism of abiotic nitrate immobilization into organic N. of nanoparticulate ferrihydrite by hydroquinone, and they
Manganese oxides also catalyze the oxidation of gaseous CO attributed the increased reactivity to increased reagent-surface
(Klier and Kuchynka, 1966). This reaction occurs by consump- encounters as indicated by a sixfold increase in the pre-exponen-
tion of the structural O22− of MnO2. The catalyst must then be tial factor when comparing 3.9 nm particles to 5.9 nm particles.
regenerated by chemisorption of O2. Whether or not a similar They hypothesized that the rate of diffusion of the reagent to the
cycle of Mn oxide reduction and O2 consumption occurs in soil nanoparticle surface is size dependent, as the structure of the
environments, where adsorbed molecules such as CO2 and H2O water is affected by the size of the nanoparticle.
can poison the catalyst surface, remains unanswered. Nanoparticulate hematite oxidation of soluble Mn 2+ in the
Soil clay minerals and metal oxides, such as montmorillonite presence of O2 is dependent on the size of the nanoparticles
and goethite, can catalyze the abiotic hydrolytic degradation of as related to surface structure and topography (Madden and
high- and low-molecular-weight silicones, such as polydimethylsi- Hochella, 2005). The surface area-normalized oxidation rate
loxane, by cleaving siloxane (Si–O–Si) bonds (Graiver et al., 2003). of hematite particles with an average diameter of 7.3 nm is at
The resultant low-molecular-weight silanol units are volatile and least one order of magnitude higher than those with an aver-
thus evaporate into the atmosphere where they are degraded to age diameter of 37 nm. The oxidation reaction proceeds most
silica, water, and CO2 by hydroxyl-free radicals in the atmosphere readily at topographic features that distort the octahedral Mn 2+
(Graiver et al., 2003). coordination environment. These distorting surface features
increase as the particle size of hematite decreases. This has the
effect of lowering the reorganization energy, which effectively
18.5  Role of Nanoparticles controls the magnitude of the transition state barrier (Madden
in Abiotic Catalysis and Hochella, 2005).
Particle diameter of nanoparticulate magnetite strongly
Mineral nanoparticles are important constituents of natural ter- affects its reactivity toward the reductive degradation of carbon
restrial and aquatic environments (Gilbert and Banfield, 2005; tetrachloride (Vikesland et al., 2007). Magnetite with a 9 nm
Waychunas et al., 2005; Wigginton et al., 2007; Hochella et al., diameter is far more reactive than 80 nm diameter magnetite on
2008; Wilson et al., 2008). Iron oxides, oxyhydroxides, and sul- both a mass and surface area-normalized basis. The aggregation
fides commonly occur as nanoparticles in nature; and various state of the 9 nm magnetite significantly affects its reactivity, and
studies have investigated the abiotic transformation of organics an increase in ionic strength leads to a decrease in reactivity due
(Klupinski et al., 2004; McCormick and Adriaens, 2004; Chun to increased aggregation of the nanoparticles. Jung et al. (2008a)
et al., 2006; Cwiertny et al., 2008) and inorganics, such as Sb compared the reactivity of biogenic and commercial nanopar-
(Kirsch et al., 2008) and Se (Loyo et al., 2008; Scheinost and ticulate magnetite toward catalyzing the ozonation of para-
Charlet, 2008) by nanoparticulate Fe-bearing minerals. chlorobenzoic acid. Biogenic magnetite was found to be a less
18-28 Properties and Processes

efficient catalyst due to its tendency to form larger aggregates and shift electron density and conformation in ways favorable
than the commercial magnetite (Jung et al., 2008a). While inves- to the reactions. A wide range of xenobiotics such as pesti-
tigating the abiotic reductive transformation of nitrobenzene by cides, antibiotics, dyes, and explosives are subject to abiotic soil
Fe(II)-sorbed on goethite nanoparticles, Cwiertny et al. (2008) mineral-catalyzed oxidative transformation. In anoxic ground-
found that aggregation of the goethite nanoparticles resulted in water and surficial waters, biogeochemical processes provide a
the decreased BET-specific surface area-normalized rate con- variety of potential reductants to catalyze abiotic transforma-
stants, implying that they are less reactive than larger particles. tion of persistent xenobiotics. Abiotic degradation pathways of
They concluded that new methods are needed to quantify the biocides (pesticides and antibiotics) are particularly important
amount of surface area accessible for reaction in wet nanopar- in the environment as the toxicity of these substances can limit
ticle suspensions rather than assuming the specific surface area their biotic degradation. Much is known about the toxicity of
of the dry nanoparticles is relevant. xenobiotic parent compounds. To date, relatively little is known
In view of the high specific surface area and the density and about the bioavailability and toxicity of xenobiotics after reac-
nature of reactive sites of nanoparticles, their role in the cata- tion with abiotic catalysts, such as metal (oxy)hydroxides and
lytic reactions in soil and related environments merits increas- oxides and clay minerals.
ing attention for years to come. The transformations of metals and metalloids are sub-
stantially influenced by Mn oxides and Fe-bearing minerals.
18.6  Conclusions Manganese(IV) oxides have the ability to catalyze many reactions
such as the oxidation of As(III) to As(V), Fe(II) to Fe(III), Pu(III,
The significance of abiotic catalysis in the transformation of IV, V) to Pu(VI), and Cr(III) to Cr(IV). The ability of Mn(IV)
natural organic, anthropogenic organic compounds, metals, oxides to catalyze these transformation reactions varies with
metalloids, and other inorganics is far greater than had previ- their structure and surface properties and can also be influenced
ously been perceived. Mineral colloids are abundant in nature. by the kinds and levels of surface coatings. Iron(III)-bearing min-
Abiotic catalysts include metal (oxy)hydroxides and oxides, SRO erals also have the ability to catalyze the oxidation of some tran-
aluminosilicates, layer silicates, and primary minerals. The abil- sition metals such as the transformation of V(II) to V(IV) and
ity of these catalysts to promote the transformation of vital ele- Sb(III) to Sb(V). On the other hand, the ability of Fe(II)-bearing
ments and environmental pollutants varies significantly with minerals to catalyze the reduction reactions of a variety of trace
their atomic bonding and structural configuration and surface metals and metalloids (e.g., Cr, Sb, V, Hg, U, Tc, Pu, Np, and Se)
chemistry and the structure and functionality of the substrates. has been demonstrated. Besides Fe(II)-bearing minerals, nonliv-
The transformation of biomolecules to humic substances is ing biomaterials are able to abiotically catalyze the adsorption-
substantially promoted by abiotic catalysis. Phenolics are the coupled reduction of Cr(VI) to Cr(III). The solubility, mobility,
most widely distributed class of plant secondary metabolites and toxicity, and food-chain contamination of metals and metalloids
play an important role in regulating nutrient cycling in the ter- can be significantly influenced by abiotic catalysis.
restrial environment. Abiotic catalysis promotes the formation Manganese(IV) oxides have been shown to catalyze the con-
of humic substances from the phenolic compounds especially in version of NO2 − to NO3 −. The reaction is theorized as mainly the
the presence of the amino acids through oxidative polymeriza- insertion of electrons from NO2 − into the overlapping electron
tion, polycondensation, ring cleavage, decarboxylation, dealkyl- orbitals of the Mn oxides. Manganese(IV) oxides also catalyze
ation, and/or deamination. Sugars and amino acids are among the oxidation of gaseous CO through consumption of struc-
the most abundant constituents of the terrestrial ecosystem. The tural O2 −. Furthermore, nitrate immobilization into dissolved
Maillard reaction, involving condensation reactions between and humic organic N fractions can be abiotically catalyzed by
reducing sugars and amino acids, is substantially promoted by reduced Fe and Mn (present in anaerobic microsites) in soils and
abiotic catalysis. In nature, the Maillard reaction and polyphe- sediments. Further research is required to elucidate the exact
nol pathways should interact closely, since sugars, amino acids, mechanism of nitrate immobilization into organic N.
and polyphenols coexist in soil solutions and natural waters. The Nanoparticles are important environmental particles, which
integrated polyphenol–Maillard reaction system under abiotic influence the pedosphere, hydrosphere, biosphere, and atmo-
catalysis is more effective in generating humic polymers than the sphere. Mineral nanoparticles exhibit considerably different
Maillard reaction or the polyphenol pathway alone. A series of chemical and physical properties, compared with their larger
mineral colloids promotes such catalytic reactions. Among abi- counterparts. This is ascribed to the exposure of a large per-
otic catalysts, Mn oxides are most reactive in the transformation centage of atoms on the surface of nanoparticles and the resul-
of these biomolecules. tant high specific surface area and the increase in density and
Mineral colloids can catalyze the hydrolysis of many xenobi- reactivity of reactive sites of nanoparticles. The catalytic role
otics through the ability of their metal-containing surfaces to of mineral nanoparticles in the transformation of organics and
behave as Brønsted acids and donate protons or to act as Lewis inorganics has been demonstrated. More in-depth research on
acids and accept electron pairs. The catalytic effectiveness of a the abiotic catalysis of environmental nanoparticles and on the
metal ion depends on its ability to complex reactant molecules biogeochemical and ecological impacts is warranted.
Role of Abiotic Catalysis in the Transformation of Organics, Metals, Metalloids, and Other Inorganics 18-29

Therefore, abiotic catalysis deserves close attention in sustain- Barrett, K.A., and M.B. McBride. 2005. Oxidative degradation of
ing environmental quality and ecosystem health. Furthermore, glyphosate and aminomethylphosphonate by manganese
abiotic and biotic catalysts coexist in soil and associated envi- oxide. Environ. Sci. Technol. 39:9223–9228.
ronments. Abiotic catalysts can influence microbial formation Bartlett, R.J. 1981. Nonmicrobial nitrite-to-nitrate transforma-
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the impact on terrestrial ecosystem integrity should, thus, be an (ed.) Soil physical chemistry. CRC Press, Boca Raton, FL.
important and exciting issue for years to come. Bartlett, R.J., and B. James. 1979. Behavior of chromium in soils.
III. Oxidation. J. Environ. Qual. 8:31–35.
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Krieger Publishing Company, Malabar, FL.
This study is supported by Discovery Grant GP 2383-2008 of the Basolo, F., and R.G. Pearson. 1968. Mechanisms of inorganic reac-
Natural Sciences and Engineering Research Council of Canada. tions, 2nd Ed. John Wiley & Sons, New York.
Bell, R.P. 1941. Acid–base catalysis. Oxford University Press,
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 19
Soil pH and pH Buffering
19.1 Introduction............................................................................................................................19-1
19.2 Definition and Determination of Soil pH...........................................................................19-1
Definition of pH  •  Determination of pH with Electrodes  •  Determination of Soil
pH Using pH-Sensitive Dyes
19.3 Acids and Bases in Soil Solutions.........................................................................................19-3
Weak Acids  •  Weak Bases
19.4 Overview of Reactions Controlling pH and pH Buffering..............................................19-4
19.5 Buffering by Soil Organic Matter.........................................................................................19-5
19.6 Proton and Al Exchange in Silicate Clays...........................................................................19-7
19.7 pH-Dependent Charge Buffering by Mineral Components............................................19-7
Oxides and Hydroxides of Iron and Aluminum  •  pH-Dependent Charges on Silicate
ClayEdges  •  Imogolite and Allophane
19.8 Buffering by Dissolution and Precipitation of Carbonates..............................................19-9
19.9 H+ Consumption by Irreversible Weathering of Aluminous Minerals..........................19-9
Weathering of Primary Silicates  •  H+ Consumption by the Destruction of High-Activity Clay
19.10 Determination of Buffer Capacities...................................................................................19-10
Total Titratable Acidity  •  Lime Requirement  •  Calcium Carbonate Concentrations
Paul R. Bloom in Soil  •  Determination of the Buffering of H+ Inputs in Noncalcareous Soils
University of Minnesota
19.11 Soil Acidification.................................................................................................................. 19-11
Ulf Skyllberg Natural Acidification  •  Acid Rain  •  Acid-Producing Fertilizers  • 
Swedish University of Acidification by Sulfur Compounds
Agricultural Sciences References..........................................................................................................................................19-12

19.1  Introduction this chapter focuses on the reactions of components that buffer
soil pH in upland soils. Factors affecting pH and buffering in
Soil pH is a measure of soil acidity or alkalinity and is prob- flooded soils are discussed in Chapter 14.
ably the single most important chemical characteristic of a
soil. In the past, soil acidity or alkalinity, reported in pH units, 19.2  Definition and Determination
was also referred to as “soil reaction” (Mason and Obenshain,
1939), and this term is occasionally still used in some publica- of Soil pH
tions. However, “soil reaction” is no longer used by soil chemists Because pH is a term that is only defined for solutions, in a strict
(SSSA, 2008). Because of the importance of acidity and alkalin- sense, it cannot be applied to a solid-phase material like soil.
ity in soils, pH has been called a master variable (McBride, 1994), However, the chemical properties of the solid-phase components
with knowledge of soil pH required to understand many chemi- in soil define the pH of the soil solution, the water in soil pores
cal processes including ion mobility, precipitation and dissolu- (Chapter 12).
tion equilibria and kinetics, and oxidation–reduction equilibria.
Soil pH also affects nutrient availability to plants and the nega-
19.2.1  Definition of pH
tive response of many plant species to soil acidity.
Soils are a complex mixture of solid-phase components that The term pH was defined by Sorensen (1909) to provide a conve-
react to yield a measured pH value. These components also buffer nient way of representing the H+ or OH− concentrations in aque-
soils against pH changes caused by natural and anthropogenic ous solutions. As currently defined, pH is the negative logarithm,
inputs of acids and bases. Knowledge of the reactions that buffer base 10, of H+ activity, log (H+), where activity is the concentra-
soil pH is necessary for an understanding of natural soil weath- tion adjusted for nonideality caused by charge–charge interac-
ering and the response of a soil to inputs of lime, acid-forming tions with other ions in solution. In all except saline soils, the
N fertilizers, acid-mine wastes, and acid rain. The discussion in ionic interaction correction is small and the difference between

19-1
19-2 Properties and Processes

H+ concentration and activity is small. The determination of H+ body as the glass electrode to form a combination electrode.
also provides a measurement of OH− in solution. At 25°C in pure The filling solution for the reference electrode is a concentrated
water, the relation between OH− activity, (OH−), and H+ activity, KCl solution, which slowly leaks into the test solution through a
(H+), is given by porous liquid junction. Because soils are cation exchangers, they
can have a disproportionate effect on the rate of K+ diffusion
K w = (H + )(OH)− = 1.0 × 10 −14 (19.1) compared to Cl− diffusion into solution, which sets up a poten-

tial across the junction (Coleman et al., 1951). This can cause a
reduction in the measured pH (Thomas, 1996).
where Kw is the ionization constant for water. Expressing
The method for measurement of pH in 0.01 M CaCl2 is the
Equation 19.1 as negative logarithms yields
same as for measurement of pH in distilled water (Thomas,
1996). Because of the displacement of H+ and Al3+ from soil
pH + pOH = 14 (19.2)
materials by Ca 2+, pH in 0.01 M CaCl2 [pH(CaCl2 )] is on an aver-
age about 0.3–0.4 units lower than in water (Essington, 2004).
where pOH is the negative logarithm of the OH− activity. The measurement of pH in 0.01 M CaCl2 results in reduction
or elimination of the problems due to variation in soil solution
salt concentration and it eliminates the junction potential effect.
19.2.2  Determination of pH with Electrodes
Calcium is used in the determination of pH because it is the pre-
Soil pH is determined by measuring the pH after equilibrating dominant soil solution cation in soils of temperate regions. The
soil with pure water or a salt solution (SSSA, 2008). The pH of 0.01 M concentration, however, is somewhat higher than that
a solution in equilibrium with a soil varies with the composition found in most soil solutions.
and concentration of the salts in the solution because cations in The measurement of pH in 1 M KCl suspensions also generally
solution displace H+ and Al3+, an acidic cation, from soil sur- yields lower pH values than in water. However, for some subsur-
faces. Three common standard methods for determining pH in face horizons of highly weathered soils of the tropics, pH in KCl
soils involve the suspension is distilled water, 0.01 M CaCl2 or can actually be greater than in water (van Raij and Peech, 1972).
1 M KCl solutions, and measurement of the solution pH in the This occurs in subsoils low in permanent charge silicate clays
solution (Thomas, 1996). In the United States, the most com- and low in organic matter. Oxides and hydroxides of iron and
monly reported pH measurements are in 1:1 (weight:volume) aluminum are the predominant ion exchangers in these soils
suspensions of air-dried soil in distilled water. A suspension of and at very acid pH values they are anion exchangers (Section
soil is prepared (e.g., 10 g of soil and 10 mL of distilled water), 19.7). The addition of KCl results in a displacement of OH− by
stirred vigorously, and then allowed to stand for 10 min. The Cl− and an increase in pH (McBride, 1994).
suspension is stirred again and the pH is measured with a glass
pH electrode and a pH meter (Thomas, 1996). The pH can also
be measured with an ion-sensitive field-effect transistor (ISFET) 19.2.3  Determination of Soil pH Using
electrode. These solid-state devices are more robust than glass pH-Sensitive Dyes
electrodes, have a more rapid response, and are well adapted
for making field measurements of soil pH (Rossel and Walter, Rapid determination of soil pH can be made colorimetrically
2004). However, the solid-state electrodes are more expensive with pH indicator dyes. Colorimetric methods are based on the
than glass electrodes. change in color that takes place upon disassociation of a weak
The determination of soil pH in a 1:1 water suspension is acid or a weak base organic dye. In solution, a weak acid dye
expected to give a higher pH value than the soil solution at field molecule can dissociate:
water contents. The quantity of water added results in a dilu-
tion of the salts in the soil solution and a lower-equilibrium salt
HI = H + + I− . (19.3)
concentration. This effect is illustrated by the 0.4 unit increase in
pH obtained for an increase in water content in the soil suspen-
sion from 1:1 to 1:10 (Thomas, 1996). The 1:1 water determina- An increase in pH will cause a change in color as the undissoci-
tion of pH is influenced by the natural seasonal variation in soil ated dye, HI, changes to the dissociated form, I−. Typically a mix-
solution salt concentrations and the effects of soil management; ture of dyes is used to yield color changes that take place over
for example, recent fertilization. Soil pH measured in water is a wide range of pH. A dye solution is mixed with soil to make a
reported as pH(H2O) or pHw. slurry, and the dye is decanted from the soil so the color can be
At low salt concentrations, an error due to the junction poten- compared with a color chart. The pH measured in this manner
tial effect can occur in determination of pH(H2O). A pH measure- corresponds with pH(H2O) measured with a glass electrode but
ment requires contact with the solution by a glass electrode and a is not as precise and can vary from the glass electrode results
porous liquid junction of a reference electrode. This is necessary by as much as 0.4 units (Mason and Obenshain, 1939). Dye-
to complete the circuit between the pH-sensitive glass electrode impregnated pH papers also can be used to get quick pH mea-
and the reference electrode, which is often built in the same surement within 0.5 units of the true pH(H2O) (Thomas, 1996).
Soil pH and pH Buffering 19-3

19.3  Acids and Bases in Soil Solutions (Chapter 11; Stevenson, 1994), with fulvic acids predominating
in soil solutions. These natural organic acids are complex mix-
Soil solutions contain a mixture of weak acids and weak bases tures that contain carboxylic acid groups.
that buffer the pH of the solution. This buffering is small com- The strength (ability to donate protons) of a carboxylic acid is
pared to the quantity of acidity or basicity (alkalinity) associated defined by the equilibrium constant:
with the solid phases in soil and has little impact on soil pH buff-
ering. However, the acid and base components in soil solutions (RCOO− )(H + )
directly impact plant roots and soil microbes and thus directly Ka = (19.7)
RCOOH
influence the vitality of the biotic community in a soil. Also, the
acids and bases in soil solution directly impact mineral weather-
ing and biogeochemical reactions involved in soil genesis. where Ka is the acidity constant. Stronger acids have greater
In this chapter, we will use BrØnsted’s definition of acids and acidity constants. Often, the strength of a weak acid is given in
bases where an acid is a hydrogen ion (H+) donor and a base is terms of the negative log of the Ka, the pKa. The lower the pKa the
an H+ acceptor (Stumm and Morgan, 1996). Because an H+ ion is greater the strength of the acid. At the pH equal to the pKa, an
just a proton, acids can be described as proton donors and bases acid is half ionized. At higher pH, it is more than half ionized,
as proton acceptors. According to this definition, reaction of an while at lower pH it is less than half ionized. Thus, at solution
acid to lose a proton produces a conjugate base that can accept a pH values less than the pKa, a weak acid has a greater ability to
proton; if the reaction is reversed. Conversely, a base that accepts donate protons than at higher pH values. Carboxylic acids in soil
a proton yields a conjugate acid. For example, when nitric acid solution have pKa values generally in the range of 3–5.
donates protons to water, the base is H2O. The reaction is The soluble fulvic acids also contain phenolic groups, ArOH,
where Ar is an aromatic six-carbon ring structure. Phenolic
HNO3 + H2O = NO3 − + H3O+ . (19.4) groups are generally much less concentrated than the carboxyl
groups and they are much less acidic having pK values ranging
The nitrate anion is the conjugate base of nitric acid and the from 7 to 11.
hydronium ion, H3O+, is the conjugate acid of water. Nitric acid The Al3+ ion can be an important weak acid component in soil
is a strong acid because at all except very high H+ concentrations solutions of highly acid soils. This ion contributes to soil solu-
Reaction 19.4 goes all the way to the right and all of the HNO3 is tion acidity and causes the acid toxicity response experienced by
ionized. The conjugate base of nitric acid, the nitrate anion, is a many plants in acid soils (Bloom et al., 2005; Fageria and Baligar,
very weak base because it has very little tendency to accept protons. 2008). In water, Al3+ undergoes a series of hydrolysis reactions,
The above reaction in aqueous solution is often abbreviated to which produce protons (Nordstrom and May, 1996):

HNO3 = NO3 − + H + . (19.5)

Al 3 + + H2O = AlOH2 + + H + pK a1 = 5.00, (19.8)

19.3.1  Weak Acids
AlOH2 + + H2O = Al(OH)2 + + H + pK a 2 = 5.1, (19.9)
The weak acids in soil solutions include organic carboxylic acids,
H2CO3, and Al3+, a metal ion that undergoes hydrolysis. Carboxylic
acids are organic compounds with one or more –COOH groups Al(OH)2 + + H2O = Al(OH)30 + H + pK a 3 = 6.7, (19.10)

that have the potential to ionize to form the carboxylate anion,
RCOO−, according to the reaction
Al(OH)30 + H2O = Al(OH)4 − + H + p K a 4 = 6. 2. (19.11)

RCOOH = RCOO + H − +
(19.6)
Although the second, third, and fourth hydrolysis reactions
where
are important in determining the chemistry of Al, only the first
RCOOH is any carboxylic acid
hydrolysis reaction is a major source of protons in soil solution.
R is an organic structure
The low solubility of solid Al(OH)3 limits the quantity of Al
ions. At a pH of 5.0, a solution in equilibrium with Al(OH)3 has
Organic acids in soil solutions include simple acids like
a total concentration of Al 3+ of less than 10 −6 M (Nordstrom
malic acid (COOH)CH2CH(OH)CH2(COOH) and citric acid
and May, 1996).
(COOH)CH2C(OH)(COOH)CH2(COOH), which are exuded
In soils, carbonic acid is also an important weak acid (H2CO3)
from plant roots or by soil microbes. These acids generally have
that is created by the dissolution of carbon dioxide:
a short lifetime in soils because they are easily consumed by soil
microbes. In addition, soil solutions contain macromolecular
CO + H2O = H2CO3 pK = 1.51 (Stumm and Morgan, 1996).
humified components produced by degradation of plant debris 2( g )
that can be operationally separated into humic and fulvic acids (19.12)
19-4 Properties and Processes

When pH is increased, this acid ionizes to produce bicarbonate to the presence of urease enzymes in soils, resulting in an over-
and H+: all reaction:

H2CO3 = HCO3 − + H + . (19.13) (NH2 )2 CO + 2H2O = HCO3 − + NH 4 + + NH3(aq ) . (19.15)

Urea

The basicity effect of the NH3-producing fertilizers is short-lived

The pKa for Reaction 19.13 is 6.35 (Stumm and Morgan, 1996)
because biological oxidation of ammonium to nitrates produces
meaning that carbonic acid is a weaker acid than organic car-
two H+ ions, and the net effect is acidification.
boxylic acids or Al3+. The concentrations of HCO− in solution
increase both with increase in pH and increase of concentration
of CO2 in the air of soil pores. At a pH value above 6, HCO3− is 19.4  Overview of Reactions Controlling
often the predominant anion in soil solution. pH and pH Buffering
For solutions in equilibrium with the earth’s atmosphere,
H2CO3 is directly proportional to the partial pressure of atmo- Reactions of the solid-phase components control soil pH and are
spheric CO2, which in 2007 was 3.83 × 10−4 atm. The concentra- the reactions that buffer soil pH against rapid pH change with
tion is increasing at the rate of 0.014 × 10−4 atm year−1 (Anon, natural or anthropomorphic inputs of acids and bases (Bloom
2008). However, in soils where root and microbial respiration et  al., 2005). Solid-phase soil materials have a much greater
are active, the partial pressure can easily be 100 times greater capacity to accept or donate protons than the soluble acids and
(Fernandez and Kosian, 1987; Magnusson, 1992). This has bases in soil solution. Magdoff and Bartlett (1985) investigated
a great effect on the content of HCO3− in soils (Andrews and the buffering in 51 surface soils of Vermont, USA by reacting these
Schlesinger, 2001). soils with H2SO4 or CaCO3 for 30 days and determining the final
pH in 0.01 M CaCl2. They found maximal buffering (minimal
slope of pH vs. added acid or CaCO3) to occur at both pH 3.5 or
19.3.2  Weak Bases less and pH 7.5 or greater (Figure 19.1). The upper bound of the
pH in the buffering shown in Figure 19.1 is fixed by the solubility
All of the anions of the weak acids above, as well as the hydro- of CaCO3 (Magdoff and Bartlett, 1985). They also showed that
lyzed Al cations, are weak bases that can accept protons in the the buffer plot was generally linear in the pH range of 4.5–6.5, a
pH range found in soils. Because of the low pKa values for organic range that encompasses most acid agricultural soils.
acids and AlOH2+, these ions are only important proton accep- The pH-buffering reactions in soils include proton desorption
tors in very acid soils. For most neutral and alkaline soils, the and adsorption reactions with mineral and organic components
concentration of bicarbonate determines the alkalinity of soil as well as ion exchange, dissolution, and precipitation. Some of the
solutions, where alkalinity is defined as the quantity of strong soil components are effective in buffering over a wide range of pH
acid needed to lower the pH of a solution to the end point for values, while others are effective over a limited pH range (Table
complete protonation of bicarbonate (about pH = 4.8) (Stumm 19.1). The buffer ranges in Table 19.1 are those that were developed
and Morgan, 1996). The carbonate ion, CO32−, is significant only by Bloom et al. (2005) and are somewhat similar to those shown
in very high pH soils because the pKa for the ionization of HCO3−
to CO32− is 10.33 (Stumm and Morgan, 1996). 8.0
Under some conditions, solution ammonia, NH3(aq), is a sig-
nificant base. These conditions are induced by the addition of 7.0
fertilizer N as anhydrous ammonia [NH3(g)], or urea. When
NH3(g) is injected into a soil, it reacts with the soil solution to 6.0
lower the H+ activity raising the pH. Ammonia is a conjugate
pH

base of NH4+ and if the reaction in water is written like the weak 5.0 Soil no.
acid reactions above: 2
16
4.0 23
51
NH 4 + = H + + NH3(aq ) . (19.14) 53

3.0
32 28 24 20 16 12 8 4 0 4 8 12 16 20 24 28 32
The pKa of this reaction is 9.5 (Stumm and Morgan, 1996) and in H2SO4 CaCO3
all except the highest pH soils, the reaction goes to the left con- cmolc kg–1
suming protons. This reaction creates localized pH values near
FIGURE 19.1  Titration of surface soils from Vermont, U.S.A, with
anhydrous ammonia injection bands that can be >9.5 (Havlin H2SO4 and CaCO3. The acid and base (CaCO3) additions are reported
et al., 2005). per gram of soils. The pHCaCl2 was measured after a 30-day reaction at
Dissolution and hydrolysis of urea fertilizer in soils can also field capacity moisture content. (From Magdoff, F.R., and R.J. Bartlett.
produce localized high concentrations of NH3(aq) that can result 1985. Soil pH buffering revisited. Soil Sci. Soc. Am. J. 49:145–148. With
in localized high pH. Fertilizer granules hydrolyze readily due permission of Soil Science Society of America.)
Soil pH and pH Buffering 19-5

TABLE 19.1  Reactions of Solid-Phase Soil Components That Buffer pH in the Range of 3.5–9.5
pH Buffer Substance pH Range Proton Acceptor or Donation Reactions
Limestone, CaCO3 7–9.5 Dissolution and precipitation
Oxides and hydroxides of Fe and Al; silicate clay edges Whole pH range H+ adsorption and desorption on surface hydroxyl sites
H+–SOM Whole pH range Dissociation and protonation of carboxyl and phenol groups
Al-SOM and Al(OH)3(s) 5–8 Precipitation of organic bound Al3+ as Al(OH)3 or dissolution of
Al(OH)3 by organic acids
Al3+/H+-exchange in SOM Less than 4.5 H+ exchange with Al3+ on carboxyl and phenol groups
Al(OH)3 4–5.5 Al(OH)3 dissolution/precipitation in soils with very low SOM content
Silicate clay interlayer Al(OH)n3−n in 2:1 clays 4.2–7 Hydrolysis and precipitation or dissolution of interlayer Al(OH)3
Permanent charge silicate clays 3.5–4.2 Ion exchange of H+ and Al3+
Irreversible dissolution of high-activity 2:1 silicate clays Less than 3.5 Consumes H+ upon release of Al3+ from reactive silicates
and poorly ordered aluminosilicates
Very slow irreversible weathering primary silicate minerals Whole pH range Consumes H+ upon dissolution of Ca2+, Mg2+, K+, and Na+ from
primary minerals
Source: Bloom, P.R., U.L. Skyllberg, and M.E. Sumner. 2005. Soil acidity, p. 411–460. In A. Tabatabai and D. Sparks (eds.) Chemical processes in soils.
SSSA, Madison, WI.

by Ulrich (1991), with modifications and additions. For example, 10

Ulrich did not include soil organic matter (SOM) and reactions
A. Peat humic acid III
on oxide and hydrous oxide surfaces. The buffer reactions in Table 9 B. Soil humic acid
19.1 will be discussed in more detail in Sections 19.5 through 19.9.

19.5  Buffering by Soil Organic Matter 8

II

Soil organic matter is a very important component of pH buffer-

7
ing in surface soils, even in typical upland soils that contain only
a few percent organic matter. Like the soluble organic compo-
pH

nents in soil solution discussed in Section 19.3.1, SOM contains 6

carboxyl and phenolic groups that can donate protons. Most of I
the acidity in SOM is contributed by the humidified compo-
nents, operationally defined as humic and fulvic acid. In soils, 5
B
A
some of the weak acid sites exchange protons with Al3+, which
alters the proton donation behavior of SOM. Based on chemical 4
analysis of humic and fulvic acids extracted from SOM (Chapter
11) various organic acids have been proposed to represent the
acidity of carboxyl and phenolic sites in SOM. Most of the acid- 3
ity is thought to arise from carboxyl and OH groups bound to 0 0.04 0.08 0.12 0.16 0.20 0.24
aromatic ring structures, which can be represented by benzoic Base added, mmolc
acid (Ar–COOH, pKa = 4.2) and phenol (Ar–OH, pKa = 10.0),
FIGURE 19.2  Titration of 2 humic acids with strong base. (From
where Ar is an aromatic ring (Smith et al., 2004). Stevenson, F.J. 1994. Humus chemistry: Genesis, composition, reactions,
Soil organic matter buffers pH over a wider range of pH val- 2nd Ed. Wiley, New York. Copyright Wiley-VCH Verlag GmbH & Co.
ues than predicted by a simple mixture of benzoic acid and phe- KGaA. With permission.)
nol. The titration plots for two humic acids with an alkali metal
hydroxide shown in Figure 19.2 illustrates that maximum buff- macromolecular structures and this charge reduces the proton
ering (minimal slope) is in the pH range of 4–6. At very low pH, donation ability of humic and fulvic acids at high pH values
the plots in Figure 19.2 have very low slopes because of the effect (McBride, 1994). The ionization of carboxyl groups is generally
of dilution of acid on H+ concentration as presented on a log (pH) complete at pH 8 and the ionization of phenolic groups is com-
scale. And at pH > 8.5, the buffering due to phenolic groups con- plete at pH 11. Thus, common methods for determination of car-
tributes to the low slope. A broadening of the buffering response boxyl acidity involve titrating to pH 8; and for the determination
occurs because the aromatic ring structures of the humic acid and of the phenol titration to pH in excess of 11 (Stevenson, 1994).
fulvic acids are polysubstituted with carboxyl –COOH and phe- The negative charge sites produced by the ionization of the weak
nolic –OH. This shifts the pKa values, resulting in aromatic ring acid sites on humic and fulvic acids bind exchangeable cations.
structures with wide ranges of individual pKa values. Also, with Organic matter contributes much of the pH-dependent cation
the ionization of the acid sites, negative charges accumulate on exchange capacity (CEC) to soils (Chapter 16).
19-6 Properties and Processes

In this calculation, the CEC value is determined at a reference

pH of 7 or 8 (Bloom and Grigal, 1985; Ross et al., 2008). In
8
less-acidic and neutral soils, the most abundant base cation
is Ca 2+.
7
As soils are acidified, base cations are displaced and the BS
value decreases. At pH values less than 5, the BS is low and pro-
6 tons can displace soil adsorbed Al3+ ions. This reaction results in
a decrease in pH without a decrease in BS because H+-saturated
pH

5 SOM is a stronger acid than Al-saturated SOM. At pH less than

4.5, this exchange can add very significant quantities of Al3+ to
4 soil solution. At these low pH values, where hydrolysis of Al3+ is
0 μmol Al–1 not very significant Al3+ is acting more like a base cation. In the
179 μmol Al–1
3
high acid A and O horizons typical of many forest soils of north-
519 μmol Al–1
ern temperate and humid tropical regions, plots of BS  vs. pH
show a better positive correlation with BS when Al3+ is included
2
0 600 1200 1800 as a base cation than if it is included as an acid cation (Skyllberg,
mmol KOH kg–1 1994, 1999; Ross et al., 2008).
SOM provides much of the pH buffering in most surface soils
FIGURE 19.3  Titration of Al-SOM containing different contents of
Al3+. (From Hargrove, W.L., and G.W. Thomas. 1982. Titration properties
and much of the CEC. Helling et al. (1964) estimated the mean
of Al-organic matter. Soil Sci. 134:216–225. With permission of Wolters CEC of SOM in 60 mineral soils of Wisconsin, USA, at pH 8, to
Kluwer Health.) be 2000 mmolc kg−1 of SOM. This value is the equivalent to the
value for the titration of the acid form of organic matter with
Ca(OH)2 to pH 8 and provides a reasonable estimate for the
The binding of Al to acid functional groups in SOM is impor- capacity of SOM in mineral soils to buffer pH in the range of
tant both for Al chemistry and for pH buffering. In acid mineral 3–8. With the exception of CaCO3, the pH-buffering capacity
soils, many of the carboxylate sites in SOM are bound to Al3+. of SOM is equal or greater than other components in the soil
This bonding is strong enough that only a small fraction of the (Table 19.2). Another indication of the importance of SOM for
Al can be extracted with 1 M KCl (Bloom et al., 1979), and most buffering in soils is the results after adding H 2SO4 and CaCO3
authors consider Al (and H+) bound to SOM to be nonexchange- to 51 surface soils (Magdoff and Bartlett, 1985). They took
able (Bertsch and Bloom, 1996). This strongly bound Al has a the data, including the four soils in Figure 19.1, and replot-
large effect on buffering. Hargrove and Thomas (1982) titrated ted it normalized to equivalent SOM contents. This yielded a
SOM with varying Al3+ contents and found that the pH buff- single plot (Figure 19.4) for soils of differing organic matter
ering of the Al3+-treated SOM occurred at higher pH than for contents suggesting that in these northern temperate region
H+-saturated SOM (Figure 19.3). Aluminum-saturated SOM is a surface soils, the pH buffering is a function mostly of organic
weaker acid than H+-saturated SOM. matter content.
As the pH of Al-SOM is raised to greater than about 5, the
Al3+ in solution exceeds the solubility of Al(OH)3 and precipita-
tion of amorphous Al(OH)3 occurs (Walker et al., 1990). This
can be illustrated by TABLE 19.2  Approximate Maximum Proton Donation or
Adsorption Capacity of Soil Materials in the pH Range of 3.5–8
2Al(RCOO)3 + H2O = 3RCOO− + 3H + + Al(OH)3(s) . (19.16) Soil Material Capacity, mmol kg−1 References

This reaction is reversible and when the pH is lowered Al(OH)3 Silicate clays
dissolves and Al again becomes bound to organic matter. As with Smectites 800–1,500 McBride (1994)
H+-SOM, increasing of pH by adding a base increases surface Vermiculite 1,500–2,000 McBride (1994)
charge and the organic matter becomes more saturated with the Illite 200–400 McBride (1994)
cation of the base. In humic materials, except at very low pH, the Kaolinite 10–50 Thomas and Hargrove (1984)
pH is positively correlated with the saturation of cation exchange SOM 2,000 Helling et al. (1964)
sites with the Ca2+, Mg2+, Na+, and K+; all cations of strong bases. Allophane and 200–500 Wada (1989)
imogolite
In soil science, these are called “base cations” and a base satura-
Hydroxides and 50–400 Borggaard (1983)
tion (BS) value, which is positively correlated to pH, can be cal- oxides of Fe and Ala
culated as a sum of charges of base cations divided by the CEC: CaCO3b 20,000 Stumm and Morgan (1996)

2Ca 2+ 2+
+ 2Mg + Na + K
+ + a Based on linear extrapolation between pH 8 and 3.5 of the data for hematite
BS = . (19.17) and goethite.
CEC b The precipitation and dissolution of CaCO takes place at pH 7 or greater.
3
Soil pH and pH Buffering 19-7

8.0 8

7.0
7

6.0
Al Mont. in H2O
pH

5.0 6

pH
4.0
5
3.0
–8 –6 –4 –2 0 2 4 6 8
OM basis amendment rate
Acidity and basicity added, mmolc g–1 Al Mont. in 10–3 M CaCl2
4
FIGURE 19.4  pHCaCl2 after a 30-day reaction of 51 soils from Vermont,
U.S.A, with varying additions of H2SO4 and CaCO3. The acid and base
addition are reported per gram of SOM. The data for all of the soils were
3
adjusted along the x-axis to coincide with the zero addition pH for soil 0 200 400 600 800
51 (see Figure 19.1). (From Magdoff, F.R., and R.J. Bartlett. 1985. Soil pH mmol OH– kg–1
buffering revisited. Soil Sci. Soc. Am. J. 49:145–148. With permission of
Soil Science Society of America.) FIGURE 19.5  Titration of an Al saturated montmorillonitic clay
with NaOH with and with without the addition 0.001 M CaCl 2 . (From
Turner, R.C., and W.E. Nichol. 1962. A study of the lime potential: 2.
19.6  Proton and Al Exchange Relation between the lime potential and percent base saturation of nega-
tively charged clays in aqueous salt suspensions. Soil Sci. 94:58–63. With
in Silicate Clays
permission of Wolters Kluwer Health.)
Ion exchange reactions on permanent charge sites in silicate
clays can contribute to pH buffering (for a detailed discussion smectite (HIS), and in the case of vermiculite, this produces
of ion exchange in clays see Chapter 16). The pH buffering by hydroxy interlayer vermiculite (HIV) (Chapter 21). Because the
permanent charge on clays can involve exchange of hydronium precipitation of interlayer Al(OH)3 blocks Al3+ in the interlayer
ions, H3O+, but the exchange of Al3+ is much more significant. from reacting with the base, the titration end point in Figure 19.5
High-activity clays; smectites, vermiculites, and illites, when is less than the CEC of the clay, which is 800 mmolc kg−1.
saturated with H+ have very low pH values and are not stable. As with SOM, buffering in Al3+-saturated clays can be
When montmorillonite, a smectite, is saturated with H+ the pH described as function of BS, assuming that both H+ and Al3+ are
is less than 3.5. After 24 h of aging, acid dissolution of the clay acid cations and that Al3+ cations represent 3 mol of acidity per
structure produces Al3+ ions resulting in an increase in pH and mole of Al3+. This is a usable generalization at pH values high
replacement of the exchangeable H+ ions with Al3+ (Coleman and enough for Al3+ to hydrolyze and act like an acid cation. In con-
Craig, 1961). Aluminum clays are proton donors because of the trast, studies of very acidic surface soils from northern temper-
ability of Al3+ on clay exchange sites to hydrolyze and to precipi- ate forests have shown that at pH values less than 4.5, Al3+ should
tate as Al(OH)3, but they are weaker proton donors than H+ clays. be treated as a base cation (Skyllberg, 1994; Ross et al., 2008).
Extraction of acid soils with neutral salt solutions, for example, The capacity of silicate clays to buffer pH varies widely because
1 M KCl, yields mostly Al3+ not H+ (Thomas and Hargrove, 1984). of the large difference in the CEC of clays (Table 19.2). Kaolinite,
Titration of Al3+ montmorillonite (Figure 19.5) shows that at a low-activity clay, has little or no permanent charge and has
pH(H2O) values in the range of 5–6, the Al3+ on permanent charge little capacity to buffer pH (Chapter 21). Illite has a much greater
sites strongly buffers pH (Turner and Nichol, 1962). Data in CEC and is a much more effective buffer of pH. Smectites and
Figure 19.5 also show that as in soil, the measured pH in CaCl2 is vermiculites are even more effective in buffering pH. Among the
lower than the pH in water. silicate clays, only the highest charge vermiculites approach the
When base is added to an Al3+-saturated smectite or vermicu- buffer capacity of SOM.
lite, the initial reaction is the hydrolysis of Al cations on exchange
sites (Bloom et al., 1977), but with sufficient addition of strong 19.7  pH-Dependent Charge Buffering
base, the Al3+ will eventually precipitate as Al(OH)3 in the inter- by Mineral Components
layer space in the clay, accounting for much of the clay-mediated
buffering at pH > 5. Because of OH− deficiencies in interlayer Like SOM, oxides and hydroxides of Fe(III) and Al, and poorly
Al(OH)3, the interlayer can neutralize the negative charge on crystalline aluminosilicates, contribute to the pH-dependent
the clay. In the case of smectite, this produces hydroxy interlayer charges in soil and to pH buffering. In addition, the edges of
19-8 Properties and Processes

crystalline silicate clays make a minor contribution to pH- 1M

dependent charge (Chapter 16.) Unlike SOM, these materials –40
have surfaces that are both proton donors and proton acceptors. 10–1 M

10–2 M
19.7.1  Oxides and Hydroxides of Iron –20 †
and Aluminum 10–3 M
†

Adsorption density (ΓH-ΓOH) μmol g–1

The oxides and hydroxides of Fe(III) and Al that accumulate 10–4 M
in response to weathering are particularly important for pH †
buffering highly weathered soils (Uehara and Gillman, 1982).
0
Common iron minerals in soil include hematite (α-Fe2O3), goe-
thite (α-FeOOH), and ferrihydrite (Fe5O7 4H2O) (Chapter 22). By †
far the most common aluminum hydroxide mineral is gibbsite, †
Al(OH)3. In water, the hydrated surfaces of these oxides and
hydroxides contain strongly bound OH groups that can act both +20 †
as proton donors and proton acceptors. For hematite, the surface
hydration reaction is

Surface Fe2O3 + 3H2O = Surface 2Fe(OH)3 . (19.18) †

+40
The strong bonding of the O atom to Fe(III) and Al weakens
†
the bond of the proton to the O atom, making the surface-OH
groups weakly acidic and at high pH, the metal-bound hydrox-
†
ide groups can donate proton creating negative surface charges +60
(McBride, 1994):
5 6 7 8 9 10 11
pH
Surface FeOH = Surface FeO − + H + . (19.19)
FIGURE 19.6  Titration of Fe2O3 with KOH and HNO3 in suspensions
containing different concentrations of KNO3. (With permission from
This reaction can also be written as an adsorption of OH−: Parks, G.A., and P.D. de Bruyn. 1962. The zero point of charge of oxides.
J. Phys. Chem. 66:967–963. Copyright 1962 American Chemical Society.)
Surface FeOH + OH − = Surface FeO − + H2O. (19.20)

unlike silicate clays and organic matter the net surface charge of
Also these surface-OH groups can accept protons at low pH to these materials is positive in all except alkaline pH soils.
become positively charged:
19.7.2  pH-Dependent Charges on Silicate

Surface FeOH + H + = Surface FeOH2 + . (19.21) Clay Edges
The layer structure of silicate clays includes an AlOH layer with
Surface adsorption of H+ and OH− is quantified by titrating oxide exposed hydroxyl groups on the edges of the structure (McBride,
suspensions in Na+ or K+ salts of anions that do strongly adsorb 1994). These Al hydroxyl groups can adsorb or desorb protons,
to the oxide surfaces (e.g., NO3−). The data of Parks and de Bruyn but because of the influence of the Si4+ ions in the structure, the
(1962) illustrate typical titrations for oxide suspensions (Figure pznc is lower than for gibbsite. For example, a reported value for
19.6). These data show the effects of increasing KNO3 concen- the pznc for the edge of kaolinite is 2.9 (Chapter 15). This means
tration on the quantity of H+ or OH− adsorbed. McBride (1994) the edge charge can contribute to the negative charge in soils.
explains this effect, in a KNO3 solution, as due to K+ displace- For high-charged clays like smectites and vermiculite, this edge
ment of H+ at high pH and the NO3− displacement of OH− at low charge is small compared to the permanent structural charge.
pH. At pH values less than 7, the oxides and hydroxides of Al and For example, for a smectite at pH 8, the pH-dependent negative
Fe are positively charged, and these surfaces are anion exchang- charge is about 50 mmolc kg−1 compared to a permanent charge
ers while at pH greater than 9 they are cation exchangers. At pH of about 750 mmolc kg−1 (McBride, 1994).
values in the range of 7–9, a point is found where the concentra-
tion of salt in solution has no effect on the pH. This is the point at
19.7.3  Imogolite and Allophane
which the net charge on the surface is zero; the point of zero net
charge (pznc, also called the point of zero salt effect). For oxides Allophane and imogolite are aluminosilicates that like silicate
and hydroxides of iron and aluminum, almost all measured clay edges have pH-dependent charge surfaces. Allophane is
pznc values are in the range of 7–9 (Chapter 15), meaning that noncrystalline, not having long-range ordering in the structure,
Soil pH and pH Buffering 19-9

and imogolite, which forms long tubes (Chapter 23; Wada, 1989) Inskeep and Bloom (1986) showed that in pots with growing
is a paracrystalline mineral with some disorder in the structure. soybean plants the PCO2 ranged from 0.0006 atm in drier soils to
Both of these materials are found in abundance in young vol- 0.031 atm at moisture contents approaching saturation. By the
canic soils. They are also found in some young soils in glacial principle of Le Chatelier (the mass action principle), Reaction
parent material (e.g., spodosols in northern forests). Imogolite 19.22 will be shifted to the left when PCO2 is raised, resulting in an
and allophane have pznc values in the range of 5.5–7 (Clark and increase in (H+) and a decrease in pH.
McBride, 1984; Wada, 1980). In soils, bicarbonate concentrations are commonly not equal
to twice the concentration of Ca 2+ because there can be other
19.8  Buffering by Dissolution and sources of HCO3− and Ca 2+ than dissolution of calcite by car-
bonic acid. When the chemistry of a calcareous soil is dominated
Precipitation of Carbonates by calcium salts other than bicarbonate, 2[Ca 2+] can be much
Carbonates are very important for pH buffering in nonacid soils. greater than [HCO3−] and pH is much less than 8.3, even at low
Calcite, CaCO3, and dolomite, CaMg(CO3)2, are common com- PCO2. Thus, calcareous soils containing gypsum (CaSO4 · 2H2O),
ponents of soil parent materials in many soils. With sufficient where [Ca 2+] is elevated by gypsum solubility, pH can be as low
rainfall and good drainage, these minerals weather from soils. as 7.0. In some arid regions, input of Mg2+, Na+, and HCO3−
In arid regions and in some areas in humid regions with poor results in concentrations of HCO3− much greater than twice
drainage, however, CaCO3 can accumulate in soils (Chapter 30; [Ca 2+] and calcareous soils can have pH values as high as 9.5.
Doner and Lynn, 1989). Under some conditions in arid regions, In arid regions, where Mg accumulates, and hydrated MgCO3
MgCO3, which is much more soluble than calcite, can accumu- forms, pH is greater than 8.5 because magnesium carbonate is
late. Calcite acts as proton acceptor according to much more soluble than CaCO3.
Calcareous soils are very strongly buffered against acidifica-
CaCO3 + 2H + = Ca 2 + + H2O + CO2 tion. One kilogram of CaCO3 can neutralize 20,000 mmol of H+
and hold pH at a value greater than 7 until all of CaCO3 is dis-
log K = 9.73 (Stumm and Morgan, 1996). (19.22) solved. Thus, CaCO3 is a much more effective buffer than SOM

or any other component in soil (Table 19.2). If CaCO3 is com-
The equilibrium equation for this reaction is pared with SOM on the basis of buffering against a decrease in
pH from 8.0 to 7.0, the difference is even greater than shown in
(PCO2 ) Table 19.2. This pH drop would result in the total dissolution of
K = (Ca 2 + ) . (19.23)
(H + )2 CaCO3 but would only neutralize about 200 mmolc kg−1 of SOM,

about one-tenth of the total buffer capacity of SOM. Because of
Calculation of this equilibrium requires knowledge of the CO2 the high buffer capacity of the CaCO3, calcareous soils are con-
content in the soil atmosphere, expressed in units of partial pres- sidered to be unaffected by acid rain and it is generally consid-
sure (P). At 1 atm total pressure, the value of partial pressure is ered impractical to artificially lower the pH of calcareous soils to
equivalent to the volume fraction in the air. This equilibrium, allow for the growth of acid-loving plants.
rewritten in a form that shows how CaCO3 weathers from cal-
careous soils, is
19.9  H+ Consumption by Irreversible
2+
CaCO3 + H2CO3 = Ca + 2HCO3 log K = −7.42. (19.24) Weathering of Aluminous Minerals
−

The buffering reactions discussed above are all reversible and
In soils, the CO2 produced by soil microbial and root respiration
can to some degree be described using equilibrium equations.
dissolves CaCO3 to produce calcium bicarbonate and over time
Some reactions that consume H+ in soils, however, are irrevers-
CaCO3 will weather out of well-drained soils.
ible. These reactions include the weathering of primary alumi-
The pH in soils that contain calcite varies widely. In a CaCO3
nosilicate minerals and the destruction of high-activity clays in
suspension in distilled water in equilibrium with the ambient
very low pH soils.
atmosphere (PCO2 ≈ 3.8 × 10 −4 atm ) will contain two bicarbonate
ions in solution for every Ca 2+ ion and the pH will be 8.3 (Stumm
and Morgan, 1996). Because the PCO2 in soils is greatly increased due
19.9.1  Weathering of Primary Silicates
to microbial and root respiration, soil solution in equilibrium with
calcite will have pH values considerably lower than 8.3 (Inskeep Over the very long term, the weathering of primary alumino-
and Bloom, 1986). The effect of PCO2 on soil pH varies due to differ- silicate minerals from soil parent material consumes protons
ences in the rate of soil respiration and the rate of gas exchange with (Chapter 20). These reactions are irreversible for most primary
the atmosphere. Gas exchange varies with depth and quantity minerals because these minerals only form at the high temper-
of air-filled pores in a soil, and PCO2 increases with depth and atures involved in rock-forming processes. An example of the
after rainfall fills soil pores with water (Flechard et al., 2007). weathering of a primary mineral is the reaction of the feldspar
19-10 Properties and Processes

anorthite to form kaolinite in acid soils. This reaction consumes negatively impact poorly buffered forest soils and the acidifying
two protons for every mole of calcium mobilized: effects depend on the capacity of soils to buffer the long-term
input of very dilute HNO3 and H2SO4 (Bloom and Grigal, 1985;
CaAlSiO8 + H2O + 2H + → 1 Al 2Si 2O5 (OH)4 + Ca 2 + . (19.25) Ulrich, 1991; Watmough and Dillon, 2004).
2
anorthite kaolinite
19.10.1  Total Titratable Acidity
The rates of weathering reactions depend on the type of pri-
mary mineral and the surface area exposed to soil solutions The total acidity in acid soils is operationally defined as con-
(Bloom and Nater, 1991). This means that, per unit mass, silt- sisting of two components, salt-replaceable (exchangeable)
sized particles weather much more rapidly than sand-sized and residual (nonexchangeable) acidity (SSSA, 2008). Salt-
particles. The rates of aluminosilicate dissolution reactions replaceable acidity is the H+ and Al3+ extractable with 1 M KCl,
are pH dependent and at pH values typical in soils, alumino- while the residual acidity is the acidity that is titratable in a soil
silicates dissolve more rapidly at lower pH (Bloom and Nater, suspension but is not easily replaceable with KCl (Bertsch and
1991; Sposito, 2004). Over time periods of less than decades, Bloom, 1996). In practice, the residual acidity is determined by
weathering of primary silicate minerals is generally not signifi- the difference between the total acidity neutralized by raising
cant in buffering pH. the pH of a soil to a reference pH, usually 7.0 or 8.0, and the salt-
replaceable acidity.
Total acidity can be determined by the titration of a soil sus-
19.9.2  H+ Consumption by the Destruction pension in a salt solution to the reference pH using a strong base
of High-Activity Clay or by the addition of increments of CaCO3 as shown in Figure
When the pH(H2O) of a soil is decreased to values less than about 19.1. This produces a plot of the pH vs. the quantity of base con-
3.5, high-activity clays can dissolve quite rapidly consuming sumed, but the response to titration with strong base and to
protons and releasing Al3+ into solution. As discussed in Section CaCO3 additions is slow, and other laboratory methods are usu-
19.6, H+-saturated high-activity clays have pH values less than ally used. A standard method for relatively rapid determination
3.5 and dissolve to release Al3+. At this pH, Al(OH)3 is too soluble of total acidity is to react a soil for several hours or overnight
to form in soils and kaolinite forms slowly, so high-activity clays with a solution containing 0.5 M BaCl2 plus a triethanolamine
tend to dissolve congruently (no solid phase is formed in the (TEA) buffer adjusted to pH 8.0 or 8.2 (Thomas, 1982). TEA is
reaction). For a Ca 2+ montmorillonite well buffered at pH 8 and the solution contains Ba 2+ to displace
acidity from soil components. A reference pH of 8.0 or 8.2 is used
to represent the pH attained when a soil is limed with excess
Ca 0.167 (Al1.67 Mg 0.333 )Si 4O10 (OH)2 + 6H + + 4H2O
lime. From a more fundamental point of view, pH 8 is a good
→ 0.167Ca 2 + + 0.167Mg 2 + + 1.67Al 3 + + 4Si(OH)4 (19.26) choice because this is the end point for the titration of organic
carboxyl acidity, as well as the Al3+ acidity bound to clays. With
the BaCl2–TEA method, the total acidity is calculated as the dif-
where five of the six protons consumed are due to the release of ference in the quantity of H+ needed to titrate the BaCl2–TEA
Al3+ from the structure of the clay. This reaction likely accounts solution to a pH of about 5, using a pH indicator dye, before and
for much of the very strong buffering at pH 3.5 that was observed after reaction with a soil. This difference represents the quantity
by Magdoff and Bartlett (1985) when they added H2SO4 to soils of acidity that reacts with the TEA buffer.
(Figures 19.1 and 19.3). An alternative method for the calculation of total acidity is the
difference between the CEC determined at pH 7.0 with ammo-
nium acetate and the sum of exchangeable bases. Determination
19.10  Determination of Buffer of CEC at pH 7.0 is the method most often used in the classifi-
Capacities cation of soils (Burt, 2004). In this method, soil is reacted with
an ammonium acetate solution at pH 7.0, the excess ammonium
The determination of the capacity of soils to buffer pH has long acetate is leached from the soil, and the NH4+ ions bound to cat-
been an interest of soil chemists. Many crops respond positively ion exchange sites are extracted with a salt solution and quanti-
to the addition of lime to acid soils, but because of the differ- fied (Sumner and Miller, 1996; Burt, 2004). Subtraction of the
ences in buffer capacity, soils of similar pH may require vastly exchangeable bases from the pH 7.0 CEC represents the total
different quantities of lime to yield the same increase in pH. acidity referenced to pH 7.0.
Horticulturists have also been concerned with decreasing the
pH of nonacid soils and they use aluminum sulfate or elemental
19.10.2  Lime Requirement
S to allow for the vigorous growth of acidophilic plants (e.g., aza-
leas, rhododendron, and blueberries). As with liming, the quan- Development of the recommendations to growers for the lim-
tity of acidifying agent necessary to lower the pH of a soil by a ing of an acid soil with ground calcitic or dolomitic limestone
given amount depends on the buffer capacity. Also, acid rain can (agricultural lime) requires a quick and easy method for the
Soil pH and pH Buffering 19-11

determination of the quantity of base needed to raise the soil flask is carefully reweighed. The content of carbonate is calcu-
pH to an optimum value for a given crop (Bloom et al., 2005; lated assuming all of the carbonate is CaCO3 with a formula
Fageria and Baligar, 2008). Because crops differ in sensitivity to weight of 100 g mol−1. For soils that have less than 2% or 3%
soil acidity, recommendations for liming may differ with crop. carbonate, the weight loss method is not accurate (U.S. Salinity
The most common methods used in the United States involve Laboratory Staff, 1954; Loeppert and Suarez, 1996).
the reaction of a mixed buffer solution with a soil and after a Determination of the evolved CO2 provides a more accurate
period of reaction, measurement of the equilibrium pH (Godsey and precise measure of calcium carbonate (Loeppert and Suarez,
et al., 2007). The commonly used Mehlich method uses a mixed 1996). Commonly used methods involve the determination of
buffer solution containing acetate, glycerophosphate and TEA, the pressure increase in a closed cell using an Hg manometer
in BaCl2, that provides for a linear buffer response to acidity at or pressure transducer CO2 (Williams, 1949; Martin and Reeve,
pH values ranging from 4 to 6.5 (Mehlich, 1976; Hoskins and 1955; Skinner et al., 1959; Evangelou et al., 1984) or the gravi-
Erich, 2008). This solution has been modified by replacing the metric determination of CO2 collected in a magnesium perchlo-
Ba with Ca to avoid the use of toxic substances (Godsey et al., rate trap (Loeppert and Suarez, 1996).
2007; Hoskins and Erich, 2008). The pH of the buffer mixture
is adjusted to 6.5 and the lime requirement is determined from
19.10.4  Determination of the Buffering
the pH after reaction with a soil using regression equations for
of H+ Inputs in Noncalcareous Soils
different target pH values. At lower equilibrium pH, the lime
requirement is greater. The regression equations are developed Routine laboratory methods have not been developed for the
using the pH response of acid soils to known additions of CaCO3 determination of the capacity of soils to buffer against acidifi-
(Hoskins and Erich, 2008). Hoskins and Erich (2008) showed cation. However, addition of increments of acid with long-term
that the inclusion of a soil pH(H2O) term increased the correla- incubation, as used by Magdoff and Bartlett (1985), can be used
tion coefficient of the regression. The Shoemaker–McLean–Pratt to determine the response of soils to acid additions (Figures 19.1
(SMP) mixed buffer method is also commonly used (McLean and 19.4). An alternative method is to equilibrate soil suspensions
et al., 1977), but this method is decreasing in acceptance because repeatedly with dilute acid. Bloom and Grigal (1985) suspended
it contains two toxic buffers, p-nitrophenol and chromate, and soils in 2.5 × 10−4 M H2SO4 for 24 h decanted and repeated 13
tends to cause plugging of liquid junctions of pH electrodes times. By measuring the pH of the equilibrated solutions, they
(Hoskins and Erich, 2008). Other mixed buffer methods for were able to determine the quantity of protons adsorbed due to
determination of lime requirement include those of Adams and pH buffering in the soil. They were also able to determine the
Evans (1962), Woodruff (1948), and Nômmik (1983). Al3+ and base cation losses in each treatment. This method much
In areas of the world where highly weathered soils are domi- more closely simulates the response to acidic deposition (acid
nant, it is common to base lime recommendations on the reduc- rain) with the resultant loss of bases and Al3+. Bloom and Grigal
tion of Al3+ saturation of the effective CEC, calculated as the sum (1985) used their plots of pH response to acid to test a numerical
of bases plus 1 M KCl extractable acidity (Fageria and Baligar, model for the response of soils to acidic deposition.
2008). When lime is added, Al3+ precipitates to form insolu-
ble Al(OH)3, decreasing Al3+ toxicity. To determine the lime 19.11  Soil Acidification
requirement, the 1 M KCl replaceable Al3+ acidity is calculated
as three times the molar quantity of extracted Al and this acidity, Soil acidification occurs as a natural process during soil for-
expressed in units of cmolc kg−1, is multiplied by a factor to calcu- mation. With sufficient inputs of acid rain to poorly buffered
late the lime requirement in Mg ha−1. The factor varies from 1, soils, natural acidification can be very significantly acceler-
or less, in sandy soils to greater than 3 in very clayey soils. Also ated (Bloom and Grigal, 1985; Ulrich, 1991). Much more rapid
an adjustment for exchangeable Ca 2+ and Mg2+ is used to yield a acidification is produced by the addition of ammonium-forming
lime requirement, even for low acidity soils, if a soil is low in Ca nitrogen fertilizers. Even more rapid acidification is produced by
and Mg. These two ions are often deficient for plant growth in the oxidation of sulfur and sulfur compounds added to soils or
highly weathered soils (Fageria and Baligar, 2008). of sulfur compounds deposited by natural processes in coastal
wetland soils that are exposed to oxidation when the water table
is lowered by artificial drainage.
19.10.3  Calcium Carbonate
Concentrations in Soil
19.11.1  Natural Acidification
The quantity of calcium carbonate in soils is generally deter-
mined by methods that measure the CO2 evolved after add- Under conditions of good drainage and rainfall sufficient to
ing acid or the weight loss due to CO2 loss. In the weight loss produce leaching, H2CO3 and soluble organic acids cause the
method, carefully weighed soil samples are added to weighed very slow acidification of soils that occurs during natural soil
flasks containing 3 M HCl and loosely covered with a rubber weathering. At pH values of about 6 and greater, the donation of
stopper (Loeppert and Suarez, 1996). The flask is swirled and protons by the reaction of H2CO3 to produce HCO3− (Reaction
uncovered periodically until all of the CO2 is evolved and the 19.13) is the predominant acidifying reaction. As the pH is
19-12 Properties and Processes

decreased to values much lower than the pKa (6.35), H2CO3 is a Under these conditions, soil pH values of less than 3 are pos-
less effective proton donor and organic acids, having lower pKa sible. This reaction has produced large areas of acid sulfate soils
values, are the predominant proton donors. In calcareous soils, in Vietnam, Malaysia, and Indonesia (Sanchez, 1976).
CaCO3 dissolution buffers the pH at values greater than 7 until it Acidification of nonacid soils for the growth of acid-loving
is all leached from the soil. (acidophilic) plants can be accomplished using elemental S.
Bacterial oxidation produces a similar effect as for the oxidation
of pyrite (Slaton, 2001):
19.11.2  Acid Rain
The dry aerosol and wet acid deposition that makes up what S + 3 2 O2 + H2O = H2SO4 . (19.29)
is popularly called acid rain contains sulfuric and nitric acid
plus NH4+ that can be oxidized in soil to produce nitric acid
(Sparks, 2003). Under preindustrial conditions, these acids were Growers using elemental S must be very careful because pH val-
of minor importance in determining the composition of soil ues of 3.5 are easily attainable when excess sulfur produces too
solutions. Industrialization has resulted in elevated strong-acid much sulfuric acid (Leitzke and Peterson, 1987) (Figure 19.4).
acidity in rainfall, which can have long-term negative impacts An alternative method is to add aluminum sulfate, Al2(SO4)3,
on poorly buffered soils in forests and other natural areas which produces acidity according to the reaction:
(Bloom and Grigal, 1985; Ulrich, 1991). Since the concentration
of acidic components of acidic deposition is small compared Al 2 (SO4 )3 + 6H2O = 2Al(OH)3 + 3H2SO4 . (19.30)

to soil buffering, even in poorly buffered soils, soil acidifica-
tion is difficult to document by field-based observations and
The lower pH generated by aluminum sulfate is limited by the
contradictory results have been reported (Courchesne et al.,
solubility of Al(OH)3 and pH will not be decreased below about
2005). One of the major difficulties is the spatial variability in
4.5 but excessive aluminum sulfate can induce Al3+ toxicity
soil properties (Likens et al., 1998). Studies that have shown
problems for plant growth (Leitzke and Peterson, 1987).
significant soil acidification that appears to be due to acid rain
include the work of Courchesne et al. (2005), who reported a
statistically significant decrease in pH in the humus layer of soil References
collected from 1993 to 2002 and Watmough and Dillon (2004),
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D.L. Sparks (ed.) Methods of soil analysis. Part 3. Chemical
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19.11.4  Acidification by Sulfur Compounds
Bloom, P.R., M.B. McBride, and B. Chadbourne. 1977. Adsorption
Sulfuric acid produced in acid mine wastes or when the soils of of aluminum by smectite: I. Surface hydrolysis during
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Godsey, C.B., G.M. Pierzynski, D.B. Mengel, and R.E. Lamond. (ed.) The environmental chemistry of aluminum. Lewis
2007. Evaluation of common lime requirement methods. Publishers, Boca Raton, FL.
Soil Sci. Soc. Am. J. 71:843–850. Parks, G.A., and P.D. de Bruyn. 1962. The zero point of charge of
Hargrove, W.L., and G.W. Thomas. 1982. Titration properties of oxides. J. Phys. Chem. 66:967–963.
Al-organic matter. Soil Sci. 134:216–225. Ross, D.S., G. Matschonat, and U. Skyllberg. 2008. Cation
Havlin, J.L., J.D. Beaton, S.L. Tisdale, and W.L. Nelson. 2005. Soil exchange in forest soils: The need for a new perspective.
fertility and fertilizers, 7th Ed. Prentice Hall, Upper Saddle Eur. J. Soil Sci. 59:1141–1159.
River, NJ. Rossel, R.A.V., and C. Walter. 2004. Rapid, quantitative and spa-
Helling, C.S., G. Chesters, and R.B. Corey. 1964. Contribution of tial field measurements of soil pH using an ion sensitive
organic matter and clay to soil cation-exchange capacity as field effect transistor. Geoderma 119:9–20.
affected by the pH of the saturating solution. Soil Sci. Soc. Sanchez, P.A. 1976. Properties and management of soils in the
Am. Proc. 28:517–520. tropics. Wiley, New York.
Hoskins, B.R., and M.S. Erich. 2008. Modification of the Skinner, S.I.M., R.L. Halstead, and J.E. Brydon. 1959. Quantitative
Mehlich lime buffer test. Commun. Soil Sci. Plant Anal. manometric determination of calcite and dolomite in soils
39:2270–2281. and limestones. Can. J. Soil Sci. 39:197–204.
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Skyllberg, U. 1994. Aluminum associated with a pH-increase Thomas, G.W., and W.L. Hargrove. 1984. The chemistry of soil
in the humus layer of a boreal haplic podzol. Interciencia acidity, p. 3–56. In F. Adams (ed.) Soil acidity and liming.
19:356–365. 2nd Ed. ASA, Madison, WI.
Skyllberg, U. 1999. pH and solubility of aluminium in acidic soils: Turner, R.C., and W.E. Nichol. 1962. A study of the lime poten-
A consequence of reactions between organic acidity and tial: 2. Relation between the lime potential and percent base
aluminium alkalinity. Eur. J. Soil Sci. 50:95–106. saturation of negatively charged clays in aqueous salt sus-
Slaton, N.A., R.J. Norman, and J.T. Gilmour. 2001. Oxidation pensions. Soil Sci. 94:58–63.
rates of commercial elemental sulfur products applied to Uehara, G., and G. Gillman. 1982. The mineralogy, chemistry and
an alkaline silt loam from Arkansas. Soil Sci. Soc. Am. J. physics of tropical soils with variable charge clays. Westview
65:239–243. Press, Boulder, CO.
Smith, R.M., A.E. Martell, and R.J. Motekaitis. 2004. NIST Ulrich, B. 1991. An ecosystem approach to soil acidification,
critically selected stability constants of metal complexes p. 28–79. In B. Ulrich and M.E. Sumner (eds.) Soil acidity.
database. National Institute of Standards and Technology, Springer-Verlag, Berlin, Germany.
U.S. Department of Commerce, Washington, DC. U.S. Salinity Laboratory Staff. 1954. Diagnosis and improve-
Sorensen, S.P.L. 1909. Enzyme studies: II. The measurement and ments of saline and alkali soils. USDA Handbook 60. U.S.
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Sparks, D.L. 2003. Environmental soil chemistry. Academic Press, some oxisols and alfisols of the tropics. Soil Sci. Soc. Am.
New York. Proc. 36:446–451.
Sposito, G. 2004. The surface chemistry of natural particles. Wada, K. 1980. Mineralogical characteristics of andosols,
Oxford University Press, New York. p.  87–107. In B.K.G. Theng (ed.) Soils with variable
SSSA (Soil Science Society of America). 2008. Glossary of soil sci- charge. New Zealand Soil Science Society, Lower Hutt,
ence terms. SSSA, Madison, WI. New Zealand.
Stevenson, F.J. 1994. Humus chemistry: Genesis, composition, Wada, K. 1989. Allophane and imogolite, p. 1051–1087. In J.B.
reactions, 2nd Ed. Wiley, New York. Dixon and S.B. Weed (eds.) Minerals in soil environments.
Stumm, W., and J.J. Morgan. 1996. Aquatic chemistry: Chemical SSSA, Madison, WI.
equilibria and rates in natural waters, 3rd Ed. Wiley, New York. Walker, W.J., C.S. Cronan, and P.R. Bloom. 1990. Aluminum solu-
Sumner, M.E., and W.P. Miller. 1996. Cation exchange capacity bility in organic soil horizons from northern and southern
and exchange coefficients, p. 1201–1229. In D.L. Sparks forested watersheds. Soil Sci. Soc. Am. J. 54:369–374.
(ed.) Methods of soil analysis. Part 3. Chemical methods. Watmough, S.A., and P.J. Dillon. 2004. Major element fluxes from
SSSA Book Series 5. SSSA, Madison, WI. a coniferous catchment in central Ontario, 1983–1999.
Thomas, G.W. 1982. Exchangeable acidity, p. 159–165. In Methods Biogeochemistry 67:369–398.
of soil analysis. Part 2. Chemical methods. Chemical and Williams, D.E. 1949. A rapid manometric method of the deter-
microbiological properties. ASA Monograph 9. ASA, mination of carbonate in soil. Soil Sci. Soc. Am. Proc.
Madison, WI. 13:127–129.
Thomas, G.W. 1996. Soil pH and soil acidity, p. 475–490. In Woodruff, C.M. 1948. Testing of lime requirement by means of a
Methods of soil analysis. Part 3. Chemical methods. SSSA, buffer solution and the glass electrode. Soil Sci. 66:53–63.
Madison, WI.
 III
Soil Mineralogy
Joseph W. Stucki
University of Illinois

20 Alteration, Formation, and Occurrence of Minerals in Soils  G. Jock Churchman and David J. Lowe.................... 20-1
Introduction  •  Alteration of Primary Minerals  •  Occurrence of Clay Minerals in Soils  •  Influence of Mode of
Formation upon Predictions of Properties of Soils from Their Clay Mineralogy  •  Acknowledgments  •  References
21 Phyllosilicates  Hideomi Kodama............................................................................................................................................21-1
Introduction  •  General Structural Features  •  Occurrence of Phyllosilicates  •  Phyllosilicates in Soil
Environments  •  Identification of Soil Phyllosilicates  •  Addendum  •  Appendix  •  References
22 Oxide Minerals in Soils  Nestor Kämpf, Andreas C. Scheinost, and Darrell G. Schulze................................................. 22-1
Introduction  •  Iron Oxides  •  Manganese Oxides  •  Aluminum Oxides  •  Silicon Oxides  •  Titanium and Zirconium
Minerals  •  References
23 Poorly Crystalline Aluminosilicate Clay Minerals  James Harsh................................................................................... 23-1
Structure of Poorly Crystalline Materials  •  Identification and Synthesis of Allophane and Imogolite  •  Occurrence
of Imogolite and Allophane in Natural Environments  •  Surface Charge Characteristics of Short-Range
Ordered Aluminosilicates and Variable-Charge Soils  •  Interaction of Allophane and Imogolite with Other Soil
Constituents  •  References

F
UNDAMENTAL TO THE EXISTENCE of soil is its of the so-called inert fraction react with organic matter, invok-
inorganic mineral fraction. Indeed, of all soil constitu- ing mutual alterations in the behavior of both the minerals and
ents only this one is required. Without it, soil ceases to the organic matter. Life-sustaining liquid water is held at their
be soil. Organic matter, bacteria, and fertilizer chemicals greatly surfaces and in their interstitial pores, and even retained in the
enhance various properties of the soil, but without the inorganic liquid state at very low temperatures to preserve plant life dur-
minerals, it is reduced to a soilless medium incapable of the ing hard winter months. Oxidation–reduction reactions alter
diverse range of functions that are often taken for granted. A the chemical and physical properties of the constituent Fe- and
correct and complete understanding of the soil requires, there- Mn-bearing minerals, thus creating real-time transformations
fore, an understanding of soil mineralogy. that are critical to many soil processes. Soil minerals come in a
A common misconception is that soil minerals are rather wide range of particle sizes and morphologies, which add tex-
inert, unchanging, and nonlabile. The chapters in this part ture and body to the soil, and vary in their degree of crystallin-
quickly dispel this view by painting a very different picture. They ity. Their colors are also diverse, ranging from intense reddish
will show that the soil minerals are not only diverse in their ori- brown to very light gray, or even green, yellow, or blue. They
gins, structures, and chemistry, but they provide the backbone are dynamic in their properties, constantly changing with cli-
for active chemical surfaces where many reactions are cata- mate, time, and other environmental conditions. Some changes
lyzed and basic behaviors of the soil are born and changed. As are rapid; others, slow. These attributes bring the soil to life, as
described here and elsewhere in this book, these active surfaces it were, and create the framework within which the plant and

III-1
III-2 Soil Mineralogy

animal kingdoms spring forth and are sustained through every iron, aluminum, and other (oxyhydr)oxides, which represent the
season and in every clime. more highly weathered mineral constituents; and amorphous
Minerals, the heart of the soil, are a dynamic and essential minerals, which display active chemical properties but lack high
resource, classified according to their properties. Presented in the order in their crystals. These are among the most important of
following chapters are descriptions of how minerals are formed the soil minerals. As such, knowledge of their characteristics will
and transformed. Specifics are given regarding the properties provide the basis from which a more complete understanding of
and behavior of the phyllosilicates, the plate-shaped minerals; soil physical and chemical properties may be acquired.
 20
Alteration, Formation, and
Occurrence of Minerals in Soils
20.1 Introduction............................................................................................................................20-1
20.2 Alteration of Primary Minerals............................................................................................20-2
Common Primary Minerals in Soils  •  Observations of Relative Stabilities of Primary
Minerals in Soils  •  Thermodynamic and Structural Explanations of Relative
Stabilities  •  Processes and Products of Alteration of the Main Types of Primary Minerals
by Weathering  •  Peculiarities of Processes and Products of Alteration by Weathering
in Soils  •  Processes of Mineral Alteration and Formation by Weathering: Summary
20.3 Occurrence of Clay Minerals in Soils................................................................................20-31
Occurrence of Kaolinite in Soils  •  Occurrence of Halloysite in Soils  •  Occurrence of Illite
in Soils  •  Occurrence of Vermiculite in Soils  •  Occurrence of Smectite in Soils  • 
Occurrence of Palygorskite and Sepiolite in Soils  •  Occurrence of Iron Oxides in Soils  • 
Occurrence of Manganese Oxides in Soils  •  Occurrence of Aluminum Hydroxides,
Oxyhydroxides, and Oxides in Soils  •  Occurrence of Phosphate, Sulfide, and Sulfate
Minerals in Soils  •  Occurrence of Pyrophyllite, Talc, and Zeolites in Soils  •  Occurrence
of Neogenetic Silica in Soils  •  Occurrence of Titanium and Zirconium Minerals
in Soils  •  Occurrence of Highly Soluble Minerals in Soils  •  Occurrence of Secondary
Minerals in Soils: Summary
20.4 Influence of Mode of Formation upon Predictions of Properties of Soils
from Their Clay Mineralogy.............................................................................................. 20-48
Introduction: The Role of Mineralogy in Soil Science  •  Contributions of Classical
Clay Mineralogy toward Explanations of Soil Properties  •  Potential of Classical Clay
G. Jock Churchman Mineralogy for Explaining Soil Properties  •  Nature of Soil Minerals and Relationship
University of Adelaide
to Their Mode of Formation
David J. Lowe Acknowledgments........................................................................................................................... 20-54
University of Waikato References......................................................................................................................................... 20-54

20.1  Introduction immobilizing contaminants, for supporting human-made struc-

tures, or for other purposes. However, most of the information
This chapter, like Churchman (2000), seeks to bring readers up about the formation of secondary minerals through the alteration
to date with information and understanding about the alteration of primary minerals derives from studies of largely inorganic pro-
of minerals and the nature of their products in the context of the cesses taking place in relatively “clean” environments. The soil, by
formation and development of soils. It complements the articles contrast, is a heterogeneous milieu that is a dynamic part of the
by Bergaya et al. (2006), and recent books by Velde and Meunier biosphere continually changing in response to climatic variations
(2008) and Velde and Barré (2010). This current chapter differs over all scales of time and space. It is not at all surprising that
from Churchman (2000) in that it discusses the manner in which the minerals in the soil can be quite different in their chemical
minerals, and especially secondary minerals, actually occur in and physical characteristics from those of the “type” minerals
soils, that is, it deals (in Section 20.3) with the occurrence, as well formed in more “geological” environments with which they may
as the alteration and formation, of minerals in soils. share a name and ideal crystalline structure (Churchman, 2010).
Secondary minerals are the most reactive inorganic materials in Chadwick and Chorover (2001) made the point that the crisp
soils. Furthermore, they occur commonly in association with the boundaries in stability diagrams are, in the real world of natural
most reactive organic materials in soils. It has often been inferred soils, not so clear-cut. However, the effort involved in understand-
that knowledge of the properties of these reactive materials should ing the real nature of minerals in soils is worthwhile in view of the
enable close predictions of the useful soil properties, whether potential reward of being able to explain and predict properties
for growing plants, for filtering and partitioning water flow, for across different sorts of soils from the nature of their constituents

20-1
20-2 Properties and Processes

TABLE 20.1  Definitions of Terms

Term Definitionsa References Issues with Definitions
Mineral An element or compound that is normally Gaines et al. (1997) Crystallinity implies a regularity of structure,
crystalline and that has formed as a result of but this is dependent on type of analysis. Some
geological processes materials (e.g., volcanic glass) lack a fixed
structure and are referred to as mineraloids;
others such as allophane, earlier thought to be
amorphous and technically thus not minerals,
are now known to be nanocrystalline and
hence do qualify as minerals
Primary minerals Mineral deposited or formed at the same time as Lapidus (1987) Minerals in sedimentary and partially
the rock containing it metamorphosed rocks may contain secondary
minerals from earlier cycles
Secondary minerals Mineral formed as a result of alteration of Adapted from Lapidus (1987) Minerals commonly altered in several steps;
preexisting minerals hence all products of 1° mineral alteration are
2° minerals
Often referred to as “clay minerals”
Weathering Weathering is the breakdown of geological Ashman and Puri (2002) Some regard weathering as encompassing both
deposits by physical, chemical, and biochemical and Buol et al. (2003) the breakdown of primary minerals and the
processes synthesis of new secondary minerals, but
• Physical weathering includes breakdown by others distinguish between two phases,
thermal and mechanical action, generating decomposition and argillization, the latter
smaller particles (comminution); chemical being the synthesis of secondary minerals
weathering includes breakdown by (mainly clays)
hydrolysis, carbonation, hydration,
dissolution, oxidation, and reduction,
changing the physical and chemical
properties of the original geological deposits
Soil The natural, 3D body (comprising pedons), Schaetzl and Anderson (2005) Most definitions of soil fail to encompass and
typically up to ∼1 to 2 m thick (thicknesses can recognize its complexity as the most complex
vary markedly), of unconsolidated mineral and ecosystem on Earth and as a biological habitat
organic material mantling the land surface that and critically important repository for genes.
can support rooted land plants, and which Soil is also being considered increasingly in
• Is characterized by one or more soil horizons policy making, for example, as a provider of
(“layers”) that have evolved through additions, “ecosystem services” (e.g., Blum et al., 2006)
losses, transfers, and transformations of and as “natural capital” (the stock of biotic and
energy and matter by interactions of climate, abiotic mass that contains energy and
biota, relief, and parent materials through organization) (see Sparling et al., 2006, and
time, and which differ from the material(s) Robinson et al., 2009)
from which they derive
• Comprises solids (inorganic and organic
matter), liquids, and gases
• Is essential to life through recycling of
nutrients, carbon, and oxygen
• Is nonrenewable in human timescales
a Working definition for this chapter.

and that of their associations. As discussed in Section 20.4, soil 20.2  Alteration of Primary Minerals
mineralogy has to some extent been in decline as a subdiscipline
of soil science and it may be that this is due, at least in part, to the 20.2.1  Common Primary Minerals in Soils
often-unjustified assumption that soil minerals are similar in their
The most common primary minerals found in soils are listed
properties to those of their well-characterized “types” formed in
in Table 20.2 within their chemical (compositional) types and
nonsoil environments. The implications of this erroneous or only
their mineralogical groupings together with the types of (crys-
partly true assumption, and new directions for soil clay mineral-
tal) structures for these groupings. Table 20.2 also lists chemical
ogy, are also discussed in Section 20.4.
formulae for the minerals or groups of minerals and summa-
This chapter deals with minerals, both primary and second-
rizes the general sorts of soils in which they occur and often also
ary, with the processes of weathering and associated clay for-
their relative abundance in these soils. Other properties of the
mation, and with soils. We define each of these terms in Table
minerals listed are given in Churchman (2006, Table 3.1). In
20.1, which also includes some alternative definitions, and some
soils, primary minerals, as residuals of physical and chemical
issues involved in these definitions.
weathering processes, most commonly occur in coarser particles
Alteration, Formation, and Occurrence of Minerals in Soils 20-3

TABLE 20.2  Structure, Composition, and Soil Occurrences of Common Primarya Minerals in Soils
Chemical Common Soils of Main
Type Group Structural Type Soil Minerals Chemical Formula Related Phases Occurrence
Silicatesb Silica Tectosilicate Quartz SiO2 Cristobalite Quartz in almost all soils,
Tridymite Nil/minor from basalt
Opal (biogenic)
Feldspar Tectosilicate Orthoclase KAlSi3O8 Microcline Feldspars occur in many
Sanidine (all soils, absent from
K-feldspars) highly weathered soils
Albite NaAlSi3O8 Oligoclase
Oligoclase NaxCayAlSizO8 (x >> y), (z = 2–3) Andesine
Anorthite CaAl2Si2O8
Labradorite CayNaxAlSizO8 (y >> x), (z = 2–3) Bytownite (all
plagioclases)
Zeolite Tectosilicate Clinoptilolite Na3K3(Al6Si30O72) · 24H2O Erionite Rare in soils; analcime
Faujasite formed in high pH
Hollandite saline soils
Analcime Na16Al16Si32O96 · 16H2O Laumontite
Mordenite
Mica Phyllosilicate Muscovite KAl2AlSi3O10(OH)2 Paragonite Widespread
(dioctahedral) Maragarite
Glauconite
Phyllosilicate Biotite K(MgFeII)3AlSi3O10(OH)2 Phlogopite Only in slightly
(trioctahedral) Clintonite weathered soils
Lepidolite
Chlorite Phyllosilicate Chlorite (Fe,Mg,Al)6(Si,Al)4O10(OH)8 Cookeite Only in very slightly
Sudoite weathered (“raw”) soils
Bonbassite
Serpentine Phyllosilicate Chrysotile Mg3Si2O5(OH)4 Antigorite Rare in soils
Lizardite
Amesite
Berthierine
Amphibole Inosilicate Hornblende (Ca,Na)2.3(Mg,Fe,Al)5(Si,Al)8O22 Tremolite Quite widespread, but
(double chain) (OH)2 Actinolite absent from highly
Cummingtonite weathered soils
Glaucophane
Pyroxene Inosilicate (single Augite (Ca,Na)(Mg,Al,Fe)(Si,Al)2O6 Enstatite Relatively rare except in
chain) Hypersthene some volcanic soils
Diopside (especially
intermediate-basic)
Pigeonite
Jadeite
Spodumene
Hedenbergite
(Cyclosilicate) Cyclosilicate Tourmaline (Na,Ca)(Li,Mg,Al) Beryl Rare
(Li,Fe,Mn)6(BO3)3Si6O18(OH)4
(Sorosilicate) Sorosilicate Epidote Ca2(Al,Fe)Al2O(Si2O7)SiO4(OH)4 Zoisite Uncommon
Olivine Nesosilicate Forsterite Mg2SiO4 Fayalite Rare
Tephroite
Monticellite
Garnet Nesosilicate Almandine Fe3Al2(SiO4)3 Rare
Zircon Nesosilicate Zircon ZrSiO4 Baddeleyite Widespread
(ZrO2)

(continued)
20-4 Properties and Processes

TABLE 20.2 (continued)  Structure, Composition, and Soil Occurrences of Common Primarya Minerals in Soils
Chemical Common Soils of Main
Type Group Structural Type Soil Minerals Chemical Formula Related Phases Occurrence
Nonsilicates Phosphates Insular, hexagonal Apatite Ca5(PO4)3(OH,F,Cl) Fluorapatite Some in “raw” soils
Hydroxyapatite
Variscite
Wavellite
Monazite
Titanium Tetragonal Rutile TiO2 Brookite Widespread in small
oxide Sphene (CaTiSi5) amounts
Carbonate Rhombohedral Calcite CaCO3 Aragonite Common in arid soils
Siderite (FeCO3)
Carbonate Rhombohedral Dolomite CaMg(CO3)2 Ankerite From dolomitic rocks
Mg calcite
Iron oxide Cubic Magnetite Fe3O4 Titanomagnetite Rare except in some
volcanic soils and in
soils derived from
detrital volcanic
deposits
Some are also formed in soils, hence may also be regarded as secondary minerals.
a

Volcanic glass (including obsidian) is an amorphous solid with a poorly ordered internal structure comprising loosely linked SiO4 tetrahedra (Fisher and
b

Schminke, 1984). Of widely varying composition, it is a common primary mineraloid in many volcanic soils and derivatives.

(of sand- and silt-size), although the phyllosilicates such as the (Batchelder et  al., 1998), industrial pollution (Rampazzo and
micas, chlorite, vermiculite, and talc, and some oxides, such as Blum, 1992; Yaron et al., 2010), and probably also global climate
those of titanium and also apatite, and volcanic glass, can also change (Berg and Banwart, 2000; Amundson, 2001; Leifeld,
be found in reasonable proportions in the clay-size factions of 2006). Most of these agents affect mineral alteration via aqueous
some soils. solutions, although in some cases, for example, the oxidation of
sulfides, particularly iron pyrite, alteration of minerals occurs
when water is absent (Dent and Pons, 1995). Nevertheless,
20.2.2  Observations of Relative Stabilities
alteration by weathering most often occurs in an aqueous envi-
of Primary Minerals in Soils
ronment and the most important determinant of the relative
In most cases, weathering involves the reaction of minerals (or stability of primary minerals to weathering is their relative solu-
mineraloids) with water, or, at least, an aqueous solution. There bility in water.
are exceptions where alteration of primary minerals occurs but All minerals have some solubility in water. Only rarely, how-
where liquid water is either absent or is not the primary agent ever, for example, for simple salts like halite (NaCl) found, for
effecting alteration. This is the case in cold (and polar) and also example, in arid and saline soils, do they dissolve congruently
hot desert zones on Earth (Shoji et al., 2006). It is probably also in water. Instead, hydrolysis commonly occurs with the more
the case in some extraterrestrial environments, such as the soluble components being removed selectively from the mineral.
Moon, but not in others, such as Mars, where there is abun- This removal may leave a solid residue, which differs in com-
dant evidence for liquid water, at least in the past (Certini and position from the original mineral, or a solid alteration prod-
Scalenghe, 2006). In environments where liquid water does not uct that precipitates out of the solution. The solid precipitate
provide the main weathering milieu, the dominant agents of will most likely have a different composition and perhaps also a
alteration nonetheless involve climatic factors; hence, they con- different crystal structure from that of its antecedent (partly or
stitute weathering. These include mainly physical actions such as completely) dissolved mineral. Some texts refer to the synthesis
frost wedging and successive freezing and thawing in cold desert or precipitation of such products as “argillization,” meaning the
zones on Earth (Shoji et al., 2006), processes such as wind abla- formation of clay; in this case, the term “weathering” encom-
tion in both hot and cold terrestrial desert zones, and such pro- passes only the decompositional phase (Figure 20.1) (e.g., Buol
cesses as solar wind irradiation on Moon (Certini and Scalenghe, et al., 2003). Another term widely used is neogenesis, effectively
2006), and perhaps also on other dry extraterrestrial bodies and the formation or synthesis of new clays and other secondary
regions. Other agents besides the purely climatic can also alter material from the breakdown products of antecedent minerals.
primary minerals, given enough time. Among these are some A simple chemical analogy of the hydrolysis undergone by sili-
resulting from various human activities (Certini and Scalenghe, cates, the most common type of primary mineral, in water, is real-
2006), including agriculture (Velde and Meunier, 2008), mining ized when they are considered as salts of silicic acid H4SiO4 and
(Murakami et al., 1996; Banfield and Murakami, 1998), landfills bases of the appropriate cation (Carroll, 1970; Chamley, 1989).
Alteration, Formation, and Occurrence of Minerals in Soils 20-5

Weathering
Argillization
Synthesis

Secondary
Primary
+
Attacking
mineral + Leaching
mineral solution (including clays) solution

Chemical Composition — Temperature,

composition and nature and rate of attack Potential loss
mineralogical concentration of of solution
constitution reagents, pH, redox
potential (Eh)

FIGURE 20.1  Weathering (and associated processes of argillization and synthesis) in relation to the factors governing the genesis of secondary
minerals including clays in soils. (Modified after Percival, H.J. 1985. Soil solutions, minerals, and equilibria. New Zealand Soil Bureau Scientific
Report 69. Department of Scientific and Industrial Research, Lower Hutt, New Zealand. With permission.)

Box 20.1  Hydrolysis of K-Feldspar,

Interpreted as a Salt, to Form Kaolinite
Silicate minerals ≡ salt of silicic acid plus base of appropriate cation

∴ K-feldspar ≡ silicic acid + hydroxyl-Al (+K+)

∴ 2KAlSi3O8 + 11H2O → Al2Si2O5(OH)4 + 4H4SiO4 + 2K+ + 2OH− (20.1)

K-feldspar kaolinite silicic acid

or 2KAlSi3O8 + 9H2O + 2H+ → Al2Si2O5(OH)4 + 4H4SiO4 + 2K+ (20.1a)

The hydrolysis of silicates in water results in an acid, namely, order in which the minerals crystallized out of a magma on cool-
silicic acid, and a base, namely, the hydroxy-Al–Si, kaolinite (see ing (Bowen, 1922). Goldich (1938) reasoned that the higher the
Box 20.1). Because most aqueous solutions in which weathering temperature at which a mineral crystallized from magma, the
takes place are acidic because water is charged with dissolved greater the extent to which it was out of equilibrium with the sur-
CO2, giving rise to a continuous supply of carbonic acid H2CO3 face temperature of Earth and, therefore, the more susceptible
and hence H+ ions, hydrogen ions are important weathering it would be to breakdown by weathering at the Earth’s surface.
agents. Therefore, Equation 20.1a represents the natural situation The alteration of a particular mineral or mineraloid begins
more realistically than Equation 20.1. with the disruption of its weakest bond. Structural explanations
The relative stabilities of the principal primary minerals in of the relative stabilities of minerals have followed this gener-
soils to alteration have long been studied. More than 70 years alization. Bonds in all silicates are based on silica tetrahedra.
ago, Goldich (1938) drew up a stability series for these miner- Their strength depends on the following: (1) the nature of the
als (Figure 20.2) that has generally stood the test of time and links between tetrahedra, (2) the extent of substitution of four-
further experimentation, for example, by Franke and Teschner- valency Si within tetrahedra by three-valency Al and hence gain
Steinhardt (1994). of negative charge (isomorphous substitution), and (3) the extent
of incorporation of charge-balancing cations, and their location,
in the structure. In Table 20.3, we show the nature of bonding in
20.2.3  Thermodynamic and Structural
the different structural types of silicates (see Table 20.2 to iden-
Explanations of Relative Stabilities
tify the relevant minerals).
Goldich’s series (Figure 20.2) makes thermodynamic sense inso- Sposito (1989) pointed to an apparent correspondence between
far as the minerals therein are in the identical (but reversed) the ordering of the molar Si:O ratios in the silicate units, namely,
order to those in Bowen’s classic reaction series describing the olivines < pyroxenes < amphiboles < micas < feldspars = quartz
20-6 Properties and Processes

Volcanic Most easily

glass weatherable
Olivines Basaltic
Andesitic
Rhyolitic
Mg-pyroxenes Ca-rich
Anorthite
M

rs
Mg-Ca-pyroxenes Bytownite

spa
afi
c Labradorite

eld
m
in

f
er Andesine

se
als

cla
Amphiboles
Oligoclase

gio
Pla
Albite
Biotite Na-rich

K-feldspars

Muscovite

Quartz Least easily

weatherable

FIGURE 20.2  Stability series for the common primary minerals (after Goldich, S.S. 1938. A study in rock weathering. J. Geol. 46:17–58.) and also
volcanic glass (not part of the Goldich series). Basaltic and other glasses, and olivines, are normally the first phases altered by weathering (Wolff-
Boenisch, D. et al., 2004).

TABLE 20.3  The Nature of Bonding and the Weakest Bonds in Different Types of Silicates That Are Common in Soils
(in Order of Decreasing Stability)a
Silicate Unit
Structural Type Group Name Formula, Structure Shared O per Si Weakest Bonds Examples
Framework Tectosilicates SiO2 4 Si–O Quartz
Tectosilicates SiO2, with Al substitution 4 With cations (K+, Na+, and Ca2+) Feldspars
Layer Phyllosilicates Si 2O2−
5 , with Al substitution, as a sheet 3 With interlayer cations, usually K+ Micas
joined to Al-, Mg-, Fe-OH sheet
Single chains Inosilicates SiO2−3 , with Al substitution 2.5 With divalent, and other cations Pyroxenes
6−
Double chains Inosilicates Si 4O11 , with Al substitution 2 With divalent, and other cations Amphiboles
Isolated tetrahedra Nesosilicates SiO2−4 0 With divalent cations Olivines
a Cyclosilicates (e.g., tourmaline) have two O bonds per Si and sorosilicates (e.g., epidote) have one O bond per Si, but neither is common in soils (Table 20.2).

and that in the Goldich series. Nonetheless, reference to Table Another danger of oversimplification arises because weath-
20.3 may lead to oversimplification concerning possible struc- ering (and argillization) is not simply a matter of dissolution of
tural control on the relative stability of silicates to weather- the silicate minerals in water. Instead, weathering often occurs
ing, especially when other silicates besides those in the broad in an acid environment and, commonly in soils, also involves
groups represented by both types of ordering are considered. a range of organic compounds, which can complex the ions in
Following Loughnan (1969), for example, we note that both zir- the silicate structure and can both enhance their breakdown
con (ZrSiO4) and andalusite (Al2SiO5) are neosilicates like olivine and affect its course and the products formed (e.g., Velde and
and have (Si:O)molar ratios of 0.25 and 0.2, respectively, which are Barré, 2010).
equal or less than those of olivine and yet are both very stable The rate at which hydrolysis affects cations released is related
(i.e., resistant) to breakdown by weathering, in contrast to oliv- to the strength of the bonds formed by the cations within the
ine, which is notably unstable according to Goldich’s (1938) series minerals, according to Pauling’s electrostatic valency principle
(Figure 20.2). Furthermore, the broad classifications shown in (Pauling, 1929). The ratio of the valency (the charge on the ion) to
Table 20.3 hide the observed differences in the stabilities between the coordination number (the number of ions of opposite charge
individual minerals within structural types. Within the phyllo- surrounding an ion) is known as the electrostatic valency. The
silicate mica group, biotites are generally much less stable than smaller its value, the greater the ease of hydrolysis (Paton et al.,
muscovites, whereas the tectosilicate feldspars include albites and 1995). The hydrolysis, or replacement of a cation in a crystal
anorthites, each with quite different stabilities. structure by H+, of K is relatively easy because it is univalent (K+).
Alteration, Formation, and Occurrence of Minerals in Soils 20-7

It is commonly found in feldspars, where its coordination num- such coarsening with depth could be more easily attributed to
ber is 9, and in micas, where it has a coordination number of 12. the translocation of clay than to its destruction.
Hence, the electrostatic valency of K in these minerals is 1:9 and Weathering and argillization, together with soil formation,
1:12, respectively (Paton et al., 1995). The hydrolysis of Al is more generally occur in a dynamic system that is open to the wider
difficult because it is trivalent (Al3+), with coordination numbers environment. Leaching—the removal or loss of material in
of 6 or 4, so the electrostatic valency of Al in primary miner- solution—commonly occurs. The driving force that provides the
als is either 1:2 or 3:4. These differences between cations, and chemical potential energy for mineral alteration is the difference
also between the same cations in different minerals, are reflected in composition between the “attacking” solution and the solid
in the relative responses of the four main groups of silicates to mineral. However, it is the rate of leaching, which governs the
weathering pressures (Paton et al., 1995). The solubility or rela- rate of removal of solutes, which most influences the rate of min-
tive mobility of various ions such as Ca, K, and Mg relates to eral alteration and any subsequent precipitation (Figure 20.1). It
ionic potential, which is the ionic charge (valency) divided by the also influences the course that the alteration takes. Garrels and
ionic radius (size), so that ions with a low ionic potential such as Mackenzie (1971) stated that, given sufficient leaching, almost all
Na+, K+, Ca 2+, and Mn2+ are more easily leached (lost) in solution, rocks or unconsolidated deposits will leave a residue that is largely
although temperature and pH affect solubility as well (Schaetzl composed of the relatively insoluble oxides of Al, Fe, and Ti.
and Anderson, 2005). Hence, the origin of primary minerals as given by their tem-
Some components of the silicate framework can greatly influ- perature of crystallization from magma influences their ther-
ence the rate and nature of their breakdown. Chief among these modynamic stability against breakdown by weathering in an
is Fe. According to Millot (1970), the most important weather- aqueous environment, as does their structure and their particu-
ing reactions involve Fe, a component of many of the primary lar chemical composition (Figure 20.1). However, such environ-
minerals involved in soil formation (Table 20.2). Along with mental factors as the particular composition of the solutions
Mn, which is less abundant in the primary soil-forming min- bathing the minerals, the dynamics of the redox conditions,
erals (Table 20.2), Fe generally occurs in its reduced form in and the rate of throughflow of water past the minerals can play
primary minerals. Fe occurs as Fe(II) and Mn as Mn(II). These a decisive role in the kinetics, course, and ultimate products of
are both easily converted to their oxidized forms—Fe(III) and their alteration.
Mn(IV)—when oxidation occurs, for example, when soils dry.
This change in valency sets up a charge imbalance in the appro-
20.2.4  Processes and Products of Alteration
priate minerals, leading to a loss of other ions from the mineral
of the Main Types of Primary
structures, which can destabilize the minerals, enhancing their
Minerals by Weathering
further breakdown by hydrolysis, which is assisted by the hydro-
gen ions produced during oxidation. The oxidized forms of Fe Early work exploring either the fate of primary minerals or the
and Mn occur as oxides and oxyhydroxides and those of Fe, in origin of secondary minerals on weathering (e.g., Jackson et al.,
particular, are almost ubiquitous in soils. Seasonal wetting and 1948) tended to take the stance that specific primary miner-
drying cause alternate oxidation and reduction of Mn(II) and als have led to particular secondary minerals as products.
Mn(IV) and lead to the common precipitation of the blue-black A  1:1  correspondence between altered rock-forming mineral
mineral pyrolusite (MnO2)—as well as other forms of MnO2 and phyllosilicate product appears justified when one domi-
such as todorokite (Churchman et  al., 2010)—as redox segre- nant type of primary mineral is altered more than others in
gations (also known as redox concentrations) in the form of the parent material and the overlying soil, saprolite, or rego-
coatings (mangans), nodules, or concretions (Vepraskas, 1992; lith more generally is dominated by just one type of secondary
Birkeland, 1999). Manganese oxides in most conditions form mineral (clay). Some modern studies have also concluded that
preferably to those of Fe during wetting and drying because of each type of primary mineral generally leads to one particular
the greater ease of acceptance of electrons by Mn than by Fe. type of secondary mineral. Thus, according to a generalization
The reduction of Fe(III) to Fe(II), commonly by organisms dur- by Wilson (2006), the weathering of granite rocks leads most
ing phases in which a soil is waterlogged, and then its oxida- commonly to kaolin minerals (kaolinite and halloysite), largely
tion on drying, leads to Fe oxides being precipitated as mottles, deriving from the alteration of feldspars, and vermiculite min-
coatings, or concretions. The persistence of reducing conditions erals from the alteration of micas. Furthermore, many clay
causes soil matrix materials to have pale, low-chroma colors minerals appear to be found in close proximity to particular
(described as redox depletions), and these grayish colors char- types of altered primary minerals, for example, halloysite tubes
acterize continuously reduced soils that, therefore, have few or on altered feldspar (Figure 20.3). Clay minerals may also have
no redox segregations (Birkeland, 1999; Vepraskas et al., 2004; a morphology that appears to mimic that of altering or altered
Morgan and Stolt, 2006). Brinkman (1970) characterized the primary minerals. The similarity in shapes between vermicu-
clay decomposition brought about by cyclical alternation of lar books of kaolinite and degraded micas, often occurring as
redox conditions by the name of “ferrolysis.” Even so, a reexam- some form of vermiculite (Figure 20.4), can be suggestive of
ination of some texture-contrast soils having coarser topsoils a micaceous origin for the particular kaolinite. To examine
than subsoils by Van Ranst and De Coninck (2002) found that whether there is always a 1:1  relationship between particular
20-8 Properties and Processes

20.2.4.1  Processes and Products of Alteration

of Olivines, Pyroxenes, and
Amphiboles by Weathering
In an open environment, generally unstable olivines easily lose
Mg2+, and Fe2+ (or Mn2+ if manganous) to give, first serpentine,
then a smectite (commonly saponite), and also goethite, which
together have been characterized as “iddingsite” (Loughnan,
1969; Nahon et al., 1982; Eggleton, 1984). Both optical (Craig and
Loughnan, 1964) and electron microscopy (Eggleton, 1984) have
enabled identification of iddingsite as a mixture of saponite and
goethite. Nahon et  al. (1982) made the important observation
that an aluminous dioctahedral smectite had formed from the
breakdown of the Mg-olivine, forsterite (Mg2SiO4), which con-
tains very little Al. They suggested that Al probably derived from
the simultaneous breakdown of a pyroxene, enstatite. Secondary
4 μM 20 KV 86 185 S minerals could, therefore, derive their elemental constituents
from the breakdown of more than one primary mineral. Indeed,
FIGURE 20.3  Scanning electron micrograph of tubular halloysite
olivines could give rise to a variety of secondary mineral prod-
occurring in close proximity to weathered feldspar in granitic sapro-
ucts, including smectite, kaolinite, halloysite, and also various
lite from Hong Kong. (Photo by Stuart McClure. Reproduced with the
permission of the Geotechnical Engineering Office, Civil Engineering oxides, hydroxides, and oxyhydroxides of Fe, and, if present,
Office, Hong Kong.) also Mn, upon leaching (Huang, 1989).
Pyroxenes and amphiboles, although slightly more stable than
olivines, tend to break down in a similar fashion to the olivines
in the field, with an initial loss of their divalent cations, typi-
cally Mg, Ca, and Fe(II). Chlorite and/or smectite often result,
although talc may also be formed. Calcite can also form as one
of the products if Ca is released in abundance (Loughnan, 1969;
Eggleton and Boland, 1982; Huang, 1989). Examination at the
fine scale of the mineral grain revealed that amphibole weather-
ing led to a dioctahedral (montmorillonite) and a trioctahedral
(saponite) smectite, and also kaolinite–smectite simultaneously
at the early stages of alteration, with halloysite developing with
time (Proust et  al., 2006). The different products were associ-
ated with different crystallographic faces of the host amphibole
(see Section 20.2.5.1). As with olivines, pyroxenes and amphi-
boles could give rise to products with simpler structures, such as
kaolinite, Fe(III) oxides, and anatase upon strong leaching (see
10 μM 20 KV 74 012 S
also Wilson, 2004). The common pathway of alteration of this
group of minerals by weathering is shown in Box 20.2.
FIGURE 20.4  Scanning electron micrograph of vermicular kaolinite Many laboratory studies have been designed to help under-
(with some halloysite tubes) occurring in close proximity to weathered stand the initial stages of alteration of these ferromagnesian
mica in granitic saprolite in Hong Kong. (Photo by Stuart McClure. minerals. At low pH, divalent ions are lost relative to silica,
Reproduced with the permission of the Geotechnical Engineering whereas the converse occurs at high pH with a preferential loss
Office, Civil Engineering Office, Hong Kong.) of Si (Schott and Berner, 1985). It has usually been inferred that
leached layers, depleted in some of their original constituents,
primary minerals and specific secondary minerals, the follow- develop as a result on mineral surfaces (Schott and Berner, 1985;
ing subsections summarize studies that have concentrated on Banfield et  al., 1995). Experimental studies (e.g., Velbel, 1985)
the fate of individual types of primary minerals to alteration by have often indicated weathering rates that far exceed those
weathering. In these subsections, the generalizations have often observed in nature by up to 5 orders of magnitude (Banfield and
been drawn from studies of the weathering of rocks or other Barker, 1994).
geological deposits, the minerals derived from these, and at However, by following evidence from electron microscopy
depth within soil profiles. The influence of particular soil fac- particularly, weathering of olivines, pyroxenes, and amphi-
tors on the alterations and products of weathering is discussed boles has been seen to involve the formation, enlargement,
in Section 20.2.5. and coalescence of etch pits developed on crystal dislocations
Alteration, Formation, and Occurrence of Minerals in Soils 20-9

Box 20.2  Initial Alteration of

Olivines, Pyroxenes, and Amphiboles
as Commonly Reported
Olivines Serpentine, Smectite
Pyroxenes –Mg2+, Fe2+ (Mn2+) chlorite, ⟶ (trioctahedral + goethite,
Amphiboles and/or talc e.g., saponite)

(Huang, 1989; Hodder et al., 1991; Seyama et al., 1996; Wilson, or neoformation, with either partial or complete dissolution
2004) rather than through an enleached layer. Velbel and Barker of solutes, then their reprecipitation as new secondary phases.
(2008) have acknowledged that surface tension upon air-drying Structural considerations appear to dictate that neither the
samples for conventional scanning electron microscopy (SEM) neosilicate olivines, with independent silica tetrahedra, nor the
may affect surface structure and have examined partially weath- inosilicate pyroxenes and amphiboles with tetrahedra in chains,
ered pyroxenes using high-pressure cryofixation (HPF) and can transform directly within the solid state to phyllosilicate
cryo-field emission gun SEM, both of which avoid the surface clay minerals with flat sheets. Nevertheless, high-resolution
tension effects of air-drying. They were thus able to view the transmission electron microscopy (HRTEM) observations of
products formed in small-scale etch pits on the pyroxenes and weathering amphiboles led Banfield and Barker (1994) to con-
have concluded that pyroxene weathers to smectite by a multi- clude that a type of transformation of amphiboles to smectites
stage process. Velbel and Barker (2008) proposed that the pro- can occur within the solid state. They observed these reactions
cess includes initial dissolution, topotactic reactions, mechanical occurring in interstitial spaces within the primary amphiboles,
disruption from wetting and drying cycles, further dissolution with secondary smectites formed in a topotactic relationship to
and, eventually, microbial colonization of the pores, with weath- the altering amphibole. The change was described as a partial
ering finally enhanced by microbial extracellular polymers. As depolymerization of the amphibole structure leading to a repo-
for the alteration of feldspars (see Section 20.2.4.2), the findings lymerization to that of smectite. There is no need for bulk water
from laboratory studies may not reflect the processes occurring to bring about this change, with the water of hydration of the
in the field because of oversimplification of the factors involved smectite product being able to supply the water required for the
in natural weathering. transformation reaction. Although Banfield and Barker (1994)
Nonetheless, Mogk and Locke (1988), using Auger electron pointed out that this type of transformation is not representa-
spectroscopy (AES), found that naturally weathered hornblende tive of all weathering reactions, it enables episodic alteration to
showed systematic cation depletion to depths of ∼120 nm. They take place within rocks or geological deposits, where it is limited
considered that the dissolution of minerals generally occurs by an intermittent supply of water and, therefore, much slower
from both their surfaces and their bulk. Furthermore, Welch than that occurring on the surfaces of rocks or rock minerals
and Banfield (2002) were able to produce microstructural chan- immersed in aqueous solution. Banfield et al. (1995) found that
neling effects in the olivine, fayalite, from laboratory dissolu- smectites could form within weathering pyroxenoids (rhodonite
tion experiments with an initial pH of 2.0, which were identical and pyroxmangite, both MnSiO3), which were studied by a simi-
to those seen in the naturally weathered mineral (e.g., Banfield lar type of in situ transformation. Periodic drying, which often
et al., 1991). X-ray photoelectron spectroscopy (XPS) had shown occurs in this situation, may promote the repolymerization of
earlier that surfaces are coated by films of Fe(III) oxides both phyllosilicates rather than depolymerized silica (Banfield et al.,
at low and high pH (Schott and Berner, 1985; Casey et al., 1993; 1995). The reaction has little significance for soil formation,
Seyama et al., 1996), and Welch and Banfield (2002) found that however, because the smectitic products are “quite ephemeral”
when either microbes that enzymatically oxidize iron or instead and disappear when transported from the altered rock into the
ferric iron was added to the system, the minerals degraded at a more open soil environment (Wilson, 2004).
greatly reduced rate. They identified the formation of laihunite, Not all workers have considered that the primary ferromag-
a ferric–ferrous olivine-like mineral containing vacant atomic nesian minerals are altered directly to phyllosilicates such as
sites, in the region of the mineral surface. This laihunite would smectites. Nahon and Colin (1982) and Singh and Gilkes (1993)
protect the mineral against further dissolution. both identified amorphous or noncrystalline intermediates in
Generally, alteration of primary minerals to give secondary the alteration of (different) pyroxenes. In comparing this obser-
products involves either transformation within the solid state vation with those of Banfield and coworkers, among others, who
20-10 Properties and Processes

observed direct formation of phyllosilicates on altering ferro- leached layer of up to 1 μm deep, especially at low pH. The
magnesian minerals, Wilson (2004) cautioned that the course of leached product from an albite was identified as an amorphous
formation of phyllosilicates may have been established by prior phase with some of the characteristics of nanocrystalline allo-
hydrothermal or deuteric alteration in the latter cases and altera- phane, which later became detached (Kawano and Tomita,
tion by weathering had continued along the predisposed course. 1994). The fate of the leached layer was found to be dependent
upon the Si:Al ratio in the parent feldspar (Oelkers and Schott,
20.2.4.2  Processes and Products of Alteration 1995). Where this ratio was 1, as in plagioclases (anorthite was
of Feldspars by Weathering studied), the removal of Al led to completely detached silica tet-
Feldspars have been thought to give rise to many different types rahedra, but where it was 3, as in alkali feldspars, Si tetrahedra
of secondary minerals, encompassing the range of structural that were still partially linked remained.
complexity from smectites through to gibbsite and quartz. On the other hand, some measurements by XPS (Berner and
Allen and Hajek’s (1989) review referred to several studies where Holdren, 1979) showed no leached layer forming, and when the
smectites have been identified as products of the alteration of artificial alteration was carried out at near-neutral pH values
feldspars. These authors surmised that the resultant smectites (between 5 and 8), rather than at low pH, the layer formed was only
would be beidellitic because the parent feldspars lacked Mg or Fe, thin (Blum and Stillings, 1995). Huang (1989) concluded that, in
and Nettleton et al. (1970) characterized a smectite seen to form any case, leached layers are not thick enough to inhibit transport
directly from a feldspar crystal as a ­beidellite–montmorillonite. and also that there were no continuous layers of secondary pre-
Reports of the alteration of feldspars to gibbsite and quartz, at cipitates on weathered feldspars. As in the case of olivines, pyrox-
the lower end of the scale of structural complexity, were given enes, and amphiboles, dissolution of feldspars probably occurred
by Allen and Hajek (1989) and Estoule-Choux et  al. (1995). at sites of excess energy such as dislocations (Huang, 1989).
Otherwise, feldspars have been considered as the source miner- HRTEM studies have shown that unweathered feldspars are
als for micas (Carroll, 1970; Millot, 1970) and very often also often turbid as a result of minute vesicles being filled with fluid
for kaolinites and halloysites (Eswaran and Wong, 1978; Calvert (Hochella and Banfield, 1995), consistent with the observation
et al., 1980; Anand et al., 1985). The micaceous minerals formed that they can have a high microporosity (Worden et al., 1990).
from feldspars, both K-feldspars and plagioclases, have often HRTEM has also shown that their alteration often occurs prefer-
been described as “sericites,” with the process of their formation entially at crystal defects (Wilson and McHardy, 1980; Holdren
being described as sericitization (Carroll, 1970; Millot, 1970). and Speyer, 1987) and that secondary minerals form throughout
However, the term sericite has also been used to describe white the primary mineral, not just at grain boundaries (Banfield and
mica formed from the reaction of biotite with plagioclase dur- Eggleton, 1989; Banfield et  al., 1991). Application of SEM and
ing metamorphism (Meunier and Velde, 1976). Furthermore, associated energy-dispersive x-ray (EDX) analyses showed etch
orthoclase (a K-feldspar) has been considered to hydrolyze to pits and secondary coatings (of a kaolin mineral) developing as
muscovite (Hemley, 1959). On the contrary, Meunier and Velde the weathering alteration of feldspars progressed (Inskeep et al.,
(1979) found that the micaceous phase, which they considered 1993). These authors saw the formation of secondary coatings
to be an illite, developed at a boundary between muscovite and on feldspars as an integral part of their alteration. These were
orthoclase within weathering granite, and contained more not observed in artificial weathering studies. Essential features
Fe and Mg than either the muscovite or orthoclase. Hence, of weathering in the field include those of seasonal wetting and
the illite formed (precipitated) out of solution. Using electron drying, a generally high solid:solution ratio, and long residence
microscopy, Eggleton and Buseck (1980) detected micaceous times for water (Inskeep et al., 1993). The net effect is a weath-
phases forming within vacuoles within microcline. They con- ering rate, determined for plagioclases, that is several orders of
sidered these to be either illite or interstratified illite–smectite. magnitude slower than the experimental dissolution rate (White
Bétard et al. (2009) found that an illite formed within nonalkali et al., 1996, 2005; White and Brantley, 2003). Maher et al. (2009)
feldspar (a plagioclase) by neoformation in Luvisols in north- have shown that other factors besides mineral dissolution rate
east Brazil, and, more generally, they considered this particular and the rate of aqueous transport of solutes, notably the rate of
weathering reaction to be typical of semiarid tropical and sub- secondary mineral precipitation, ensure a much slower rate of
tropical climates. weathering of minerals, including feldspars, in the field than in
Studies of the artificial weathering of feldspars in controlled the laboratory. Furthermore, fungi have been shown to contrib-
conditions in the laboratory have largely focused on the possibil- ute to the breakdown of feldspars on weathering, partly, at least,
ity of the formation of a leached layer on feldspar surfaces during through their tunneling by organic anions exuded at the tips
their alteration. On the one hand, different types of surface- of the hyphae of (presumably ectomycorrhizal) fungae (Smits
sensitive analyses—including secondary ion mass spectrometry, et al., 2005; see also Section 20.2.5.3 on podzolization). Failure
SIMS (also known as ion microprobe) (Muir and Nesbitt, 1997); to reproduce these features in necessarily hastened artificial
elastic recoil detection, ERD, and Rutherford backscattering, weathering studies under closely controlled conditions almost
RBS (Casey et al., 1988, 1989); and XPS (Muir et al., 1989, 1990; certainly means that their results cannot be applied readily to
Hellmann et al., 1990)—indicated the formation of a dealkalized the understanding of natural weathering.
Alteration, Formation, and Occurrence of Minerals in Soils 20-11

20.2.4.3  Processes and Products of Alteration spacings of the unaltered mica layers (1.0 nm) and the hydrous
of Micas by Weathering vermiculite layers (1.4 nm), giving a resultant spacing of 2.4 nm.
Changes from any of the neosilicate olivines, with indepen- Alternating layer types in regular 1:1 interstratifications are
dent silica tetrahedra, the inosilicate pyroxenes and amphi- explained by the replacement of the K ions in one interlayer by
boles with tetrahedra in chains, and the tectosilicate feldspars hydrated divalent ions, leading to the expansion of this inter-
with continuous frameworks of silica and alumina tetrahedral, layer, causing, in turn, a strengthening of the bond between K+
to yield phyllosilicate clay minerals with flat layers, all involve and the aluminosilicate layers in the two adjacent interlayers
some dissolution and recrystallization. These processes usually (Bassett, 1959). These bonds probably strengthen because of a
occur within the solution phase, when they can confidently be shift of structural hydroxyl groups toward the opened interlayer
labeled as neogenesis, although, as we have seen from Banfield (Norrish, 1973). Regular interstratifications of micas with ver-
and coworkers, descriptions (see Section 20.2.4.1), neogenesis miculite (and also with smectites, as products of further trans-
can also take place by a type of transformation within the solid formation of micas) tend to occur in soils in colder climates,
phase that involves successive depolymerization and repolymer- such as the upland regions of the former Yugoslavia (Gjems,
ization. By contrast, phyllosilicate micas can transform easily to 1970), Scotland (Wilson, 1970), Scandinavia (Kapoor, 1973), and
phyllosilicate clay minerals in the solid state. the South Island of New Zealand (Churchman, 1980). In these
The main changes that occur in these transformations are cold climates, the displacement of interlayer K+ occurs more
exchange of the interlayer cations and reduction in the charge slowly and in more discrete steps, that is, via alternate interlayer
of the layers. Potassium ions occupy the interlayer regions of the regions, than in warmer climates, where the transformation
common micas, biotite and muscovite. The replacement of K+ occurs more rapidly and in a relatively haphazard fashion to give
by hydrated cations such as Mg or Ca leads to a loss of strength irregular layer stacking. The release of K+ from micas is consid-
of binding between adjacent layers. The interlayers expand, so ered to occur by either layer weathering, as proposed by Jackson
that, with complete replacement by hydrated divalent cations, et al. (1952), or edge weathering, as proposed by Mortland (1958),
the basal spacing increases from 1.0 to 1.4 nm and vermiculite or both. In the former, most, if not all, of the K+ in a particu-
is formed. The concomitant reduction in layer charge has been lar interlayer is released virtually simultaneously. This release
supposed to occur by a wide variety of mechanisms. These commonly occurs in the alteration of clay-sized micas. In edge
include incorporation of protons into the layers (Raman and weathering, K ions are released by diffusion from edges and frac-
Jackson, 1966; Leonard and Weed, 1967), exchange of Si for Al in tures. This loss by diffusion commonly occurs in the alteration
the tetrahedral sheet (Jackson, 1964; Sridhar and Jackson, 1974; of larger mica flakes and has been observed as fraying in arti-
Vicente et al., 1977), loss of hydroxyls (Stucki and Roth, 1977), ficially altered micas, but it can also take place alongside layer
and the deprotonation of hydroxyl groups and the loss of octa- weathering in clay-size micas (Fanning et al., 1989).
hedral Fe, both occurring together (Farmer et al., 1971; Douglas, Trioctahedral micas, among them biotite and phlogopite,
1989; Fanning et al., 1989). weather more readily than dioctahedral micas, including mus-
In soils particularly, micas rarely transform completely to covite and most illites. Plants can bring about the transforma-
vermiculite. In soil science, the term “illite” is most commonly tion of biotite to vermiculite through their extraction of K from
used to describe clay-sized micaceous minerals. According to the mineral (Section 20.2.5.3). Among vermiculites in soils, the
Grim et al.’s (1937) original definition of illite, it was “a general dioctahedral forms are more common than their trioctahedral
term for the mica-like clay minerals occurring in argillaceous counterparts (Jackson, 1959). Not only are the dioctahedral ver-
sediments,” which also “showed substantially no expanding lat- miculites more stable, but also they can form from biotites at the
tice characteristics.” It tends to be used more widely in practice. expense of the trioctahedral varieties as a result of a structural
Illites commonly show a deficit of K and an excess of water in rearrangement whereby some octahedral cations are lost from
comparison with muscovite or biotite. This deficit reflects the the structure only to be replaced by some Al cations that are lost
greater ease of loss of K from micas that are fine grained rather from tetrahedral sites (Douglas, 1989).
than coarse, together with a paradoxical especially strong reten- Transformation of micas in soils to expandable phases often
tion of some K in the fine-grained micas against replacement, occurs under acidic conditions. When pHs are relatively low
both in nature and in the laboratory (Fanning et al., 1989). (ca. 5 ± 0.5) and organic matter contents are low, Al is mobile in
Fine-grained micaceous minerals that include some the aqueous phase as hydroxyl cations, and, where wetting and
expanding layers are sometimes also called illite (Grim, 1968; drying frequently occur, the conditions favor the deposition of
Wentworth, 1970; Norrish and Pickering, 1983; Weaver, 1989; Al-hydroxy species in the interlayers of vermiculites (and also
Laird and Nater, 1993). Strictly speaking, however, these are smectites; Rich, 1968). The products, which are nonexpandable or
interstratified illite (or mica)–vermiculites (or smectites). The only poorly expandable, are known by a variety of names includ-
interstratification may be either random or regular. If they are ing dioctahedral chlorite, pedogenic chlorite, 2:1–2:2 intergrade,
regular, with close to a 1:1 mix of the two constituent layer types, chloritized vermiculite, and hydroxyl-interlayered vermiculite
these two types alternate and the basal spacing is a sum of the (HIV), and also their smectitic counterparts, such as hydroxyl-
interlayered smectite (HIS) (Barnhisel and Bertsch, 1989).
20-12 Properties and Processes

Aluminous interlayers can protect vermiculites from further where smectites were among the transformation products of
breakdown (Douglas, 1989) but can be destroyed by chemicals micas (Boyer, 1975). Smectites formed this way have generally
that dissolve Al hydroxyl species, including citrates. Citrates been identified as beidellites. Their genesis contrasts strongly
were once used routinely prior to x-ray diffraction (XRD) analy- with those of most smectites, which form at high pH under poor
ses (Mehra and Jackson, 1960) but their use can lead to the loss drainage (see also Section 20.3.5).
of potentially useful genetic information from the occurrence of Under cool climates, and, with sufficient rainfall, vermiculitic
the aluminous interlayers (Churchman and Bruce, 1988). layers that are interstratified with mica layers can themselves
Vermiculitization of micas/illites has been found to occur be further transformed while the adjacent mica layers remain
by the expansion of the interlayer region into a wedge shape, essentially unaltered. Thus, stepwise transformations of (mus-
known as the “frayed edge site” (Sawnhey, 1972; Nakao et  al., covite) mica, first to regularly interstratified mica–vermiculite,
2009). Through the use of a measurement known as “radioce- then to regularly interstratified mica–beidellite, have occurred
sium interception potential” (RIP), which gives the amount of over a climosequence on increasing rainfall on mica–chlorite
these frayed edge sites, Nakao et al. (2009) have compared min- schist in South Island, New Zealand (Churchman, 1978, 1980).
erals in soils that have formed from parent materials containing These changes to alternate layers have occurred under a current
micas in various parts of Asia for their vermiculitic character in grassland vegetation, rather than under native forest. Indeed,
relation to the moisture regimes in which they have formed. RIP soils within the area that have formed under forest, but with the
measures the selectivity of the frayed edge sites for Cs+ in com- same precipitation regime as one of the wetter sites in the climo-
parison with hydrated ions. A high RIP value, indicating a high sequence under grassland, showed advanced transformation of
selectivity for Cs, indicates a high concentration of vermiculite the mica to a discrete beidellite phase. It appears that the often
per se, whereas a low value can indicate either that little trans- more acidic exudates from trees (e.g., Courchesne, 2006) impose
formation of illite/mica has occurred or else that hydroxyl-Al a stronger weathering regime than that under grassland, so that
interlayering has blocked the frayed edge sites that develop with the driving force exceeds that leading to transformation of alter-
vermiculitization. Nakao et  al. (2009) discovered that, in sub- nate layers alone.
tropical Thailand, with an ustic moisture regime in which there An advantage of many cool-climate studies is that not all pri-
is a distinct dry season, illites showed little alteration and, conse- mary minerals alter at the same rate, and the origin of second-
quently, RIP was low. However, in a strongly leaching udic mois- ary minerals can, therefore, be traced to the few, if not single,
ture regime and hyperthermic temperature regime in Indonesia, primary minerals that have altered. In the bulk of Churchman’s
an advanced degree of vermiculitization was indicated by a high (1978, 1980) studies, feldspars were fresh and only mica and
RIP. By contrast, an udic and mesic moisture regime in temper- chlorite showed signs of alteration. In warmer climates and,
ate Japan, while also producing a high degree of vermiculitiza- with sufficient throughflow of water and passage of time, micas
tion, nonetheless gave a low RIP value. This result arose because break down further to form 1:1 minerals, both kaolinite and hal-
hydroxyl-Al interlayers blocked frayed edges. Nakao et al. (2009) loysite. Although the direct formation of kaolin minerals from
noted that an index of weathering that is based on the degree micas alone cannot be concluded when other primary miner-
of vermiculitization showed no relationship with one based als have also altered, many workers have established that micas
on the oxidation status of Fe, which implied that the Thai soil have altered to form kaolins mainly because of the appearance
was highly weathered despite its mica/illite showing little or no of the secondary minerals as pseudomorphs after the micas.
alteration. The factors that affect the development of Fe oxides in This apparent pseudomorphic replacement applies for kaolinites
soils and those that affect loss of K+ from the interlayers of micas formed in tropical Nigeria (Ojanuga, 1973), from tertiary weath-
and illites need bear no relation to one another. In particular, ering in Europe (Stoch and Sikora, 1976), in ferralitic (lateritic)
Nakao et al.’s (2009) results showed that the balance between the soils in Western Australia (Gilkes and Suddhiprakarn, 1979),
time spent by a soil in a dry season and the extent of leaching and in deeply weathered soils in the continental United States
that occurs plays an important role in determining the extent of (Rebertus et al., 1986), and also for both halloysite and kaolinite
vermiculitization of its constituent micaceous phases. formed alongside each other in close association with biotite in
Under low pH conditions, commonly where organic mat- tropical Malaysia (Eswaran and Yeow, 1976).
ter contents are high, as they often are under forests, micas Mainly with the help of electron microscopy, some workers
may transform to smectites in soils as a result of acid leaching. have even found that kaolin minerals can form from micas early
These conditions typify podzolization and smectites often form in the weathering process including from both biotite (Ahn
through the transformation of micas in the eluviated horizons and Peacor, 1987; Banfield and Eggleton, 1988) and muscovite
of podzols. The resulting smectites are generally Al-rich and (Robertson and Eggleton, 1991). Ahn and Peacor (1987) showed
hence beidellitic (Ross and Mortland, 1966; Churchman, 1980; that kaolinite can also form as (irregularly) intercalated layers
Borchardt, 1989), but may also be montmorillonitic (Aragoneses between biotite layers, presumably by a dissolution/crystallization
and García-González, 1991). Strong weathering without podzol- process whereby one biotite layer gives rise to two kaolinite
ization can also transform micas to smectites (Stoch and Sikora, layers. This change takes place within “plasmic microsystems”
1976; Egashira and Tsuda, 1983; Senkayi et al., 1983; Singh and (Velde and Meunier, 2008) involving small differences in chemi-
Gilkes, 1991; van Wesemael et al., 1995), even in Antarctic soils, cal potentials, which arise because of connections with a major
Alteration, Formation, and Occurrence of Minerals in Soils 20-13

passageway for water outside a rock or geological deposit. Such chlorite/vermiculite intergrade (Murakami et  al., 1996). There
an occurrence—the kaolinization of biotite—may have occurred is also a strong tendency to form 1:1 regular, or “semiregular,”
in weathered tephra beds aged ca. 350,000 years in northern chlorite–vermiculite interstratifications at the next early stage of
New Zealand and which contain biotite in the unweathered par- weathering. This mineral type has been observed in weathering
ent tephra (Rangitawa tephra). The kaolinized mineral occurs by Johnson (1964), Herbillon and Makumbi (1975), Churchman
as a sand-sized golden platy mineral. It comprises (using SEM) (1980), Banfield and Murakami (1998), and Aspandiar and
nearly nine primary (6–8 μm thick), four secondary (1–1.5 μm), Eggleton (2002a, 2002b) among others. A  study  with atomic-­
and five to seven tertiary (0.7 μm) lamellae units, and was char- resolution transmission electron microscopy (TEM) led Banfield
acterized via XRD as a K-depleted, partially random interstrati- and Murakami (1998) to propose that there was a tendency
fied micaceous kaolinite intergrade containing <50% of 1 M toward regular 1:1 interstratification because interlayer Mg and
trioctahedral mica and >50% of partially disordered dioctahe- Fe (oxyhydr)oxides are removed from every second interlayer on
dral kaolinite (Shepherd, 1984; Lowe and Percival, 1993). account of a layer shift (of ∼a/3) occurring after the removal of
Conversely, some (Eswaran and Yeow, 1976; Gilkes and one interlayer (oxyhydr)oxide that thereby stabilizes the  adja-
Suddhiprakarn, 1979) have found that vermiculite—often con- cent interlayer (oxyhydr)oxide. The stabilization means that the
sidered to be an unstable intermediate phase (Kittrick, 1973)— (oxyhydr)oxide in the next interlayer is more labile to replace-
nonetheless occurred alongside kaolin minerals in soils formed ment. However, Wilson (2004) warned that observations of reg-
under strong leaching. One of the likely reasons for the appear- ular chlorite–vermiculite interstratifications should be treated
ance of apparently early weathering products such as vermic- with caution as products of weathering alone because some, at
ulite alongside apparently late stage products such as kaolin least, of the parent rocks may have undergone prior hydrother-
minerals is that iron (oxyhydr)oxides are very common prod- mal alteration. Interstratified chlorites and also vermiculite-like
ucts of the weathering of micas. The secondary iron phases coat phases have been found to occur in some metamorphosed rocks.
other minerals such as vermiculites and preserve them against Nonetheless, not all sequences of alteration of chlorites are the
further breakdown. They include goethite (Sousa and Eswaran, same, with several authors (e.g., McKeague and Brydon, 1970;
1975; Eswaran and Yeow, 1976; Gilkes and Suddhiprakarn, Bain, 1977; Churchman, 1980; Ross et al., 1982; Righi et al., 1993;
1979; Banfield and Eggleton, 1988) as well as hematite (Gilkes Carnicelli et al., 1997) finding that the chlorite component, often
and Suddhiprakarn, 1979). Several studies of the products of of chlorite–mica schists, disappeared as a result of acid weather-
natural weathering of micas (Rice and Williams, 1969; Aldridge ing in a podzolized soil, or spodosol. Chlorite dissolved, typi-
and Churchman, 1991; Aoudjit et al., 1996; Seyama et al., 1996), cally leaving a solid residue of iron oxides and oxyhydroxides,
using variously Mössbauer and XPS spectroscopy, as well as the for example, goethite (Bain, 1977; Ross et al., 1982). Frequently,
laboratory study of Farmer et al. (1971), have shown that total however, there is further development of the interstratifications
Fe and Fe(II) were depleted from micas on weathering while of chlorite with vermiculite to discrete vermiculite (Loveland
Fe(III), Fe gels, and Fe(oxyhydr)oxides built up outside the and Bullock, 1975; Murakami et al., 1996). Often also, smectites
micas. Oxides and hydroxides of other metals, including Al, as are considered to form from chlorite (Herbillon and Makumbi,
gibbsite (Gilkes and Suddhiprakarn, 1979), and also titanium 1975; Carnicelli et  al., 1997). Although the primary chlorites
dioxide (Milnes and Fitzpatrick, 1989), may also have formed, at are trioctahedral, the resulting vermiculites and smectites are
least partially, from micas. mostly dioctahedral (Wilson, 2004). Ultimately, kaolin miner-
als, both kaolinite (Herbillon and Makumbi, 1975; Murakami
20.2.4.4  Processes and Products of Alteration et  al., 1996) and also halloysite (Cho and Mermut, 1992), can
of Chlorites by Weathering result from the strong weathering of chlorites.
Chlorites occur most commonly as trioctahedral minerals in
parent materials for soils. They originate mainly from low-grade 20.2.4.5  Processes and Products of Alteration
metamorphic rocks and as products of the early alteration of of Serpentines by Weathering
Fe- and Mg-containing primary minerals such as augite, horn- Serpentinite rocks, which are dominated by serpentines (mainly
blende, biotite, and serpentines (see Section 20.2.4.5). They are chrysotile, antigorite, and minor lizardite), together with iron
not common in soils mainly because of their low stability with oxides and such minerals as amphiboles, pyroxenes, and talc
regard to weathering. The initial stages of their alteration are (e.g., Bonifacio et al., 1997), are generally unstable in soils. In
similar to those of micas and involve the loss of their interlayer central California, this rock type gave rise to virtually pure
species, most often hydroxides of Mg (i.e., brucite structures), Fe-rich smectite in the fine clay (<0.2 μm) fraction (Wildman
but also those of Fe and other cations. Products of the earliest et al., 1968). These authors attributed the mineralogical change
stages of weathering of chlorites have been identified variously to the loss of the more mobile elements Mg and Si and rela-
as a randomly interstratified hydrous phase (Churchman, 1980), tive enrichment of Fe and Al. In the Massif Central in France,
swelling chlorite, which is a type of chlorite depleted of some of alteration of serpentinite in a poorly drained B horizon led to
its interlayer hydroxides (Stephen and MacEwan, 1951; Bain and a trioctahedral chlorite, which is normally regarded as a pri-
Russell, 1981), and sometimes also regular interstratifications of mary mineral, and also to its alteration products: a regularly
chlorite and swelling chlorite (Churchman, 1980), as well as a interstratified chlorite–vermiculite and a nontronitic smectite
20-14 Properties and Processes

(Ducloux et al., 1976). This change, while involving some loss of (in which cations such as sodium occur) (Fisher and Schminke,
Mg and Si—as expected in an open soil system—is more typical 1984). The hydration and breakdown of glass results in fluxes of
of a closed system (Ducloux et al., 1976). The weathering prod- some elements from the glass into interstitial pore waters, and
ucts of a serpentinite in northwest Italy were found to depend the very rapid precipitation of secondary minerals from such
strongly on drainage conditions (Bonifacio et al., 1997). Low- solutions as well as replacement of glass shards by new miner-
charge vermiculite sometimes formed but either dissolved or als (e.g., Daux et  al., 1994). Dissolution of basaltic glass, and
was transformed to smectite if drainage was poor. An alumi- probably also other glass types, as determined by Oelkers and
nous chlorite could result from either the preformed vermicu- Gislason (2001) and Gislason and Oelkers (2003), proceeds in
lite or smectite as a result of interlayering by hydroxy-Al. Lee effectively three steps: (1) relatively rapid and largely complete
et al. (2003) in California and Caillaud et al. (2004) in France removal of univalent and divalent cations from the near-surface
also found that vermiculite and smectite were formed in the glass structure via the breaking of metal–oxygen bonds and
course of weathering of serpentinites. In general, the smec- their replacement with proton–oxygen bonds, (2) Al-releasing
tites formed from serpentinites per se are complex and het- exchange reactions between three aqueous H+ ions and Al in the
erogeneous according to Caillaud et  al. (2004). Caillaud et  al. glass structure, and (3) relatively slow detachment of partially
(2004) focused on a microsystem in the serpentinite weathering liberated silica. The tetrahedrally coordinated Si–O bonds are
system. The types of vermiculite and/or smectite formed var- the most stable bonds in the glass framework. Si tetrahedra on
ied, with both trioctahedral and dioctahedral structural types the glass surface may be connected to the glass framework via
covering a range of layer charges, depending upon their origi- one to three bridging oxygens, and the rate of release of any Si
nating primary minerals. For instance, a thin lizardite bastite atom at the surface decreases markedly as the number of bridg-
gave rise to Al-poor trioctahedral saponite, whereas a diocta- ing oxygen bonds increases (Gislason and Oelkers, 2003). The
hedral Fe-rich montmorillonite appeared to derive directly breaking of Al–O bonds does not destroy the glass framework
from chrysotile. Using a toposequence in Taiwan on serpen- but instead only partially liberates the silica tetrahedral chains
tinite containing chrysotile, antigorite, and lizardite, and also by removing adjoining Al atoms (Gislason and Oelkers, 2003).
chlorite and talc, Hseu et  al. (2007) were able to identify the Glass dissolution rates demonstrably increase with decreasing Si
products of weathering as, first, smectite that was dominantly content (Wolff-Boenisch et al., 2004), and, hence, basaltic glass
trioctahedral, then interstratified chlorite–vermiculite, and, (low in Si) usually dissolves faster than andesitic glass (inter-
finally, kaolinite and quartz. mediate Si content) or rhyolitic glass (high in Si) under simi-
lar environmental conditions (Neall, 1977; Hodder et al., 1990;
20.2.4.6  Processes and Products of Alteration of Shoji et al., 1993b; De Vleeschouwer et al., 2008; Sigfusson et al.,
Volcanic Parent Materials by Weathering 2008; Figure 20.2). In all cases, fragmental and vesicular glass
One outstanding feature of volcanic materials as parent materi- components, such as those which occur in tephra deposits, have
als for clay-size minerals is that they usually contain glass, which high surface areas and are very porous and so break down very
is a fast-weathering source of Si and Al (and other elements) for quickly, and at rates closely proportional to geometric surface
mineral neogenesis. They can also contain other weatherable areas (e.g., Dahlgren et  al., 2004; Wolff-Boenisch et  al., 2004).
minerals, depending on their origin, nature, and composition. The initial alteration of basaltic glass, described widely as “palag-
Broadly, volcanic materials may originate from effusive erup- onitization,” is described as a special case in Section 20.2.4.6.3.
tions, forming lavas, or explosive eruptions that generate frag-
mental, unconsolidated deposits called pyroclastic materials, or 20.2.4.6.2  F
 ormation of Allophane and Halloysite
tephra, which may be distributed widely by the wind. Among from Volcanic Parent Materials
the latter, there are three main types, based on composition. Allophane and halloysite are the most common secondary min-
These are (1) basaltic, which are rich in Fe and Mg, reflecting erals that are formed in soils developed from loose volcanic
usually high contents of ferromagnesian, or mafic, minerals, material or tephra, which may be ash, pumice, and cinders (the
namely, olivines, amphiboles, and pyroxenes, as well as feldspars last also referred to as scoria).
and brownish-colored basaltic glass low in Si and relatively high Using 27Al and 29Si NMR, Hiradate and Wada (2005) have
in Al; (2) rhyolitic, which have abundant Si-rich glass compara- deduced a mechanism for the formation of allophane from glass
tively low in Al, and which may contain minor amounts of mafic as another step in the weathering-synthesis process (Figure
minerals including biotite, and also feldspars; and (3) andes- 20.5). This mechanism involves (1) dissolution of Al mainly
itic or dacitic, which are intermediate in composition between from volcanic glass (via Al-releasing exchange reactions with
basaltic and rhyolitic eruptives (see Section 33.3, for more details protons) and its concomitant transformation from its tetrahe-
on their composition, occurrences, and properties). dral to octahedral state, from IVAl to VIAl; (2) hydrolysis of the
Al released into solution to give a gibbsite-like sheet; (3) disso-
20.2.4.6.1  Glass lution (via breaking of Si–O bonds) of Si from volcanic glass,
The alteration of glass is a special case. Glass is an amorphous where it occurs as a silica gel-like polymer, to give monosilicic
solid with a poorly ordered internal structure comprising loosely acid in solution; and (4) reaction between the gibbsite-like sheet
linked SiO4 tetrahedra with considerable intermolecular space and monosilicic acid to generate allophane.
Alteration, Formation, and Occurrence of Minerals in Soils 20-15

Volcanic glass comprise tiny hollow spherules or “nanoballs” (Parfitt, 2009). In

Formation of soils, there are two main types: (1) Al-rich, with Al:Si ∼ 2:1—
gibbsite-like sheet
these are imogolite-like or proto-imogolite allophanes—and
IV Dissolution of Al
Al (2) Si-rich, with Al:Si ∼ 1:1—these are halloysite-like allophanes.
Q4 0Al, Q3 0Al, VI
Al The imogolite-like nanocrystalline structure applies only to
Q4 1Al, Q3 1Al
Al-rich allophane, which is the most common type (Parfitt,
2009). Generally, it has an XRD pattern that is often indefinite,
even if distinct peaks appear for some samples (Parfitt, 1990),
Dissolution of Si but the pattern is likely to be indistinct when allophane is associ-
(breaking of Si–O–Si bonds)
ated with long-range-ordered crystalline minerals. Therefore, a
number of other sophisticated instrumental methods have been
proposed for its identification. Earlier, these included infrared
spectroscopy, differential thermal analysis, and TEM (Fieldes,
VI
Al 1955). More recently, electron diffraction (Wada and Yoshinaga,
Si(OH)4 Q33Al 1969), small-angle neutron scattering (Hall et  al., 1985), 27Al
and 29Si NMR (Goodman et al., 1985; Hiradate and Wada, 2005;
Monosilicic acid Formation of allophane Hiradate et al., 2006), and XPS (He et al., 2008) have also been
used. Yet, it is a chemical method, for the extraction of Al and
FIGURE 20.5  Model depicting the formation of allophane. Q notation
Si, among other metals, using acidified ammonium oxalate and
describes the connectivity of a Q unit—that is, an Si atom surrounded
by four oxygen atoms—to other Si atoms (Wright and Sommerdijk, developed long ago by Tamm (1922), which has become the stan-
2001): Q4 indicates that the Q unit is fully interconnected with sili- dard (and critically important) procedure for both identifying
cate groups, and Q3 indicates that the Q unit is linked in three places and quantifying allophane (Parfitt and Henmi, 1980; Parfitt and
(referred to as branching points). (Redrawn from Hiradate, S., and S.-I. Wilson, 1985; Wada, 1987, 1989).
Wada. 2005. Weathering processes of volcanic glass to allophane deter- Halloysite often also forms by the weathering of tephra.
mined by 27Al and 29Si solid-state NMR. Clays Clay Miner. 53:401–408, Although halloysite, as a 1:1 Si:Al mineral with the same alu-
Fig. 4. With permission of The Clay Minerals Society.) minosilicate composition as kaolinite, has often been identified
by a peculiar shape in electron micrographs (see Section 20.3.2),
This process is consistent with modern understanding about it is only the occurrence, or else evidence for prior occurrence,
the crystal structure of allophane. Its structure is regarded as of interlayer water that distinguishes halloysites unequivo-
being based on that of imogolite, another aluminosilicate that cally from kaolinites (Churchman and Carr, 1975; Churchman,
is sometimes found (typically in small amounts) in soils derived 2000). With the knowledge that allophane is a fast-forming SRO
from tephra and in some other soils including podzols. Imogolite (nanocrystalline) product from the dissolution mainly of glass
has an ideal chemical formula of SiO2 · Al2O3 · 2H2O and, there- whereas halloysites, being crystalline with long-range order, gen-
fore, an Al:Si ratio of 2:1. The imogolite structure, established by erally give distinct peaks in XRD, there has been much debate
Cradwick et al. (1972), consists of a defect gibbsitic Al-octahedral over the question of whether allophane alters to halloysite and,
sheet framework. Si in each silica tetrahedron is attached to this if so, how this change occurs. There have been two main schools
framework by sharing three of its O atoms (hence the Q3 nota- of thought regarding this question. One of these, proposed by
tion shown in Figure 20.5) with an octahedrally coordinated Al Fieldes (1955) and which was the predominant idea until around
on the gibbsitic sheet while the remaining O atom on the tet- the 1980s, held that allophane altered to halloysite with the pas-
rahedrally coordinated Si acquires an H atom to form a Si–OH sage of time. This mineralogical change was considered to occur
bond pointing away from the gibbsitic sheet. Although imogo- by a solid-phase transformation involving dehydration and
lite, which comprises long, thin hollow nanotubes, always in “crystallization” from an “amorphous” material.
bundles, has a definite XRD pattern (Yoshinaga and Aomine, According to the alternative view, which was formulated in
1962), and, hence, some long-range order, allophane gives Parfitt et  al. (1983) and subsequent papers (e.g., Parfitt et  al.,
extremely broad, low-intensity humps in XRD and is regarded as 1984; Parfitt, 1990, 2009), it is the concentration of Si in soil
a mineral with short-range order (SRO), or a poorly ordered alu- solutions [Si], and availability of Al, which largely determine
minosilicate, as well as a “structured nanomineral” (Hochella, the nature of the aluminosilicate secondary minerals that form
2008; Theng and Yuan, 2008; McDaniel et al., Section 33.3). The from volcanic parent materials by weathering. In particular,
best term for it is “nanocrystalline,” meaning structured at the allophane is favored by a lower [Si], whereas halloysite tends to
nanometer scale, that is, 1–100 nm. (Another nanocrystalline result when [Si] is relatively high. This theory was based on min-
mineral that occurs commonly but usually in relatively small eralogical and soil solution data from a rainfall sequence of soils
amounts in weathered tephras and other materials, and which formed on tephra-derived deposits in northern New Zealand. It
is analogous to allophane, is ferrihydrite, described later herein.) was supported by Singleton et al. (1989) who measured in detail
Allophane composition varies over a much greater range than modern solution [Si] in soils forming a drainage sequence on
that of imogolite, although morphologically all unit particles tephric materials of similar composition and age.
20-16 Properties and Processes

Parfitt’s theory helped to explain some anomalies concerning wet interglacial periods but that halloysite predominated during
the application of Fieldes’ (1955) hitherto pervasive theory that cool, dry glacial periods, implying that changing environmen-
allophane seemed to inevitably alter or “transform” to halloysite tal conditions had led to changing [Si] and hence different clays.
with time. Fieldes’ theory was based on the worldwide recogni- A similar finding was recorded by Bakker et al. (1996). Thus, the
tion that halloysite tended to occur at depth in many tephra- weathering of tephra followed separate pathways leading to the
derived soil sequences whereas allophane predominated in formation either of allophane or halloysite, rather than follow-
surface horizons. Because such sequences become stratigraphi- ing a single pathway governed by time (Lowe, 1986).
cally older with increasing depth, the assumption was made that The idea that a high [Si] favored halloysite also made sense
allophane formed first and then, after ca. 10,000–15,000 years, of reports of the formation of halloysite instead of allophane
it apparently transformed to halloysite (see review by Lowe, when there was a thick overburden (Mejia et al., 1968; Aomine
1986). However, in northern New Zealand, McIntosh (1979) and Mizota, 1973; Wada, 1987; Cronin et  al., 1996), and also
showed that authigenic halloysite (both spheroidal and tubular) where drainage was impeded or poor (Aomine and Wada, 1962;
had formed by recent processes in tephra deposits only ∼1800 Dudas and Harward, 1975; Stevens and Vucetich, 1985; Cronin
years old. He demonstrated that such halloysite formation was et al., 1996). Both these situations would give rise to a buildup
a consequence of resilication from a Si-rich soil solution—the of Si that, it was then thought, would react with preformed allo-
resilication was indicated by Si:Al ratios of ∼2 at depths of ≥ 2 m, phane to form halloysite (Aomine and Wada, 1962; Dudas and
in contrast to values of ≤1 in surface horizons, and by modern Harward, 1975; Saigusa et al., 1978).
lysimeter leachate compositions (McIntosh, 1980). Other reports Zehetner et al. (2003), in Andean Ecuador, Rasmussen et al.
had previously demonstrated the seemingly “anomalous” occur- (2007), in the Sierra Nevada in California, and Chadwick et al.
rence of halloysite in young soils (Hay, 1960; Bates, 1962; Bleeker (2003), on Kohala Mountain in Hawaii, studied the mineralogy
and Parfitt, 1974), and electron micrographs showed a close of soils formed at different altitudes but from a common vol-
association of halloysite with the surfaces of parent minerals/ canic source (andesitic/dacitic ash, andesitic lahar, and basal-
mineraloids, both glass (Dixon and McKee, 1974) and feldspars tic lava, respectively). In each case, it was found that allophane
(Tazaki, 1979; see Lowe, 1986, and also Figure 20.3 herein). (with imogolite and ferrihydrite in Hawaii) was dominant in
Similarly, Ogura et  al. (2008) showed in recent, proximal sco- soils at higher altitudes and halloysite in soils at lower altitudes,
riaceous tephras (deposited since AD 800) near Mt. Fuji, Japan, confirming the trends discovered by Nizeyimana et  al. (1997)
that the coarse particle sizes and large pores facilitated rapid in a similar study on volcanic materials in Rwanda. At higher
drying, aiding the concentration of Si and hence neoformation altitudes, the precipitation is greater; hence, leaching is stronger,
of tiny spherical halloysite particles. Thus, it became clear that solution [Si] is lower, and allophane prevails in the soils formed
halloysite, rather than allophane, was able to form directly from there. Conversely, precipitation and degree of leaching are lower,
tephra materials in young soils under certain conditions where and [Si] in solution is higher, at lower altitudes and so halloysite
[Si] was relatively high. In reality, [Si] may vary seasonally, and dominates in these soils. Chadwick et al. (2003) emphasized in
kinetic considerations can lead to the formation of halloysite if their Hawaiian study, however, that as moisture increased along
the periods of high [Si] greatly exceed those when [Si] is low. The the sampling transect, different sets of secondary minerals were
use of oxygen isotopes to trace the temperature of formation of favored in response to conditions controlled by arid conditions,
minerals, among other techniques, led Ziegler et  al. (2003) to by rapid and intense cycles of wetting and drying, or by essen-
conclude that halloysite has formed continuously from the early tially continuously wet conditions. They developed a leaching
stages of formation from basalt in an arid zone in Hawaii as the index as the ratio of water balance to the integrated porosity of
result of prolonged extremely dry seasons following short peri- the top meter of soil on an annual basis. The index reached 1
ods of intense rainfall. The release of Al in the latter had been (total filling of the pore space each year) where the mean annual
followed by a prolonged buildup of Si and hence halloysite for- precipitation (MAP) was ∼1400 mm. Index values >1 indicated
mation. In addition, it had long been known that allophane was intense leaching conditions because of pore water replacement;
present in some very old weathered-tephra sequences (Ward, leaching losses of soluble base cations and Si were nearly com-
1967; Tonkin, 1970), which had always been a puzzle in view of plete at such index values, whereas only 60% of Al had been lost.
the Fieldes’ model (although the amounts of allophane were not Where index values were <1, leaching losses were progressively
well quantified at that time). A key study was that by Stevens lower with the lowest rainfall sites having lost 10%–20% of the
and Vucetich (1985) who used ammonium oxalate dissolution original base cations and Si, but none of the Al.
methods to quantify allophane content in a 10 m high tephra Rasmussen et al. (2007) found further that soils in interme-
weathering sequence in northern New Zealand dating back ca. diate zones of altitude contained both allophane and halloysite
350,000 years (the basal tephra being reidentified more recently and also that soils at extremely high altitudes had neither allo-
as the Rangitawa tephra: Lowe et al., 2001). They demonstrated phane nor halloysite but instead were dominated by interlayered
unequivocally that abundant allophane was present in many 2:1 Si:Al layer silicates, which they considered to be inherited
beds in the sequence. Moreover, through tephrochronology, from the parent material. These authors considered that climate
Stevens and Vucetich (1985) were able to show that allophane controlled the clay minerals formed from the volcanic materials.
(as well as subordinate gibbsite) was predominant during warm, Rainfall explained the secondary phases formed except at the
Alteration, Formation, and Occurrence of Minerals in Soils 20-17

Tephra Phytoliths Dominant clay- Environmental Age (cal ka)

fraction minerals in interpretation or date
Tree origin (total) Grass origin (total) buried soil horizons
Rotomahana 10 June AD 1886
Glass, allophane Deforestation (human)
Kaharoa AD 1314 ± 12
Taupo AD 232 ± 5
Rotokawau 3.6
Whakatane Al-rich allophane Relatively warm, wet 5.5
Mamaku 8.0
Rotoma 9.5
Waiohau
13.7
Rotorua 15.4
Halloysite,
Rerewhakaaitu Relatively cold, dry 17.6
Si-rich allophane
Okareka 21.8
Te Rere 25.3
0 20 40 60 80 100 0 20 40 60 80 100
%

FIGURE 20.6  Dominant clay minerals and phytoliths identified in buried soil horizons in a sequence of 11 rhyolitic tephras and one basaltic
tephra (Rotokawau) deposited near Rotorua, New Zealand, since ∼25,000 calendar (cal) years ago showing the relationship between the clay min-
eral assemblages and environment (based on Green, 1987; Sase et al., 1988; Lowe and Percival, 1993; Kondo et al., 1994). ka, thousands of years
before present. Dates for Kaharoa and Taupo eruptions are from Hogg et al. (2003, 2011); other ages are from Lowe et al. (2008). (Modified after
Newnham, R.M., D.J. Lowe, and P.W. Williams. 1999. Quaternary environmental change in New Zealand: A review. Prog. Phys. Geog. 23:567–610.
With permission of SAGE Publications.)

higher, colder sites, where temperature inhibited mineral altera- allophane had formed in soils developed in younger, porous,
tion and the formation of new mineral phases. These altitudinal permeable ash deposits, while soils formed in older, less porous
(hence rainfall) studies have further demonstrated the validity and less permeable scoria and consolidated tuffs contained crys-
of Parfitt et  al.’s (1983) model for the effect of [Si] in control- talline minerals, especially halloysite, but no allophane.
ling the formation of secondary minerals from the weathering Other aluminosilicate minerals can also form from volcanic
of volcanic parent materials (where Al availability effectively is parent materials by weathering. Possible products include 2:1
unlimited). Further evidence for the validity of this model was Si:Al aluminosilicates, which are most likely to occur where bio-
demonstrated in a succession of buried soil horizons formed tite is present as a product of the transformation of this mineral
on rhyolitic tephras dating back ∼25,000 years near Rotorua through the replacement of interlayer potassium ions, most prob-
in New Zealand (Figure 20.6; Newnham et al., 1999). Cold and ably by hydrated divalent cations (see Section 20.2.4.3). Various
dry conditions and grassland vegetation before ∼13,000 years workers in the past (reviewed by Lowe, 1986) have proposed
ago resulted in halloysite (with minor Si-rich allophane) being that a wide variety of 2:1 Si:Al aluminosilicates have formed in
formed because of limited Si leaching under lowered rainfall. soils from volcanic parent materials, including volcanic glass,
Al-rich allophane was formed after ∼13,000 years ago when Si but several more recent publications (e.g., Nieuwenhuyse et al.,
loss increased through stronger leaching as rainfall and temper- 2000; Kautz and Ryan, 2003; Mirabella et al., 2005; Rasmussen
atures increased and forest replaced the grassland. In addition, et al., 2007) have confirmed that these types of phyllosilicates,
halloysite formation was likely enhanced through enrichment including illite, smectite, vermiculite, chlorite, kaolinite, and
by SiO2 in leachates carried down the section as the tephras their interstratifications with one another, may be inherited
accumulated above, and by a concomitant reduction in perme- either from the parent pyroclastic material, where they may have
ability in the halloysitic horizons, which have a greater bulk formed by hydrothermal processes prior to weathering, or else as
density (Parfitt et  al., 1983; Bakker et  al., 1996). The paleoen- a contaminant of other, nonvolcanic origin such as aeolian dust.
vironmental interpretation was established by analyses of phy- Nonetheless, some aluminosilicate, and also more aluminous
toliths (siliceous plant cell remains) at the same site together minerals, do form from volcanic parent materials either along-
with palynological and other evidence from sites elsewhere in side, or instead of, allophane and halloysite (Theng et al., 1982).
the region (Sase et al., 1988; Kondo et al., 1994; Newnham et al., Parfitt et al. (1983) noted that gibbsite was recognized in a 1968
1999). A similar conclusion was reached in a parallel study in report as a product of the weathering of volcanic ash that was
Mexico (Sedov et al., 2003). deposited in root channels in soils from Japan while it has also
The model was further supported by a study of seven pedons been found to occur in the weathering products of volcaniclastic
within the caldera of a volcano in Italy, which showed that the materials in northern California that have rhyolitic, andesitic,
secondary minerals reflected the hydraulic properties, namely, and basaltic inputs (Takahashi et al., 1993). In these latter soils,
drainage, of the parent materials (Vacca et al., 2003). In this case, gibbsite occurs alongside imogolite (or imogolite-like 2:1 Al:Si
20-18 Properties and Processes

allophane) and also halloysite. This concurrence suggests that considered that both are products of the early stages of weath-
gibbsite formation may occur during the wet season (winter and ering of volcanic glass. In a hot, wet (perudic) climate in
early spring) of the Mediterranean (or xeric) climate in northern Guadeloupe similar to those studied by Nieuwenhuyse et  al.
California, while, as soils dry out in the approach to summer (2000), Ndayiragije and Delvaux (2003) found that gibbsite,
(the dry season), first imogolite/allophane,  and  then  halloy- allophane, kaolinite, and hydroxyl-Al-interlayered smectite/
site, is formed. In humid tropical conditions in Cameroon, the vermiculite coexisted in a soil from andesitic–dacitic ash, but
occurrence of minor gibbsite in a soil developed on hydrother- there was no halloysite in this soil. This soil appears to be similar
mally altered nephenelitic materials (Si-poor, alkali-rich lavas) mineralogically to those studied by Nieuwenhuyse et al. (2000),
was attributed to the development of a strongly developed which occurs in a similar climate, except for the hydroxy-Al 2:1
microporosity that facilitated the elimination of silica through Si:Al aluminosilicate. This last mineral was seen by Ndayiragije
leaching (Etame et al., 2009). and Delvaux (2003) as an inheritance from the parent tephra
There appears to be an annual cycle among the secondary min- and its aluminous interlayers were regarded as performing an
erals resulting from the continually dissolving volcanic parent antigibbsite (Jackson, 1963) or analogous antiallophane effect by
materials, particularly glass. Fieldes (1968) had proposed that hal- preferentially sequestering Al, at least until the available inter-
loysite formation occurred from allophane precursors as a result layers became saturated.
of seasonal drying (a process invoked also by Chadwick et  al., Although activity of Si is clearly critically important in gov-
2003, whereby rapid wetting and drying cycles in arid zones were erning the formation of halloysite, allophane, or gibbsite in
said to destabilize allophane, forcing it to “dewater and transform soils from volcanic parent materials (especially tephra) (see,
into halloysite”). Lilienfein et al. (2003) studied a chronosequence e.g., a stability diagram for these minerals in Churchman,
of quite young soils on andesitic mudflows in northern California 2000, Figure 1.11), there may also be competitors for Al, such as
nearby those in Takahashi et al.’s (1993) study and found that the hydroxyl-Al-interlayered smectite/vermiculite, as discussed by
amount of allophane increased linearly and quite rapidly in soils Ndayiragije and Delvaux (2003) (see also Kleber et al., 2007).
up to 600 years of age, although the oldest of these soils had less Quite often competition for Al also arises from organic mat-
than half as much allophane as those studied by Takahashi et al. ter (especially large quantities are derived from, e.g., pampas
(1993) and hence were probably less well developed than the latter grass Miscanthus sinensis in Japan), which gives rise to fast-
soils. Lilienfein et al. (2003) did not record any gibbsite in their forming, resistant Al-humus complexes in soils with pH < 5
soils. (Shoji et al., 1993a; Dahlgren et al., 2004; Hiradate et al., 2004;
By contrast, Nieuwenhuyse et al. (2000), who also studied a Parfitt, 2009). Carboxyl groups of humic materials and the
chronosequence on andesitic parent materials (lava, in this case) 2:1 layer silicates effectively compete for dissolved Al, leaving
but in a humid tropical climate in Costa Rica, found all of allo- little Al available for coprecipitation with Si to form allophane
phane, kaolin minerals—kaolinite and halloysite—and gibbsite or imogolite (Dahlgren et  al., 2004; Theng and Yuan, 2008).
(as well as Al- and Fe-humus complexes and ferrihydrite) in The preferential incorporation of Al into Al-humus com-
soils from all ages of the parent lavas, ranging from 2,000 to plexes, as with hydroxyl-Al interlayers of 2:1 layer silicates as
∼450,000 years. Currently, mean monthly precipitation exceeds noted above, is another example of the “antiallophane” effect
potential evaporation every month of the year in the present cli- (McDaniel et al., Section 33.3). Thus, preformed allophane dis-
mate for these soils, so there is no dry season to explain the pos- integrated and was replaced by Al-humus after only 30 years
sible formation of relatively Si-rich kaolin minerals along with under bracken fern, consistent with a fall in pH from 5.2 to
Si-free gibbsite and Si-poor (i.e., Al-rich) allophane. To explain 4.6 (Johnson-Maynard et  al., 1997). Furthermore, weather-
the simultaneous appearance of these different minerals, ing of tephra from the 1980 eruption of Mt. St. Helens led to
Nieuwenhuyse et al. (2000), like Newnham et al. (1999), pointed Al-humus and also hydroxy-Al interlayers in 2:1 Si:Al alumi-
to palynological evidence of a past drier climate, which evi- nosilicates rather than to any of allophane, imogolite, or opal-
dently occurred in this region around the last glacial maximum. ine silica (Dahlgren et al., 1997). However, opaline silica can
This drier climate, as at Rotorua in New Zealand (Figure 20.6), form alongside Al-humus complexes, and Fe may also become
would have enabled Si-rich halloysite to form at that time, and incorporated into complexes with humus (Wada, 1989). Recent
some of it, at least, has persisted into the current strong leaching studies in Ecuador (Poulenard et al., 2003) and Japan (Yagasaki
regime, with an average annual precipitation of 4500 mm year −1. et  al., 2006) have shown, respectively, that Al-humus com-
Nieuwenhuyse et al. (2000) proposed that gibbsite is formed in plexes form rather than allophane when the content of organic
the soils as a result of the disintegration of the kaolin minerals C is particularly high or that allophane is dissolved in favor
under strong leaching. This mechanism explains the dominance of Al-humus complexes when organic C content increases. As
of gibbsite among secondary minerals after 450,000 years of well, Al-humus complexing predominates at sites more distal
soil formation. By way of contrast, Certini et  al. (2006) found to volcanoes because such sites infrequently receive a “top up”
that soils formed from 200,000 year old trachyandesite pyro- of Al through the deposition of weatherable tephras in com-
clastic materials in Italy showed only well-formed gibbsite and parison with sites closer to volcanic sources that are more reg-
an “embryonic” halloysite in their clay fractions. These authors ularly dusted with tephra.
Alteration, Formation, and Occurrence of Minerals in Soils 20-19

Crystalline
minerals
80
Mt Gambier
Volcanic
crystals
60

%
100
40 Allophane (≤12%)
%

SRO
Exotic Ferrihydrite (≤4%)
minerals 70
Glass Kaolinite-smectite
20 interstratification

silicates
Layer
Unaltered
Illite
Altered Occas. smectite

0 0

80

Mt Schank
Glass
60

Crystalline %
minerals 100
40 Unaltered
%

Volcanic Allophane (≤20%)

crystals SRO
Ferrihydrite (≤7%)
20

Exotic 30
minerals Altered Layer Kaolinite-smectite interstr.
silic. Occas. smectite
0 0
Primary tephra composition Soil clay composition

FIGURE 20.7  Contrasts in sand mineral assemblages of soils on mid-Holocene basaltic tephra erupted from Mt. Gambier and nearby
Mt. Schank in South Australia have led to markedly different soil clay compositions under a xeric moisture regime. SRO, short-range order (i.e.,
nanocrystalline); interstr., interstratification; occas., occasional. (Modified after Lowe, D.J., and D.J. Palmer. 2005. Andisols of New Zealand and
Australia. J. Integr. Field Sci. 2:39–65. With permission of Tohoku University.)

A variety of secondary minerals could be found in soils devel- former are dominated by layer silicate minerals, including inter-
oped in the erupted material from the basaltic volcanoes at Mts. stratifications of kaolinite and smectite, illite, and some discrete
Gambier and Schank in southeast South Australia, which are smectite. The secondary minerals in soils in the vicinity of Mt.
only 10 km apart and both about 5000 years old (Lowe et al., 1996; Schank show less variety. They tend to contain more allophane
Lowe and Palmer, 2005; Takesako et al., 2010). The main types of and ferrihydrite than those from the Mt. Gambier area. For the
clay minerals formed in a xeric moisture regime with a relatively soils from both sites, while both kaolinite–smectite and illite
low average annual precipitation of 700 mm are shown for each occur in many Australian soils (Norrish and Pickering, 1983;
location in Figure 20.7. They are compared with the categories Churchman et al., 1994) and probably do not originate from the
of primary minerals in the parent materials, which comprise recent volcanic material, the discrete smectite found in poorly
both volcanic and nonvolcanic “exotic” minerals incorporated drained subsoils is probably formed by neogenesis from elements
into the eruptives from underlying calcareous sands and lime- from the dissolution of the basaltic tephra (Lowe et  al., 1996;
stone. There is a contrast between the clays found at or near Mt. Lowe and Palmer, 2005; Takesako et  al., 2010). Notably, there
Gambier, on the one hand, and Mt. Schank, on the other. The was no halloysite formed in any of the soils at either Mt. Gambier
20-20 Properties and Processes

or Mt. Schank. Allophane showed a range of composition within climatic conditions from late glacial to postglacial periods;
profiles; its Al:Si ratio determined using acid oxalate-extractable increasing rainfall and fewer prolonged dry periods resulted in
Al (minus organically associated pyrophosphate-extractable Al) higher Al:Si ratios because of increasing desilication.
as a ratio to acid oxalate-extractable Si was Al:Si ∼ 2 in upper Lowe (1986, 1995) and Lowe and Percival (1993) summarized
parts of the soil profiles but dropped to Al:Si ∼  1 lower in the data on the critical conditions for the formation of each of the
same profiles (Lowe et al., 1996; Lowe and Palmer, 2005). Lowe main products of the weathering of volcanic ash. These are given
et al. (1996) suggested that there had been seasonal leaching dur- in Figure 20.8, which also shows if Andisols are likely to have
ing winter and early spring, leading to the formation of Al-rich formed, and if they are of the allophanic or Al-humus (nonal-
allophane toward the surface, but weaker leaching (or even slight lophanic) type (McDaniel et al., Section 33.3).
accumulation of Si) at depth, leaving Si-rich allophane rather A consideration of rates of chemical processes brings in
than halloysite. the question of kinetics. Examples of kinetic studies dealing
The volume of water draining through the upper part of the with the dissolution of glass in tephras and associated soils
profile each year has been measured as about 280 mm, which just include those of Hodder et al. (1990, 1996) for rhyolitic teph-
exceeds the threshold of about 250 mm for Al-rich allophane to ras, Ruxton (1988), and Neall (1977) for dacitic and andes-
form according to models derived from New Zealand data (Parfitt itic tephras, respectively, and Gislason and Oelkers (2003),
et al., 1984; Lowe, 1995). Jongmans et al. (1994) also found both Ziegler  et  al.  (2003), Wolff-Boenisch et  al. (2004), Shikazono
Al-rich and Si-rich forms of allophane, respectively, in the B and et  al. (2005), and Sigfusson et  al. (2008) for basaltic teph-
C horizons, in the same profiles in soils in Guadeloupe. Alloway ras or lavas. Generally, basaltic and intermediate (andesitic,
et al. (1992) similarly found differences in Al:Si ratios (and 15 bar dacitic) tephras, with lower Si contents, tend to weather more
water retention) in upbuilding Andisols in the Taranaki region of readily than rhyolitic tephras, but in all cases glasses weather
North Island, New Zealand, which they attributed to changing very quickly as noted earlier (Kirkman and McHardy, 1980;

Main environmental factors

Climate (rainfall, temp.)
Depth of burial
Parent material composition
Tephra thickness
Frequency and thickness of tephra (or aeolian dust) additions
Drainage
Vegetation
Humans (deforest., burning)
Control

Leaching pH Organic cycle (incl. Si biocycling)

Govern

Silicic acid conc. Al availability

Thermodynamics + kinetics determine

[Si] < 0.5 ppm [Si] ≤ 10 ppm [Si] ≤ 10 ppm [Si] varies ≤10 [Si] > 10 ppm
to >10 ppm Al unlimited
Al unlimited Al limited Al unlimited Al unlimited or limited

Gibbsite Al-humus complexes Al-rich allophane Al-rich allophane Halloysite

± imogolite + halloysite ± Si-rich allophane
± imogolite ± secondary silica
± gibbsite polymorphs
Non-allophanic Allophanic Andisols if
Not Andisols Not Andisols
Andisols Andisols andic criteria met

FIGURE 20.8  Environmental influences and controls that govern the critical conditions leading to the formation of different clays from the
weathering of tephras, and the likely occurrence or not of Andisols as a result. ± indicates that the clay mentioned may also be present. (Modified
after Lowe, D.J. 1986. Controls on the rates of weathering and clay mineral genesis in airfall tephras: A review and New Zealand case study, p. 265–330.
In S.M. Colman and D.P. Dethier (eds.) Rates of chemical weathering of rocks and minerals. Academic Press, Orlando, FL; Lowe, D.J. 1995. Teaching
clays: From ashes to allophane, p. 19–23. In G.J. Churchman, R.W. Fitzpatrick, and R.A. Eggleton (eds.) Clays: Controlling the environment. Proc. 10th
Int. Clay Conf., 18–23 July 1993, Adelaide, Australia. CSIRO Publishing, Melbourne, Australia.)
Alteration, Formation, and Occurrence of Minerals in Soils 20-21

Wolff-Boenisch et  al.,  2004). Compared with hard rock, the that an Al-rich allophane, with isolated tetrahedra on the inside
fragmental tephra components, especially vesicular glass and of a spherule of coiled gibbsite-like sheets, cannot transform in
pumice, have a much greater surface area and high porosity the solid state into halloysite, where sheets of linked silica tet-
and permeability, and so break down to constituent com- rahedra are generally coiled around alumina octahedra and
pounds very readily (Wolff-Boenisch et al., 2004). hence are in the opposite conformation one to each other as in
Ziegler et  al. (2003) suggested that kinetics controlled the the allophane spherule. Therefore, dissolution and recrystalliza-
formation of allophane and halloysite in arid soils on the basis tion must be involved in the change from allophane to halloy-
of their work on a chronosequence of Hawaiian soils on basaltic site. Nonetheless, it is likely that the passage of time effects other
lavas (with ash overlying lava in one case) in arid conditions changes, which affect the environment in which mineral altera-
(MAP 180–225 mm). Thermodynamics do not control the com- tion and formation take place, so that conditions that favor the
position of soils unless soil solutions remain in contact with formation of allophane early in the weathering process change
the mineral surfaces until equilibrium is reached. Where this to those favoring halloysite formation. Most often in upbuild-
does not occur, such as under arid conditions, kinetic factors ing terrains, this comes about through an increase in [Si], which
control the soil system (Ziegler et al., 2003). Clay mineral syn- may result from a buildup of overburden through ongoing
thesis in the Hawaiian arid-zone chronosequence was thus tephra deposition, or the development of impediments to effi-
shown by Ziegler et al. (2003) to be controlled by the kinetics cient drainage (e.g., Cronin et al., 1996). Another possible change
of soil drying, rather than thermodynamics, so that halloysite may be toward a drier climate, so that there is less throughflow
was the favored aluminosilicate end product with the formation of water and hence a buildup of Si in solution. An alternative
of smectite inhibited by kinetic factors (and a lack of micas to situation is that reported by Chadwick and Chorover (2001) for
“fuel” the dominant pathway for smectite formation; Chadwick a Hawaiian chronosequence on basaltic lavas and ash deposits
et  al., 2003). In Cameroon, the depth distributions of 0.7 and not subject to ongoing burial by later eruptives. There, the ongo-
1 nm halloysite in soils developed on weathered nephelinite ing depletion of [Si] and increase in [H+] under high rainfall
lavas were able to be related to both kinetic and thermodynamic after ca. 400,000 years eventually led to the formation of more
factors by Etame et al. (2009). That Si concentrations increased stable kaolin (halloysite and kaolinite) and gibbsite. Previously,
with depth in the profiles while Al remained relatively constant, conditions had apparently favored the formation of allophane.
and 1 nm halloysite occurred exclusively in lower horizons Chadwick and Chorover (2001) noted that [Al] in solution also
whereas both 0.7 and 1 nm halloysites were present in upper declined over time, a result that follows from increasing crys-
horizons, led Etame et al. (2009) to two suggestions. First, the tallinity and decreasing solubility of gibbsite and kaolin in the
1 nm halloysite formation was controlled by direct precipita- soil. Inconsistencies between observed soil mineral composition
tion from Si–Al-rich solutions (released from the weathering and stability-field plots of solution chemistry data are evidence
of primary minerals), and, therefore, the availability of Si was of kinetic limitations to mineral transformations according to
the only factor that controlled its formation at the base of the Chadwick and Chorover (2001), who also noted that such dis-
profile. Second, the presence of both forms of halloysite in the crepancies can be resolved through consideration of mineral
upper parts of the profiles implied that kinetics, hence time, transformation rates and Ostwald ripening processes but that
controlled the evolution of halloysite through wet–dry season- the requisite kinetic data are often lacking.
ality, aided by the thermodynamically favorable factor of the In considering longer timescales of glacial and intergla-
availability of Si (Etame et  al., 2009). In tropical Costa Rica, cial cycles in temperate volcanic landscapes not directly gla-
the predominance of 1.0 nm over 0.7 nm halloysite in the wet- cierized, the marine oxygen isotope records show that cooler
ter, lower subsoil horizons of profiles studied by Kleber et  al. and drier conditions associated with glaciations persisted
(2007) was attributed to Si enrichment by percolating waters ∼80%–90% of the time whereas warmer and wetter conditions
(i.e., mainly for kinetic reasons). associated with interglaciations occurred for ∼10% to 20% of
Returning to the question of whether it is time (Fieldes, 1955) the time. In these landscapes, where long sequences are well
or solution concentration/activity, particularly of Si (Parfitt et al., preserved, therefore, it might be expected that soils developed
1983, 1984), that governs whether or not allophane or halloysite from accumulations of weathered tephras of similar compo-
persists in soils from volcanic parent materials (leaving aside sition dating back several hundreds of thousands of years to
Al-humus complexing), it may be said that while the evidence one or two millions of years should be dominated by halloysite
is very strongly in favor of solution conditions determining the rather than allophane (e.g., as evident in the so-called Kauroa
nature of the minerals formed, the passage of time also appears and Hamilton ash tephra sequences in northern New Zealand
to enhance halloysite formation at the expense of allophane that date back to ca. 2.3 Ma; Lowe and Percival, 1993; Lowe
via the so-called Ostwald ripening process (e.g., Chadwick and et al., 2001).
Chorover, 2001; Dahlgren et al., 2004; Rasmussen et al., 2007). Overall, the relationship between the minerals formed from
This direction of change is consistent with the thermodynamic volcanic parent materials (especially tephra) and solution [Si], as
stabilities of the two mineral types (see, e.g., Figure 1.11 in it is affected by the throughflow of water and given appropriate
Churchman, 2000). Structural considerations, however, mean kinetic circumstances, can be expressed by Box 20.3:
20-22 Properties and Processes

Box 20.3  Relationship between

Throughflow of Water, Si
Concentration, and Types of Clays
Formed from Volcanic Parent Materials
Smectite Halloysite/Si-rich Allophane Al-rich Allophane Gibbsite
Al:Si 0.5 1.0 2.0 ∞

Increasing rate of throughflow of water

Decreasing Si concentration/activity

We note in addition that allophane can be formed in a range the aluminosilicates, with poorly crystalline forms giving a high
of nonvolcanic materials through strong leaching and acid con- oxalate-Fe analysis dominant in soils at higher altitudes and
ditions, as occur, for example, in loess in upland areas of south- more crystalline forms giving a high dithionite-Fe analysis in
ern New Zealand (e.g., Eger and Hewitt, 2008), and as a result of soils at lower altitudes (Rasmussen et al., 2007). There was a fur-
podzolization (see Section 20.2.5.3.2). ther subtlety with Fe analyses, however, insofar as the proportion
Parallel to the alteration of aluminosilicate minerals and the of oxalate-Fe to dithionite-Fe rose again at the lowest altitude,
formation of allophane, halloysite, and perhaps also gibbsite or where the MAP was also lowest. In this drier zone, less leach-
smectites, iron is also lost from parent Fe-bearing minerals and ing probably led to higher retention of Si in soil solution, which
incorporated into secondary solid phases. Ferrihydrite forms would inhibit Fe oxide crystallization (Rasmussen et al., 2007).
early in the process of weathering of volcanic parent materi-
als from the precipitation and oxidation to Fe(III) of soluble 20.2.4.6.3  The Special Case of “Palagonite”
Fe(II) that had been released into solution from volcanic glass In the volcanic and geochemical literature especially, the term
and also feldspars and mafic minerals (e.g., McDaniel et  al., “palagonite” is widely used to describe the first stable product of
Section 33.3). It is the presence of other species in solution such basaltic volcanic glass alteration (e.g., Fisher and Schminke, 1984;
as silicate and phosphate ions and soluble organic compounds Cas and Wright, 1987; Daux et al., 1994). Palagonite has also been
that inhibit the formation of the more crystalline forms of iron, described in the clay science literature but uncommonly (e.g., Singer
such as goethite and hematite (e.g., Childs, 1992; Bigham et al., and Banin, 1990; Drief and Schiffman, 2004) and it thus deserves
2002). However, the type of iron oxide that is formed is a func- some attention here. As reviewed by Stroncik and Schmincke
tion of the same environmental conditions that also affect which (2002), palagonite (named after the location Palagonia in Sicily)
particular aluminosilicates are formed in volcanogenic soils. is a heterogeneous substance, usually with highly variable optical
Hence, in young soils on andesitic mudflows, the buildup of fer- and structural properties ranging from a clear, transparent, isotro-
rihydrite with time paralleled that of allophane, albeit that the pic, smooth, and often concentrically banded material, commonly
amount of allophane formed was ∼10 times or more than that called “gel-palagonite,” to a translucent, anisotropic, slightly to
of ferrihydrite (Lilienfein et  al., 2003). In a chronosequence of strongly birefringent material of fibrous, lath-like, or granular
soils in the humid tropics, Nieuwenhuyse et  al. (2000) found structure, commonly called “fibro-palagonite.” It ranges in color
that Fe occurred mainly as Fe-humus in the two younger soils, from yellowish to shades of brown. Since it was first defined in
especially in their A horizons, but also as ferrihydrite, especially 1845 as a new mineral, palagonite has been interpreted in numer-
at depth, whereas it occurred mainly as goethite throughout ous studies to be a heterogeneous material composed variously of
the oldest soil in the sequence. Further, the iron oxides in soils different aluminosilicate clays, zeolites, and oxides, or mixtures of
in a xeric moisture regime that contain all of gibbsite, imogo- these. Based on XRD, HRTEM, atomic force microscopy (AFM),
lite and/or Al-rich allophane, and halloysite as aluminosilicates and electron microprobe analyses, palagonite is now interpreted
were dominantly highly crystalline—they were mainly goethite, by most to be composed of a variety of smectites and very minor
reflecting strong seasonal drying (Takahashi et al., 1993). Soils amounts, if any, of zeolites and oxides (Stroncik and Schmincke,
in a toposequence on andesitic lahar deposits covering a range 2002). At more advanced stages of alteration, other secondary
of climatic zones generally showed a similar pattern to that for phases are known to form following Ostwald “ripening” processes.
Alteration, Formation, and Occurrence of Minerals in Soils 20-23

Palagonite evidently comprises spherical structures 20–60 nm the genesis of soil minerals than in those from rocks subject to
in diameter, which have been interpreted as “microcrystallite largely abiotic weathering. Furthermore, some processes, notably
precursors of smectite” (Stroncik and Schmincke, 2002)—that podzolization, occur within permeable soils but not in imperme-
is, palagonite would seem to be a nanocrystalline variety of able rocks under certain environmental conditions and deserve
smectite(s). Drief and Schiffman (2004) identified an Fe-rich particular attention. In addition, soils can be further developed
montmorillonite-like composition in their study on Hawaiian even following the depletion of easily weatherable rock-derived
basaltic deposits. The atomic structure of palagonite and, espe- minerals. Secondary minerals can themselves be altered and new
cially, its structural evolution are not yet fully understood, but phases formed. Each of these particular aspects of mineral devel-
both are important to glass-alteration rates and to the evolution opment in soils will be discussed in the following sections.
of the whole water–rock–soil system (Stroncik and Schmincke,
2001). Because kinetic and thermodynamic modeling and mass– 20.2.5.1  The Effect of Position within Soil
balance calculations necessitate exact differentiation of all the Profiles on Hard Rock
secondary products developing during alteration, the term In a recent review, Wilson (2004) showed that position in the
“palagonite” should be used only for the hydrous nanocrys- weathering profile on indurated rock has a crucial influence on
talline alteration product (“gel-palagonite”), not for the long- the nature of the environment for weathering and hence on the
range-ordered crystalline material evolving from the palagonite processes involved and products formed, as well as the rates at
itself (Stroncik and Schmincke, 2001, 2002). which changes occur. Note that modified models are required
The so-called palagonitization of basaltic volcanic glass is a for soils formed on unconsolidated materials or, especially,
continuous process of glass dissolution and palagonite forma- those developed through upbuilding pedogenesis. Following
tion and evolution, which, according to Stroncik and Schmincke Delvigne (1998), a fully developed weathering profile comprises
(2001), can be subdivided into two different reaction stages with a soil, which is delineated (in a straightforward case) into A and
changing element mobilities. Stage 1 is the congruent hydration B horizons (solum) and usually C or CR horizons comprising
and dissolution of thermodynamically unstable glass and con- saprolite/alterite, which consists of completely disaggregated
temporaneous precipitation of “fresh,” gel-like, amorphous (or rock grading to the rock base, with fabric and texture changing
nanocrystalline), optically isotropic, mainly yellowish palago- with depth. At the base of the whole profile is the (partly) weath-
nite. This stage, kinetically controlled and consistent with the ered rock (R horizon), which may be hard and coherent but also
models of Hodder et al. (1990, 1993), is accompanied by the loss incorporates fractures and fissures. Among other features, an
of Si, Al, Mg, Ca, Na, and K, active enrichment (gain) of H2O, increase in surface area characterizes the upward change from
and the passive enrichment (“default” accumulation relative to the rock to the solum (Hochella and Banfield, 1995).
other elements) of Ti and Fe. Stage 2 is an aging process during There is also a trend of decreasing porosity and permeability
which the thermodynamically unstable palagonite reacts with from soil down to rock, so that water can flow quite freely within
the surrounding fluid and crystallizes to smectite. This stage the soil, but can be either stagnant or held in capillaries in the
is accompanied by uptake of Si, Al, Mg, and K from solution rock. Hence, there is a much greater chance of an equilibrium
and the loss of Ti and H2O. Ca and Na are still showing losses, being established between the minerals and the largely immo-
whereas Fe reacts less consistently, remaining either unchanged bile solution within the rock than between the minerals and the
or showing losses (Stroncik and Schmincke, 2001, 2002). highly dynamic water in the soils zone.
Following Velde and Meunier (2008), we note that alteration
within the rock proceeds in microsystems. Meunier and Velde
20.2.5  Peculiarities of Processes and Products
(1979) followed the alteration of granites by weathering through
of Alteration by Weathering in Soils
developments occurring at the scale of microsites. The system
Much—although not all—of the information on the processes is highly heterogeneous at this fine scale; grains of the primary
and products of alteration of primary minerals by weathering minerals, muscovite, orthoclase, and biotite each give rise to mul-
that is summarized in the preceding Section 20.2.4 comes from tiphase assemblages upon alteration. Alteration of the whole min-
observations of rocks or geological deposits, minerals associated eral assemblage appears to take place in three stages. In the first
with these materials, and saprolites deep within soil profiles. stage, alkalis are lost but the Si:Al ratio is preserved as illitic mica,
However, soil profiles can encompass a range of conditions, from beidellite, and vermiculite are variously formed. The second stage
fragmented, almost abiotic, rock through to organic-rich mate- involves a loss of both alkalis and silica with kaolinite and oxides
rial containing a great variety of microbial, faunal, and also plant resulting. The authors surmised that there is a third stage where
life. The different parts of soil profiles represent different regimes quartz is dissolved, leaving only oxides, but not silica. This last
for water, from abundant and mobile to scarce and largely stage is seen in tropical weathering. The processes of in situ altera-
immobile, so studies of some nonsoil situations where each of tion of ferromagnesian minerals to smectites and of feldspars to
these prevail are relevant to weathering in some parts of soils but illite that were studied by Eggleton and coworkers and Banfield
not in others. Most soils have a significant biological input, at and coworkers, among others, and cited in Section 20.2.4 herein,
least in their surface layers, and, therefore, the biological factor also occur within microsites where the physical constraints as
in mineral alteration and formation tends to play a larger role in well as the chemical availability of reagents limit the reactions that
20-24 Properties and Processes

can take place. In a particularly close study of microsites within those seen in other terrestrial environments, but occurring at a
one mineral type (amphibole) on weathering, Proust et al. (2006) much slower rate (Claridge, 1965). Some, but not all, clay miner-
found that montmorillonite formed on the (001) amphibole face als in Antarctic soils could be inherited from other land masses
and saponite on the (110) face, while the sawtooth (001) face frac- to the north (e.g., dust blown from southern South America;
ture surface hosted a kaolinite–smectite and, with time, also hal- Delmonte et al., 2004). Boyer (1975) collected weathering prod-
loysite and montmorillonite. The establishment of local equilibria ucts such as rinds on rocks from part of Antarctica and iden-
may occur at different sites, within both a single crystal, as in the tified various 2:1 minerals, including chlorite–vermiculite and
amphibole studied by Proust et al. (2006), and also within differ- also identified montmorillonite. These products all indicated
ent fractures and fissures in a rock (see the diagrammatic repre- that chemical weathering had taken place. In the arid Sahel in
sentation for granite in Figure 4.19 of Velde and Meunier, 2008). west Africa, Ducloux et al. (2002) identified beidellite, kaolinite,
Within microsites where secondary products remain in close and mica in soils. They concluded that these minerals formed by
proximity to host primary minerals, reactions may even occur a process called “xerolysis,” whereby desiccation in a hot climate
between product and host minerals (Velde and Meunier, 2008). As leads to protons from dissociated water reacting with crystalline
a result, vermiculite may form by recrystallization in a microsite minerals to produce secondary products.
from the dissolution products of the adjacent secondary minerals, The new frontier for clay mineralogy is outer space, and espe-
saponite or Fe–beidellite and their primary precursor, amphibole cially other planets in our solar system, and there has been a
for one example (Velde and Meunier, 2008). For another example particular focus on Mars from a clay mineralogical viewpoint
(Velde and Meunier, 2008), product smectite and host K-feldspar quite recently. Earlier exploration of Mars involved fly-bys, with
may react together to give rise to illite and kaolinite. spectra being used to identify materials on the Martian surface
The solid:solution ratio is very high in hard rocks that remain by remote  sensing. These data could have been interpreted to
coherent yet contain small fractures and fissures. By great con- indicate the presence of some phyllosilicates (Hamilton et  al.,
trast, the solid:solution ratio in the solum or unconsolidated 2003), but the evidence was equivocal. The collection of samples
geological deposits within the weathering profile is likely to be by Exploration Rover from the planet’s surface showed that the
both very low and quite variable on both a daily and seasonal ferric sulfate, jarosite, which is commonly associated with acid
basis, except in special circumstances, for example, in a desert sulfate soils on Earth (see Section 20.2.5.3.4), and also possible
or frozen soil. The dynamic nature of soils alone ensures that relicts of gypsum at the Meridian Planum landing site (Madden
the possibility of predicting the course of weathering via sta- et  al., 2004). Other work on samples from a number of differ-
bility diagrams for the component clay minerals (e.g., Kittrick, ent locations on the planet has confirmed the widespread occur-
1967) cannot be realized. Minerals awash in the dynamic water rence of secondary sulfates and also iron oxides (Hurowitz and
phase in soils almost certainly remain well out of equilibrium McLennan, 2007). Hurowitz and McLennan (2007) considered
with those solutions (Chadwick and Chorover, 2001; Wilson, that they originated from altered olivines in Martian rocks.
2004). However, those formed in microsites within weathering These various localized occurrences of sulfates and iron oxides
rocks deeper in the weathering profile may not appear in bulk were compared with the results of a general survey of most of the
analyses of soils above the weathering rock. In particular, trioc- surface of Mars that was carried out by an image spectrometer
tahedral smectites formed during early stages of alteration are during an aerial survey of the planet (Poulet et al., 2005). The sur-
rarely reported in soils. Either they are unstable in the soil envi- vey had earlier identified sulfates in localities in addition to those
ronment (Wilson, 2004) or they are present in only vanishingly reported by Madden et al. (2004) and Hurowitz and McLennan
small concentrations (Proust et al., 2006), or both. (2007), but Poulet et  al. (2005) also identified phyllosilicates in
several localities, albeit that their distribution was quite heteroge-
20.2.5.2  Weathering in the Absence neous. They included Fe/Mg smectites in some areas and mont-
or Shortfalls of Water morillonite in others. These occurrences suggested that there had
Generally on Earth, weathering occurs because there is sufficient— been water in some localities on Mars, in order to alter basaltic
and usually excess—water to effect alteration of primary min- and similar rocks to give phyllosilicates, although the sulfates
erals and either transformation to related secondary phases derive from a different, more acidic, environment. More recent
or neogenesis of new (secondary) minerals. However, mineral work (e.g., Bishop et  al., 2008; Mustard et  al., 2008; Ehlmann
alteration and formation are also observed to occur where there et al., 2009) has identified phyllosilicates in a number of localities
is little, or no, water. Studies in the normally frozen Antarctic on the surface of Mars. The discovery of phyllosilicates has aided
have shown clear evidence for chemical weathering occurring our understanding of the climatic history of Mars (Newsom,
there. As well as salts such as gypsum and sodium sulfate formed 2005; Poulet et  al., 2005). On Earth, meteorites considered to
by recrystallization from elements leached from rocks by occa- have come from Mars have been studied for their mineralogy,
sional (liquid) water, abundant iron oxides also occur (Claridge, and iddingsite, comprising a mixture of smectites, iron oxides,
1965). Furthermore, clay minerals occur—most commonly and silica, has been identified on the altered surfaces and in the
transformation products of micas such as vermiculites, but also veins of the meteorites (Wentworth et al., 2005). These authors
montmorillonite. This last mineral was thought to form in the drew an analogy between mineral alteration and formation that
arid and highly alkaline environment by similar processes to has taken place on Mars with that which has occurred—and is
Alteration, Formation, and Occurrence of Minerals in Soils 20-25

occurring—in the Dry Valleys of Antarctica. Examined at the though vermiculites are rare in prairie soils, they can occur in
submicroscopic scale, the patterns of alteration of primary sili- significant amounts in young mountain soils according to Velde
cates, for example, amphiboles and pyroxenes, were similar in an and Meunier (2008). Expanded (to vermiculite or smectite)
Antarctic Dry Valley (Wright Valley) and in the Mars meteorites and partially expanded (to mixed-layer illite–smectite) prod-
(Wentworth et al., 2005). In addition, soils in the Dry Valleys con- ucts occur, and these often acquire Al-hydroxy interlayers (see
tain evaporated salts at their surfaces, as have been seen in soils Section 20.2.4.3) under forest (Velde and Meunier, 2008). It was
on Mars. In both of these arid situations, alteration processes the development of a method of XRD peak decomposition by
and their products are distributed heterogeneously, indicating Lanson (1997) that enabled the detection of some of these min-
an uneven distribution of water available for the alteration and eral changes attributable to plants, which can be subtle.
subsequent formation of minerals, both in space (in the Antarctic Acidification can be an important effect of plant growth and
Dry Valleys) and in time (in the Martian past). consequently can play an important role in alteration by weather-
ing. Protons are released into soil solutions to balance the over-
20.2.5.3  Biota as Important Agents in Mineral all charge when roots take up more cations than anions (e.g.,
Alteration and Formation Hinsinger et al., 2001; Courchesne, 2006; Calvaruso et al., 2009).
It has long been recognized, including by the pioneers in pedol- For some tree species, it is the uptake of NH +4 in preference to
ogy, for example, V.V. Dokuchaev and Hans Jenny, that biota play NO3− by roots that ensures acidification, specifically in the rhi-
an important, sometimes dominant, role as one of the agents in zosphere (Calvaruso et al., 2009). Roots (and fungal hyphae tips
the development of soils from rocks and other geological materi- as noted above) also exude organic acids into soils (Courchesne,
als. Plants, animals, and microbes share an equivalent status to 2006). More Ca, Na, Mg, Si, and especially Fe were released from
parent materials, climate, topography, and time as soil-forming leached basalt when plants were grown in the fresh rock than
factors. Therefore, it comes as no surprise to find that biota in their when there were no plants (Hinsinger et  al., 2001). When soils
different forms demonstrably play a major role in the alteration of within the rhizosphere of a Norway spruce and an oak were com-
primary minerals and the formation of secondary clay minerals. pared with the bulk soil, it was found that Fe and Al, and there-
Even so, it is arguable that the role of biota in the formation of fore their “amorphous” (i.e., nanocrystalline) mineral phases, as
clay minerals has been relatively neglected in comparison with well as Al-hydroxy interlayers in 2:1 Si:Al aluminosilicates, were
those of other soil-forming factors, such as parent materials and dissolved as a result of acidification by the plant roots (Calvaruso
climate. Churchman (2000) noted that studies of the alteration et  al., 2009). Forest soils in Taiwan showed a lack of hydroxyl
and formation of minerals had largely concentrated on processes interlayering of 2:1 Si:Al aluminosilicates in the surface O, A,
involving inorganic agents, while observing that there had been and E horizons but there was interlayering, which was shown to
an upsurge in studies of the role played by biological and bio- involve both Al and Fe, in deeper horizons (Pai et al., 2004). It
chemical agents in the previous decade. The effect of these agents was thought that a low pH and possible chelation of Al and Fe by
on weathering changes is now one of the more active areas of organic material, which was abundant in and on the surfaces of
research on mineral alteration and formation in relation to soils the soils, led to the clean interlayers in the expandable aluminosil-
(e.g., Dong et al., 2009). icates near the surface, whereas the higher pH and lower organic
contents in lower horizons were conducive to their formation in
20.2.5.3.1  Plants as Weathering Agents the clay minerals there (Pai et al., 2004). In a later study, Pai et al.
Plants have been shown to be important weathering agents. (2007) found that acidification at the surface of forest soils else-
Mortland et  al. (1956), Hinsinger et  al. (1992, 1993), and where in Taiwan decreased the charge of the K-depleted alumino-
Hinsinger and Jaillard (1993) showed that trioctahedral micas silicate layers, which they characterized as vermiculite, occurring
in soils lost potassium from their interlayers as a result of the either as the discrete phase or in mixed-layers with vermiculite.
growth of plants in the soils. In general, this process is that of In the North Island of New Zealand, Jongkind and Buurman
vermiculitization (or the formation of beidellitic smectites) (2006) found that weathering under kauri (Agathis australis)
(Section 20.2.4.3). However, it generally occurs via mixed-layer trees, which produce especially low pHs (4.0 ± 0.2) left vermicu-
randomly interstratified species. In soils, illite–smectites are the lites depleted of hydroxyl interlayering and even brought about
most common form of these (Velde and Meunier, 2008). Indeed, some conversion of vermiculite to smectite, as Churchman (1980)
since this type of clay mineral is not found in buried sediments had found to occur in soils under another native (beech) tree
or rocks, it is peculiar to the soil environment, according to these species (Nothofagus sp.) in the South Island of New Zealand. By
authors. Furthermore, it is found particularly in the A  and  B matching the rare-earth compositions of the silica particles found
horizons of soils (the solum), confirming its origin in surface within the roots of ferns with those of aluminosilicate minerals
alteration processes (ibid.). Although plants, in general, are the in the soil surrounding the roots, Fu et al. (2002) found strong
main agents of alteration of trioctahedral micas to produce evidence for the dissolution of clay minerals to leave deposits of
illite–smectites, Velde and Meunier (2008) summarized obser- silica following their incorporation into plant roots.
vations in the literature to conclude that prairie soils (Mollisols) Plants can bring about very rapid changes in soil minerals
dominated by grasses contain illite–smectite together with vary- (Turpault et al., 2008). A seasonal study by these authors showed
ing amounts of illite under different climate conditions. Even that in the rhizosphere close to tree roots, mineral dissolution,
20-26 Properties and Processes

with loss of citrate-extractable Al and Si, occurred in surface The fungal hyphal tips, which produce organic acids (e.g., citric
layers in spring because of enhanced biological activity. That or oxalic), “drill” directly into mineral grains including feldspars,
some of the Al came from interlayers was shown in XRD by an thereby bypassing the external acid soil solution, and hence the
increased ease of collapse of these upon K-saturation and also E horizon is regarded as the fungal “eaten” part of the soil.
an increase in cation exchange capacity (CEC). There was a cor- An eccentric view is that of Do Nascimento et  al. (2004,
responding migration of Al and Si to lower layers. Perceptible p. 536) who have described podzolization as a deferralitization
changes in the XRD patterns occurred within only 3 months. process whereby the chemical elements that had accumulated
during ferralitization are “progressively exported towards the
20.2.5.3.2  The Special Case of Podzolization drainage network under the combined effects of waterlogging,
Organic compounds from the activities and decomposition of organic matter accumulation, and lateral subsurface and surface
biota have long been thought responsible for extracting and water flows.” In a somewhat related study, Lucas (2001) com-
transporting Fe and Al ions and incidentally producing new pared the dynamics operating in podzols with those in ferralsols
minerals from them in the process of podzolization (e.g., Russell, (Oxisols) regarding the rates of Si recycling (including storage as
1973), even if equally valid inorganic mechanisms have also been phytoliths) by plants and the rates of loss, by leaching, of Si and
put forward for this process (e.g., Farmer et al., 1980; Wang et al., organometallic complexes involving Al, Fe, and organic matter.
1986), as will be discussed further. This author concluded that the main constituents of the “weath-
Podzolization usually involves the intense leaching of par- ering mantle” ultimately depended on the balance between
ent materials and soils with acidic solutions. In podzolization, (1) the stability of the clay minerals, sustained by the plant Si
Al, Fe, Mg, and Si are mobilized (e.g., Farmer, 1982; Farmer and cycling, and (2) the leaching of plant-induced organo-Al com-
Fraser, 1982; Farmer et al., 1983; Taylor, 1988; Churchman, 2000; pounds. These findings were evident in equatorial areas where
Giesler et  al., 2000). Podzolization can be contrasted with the old soils are markedly affected by biological activity, and they
processes, sometimes collectively referred to as “andosolization,” were also seen in temperate areas (Lucas, 2001).
involved in forming allophane and other andic soil materials After reviewing the literature, Lundström et  al. (2000) con-
mainly in tephra-derived soils (Section 20.2.4.6). Normally, allo- cluded that organic complexes were important in both the
phane and other nanocrystalline clays are formed in situ dur- weathering and deposition (or immobilization) processes and
ing andosolization (even though the process typically requires Jansen et al. (2005) also decided, on experimental grounds, that
desilication via leaching) whereas podzolization always involves organic matter played an important role in the transport of Al
the translocation of mobile constituents as organic or inorganic and Fe down profiles to create illuvial horizons, at least in podzols
complexes, or both, from very acid horizons in the upper profile in the Netherlands and similar climatic zones, while conceding
and subsequent immobilization in lower horizons through an that podzols may form by slightly different mechanisms in both
increase in pH, via microbial action, or by adsorption, precipita- cooler and warmer climatic zones. Contrary views are evident in,
tion, etc. That such movement takes place has been confirmed by for example, Farmer and Lumsdon (2001) who argued that “fulvic
micromorphological studies (e.g., Farmer et al., 1980, 1983, 1985; acid plays no active role in podzolization, but only recycles Al and
Farmer and Lumsdon, 2001). Broadly speaking, the processes Fe, that has been transferred by biological processes to the O hori-
involved in podzolization are as follows: (1) enhanced mineral zon, back to the Bh horizon” (p. 177). Buurman and Jongmans
weathering in upper A and E (“eluvial”) horizons; (2) transport of (2005) proposed that podzolization in boreal zones, on nutrient-
Al, Fe, and Si and probably also organic matter from upper hori- rich parent materials at high latitudes and high altitudes, hence
zons to lower B horizons—either in metal–organic complexes cold climates, occurred with organic matter (OM) dynamics that
(chelates) or as independent inorganic complexes including led to little accumulation of OM (so-called “fast” OM dynamics),
“proto-imogolite sols,” and as independent organic complexes; and, hence, illuvial B horizons were dominantly inorganic. These
and (3) deposition of the Al and Fe as oxides, together usually authors proposed an alternative route for podzolization in hydro-
with allophane, from (according to Farmer et al., 1985) a mixed morphic situations on nutrient-poor parent materials, including
Al2O3–Fe2O3–SiO2–H2O sol, in so-called illuvial Bs horizons. in warmer climates, where OM dynamics were “slow,” by their
There have been a number of theories put forward to explain nomenclature and would lead to organic-rich illuvial horizons.
the changes that take place in soils as a result of podzolization (see Regardless of mechanism, podzolization leads to essentially
Churchman, 2000, for proponents and arguments involved in ear- two compartments of the soils according to their weathering
lier discussions, and elsewhere in this handbook). Briefly, these can status and the nature of the secondary phases (Ugolini et  al.,
be grouped into two main hypotheses, both of which may apply 1991). These are (1) the upper horizons, and especially the dis-
to some degree depending on site-specific soil environments (e.g., tinct eluvial (or “fungal eaten”) E horizon, and (2) the taxo-
Wang et al., 1986; Lundström et al., 2000): (1) the organic or “ful- nomically diagnostic lower illuvial horizons, and especially the
vate” hypothesis and (2) the inorganic or “proto-imogolite” hypoth- equally distinct Bh and Bs horizons. (Both or only one of the Bh
esis. A third is the so-called rock-eating fungi hypothesis, which or Bs may be present in podzol soils.) Considerable recent effort
is associated with mycorrhizal fungi found in many soils under has been expended into studying the early stages of podzoliza-
pines and heaths commonly in parts of Europe and Scandinavia tion, largely in soils in the boreal zone, namely, under forests, in
and elsewhere (Jongmans et al., 1997; van Breemen et al., 2000a). northern and/or alpine Europe, from a mineralogical viewpoint
Alteration, Formation, and Occurrence of Minerals in Soils 20-27

(Melkerud et al., 2000; Mossin et al., 2002; Mokma et al., 2004). product of dioctahedral micas (muscovite and phengite). In older
Mokma et al. (2004), tracing the earliest stages of podzolization soils, smectites with a lower charge resulted from both the dis-
in sandy soils in Finland, found visual evidence for transloca- solution of the higher charged trioctahedral smectites and also a
tion of C, Al, and Fe after 230 years of soil formation while there progressive decrease in the charge of the dioctahedral expanded
was evidence of allophane in a Bs horizon after 900 years. There phases (Gillot et  al., 2001). Righi et  al. (1999) found the nature
were few differences between the crystalline minerals in the of the aluminosilicate products of podzolization in the eluvial A
soils of different ages (up to 11,300 years). Buried podzol profiles and E horizons differed from those in the B horizons within a
in northern New Zealand exhibit thin E, Bh, and Bs horizons different chronosequence of soils. The A and E (eluvial) horizons
(about 20, 2, and 5 cm in thickness, respectively) formed on a contained a mixed-layer mica–smectite, and, given time, also dis-
pumiceous rhyolitic tephra layer deposited in ca. AD 232. The Bs crete smectite from the transformation of dioctahedral mica. The
horizons contain allophane. The developing podzols were subse- B (illuvial) horizons, by contrast, contained mixed-layered mica–
quently buried in ca. AD 1314 by deposition of another rhyolitic vermiculite and smectite. These last clays were the products of the
tephra (Lowe, 2008). The profiles thus reflect about 1082 years of alteration by transformation of trioctahedral minerals, notably
podzolization under ∼1500 mm annual rainfall in a mesic tem- biotite and chlorite (Righi et al., 1999). These authors explained
perature regime under broadleaf–podocarp forest. the differences between the transformational products by a dif-
In three soils on Quaternary deposits in Fennoscandia, ference in the nature of the acids involved as weathering agents
Melkerud et  al. (2000) found that the most easily weather- in the two different parts (or compartments) of the soil profile. In
able primary minerals, biotite, chlorite, and hornblende, were the upper, eluvial compartment, organic acids are responsible for
depleted from the eluvial horizon, which had the highest con- the mineralogical changes and these are more aggressive than the
centration of quartz. Vermiculite dominated the clay mineralogy carbonic acid in the lower compartment, which includes the illu-
of the E horizons and was also present, but with incorporated vial horizons (Righi et al., 1999). It is only in the upper compart-
Al-hydroxy interlayers, in the B horizon, where poorly ordered ment that dioctahedral minerals become altered, and the organic
or nanocrystalline imogolite-type materials (i.e., allophane) also acids responsible for the alteration there dissolve the products
occurred. Mossin et al. (2002) specifically searched for imogolite of weathering of the trioctahedral minerals. Their dissolution
in three Danish podzols. Some proto-imogolite allophane rather leads to phases that are translocated to the illuvial Bh and Bs
than imogolite per se was found, but in smaller amounts than horizons where they accumulate as “amorphous” (i.e., probably
had been found in podzols further north in Scandinavia and not nanocrystalline) Fe and Al oxides and as recrystallized gibbsite
at all under spruce, which was responsible for the lowest pH for in these particular soils (Righi et al., 1999). Studying an altitu-
the soils. They ascribed the generally relatively lower contents of dinal sequence of five podzolized soils in Italian alpine regions,
allophane to a lower pH, an increase in organic matter, and a par- Mirabella and Egli (2003) also found that the smectites formed
ent material with a low content of easily weatherable minerals. in either eluvial or illuvial horizons were highly heterogeneous,
The pH conditions and other factors such as aluminum extract- mostly comprising mixtures of montmorillonite with interstrati-
ability and solubility are important in explaining the differences fied beidellite–montmorillonite, but never consisting of beidel-
in composition in different parts of the podzol profile (e.g., Zysset lite alone. Some were interlayered with hydroxy-Al species, which
et al., 1999; Lundström et al., 2000; Farmer and Lumsdon, 2001). needed to be removed by citrate treatment before the underlying
Recently, several other authors have particularly examined the phases could be distinguished, but their removal showed that the
effect that the podzolization, namely, acid leaching, process has specific expandable micaceous phases with their variety of layer
had upon micaceous clay minerals. The results of some earlier charges had been formed prior to interlayering (Mirabella and
studies of this kind are discussed in Section 20.2.4.3 and also ear- Egli, 2003). The most intense weathering, leading to the lowest
lier in this section herein and in Churchman (2000). While the charged smectites, occurred in podzols below the tree line but
general consensus from earlier studies was that beidellitic smec- closest to it. Clearly, in many of these studies, certain trees are a
tites are often identified as a stable phase, if not an end product, major factor in the intensification of the podzolization process, if
of the alterations of micaceous minerals that take place in podzol not in its occurrence, in some environments. Churchman (1980)
E horizons as a result of eluviation, Righi et al. (1999), Gillot et al. also found that, although podzolization could occur under grass-
(2001), Mirabella and Egli (2003), and also Egli et al. (2004) have lands provided the rainfall was sufficiently high, the mineralogi-
all found that the smectites that form in this way can be quite com- cal changes to micaceous phases were more advanced in soils that
plex. They constitute a mixture of several populations with vari- were just a few meters away, but which were below the tree line.
ous layer charges (Gillot et al., 2001). A chronosequence of soils In the podzols under grassland on both mica–chlorite schist and
in Finland enabled these last authors to find that the products of graywacke lithologies, regularly interstratified mica–beidellite
mica transformation included both a relatively high-charge ferro- dominated the clay fractions and there was no discrete beidellite
magnesian smectite and also a vermiculite with higher charge in present, but discrete beidellite occurred in substantial amounts
younger soils. They thought that the Fe–Mg smectite arose from in podzols under native Nothofagus beech forest in New Zealand
the transformation of the ferromagnesian primary mineral biotite (Churchman, 1980).
and from Fe–Mg-bearing chlorite present in the rocks, whereas Although beidellitic smectites appear to constitute a stable
the vermiculite, which was aluminous, was a transformation phase in podzols formed in boreal zones, there can be a sequence
20-28 Properties and Processes

of products formed at different stages during the podzolization operation of the other main weathering agents such as climate.
process, as discussed by, for example, Churchman (2000), and Thus, in a chronosequence on basalt in the tropics, both the
also by Righi et al. (1999). Studying seven podzol profiles in the early formation of an illite and also a lower content of gibbsite
Tatra Mountains in Poland, Skiba (2007) has concentrated on in A horizons than in C horizons across much of the sequence
the alteration processes of dioctahedral micas within all parts were attributed by He et al. (2008) to the transport by plants of
of these soils. This author found a variety of transformational nutrients (K, and also Si, as siliceous phytoliths) to the surface
products of dioctahedral micas that varied in the regularity of of soils. Together the increases in these nutrients have led to the
ordering of their interstratifications with (at first) vermiculites, formation and retention of illite and 2:1 aluminosilicates more
in the expandability of the vermiculites formed, both as inter- generally, at least until they are finally weathered out in the old-
stratified layers and also as discrete phases, and in the degree of est soils. Both April and Keller (1990) and also Calvaruso et al.
interlayering of vermiculites with smectite, leading ultimately to (2009) found that there was a buildup of the discrete mica phase
a discrete smectite phase. Many of these also exhibited interlay- (respectively muscovite and illite in the two reports) relative to
ering with hydroxy-Al species when pH was ≥ 4.4. Skiba (2007) its degraded counterpart in the rhizospheres of trees in compari-
also claimed that kaolinite formed neogenetically in these pod- son with the bulk soils. Barré et al. (2009) have concluded from a
zols from Al and Si released by weathering. review of the literature that this effect of plants retarding weath-
Three podzols forming in tropical and subtropical climatic ering changes, which is known as “nutrient uplift,” “element
zones have been studied in Taiwan by Lin et al. (2002), among translocation,” or “biological pumping,” is widespread, and that
others. There was a very similar mineralogical pattern to those “the clay mineralogy observed in surface soils is probably largely
seen in podzols in the cooler boreal zone. Illite was altered to plant mediated.” The uptake and biocycling of Si by plants has
vermiculite, or sometimes to interstratified illite–vermiculite also been studied by Drees et al. (1989), Lucas et al. (1993), Derry
in eluvial horizons. There was no interlayering with hydroxy-Al et al. (2005), Farmer (2005), and Henriet et al. (2008). The con-
species in the eluvial horizons, which exhibited very low pHs centration of Si by “nutrient uplift” has probably contributed, at
under forest but some occurred in B horizons at higher pHs, least, to the preservation of kaolinite and halloysite, respectively,
and Lin et  al. (2002) also considered that translocated Fe, Al, in the surfaces of forest soils in Brazil (Furian et al., 2002) and
and organic acids coated the Al-interlayered vermiculitic phases Costa Rica (Kleber et al., 2007), while strong tropical weather-
with organometallic compounds and thus stabilized them ing has led to gibbsite dominating the mineralogy of the sapro-
against breakdown. As in many other podzols, the system was lite in the Brazilian case and the subsoil in the Costa Rican one.
characterized by the eluviation, translocation, and deposition of An examination of published data on Si concentrations in Bs
mainly Al and Fe by organic acids. horizons in several European forest soils, as well as experimen-
The general mineralogical pattern in podzols is summarized tal data for some of these, led Farmer et al. (2005) to postulate
in Box 20.4. It is given for podzols on micaceous parent mate- that plant phytoliths provide a sink, hence short-term nutrient
rials, which are common for many podzolized soils, although uplift, for Si from soil solutions during the growing season that
podzols can form on many parent materials or lithologies. is released back to solutions during winter and spring. Such a
viewpoint is supported by data derived from studies of plant-
20.2.5.3.3  Apparent Counteraction of Weathering by Plants related movement in soils of Al and Fe as well as that of Si in both
Some work has indicated that plants, as well as acting as poten- temperate and tropical soils that were reviewed by Lucas (2001),
tial weathering agents, may also act to counter the course of although differences are evident for different environments (see
mineral development that might otherwise be expected from the Figure 6 in Lucas, 2001). Nonetheless, Lucas (2001) concluded

Box 20.4  Mineralogical Pattern

in Podzols Developed on Micaceous
Parent Materials
Horizons Type Alteration Phyllosilicates Nanocrystalline (SRO) Minerals
Incr. Al, Fe, pH

A, E Eluvial Accelerated loss of cations including Beidellitic or smectite or vermiculite; —

Al, Fe, K, Si interstratified with illite, or discrete
Bs, Bh Illuvial Normal extent of alteration, for Vermiculitic, not smectitic, i/strat. Allophane and/or imogolite,
example, for climate or discrete, poss. Al-interlayered Fe oxides, especially ferrihydrite
Alteration, Formation, and Occurrence of Minerals in Soils 20-29

that in most places (tropical as well as temperate), the weather- sulfate soils, the effects of human intervention in certain envi-
ing mantle can be regarded as being in a “dynamic equilibrium ronments have been to promote mineralogical changes that are
sustained by plants.” Derry et al. (2005) found that most of the mediated by microbes.
silica released to Hawaiian stream water had passed through the Agriculture brings about disequilibrium in soils (Velde and
biogenic silica pool rather than originating directly from min- Meunier, 2008). The effect of cropping on clay mineralogy was
eral–water reactions in soils in this basaltic environment. assessed through analyses of samples taken from the long-term
Morrow experimental plots at the University of Illinois for >80
20.2.5.3.4  Humans and Other Fauna as Weathering Agents years cropping of different types and with different management
The human being is one biological agent with a potential to affect regimes (Velde and Peck, 2002). Continuous cropping with corn
soil mineralogy, which cannot always be ignored. Apart from has led to a marked loss of illite in favor of illite–smectite phases.
such effects on soil mineralogy as those from enhanced erosion— In contrast, rotation cropping over the same period has had little
leading to, for example, truncation of profiles and transportation effect on clay mineralogy. However, 80 years of growing rice in
of soil minerals over distances from a few meters to the diameter flood-irrigated soils in China showed strong effects on clay min-
of an entire hemisphere (e.g., Syers et al., 1969) by water or wind– erals in the soils (Li et  al., 2003). Micaceous phases, including
people’s activities can also either enhance or retard the influence interstratified phases, have largely been lost, as have Fe oxides, but
of other organisms on mineral weathering, whether through the a Si-poor ferromagnesian chlorite has formed. Pastures can also
effects of agriculture, pollution, construction, and engineering influence clay mineralogical development. Poldered sediments
activities and/or effects on climate and hydrology at either local in France with up to ∼850 years of development under prairie
or global scales (e.g., see Yaron et  al., 2010). In the particular enabled Velde et  al. (2003) to show that the dominantly illite–
case of acid sulfate soils, which are increasing in area globally smectite clay minerals in topsoils, which were influenced the most
because of human activities, and which are of increasing concern by grass growth, hardly changed with time from those in the sedi-
as a form of both soil and environmental degradation (Dent and ment. On the other hand, the same type of clay minerals in the
Pons, 1995; Ritsema et al., 2000), large-scale changes wrought by subsoils became more smectitic over the same time period. The
humans have led to mineralogical changes, which contribute to subsoils had a higher pH than the topsoils, which were more-or-
the properties of these soils, which have been labeled “the nasti- less neutral in pH. The grasses appeared to stabilize the particular
est soils in the world” by Dent and Pons (1995). Classed often as mixed-layer composition of the original clay minerals.
Sulfaquents, acid sulfate soils, which are most commonly coastal, The common agricultural practice of adding fertilizers to soils
but may also occur in nontidal seepage and marsh areas affected can also have effects on the mineralogy of soils. Thus, Simonsson
by dryland salinity (Fitzpatrick et al., 1996), originate from the et al. (2009) found that soils subjected to the long-term use of K
oxidation of sulfides, most commonly of Fe and most often pyrite fertilizers had contents of illite, both as a discrete phase and also
FeS2, but sometimes also Fe monosulfides such as mackinawite within mixed layers, which reflected the rate of addition of the
(tetragonal FeS), pyrrhotite (hexagonal FeS), and greigite (Fe3S4) fertilizers—illite was more concentrated where fertilizer addi-
(Burton et al., 2009). These Fe sulfides are themselves products tions had been higher. K release from the soil minerals appeared
of earlier bacteria-mediated reduction of sulfate ions (Dent and to be reversible except where hydroxyaluminum interlayers
Pons, 1995; Fitzpatrick et al., 1996). Sulfuric acid results from the occurred, presumably blocking K+ from entering or leaving the
oxidation of the sulfides (such as occurs after draining the soils), interlayers (Simonsson et al., 2009). Velde and Peck (2002) also
which occurs only slowly in an abiotic environment, but which found that additions of NPK fertilizer after >40 years of con-
is greatly accelerated in the presence of Fe-oxidizing bacteria tinuous cropping with corn restored the clay minerals to their
(Ritsema et al., 2000). The sulfuric acid thus produced reacts with original state whereas, as already noted, illite was sufficiently
soil minerals generally to give a range of compounds. Of these, depleted of K over >80 years of this treatment without fertilizer
jarosite (KFe3(OH)6(SO4)), also known as “cat clay” because of additions to register a significant change to illite–smectite (I–S).
its yellow, fecal-like color, is most widely recognized as a com- These authors suggested that I–S plays the role of a K buffer that
ponent of acid sulfate soils (Dent and Pons, 1995; Fitzpatrick releases K when plants cannot access other sources of this essen-
et  al., 1996), and schwertmannite (Fe8O8(OH)8–2x(SO4)x), has tial nutrient and stores it when there is an excess of K. Pernes-
been recognized in some under very acid conditions (Fitzpatrick Debuyser et al. (2003) found that the content of nonexpandable
et al., 1996; Burton et al., 2006, 2008). The Fe oxidic phases, fer- illite increased at the expense of expandable I–S in long-term
rihydrite Fe5HO8 · 4H2O and goethite, can also form (op. cit.), but K-addition treatments of soil without plants with either KCl or
many other minerals have been found to form as a result of the manure at Versailles in France. Fertilization with ammonium-
processes contributing to the evolution of these soils. These min- based N-fertilizers has also been shown to affect clay miner-
erals include hydrated sulfates of Na and Fe (sideronatrile and alogy through an increase in the contents of nanocrystalline
natrojarosite), Na and Al (tamarugite), Mg and Fe (copiapite), aluminosilicates and also hydroxyl-Al interlayers in 2:1 minerals
and Pb and Fe (plumbojarosite), as well as gypsum, halite, the Fe (McGahan et al., 2003). On the contrary, Tye et al. (2009) noticed
oxyhydroxide, akaganéite, and a poorly ordered Al oxyhydroxide that the greatest mineralogical changes in the long-term plots
(R.W. Fitzpatrick and M.S. Skwarnecki, unpublished results), as at Rothamsted in the United Kingdom occurred when fertiliza-
well as elemental sulfur (Burton et al., 2009). In the case of acid tion with ammonium sulfate led to pHs falling below 3.7, when
20-30 Properties and Processes

hydroxyl-Al interlayers in 2:1 minerals became solubilized, bacteria and microorganisms create a local microenvironment
allowing entry of the interlayers to K+ and NH +4 . as a result of the fluids of their metabolic products. These fluids
Fauna can also aid weathering processes by moving soil mate- are either acidic or basic in pH, depending on the type of bacte-
rials, especially by bringing less-weathered or unweathered ria: an acidic pH essentially results in incongruent glass dissolu-
subsurface materials to the soil and land surface as occurs by tion, whereas a basic pH results in congruent glass dissolution,
termites for example in building mounds, and worm ingestion leaving large pits on the glass surface (Stroncik and Schmincke,
and excretion (e.g., Paton et al., 1995; Johnson, 2002; Meysman 2002). Microbial activity thus enhances the rate of dissolution of
et al., 2006). In maritime Antarctica, which receives more liquid volcanic glass and microbial alteration also results in the forma-
water than the Antarctic continent, ornithogenic soils formed tion of authigenic phases and is accompanied by redistribution
on basaltic and andesite rocks in abandoned penguin rookeries of elements.
and which are organic-rich due to penguin guano show consid- Hence, microorganisms may play a number of roles in min-
erable development of secondary minerals, mainly as noncrys- eral weathering. As summarized by Barker et  al. (1997), these
talline or nanocrystalline phases, including 1:1 (Al:Si) allophane include the following: (1) physical disintegration of rocks; (2)
(Simas et al., 2006). production of acids and chelating ligands to accelerate chemi-
cal alteration; (3) stabilization of soils to increase their time
20.2.5.3.5  Microorganisms as Weathering Agents of exposure to chemical agents; (4) production of extracellu-
It is well recognized that microbes act as reducing agents and lar polymers to moderate water potential, maintain diffusion
thereby contribute to the reassignment of Fe and Mn from pri- channels, and themselves act as ligands for chelation and also
mary minerals or secondary oxides, oxyhydroxides, and hydrox- as nuclei for mineral neoformation; and (5) absorption of nutri-
ides into solution and ultimately into new oxidic phases upon ents to lower solution concentrations and increase the chemical
drying, sometimes with the solubilization and release of trace potential for weathering. All these roles may also be performed
metals such as Co and Ni (e.g., Quantin et al., 2001). Microbes by plants, including grasses, crops, and trees (e.g., Courchesne,
also act commonly as oxidizing agents (such as in the forma- 2006). In addition, they may be carried out by other biological
tion of ferrihydrite in seepages). Their activity, when simulated agents, including lichens (Adamo and Violante, 2000; Chen
by a series of oxidation-reduction cycles, transformed the short- et al., 2000), fungus-growing termites (Jouquet et al., 2002), and
range-ordered iron oxide “nanogoethite” to microcrystalline mycorrhizal fungae (Jongmans et al., 1997; van Breemen et al.,
goethite and microcrystalline hematite (Thompson et al., 2006). 2000a, 2000b; Certini et al., 2003). With regard to mycorrhizal
They may also bring about mineral alteration through root exu- fungae, the cited authors concluded that the fungal hyphae dis-
dates, as in the tunneling action of fungal hyphae on feldspars solved and extracted nutrients directly from mineral grains,
and other mineral grains (van Breemen et al., 2000b; Smits et al., such as feldspar and hornblende, through their intrusion into
2005, see Section 20.2.4.2). Müller (2009) has shown that the fractures and fissures in the geological deposits and by “drilling”
weathering effect of bacteria can vary greatly between differ- directly into minerals, thereby bypassing the external solution
ent genetic derivatives of a single strain. Organic acids resulting phase. However, in studying the microbiological colonization
from the life and death of organisms have also been recognized of primary mineral weathering in volcanic soils in Italy, Wilson
as important agents in mineral alteration (e.g., Huang and et al. (2008) found in this case that microbial activity, particu-
Schnitzer, 1986; Robert and Chenu, 1992). In particular, dicar- larly fungal activity, was not an effective agent of mineral weath-
boxylic acids have been identified in soils (Hue et al., 1986) where ering, that the association with clay minerals was indirect, and
they greatly enhance rates of dissolution (Amrhein and Suarez, that fungal weathering of primary minerals was probably less
1988) through ring compounds as ligands for sequestering met- important than previously claimed as a source of plant nutrients.
als on mineral surfaces (Casey, 1995). One of the main effects These authors concluded that preformed cleavages and micro-
of organic acids on weathering may come through their supply porous features in primary minerals enable the penetration of
of protons (Ugolini and Sletten, 1991; Nesbitt, 1997). It has also fungi for them to bring about mineral alterations and noted that
been shown in nature and in experiments that both aluminosili- these features were generally absent in the soils they studied.
cate minerals and oxides of Fe and Mn can form by nucleation
on bacteria (Urrutia and Beveridge, 1994; Ferris, 1997; Tazaki, 20.2.5.3.6  The Ecology of Biota and Soil Minerals
1997, 2005; Chan et al., 2009). Magnetite formed partly by bac- Bennett et  al. (2001), in noting that microbes bring about the
teria in soils has been described, for example, by Maher and alteration of minerals through their selective extraction of essen-
Taylor (1988) and Geiss and Zanner (2006). Observations made tial nutrients from the minerals, posed the question of whether
by Ueshima and Tazaki (2001) in both deep-sea sediments and the suite of microorganisms is partly, at least, controlled by the
laboratory experiments showed that aluminosilicates (nontronite mineralogy and by the ability of particular microorganisms to
in this case) could be formed on extracellular polysaccharides use the nutrients contained within the minerals present. Soil
from microbes. The role of microorganisms in the weathering of minerals, both primary and secondary, may thus be viewed in the
glass or volcanic materials has been described, amongst others, ecological context that is characterized by Young and Crawford
by Thorseth et al. (1995), Kawano and Tomita (2001, 2002), and (2004) as “the soil-microbe complex.” Building on the concept of
Stroncik and Schmincke (2002). According to the last authors, plants as ecosystem engineers, and on published information on
Alteration, Formation, and Occurrence of Minerals in Soils 20-31

the effects of particular plant species on soils, van Breemen and work has shown both that (1) bacteria can effect the produc-
Finzi (1998) reviewed the evidence that such effects can provide tion of polymeric molecules within the structures of (smectitic)
a positive feedback to such plants. They concluded that there was clay minerals, hence probably improving the environment for
strong evidence for plant-soil feedbacks in a variety of ecosys- the survival of the bacteria (Alimova et  al., 2009), and (2) the
tems, and they argued that these feedbacks could have played a structure of bacterial communities in soil is influenced by the
role in the evolution of the plant species in question. Earlier, van (primary) minerals in their microhabitat (Carson et al., 2009).
Breeman (1992) had asked the question: “have soils merely been Chickens and eggs come to mind in assessing whether biota or
influenced by biota or have biota created soils as natural bod- minerals are the limiting factors in the ecology of the soil, but
ies with properties favorable for terrestrial life?” Coleman and it is clear that, while both are important, it is their interactions
Crossley (2003) argued for the latter by reference to the storage that are of overriding and vital importance to the sustainable
in soils of the life-limiting element, phosphorus. They contended functioning of soil and the life it supports.
that (1) the interaction of biota with primary minerals produces
soluble Fe (and other cations) by weathering; (2) Fe in particu- 20.2.6  Processes of Mineral Alteration and
lar is brought into the solid phase as oxides (including oxyhy- Formation by Weathering: Summary
droxides) by oxidation aided by (iron oxidizing) bacteria; and
(3) the Fe oxides are kept in a largely amorphous or nanocrystal- Secondary minerals are formed as a result of the alteration of
line form, from which P can be extracted by plants more effi- primary minerals or mineraloids by either (1) transformation in
ciently than from crystalline oxides, through their interaction the solid state or (2) hydrolysis, dissolution, and recrystalliza-
with (biota-derived) humic substances. Recent experimental tion out of solution, namely, neogenesis. Figure 20.9 summarizes
these two possible mechanisms.
Interlayering with hydroxy-Al, Mg, Fe

Mica Chlorite
20.3  Occurrence of Clay Minerals
in Soils
Transformation

Interlayered hydrous mica

(solid phase)

Illite
Loss of cations

This section concentrates on the particular forms in which clay

(Chlorite-swelling chlorite)
minerals occur within soils, rather than the general groups of
(Illite-vermiculite)
Swelling chlorite soils in which they occur, or even their distribution in particular
Hydroxy-Al
interlayered variant environments or globally. These aspects are dealt with elsewhere
(Chlorite vermiculite) in this handbook. Instead, our focus is on the sizes and shapes
(Illite-smectite)
of mineral particles and peculiarities of their chemical composi-
Vermiculite tions and crystal structures, largely in relation to those of “type”
occurrences of minerals with the same names in more or less
Smectite (Smectite-kaolin) (Kaolin-smectite) Kaolinite pure “geological” deposits, including those often used as stan-
dard specimens of each type. In this section, we also explore the
Palygorskite Halloysite
associations of minerals within soils in relation both to other
Allophane types of minerals and also to organic materials. In particular,
Recrystallization

(solution phase)

we examine the possibility that there is a relationship between

Neoformation

the mode of formation (and alteration) of clay minerals, on the

one hand, and on the other, the forms they adopt and also their
associations within soils.

20.3.1  Occurrence of Kaolinite in Soils

Si, Al, Fe, Mg, K, Na, Ca, Mn, Li, Ti, OH, P, F, Cl
Kaolinite is the most ubiquitous phyllosilicate in soils (White
Dissolution and Dixon, 2002). Nonetheless, kaolinites are most abundant
in highly weathered soils, which are formed in warm humid
climates, although a high rainfall can result in their formation
Olivines Pyroxenes Amphiboles Feldspars Serpentines within soils in temperate climates (Weaver, 1989; White and
Volcanic glass Apatite Quartz
Dixon, 2002). They can also be found in soils in colder climates
that were nevertheless formed under an earlier, warmer climate,
FIGURE 20.9  Main pathways for mineral alteration and formation
in soils via either neoformation (lower part of figure) or transformation for example, by preglacial weathering in Scotland (Wilson et al.,
(upper part). (After Churchman, G.J. 1978. Studies on a climosequence 1984). Generally, kaolinites in soils are highly disordered and
of soils in tussock grasslands. 21. Mineralogy. N.Z. J. Sci. 21:467–480; many of the peaks in their XRD patterns are poorly resolved. As
Wilson, M.J. 2004. Weathering of the primary rock-forming minerals: a result, the common index for assessing the degree of crystal-
Processes, products and rates. Clay Miner. 39:233–266.) line order by XRD, namely, the Hinckley index, is impossible
20-32 Properties and Processes

to measure and an alternative, empirical index was devised by form, for example, vermiculite or beidellitic smectite, provide
Hughes and Brown (1979), which remains in use for soil kaolins nucleation sites on their 001 surfaces for authigenic kaolinite
(including halloysite). In developing this index, Hughes and formation, as shown in Figure 20.4.
Brown (1979) noted that kaolinites in the set of 26 soils they A number of papers (Singh and Gilkes, 1992a; Melo et  al.,
mainly studied, which were from Nigeria, invariably occurred 2001; Hart et al., 2002; Kanket et al., 2005) have compiled data
along with other minerals in their clay fractions, as well as con- describing crystal form, measures of crystal order, and related
taining weatherable minerals in the coarser fractions. These properties such as Fe contents for kaolinites extracted from
authors suggested that the weatherable minerals present hin- highly weathered soils in (Western) Australia, Brazil, Thailand,
dered the crystallization of well-ordered kaolins. Millot (1970) and Indonesia, although the last also included some halloysite or
had come to a similar conclusion, suggesting more specifically “tubular kaolins” (Churchman and Gilkes, 1989), so the total set
that alkaline-earth cations had caused the inhibition of crystal- is better described as kaolins. Together with information from
lization. Iron is a common impurity in the kaolinite structure, Hughes and Brown (1979) for Nigerian soils, these properties are
and there appears to be a relationship between structural Fe and able to be compared in Table 20.4 (from Kanket et al., 2005, with
crystalline order (Herbillon et al., 1976; Mestdagh et al., 1980). data for the reference kaolinites from Hart et al., 2002). The vari-
As Fe increases in amount, displacing the smaller Al atoms ous kaolins had many properties in common. Although there
from the structure, crystal strain may increase, thereby limiting was a range for each value within each set of soil kaolins, their
crystal growth, so that particle size as well as structural order specific surface areas (overall range 34–88 m2 g−1) all exceeded
is likely to be diminished by a high Fe content. Lim et al. (1980) those of any of the reference samples (all ≤25 m2 g−1) and their
had found that nonsoil kaolinites could also be poorly crystal- particle sizes, given by coherent scattering domains (CSDs), were
lized. Compared with their well-crystallized counterparts, generally less than half those of the reference kaolinites. Surface
seven examples of these poorly ordered kaolinites, from Georgia areas and particle sizes are expected to be inversely related to each
in the United States of America, showed not only much higher other. Their Hughes and Brown (HB) index values were always
values for specific surface area particularly (between 78 and less than those of the reference kaolinites, and, although some of
114 m2 g−1, cf. 10–15 m2 g−1 for the well-crystallized kaolinites), the soil kaolins had quite high CECs, some were comparable to
but also some relatively high values for CEC. All were shown to those of several, at least, of the reference kaolinites. Regardless
comprise some montmorillonite and vermiculite as impurities, of their other characteristics, however, all of the soil kaolins on
while six of them also contained mica. Kaolinites often occur in which Fe was measured (those from Thailand, Western Australia,
vermiform books, suggesting a micaceous precursor. White and and Indonesia) had much higher contents of Fe than the reference
Dixon (2002) suggested, rather, that micas, or, more commonly, kaolinites. With the most clear-cut differences between soils and
their expanded transformation products with the same crystal reference kaolinites being in their surface areas, the HB measure

TABLE 20.4  Properties of Kaolins in Groups of Soils (with Standard Deviations, Where Given, in Brackets) and of Standard Kaolinites
Location No. of Samples d001 (Å) CSDa (nm) HBb Index % Fe2O3 (g kg−1) CEC (cmol+ kg−1) SSAc (g kg−1)
Soils
Thailand (1)d 20 7.208 (0.042) 19.3 (8.9) 6.7 (1.6) 19.6 (1.8) 8.5 (2.9) 47.4 (8.8)
Thailand (2)e 18 7.19 (0.03) 15.4 (5.5) 6 (1) 25.3 15.2 (4.7) 44.9 (12.1)
Western Australia 7 7.213 22.9 5.6 25.7 5.0 50.8
Indonesia 6 7.212 10.8 5.6 25.4 9.4 72.8
Nigeria 26 — — 8.0 — — —
Brazil 21 7.19 — 12.7 19.6 — 48.5
Standards
Georgia #1460 1 7.148 26.6 18.9 8.9 3.2 25
Georgia #1261 1 7.160 43.4 32.6 2.5 3.9 10
Georgia #MP5 1 7.132 47.6 34.2 4.2 0.4 5
New Mexico (Wards) 1 7.148 43.1 60.5 4.3 4.6 13
Cornwall (ECC) 1 7.160 48.8 26.3 4.2 0.5 11
Source: Data for the soil kaolins from Kanket, W., A. Suddhiprakern, I. Kheoruenromne, and R.J. Gilkes. 2005. Chemical and crystallographic prop-
erties of kaolin from Ultisols in Thailand. Clays Clay Miner. 53:478–489, with data for the reference kaolinites from Hart, R.D., R.J. Gilkes, S. Siradz,
and B. Singh. 2002. The nature of soil kaolins from Indonesia and Western Australia. Clays Clay Miner. 50:198–207.
a CSD, 001 peak.

b Hughes and Brown (1979).

c Specific surface area from N -BET.

2
d From Hart et al. (2003).

e From Kanket et al. (2005);

– Not determined.
Alteration, Formation, and Occurrence of Minerals in Soils 20-33

Sample #167 Sample #239

Sample #169 Georgia kaolinite

Eh

1 μm

FIGURE 20.10  Transmission electron micrographs showing comparisons between some soil kaolinites from Western Australia and a reference
kaolinite (from Georgia). Eh indicates a euhedral hexagonal shape for particles in the reference sample. (Micrographs copied from Singh, B., and
R.J. Gilkes. 1992a. Properties of soil kaolinites from south-western Australia. J. Soil Sci. 43:645–667. Reproduced with permission of Wiley-Blackwell.)

of structural order, and their Fe contents, these results bear out kaolin–smectite interstratified phases (or “kaolin–smectites”)
the proposition from Herbillon et al. (1976) and Mestdagh et al. are likely to be a very common component of Australian soils.
(1980) that a high Fe content leads to a low degree of structural In Australia, and elsewhere, they have probably been often over-
order and small particles. Their small size, particularly, is illus- looked in identifications using XRD patterns. This “omission”
trated by transmission electron micrographs showing com- is because the main effect of the mixed layering is to broaden
parisons between some soil kaolinites from Western Australia and weaken XRD peaks, so that basal peaks may become invis-
from Singh and Gilkes (1992a) and a reference kaolinite (from ible even though nonbasal peaks appear (Norrish and Pickering,
Georgia) (Figure 20.10). Furthermore, Singh and Gilkes (1992a) 1983). In part, this effect is a consequence of the inherent vari-
found that the kaolinites contained both K and Mg, which are ability of clay minerals in soils, so that the properties of the two
largely absent from pure, well-crystallized kaolinites. Brazilian (and sometimes more) components and their degree of order
soil kaolinites were also found to contain considerable K and Mg can vary from particle to particle (ibid.). Most kaolinite–smec-
(Melo et al., 2001). These authors suggested that there are resid- tites described in the literature are more kaolinitic than smectitic
ual micaceous layers incorporated in the kaolinites. This finding (Churchman et al., 1994), although Bühmann and Grubb (1991),
is consistent with the results of Lim et al. (1980) and also with the Churchman et al. (1994), and also Ryan and Huertas (2009) each
common observation that kaolinites appear in vermicular books found examples where the proportion of smectite layers was
by crystallization on the surfaces of micas and their transforma- >60%. In the same way that many interstratified specimens with
tion products (Figure 20.4). The crystal growth of the kaolinites high concentrations of kaolinite have been identified incorrectly
may have been constrained by interleaved micaceous layers as as kaolinites (Norrish and Pickering, 1983; Churchman et  al.,
well as by Fe incorporated into the kaolinite layers. 1994), so also some with high contents of smectite have been mis-
Kaolinite (and also, we shall see, halloysite) quite often identified as smectites (Cuadros et al., 1994). Some with a high
occur in interstratifications with a smectite. Kaolinite–smectite kaolinite content were probably misidentified as halloysites that
interstratified phases have been found to occur worldwide, have a platy morphology (Carson and Kunze, 1970; Wada et al.,
including in Scotland, Canada, throughout Africa, Australia, 1987), but each of these was later interpreted as a kaolin–smectite
Central America, India, Japan, China, and the United States by Sakharov and Drits (1973) and Parfitt and Churchman (1988),
(see Churchman, 2000, for citations), and a more recent respectively. The identification of phases as kaolin–smectites
report (Vingiani et  al., 2004) described their occurrence in rather than as either of their components is important in order
Italy (Sardinia). Norrish and Pickering (1983) speculated that to fully describe the effect of clay mineralogy on soil properties
20-34 Properties and Processes

such as CEC (e.g., Seybold et al., 2005) because they give rise to authors proposed that the (subtraction) mechanism operated
higher values than can be expected from kaolinites and lower val- through a preferential loss, by either transformation or dissolu-
ues than from smectites. tion of the ferrous smectite layers, to give kaolinite layers, with
Kaolinite–smectites have been found in intermediate zones in the excess Fe forming either Fe oxides (or oxyhydroxides) or
toposequences spanning smectitic black soils at their base and becoming incorporated in kaolinite layers, or both.
kaolinitic red soils near their summits and on their steep slopes Kaolinites can also form interstratifications with other types
(Herbillon et al., 1981; Bühmann and Grubb, 1991; Delvaux and of layers besides smectites, for example, vermiculite (Jaynes
Herbillon, 1995; Vingiani et al., 2004). They have also been rec- et  al., 1989), and can also participate in interstratified phases
ognized within single soil profiles on basalt (Churchman et al., involving several different types of layers. The elevated CECs
1994; Vingiani et al., 2004). From the base of the profile to near and also high K 2O contents of some of the soil kaolins studied
its surface, their composition changed from highly smectitic by Singh and Gilkes (1992a), Melo et al. (2001), and Kanket et al.
to highly kaolinitic, but nonetheless with both phases being (2005), in particular, are at least partly ascribed to their inter-
interstratified kaolinite–smectites (Churchman et al., 1994), or stratifications by micas and/or vermiculites. Ma and Eggleton
else more subtly, from ∼35% to 40% to ∼40% to 45% kaolinitic (1999) found that some soil kaolinites in Queensland, Australia,
within the interstratifications (Vingiani et al., 2004). Ryan and had quite high CECs (16–34 cmol+ kg−1) and HRTEM had shown
Huertas (2009) have also located kaolinite–smectites in a set of that their crystals commonly comprised stacks of many kaolin-
soils within a chronosequence on mostly basaltic and andesitic ite layers, which terminated in smectite layers, possibly as single
parent materials. As it was within the residual soil profiles on layers. These stack-end smectite layers affected CEC but were
rock (Churchman et al., 1994; Vingiani et al., 2004), the progres- usually not detectable by XRD (Ma and Eggleton, 1999).
sion from youngest (found at the base of the profiles) to the
oldest (at the surface in the case of the profiles) was from more
20.3.2  Occurrence of Halloysite in Soils
smectitic (or pure smectite, in the chronosequence) to more
kaolinitic. Kaolinite also occurred as a discrete phase alongside As already noted (Section 20.2.4.5), halloysite is a common com-
its interstratifications with smectite in the most developed (i.e., ponent of soils formed from volcanic parent materials, particu-
oldest) soil in the chronosequence of Ryan and Huertas (2009) larly tephra including finer components referred to as volcanic
and also in the soil profiles of Churchman et  al. (1994) and ash (e.g., Kirkman, 1981; Lowe, 1986). It has also been identified
Vingiani et al. (2004). A variety of techniques, including XRD, as a weathering product of a wide range of rock types including
together with modeling of the effect of interstratifications and nephelinite, granite, gneissic granite and granitic gneiss, gneiss,
sometimes also peak decomposition, FTIR, HRTEM, differen- dolorite, schist, graywacke, greenstone, granodiorite, gabbro,
tial thermal analysis (DTA), and permanent and variable charge shale, and amphibolites (see Churchman, 2000, and also Joussein
analysis, have enabled various authors to seek an understanding et  al., 2005, for citations). Halloysite can occur in a variety of
of the origin of the process of interstratification of the 2:1 and 1:1 particle morphologies including tubes and microtubules, spher-
layers. Ryan and Huertas (2009) concluded that a layer-by-layer oids and microspheres, crumpled lamellae, crinkly films, needle-
transformation occurs as smectite is progressively altered to like or fiber-like forms, and prismatic forms (ibid.; see also Hong
kaolinite via an interstratification of the two endmember phases and Mi, 2006; Etame et  al., 2009). Its morphology appears to
with each other. The transformation proceeds by localized dis- relate to the content of impurity iron with substitution of the
solution of the 2:1 layers with initial loss of Fe and Mg from octa- larger Fe(III) for Al in the octahedral sheet, which, without sub-
hedral sheets and of Al from tetrahedral sheets followed by a loss stitutions, is smaller than the tetrahedral sheet. This situation
of Si from tetrahedral sheets (“subtraction”) and/or a deposition leads to partial or full correction of the misfit between the octa-
of hydroxyl-Al species in interlayers, leaving 1:1 layers (“addi- hedral and tetrahedral sheets that, therefore, causes curling (as
tion”) (Ryan and Huertas, 2009). These two alternative types of in tubes) in halloysites with little or no Fe. The impurity Fe also
mechanism for the alteration had been proposed earlier by Wada constrains crystal growth and leads to smaller particles being
and Kakuto (1983, 1989), who favored a subtraction mechanism, formed. Recently, Singer et al. (2004) have found halloysites with
and by Altschuler et al. (1963) and Poncelot and Brindley (1967), high contents (up to 6.5%) of Ti in their aluminosilicate struc-
who favored an addition mechanism. Albeit through studying ture that were plate-like, probably from the same cause: larger Ti
a clay deposit rather than a soil, Watanabe et  al. (1992) found atoms replace some Al in the octahedral sheets, hence also cor-
support for a subtraction mechanism as a result of their discov- recting at least some of the mismatch with the tetrahedral sheet.
ery that opal C–T, or microcrystalline opal comprising clusters Even so, whereas a peculiar shape was once regarded as the dis-
of stacking of cristobalite and tridymite over very short length tinguishing feature of halloysite in comparison with kaolinite, it
scales, forms during the early stages of formation of kaolinite is rather the occurrence, or else evidence for prior occurrence, of
from smectite. Vingiani et al. (2004) discovered that the smectite interlayer water that demarcates halloysites from kaolinites (see
in the sequence they studied consisted of a mixture of a more Section 20.2.4.6.2 earlier herein). Interlayer water is lost irrevers-
ferric and a more aluminous type. In the course of mineralogical ibly from halloysites on drying.
evolution, there was a decrease in the proportion of the ferrous However, some shapes, particularly spheroidal, appear to
smectite layers relative to their aluminous counterparts. These reflect a particular mode of formation for halloysite (Churchman,
Alteration, Formation, and Occurrence of Minerals in Soils 20-35

2000). Spheroidal forms of halloysite appear often in weather- of Al by Fe than tubular halloysite, whereas the platy form had
ing products of volcanic glass, which has a fast dissolution rate, the most structural Fe among the halloysites. The poorly ordered
and recrystallization from the resulting supersaturated solution kaolinite that developed from halloysite in the third stage had a
appears to favor this particular shape (review by Bailey, 1990; comparable degree of substitution of octahedral Al by Fe as its
Adamo et al., 2001; Singer et al., 2004), possibly when physically supposed platy halloysite precursor, and the disordered kaolinite
constrained, for example, within pumice cavities (Adamo et al., formed first in the fourth stage had even more substitution of
2001). Nevertheless, both Churchman and Theng (1984) and Fe for Al. However, the book-type kaolinite had a vanishingly
Singer et al. (2004) found that spheroidal particles had higher Fe small content of structural Fe. It was almost pure aluminosili-
contents than even short tubes, suggesting a structural control cate. Overall, Papoulis et al. (2004) attributed the changes in the
on shape for spheroids as well as for tubes. By contrast, Johnson sequence from small spheroidal particles of halloysite through
et  al. (1990) found a spheroidal halloysite with virtually no Fe tubular and play halloysite to poorly ordered platy, then well-
whereas Noro (1986) and also Adamo et al. (2001) found few, or ordered book-type kaolinite, largely to a changing chemistry of
only minor, differences in composition between spheroidal and the ambient solutions, with a successively decreasing availability
tubular forms of the mineral. In any case, Soma et al. (1992), using of Fe for incorporation in the aluminosilicate layers, although
XPS, found that Fe content varied between different layers in a they conceded some role to microenvironmental conditions
halloysite, whether spheroidal or tubular. Furthermore, spheroi- (e.g., time, and space available) in affecting particle morphology.
dal- and tubular-shaped particles occur together in halloysites Bailey (1990) concluded that the structural difference
(Saigusa et al., 1978; Churchman and Theng, 1984), and one may between halloysite and kaolinite is substantial enough to make
alter to another in situ (Sudo and Yatsumoto, 1977), suggesting it impossible for one to give rise to the other without dissolu-
there may be no clear-cut distinction between the conditions that tion and recrystallization. Nonetheless, there have been many
lead to the different particle shapes for halloysite. On the other studies showing an apparent genetic relationship between hal-
hand, a very detailed microtextural and microanalytical study of loysite and kaolinite in weathering profiles including soils
samples taken at various depths in a weathering profile on gneiss and deeper regolith. There is a general trend from halloysite at
in Greece led Papoulis et al. (2004) to deduce a sequence of min- depth toward kaolinite at the surface of profiles on residual rock
eral alteration that encompasses different morphologies for hal- materials (e.g., Eswaran and Wong, 1978; Calvert et  al., 1980;
loysite and includes two forms of kaolinite while simultaneously Churchman and Gilkes, 1989; Churchman, 1990; Takahashi
indicating a correlation between structural Fe and the various et al., 2001, Singer et al., 2004; Jongkind and Buurman, 2006).
products in the alteration sequence. Papoulis et al. (2004) divided These studies together have covered a range of parent rock
the alteration sequence into four successive stages. In the earli- types and also climates, including tropical (Eswaran and Wong,
est stage, halloysite formed in very small spheres (∼0.1 to 0.3 μm 1978, and part of Churchman, 1990), temperate (Calvert et al.,
in diameter) that were located on the surfaces of plagioclase in 1980; part of Churchman, 1990; Jongkind and Buurman, 2006),
this case. These small spheres then apparently coalesced to form and Mediterranean, or xeric (Churchman and Gilkes, 1989;
tubes while new tubes also formed in the second stage. These Takahashi et al., 2001; Singer et al., 2004). According to Papoulis
tubes were generally quite short (<1 μm in length), although they et al. (2004), these trends with depth were explained in the con-
could develop with time to form longer tubes with tapered ends, text of their morphological and compositional development
which, together with a relatively loose packing and subparallel sequence of halloysite and kaolinites. They pointed out that a
orientation, suggest crystallization from solution (a conclusion depth sequence in a residual weathering profile on rock is inter
supported by studies on halloysite with tapered ends by Hong alia also a time sequence, with the earliest stages concentrated
and Mi, 2006). In the third stage, platy halloysite formed appar- at depth and the latest (oldest) stages to be found near the sur-
ently by interconnection of the preformed tubes. This form even face (unlike we note the situation in upbuilding profiles where
occurred in crude booklets, which are commonly regarded as the opposite is true). Like Churchman and Gilkes (1989), these
more typical of kaolinites, albeit interleaved with a low pro- authors considered that the products of the different stages could
portion of kaolinite plates, according to Papoulis et  al. (2004). also exist simultaneously with one another. Singer et al.’s (2004)
These authors considered that the platy halloysite was unstable examination of the weathering of basaltic scoria at a fine scale
and led to the formation of plates of a poorly ordered kaolin- showed that, whereas 1.0 nm halloysite was found in vesicles
ite, with dimensions of ∼1 μm in length and ∼0.1 to 0.2 μm in in the scoria, where it was protected from dehydration, 0.7 nm
thickness. The change from halloysite plates to kaolinite was halloysite and also kaolinite were found in the less scoriaceous
considered to occur within the single (third) stage by Papoulis basalt, where minerals had been exposed to seasonal drying.
et al. (2004). The fourth stage was one of kaolinization, with a 1.0 nm halloysite was also found in a buried paleosol in the same
disordered kaolinite forming first but with a well-formed book- region. Its burial in the paleosol had protected it from drying. In
type kaolinite as the ultimate product. Concomitant with these New Zealand, Lowe (1986) found that 0.7 nm halloysite predom-
changes in morphology, increasing Fe in EDAX/EDS analyses of inated in the surface horizons of a soil developed on weathered
the products through the first three stages led these authors to tephra subject to reasonably frequent seasonal drought, whereas
allocate increasing proportions of Fe in octahedral sheets at the 1.0 nm halloysite occurred in deeper horizons that were less
expense of Al, so that spheroidal halloysite had less substitution affected by drying. An intermediate zone of variably dehydrated
20-36 Properties and Processes

halloysite with XRD peaks between 1.0 and 0.7 nm occurred apparently form on the surface of kaolinite platy particles.
between upper and lower subsoil horizons. Dissolution of kaolinite and recrystallization of halloysite could
These findings were corroborated by Churchman et al. (2010), have occurred in both situations.
who found that alteration of granite and volcanic tuff in Hong Like kaolinites, halloysites have been found to form interstrat-
Kong had led to halloysite forming only in veins within the ified phases with smectites. However, halloysite–smectites form
rocks where there was no evidence of drying, namely, no Fe or under conditions different from those that result in kaolinite–
Mn oxides were present. By the same token, this study showed smectites (Delvaux and Herbillon, 1995). Delvaux and Herbillon
that kaolinite formed in these veins, either alone or in associa- (1995, and earlier papers cited therein) have generally found
tion with halloysite, where the appearance of Fe and Mn oxides interstratified halloysite–smectites in soils formed from volcanic
indicated that drying had occurred. A weathering sequence on ash. They form under similar (usually alkaline) conditions, which
trachy-basaltic parent materials in Sicily was found to produce give rise to smectites but where the drainage is less restricted (i.e.,
imogolite-like allophane (i.e., Al-rich allophane) in the early more leaching occurs) than for smectite formation (Glassmann
stages of alteration of volcanic glass and kaolinite, but no hal- and Simonson, 1985; Smith et al., 1987).
loysite in later stages (Egli et  al., 2008). This absence is prob- There do not appear to be any studies of the form of halloy-
ably because of the xeric moisture regime in the area. Similarly, sites and their associations in soils that are similarly detailed to
basaltic parent materials in a xeric moisture regime in South those of soil kaolinites by Singh, Gilkes, and coauthors (Section
Australia were found to produce allophane, but not halloysite 20.3.1). However, many electron micrographs, including those of
(Lowe et al., 1996; Lowe and Palmer, 2005; Takesako et al., 2010; the highly halloysitic Naike and Hamilton soils in New Zealand
also Section 20.2.4.6). Kaolinite per se was not formed in this (formed from strongly weathered tephra) that are shown in
case, and, although kaolinite–smectite was often present in the Fieldes (1968) and Churchman and Theng (1984), respectively,
soils, it could have been derived ultimately from limestones and display mainly tubular particles that are practically all <0.2 μm.
calcareous dune sands underlying the basalt that were incorpo- Lowe (1986) also found tubes, some split, between ∼0.07 and
rated into the soil parent material during the basalt emplacement, ∼0.3 μm in length in similar materials. Furthermore, high val-
with 1:1 Al:Si allophane the likely result of further development ues for surface areas of halloysites in soils or halloysite-rich soils
of initially formed 2:1 Al:Si allophane by resilication. Albeit that from around the world have been recorded by several workers
a drier regime tends to favor halloysite over allophane in soils (Quantin et al., 1984; Theng, 1995; Takahashi et al., 2001; Singer
from volcanic ash (see Section 20.2.4.6.2), these various obser- et  al., 2004). Specific surface areas >100 m2 g−1 were measured
vations suggest that the presence of water is a necessary condi- for soil halloysites or halloysitic soils in all of the studies cited.
tion for the formation and preservation of halloysite rather than These area measurements point to the likelihood that halloy-
kaolinite under similar conditions of, for example, parent mate- sites, like kaolinites, commonly occur as quite small particles in
rial, temperature, and time. soils. The fineness of their particles very likely reflects compo-
Even so, a trend from halloysite at depth toward kaolinite at sitional or structural features that have limited crystal growth.
the surface in residual soil profiles does not necessarily imply In the case of the high surface area halloysites studied by Singer
that halloysite transforms to kaolinite as weathering intensi- et al. (2004), it is likely that the high degree of substitution of Al
fies with time. Churchman and Gilkes (1989) found rather by Fe and/or Ti introduced strains into the layer structure that
that hydrated, tubular halloysite, which dominated the clay limited the size of particles. The clay fractions of two halloysitic
fraction of the saprolite deep in a lateritic profile in dolerite in soils studied by Takahashi et al. (2001) were found to have high
Western Australia, became progressively more dehydrated and CECs and a high selectivity for K+ in addition to high surface
progressively more difficult to intercalate with the polar liquids— areas, and 27Al-NMR showed that their constituent halloysites
formamide, hydrazine, and a concentrated potassium acetate had ∼2% tetrahedral Al and probably also some Al vacancies
solution—with closer approach to the surface. As weathering and impurity Fe in their octahedral sheets. They contained some
intensified up the profile, kaolinite began to appear as hexagonal Fe as oxides, which could have been present as surface coatings,
particles but by a different pathway from that for halloysite. As and some 2:1 Si:Al minerals could also have been present in the
has been found elsewhere in the old, strongly leached landscapes clay fraction, even if not detected there, because of their obvious
of much of Australia (Janik and Keeling, 1993), Churchman and appearance in coarser fractions. While these authors could not
Gilkes (1989) observed that tubular particles with a kaolin layer reach unequivocal conclusions about the extent to which hal-
structure and composition appeared even in the uppermost loysite per se contributed to the unusual properties of these soils,
duricrust of the weathering profile, but they were dehydrated the dilemma they encountered was the result of the complex
and completely resistant to intercalation by polar liquids. mineral assemblages that could involve halloysites in soils and
In seeming contradiction to this trend and also to Bailey’s emphasizes how halloysites, like kaolinites, can be bound into
(1990) contention that halloysite and kaolinite cannot transform multiphase associations in soils.
from one to the other in the solid phase, both Robertson and Halloysites often occur in close associations with iron oxides
Eggleton (1991) and also Singh and Gilkes (1992b) showed elec- and oxyhydroxides in soils (Churchman and Theng, 1984;
tron micrographs from within weathering profiles in Australia Bakker et  al., 1996; Takahashi et  al., 2001; Pochet et  al., 2007;
in which tubular particles, suggesting halloysite, are seen to Etame et  al., 2009). Pochet et  al. (2007) showed that they can
Alteration, Formation, and Occurrence of Minerals in Soils 20-37

form stable microaggregates with Fe oxides, and especially fer- On the other hand, illite that has undergone considerable
rihydrite that probably preserve the halloysites in spite of nearby transformation to include expansible 2:1 layers of vermiculite
soils being at an advanced state of weathering, which would and/or smectite is more likely to occur in the fine clay (<0.2 μm)
normally drive the change toward kaolinite in a humid tropical size fraction (Fanning et al., 1989; Laird et al., 1991; Robert et al.,
environment. 1991). Studying soil clays derived from the major sedimentary
In a study of soils formed from nephelinite (alkali- and rare- rocks, Robert et al. (1991) found that illite–smectite interstrati-
earth-rich lava) in tropical Cameroon, Etame et al. (2009) dem- fied phases (I–S) are “the most widespread and representative
onstrated a chemical dependence of the halloysites upon parent soil clays,” a conclusion that was echoed by Velde and Meunier
minerals: Ce-rich halloysite characterized alteromorphs formed (2008; see also Section 20.2.5.3). Generally, they are randomly
from the mineral phillipsite, Fe-rich halloysite characterized interstratified (Thompson and Ukrainczyk, 2002). Robert et al.
alteromorphs on clinopyroxene, Ca-rich halloysite character- (1991) distinguished two types of I–S. One, which they termed
ized alteromorphs on hauyne, and K-rich halloysite characterized “micromicas,” may occur as large crystals and have layers with
alteromorphs on leucite. A Ce-rich halloysite (Ce2O 0.1%) was 1 nm periodicity that are separated by “swelling spaces” (Robert
also identified in saprolite derived from hydrothermally altered et  al., 1991). It is a “structural” type of interstratification. The
nephelinite (Etame et al., 2009). other type consists of random superpositions of elementary
particles, “like monolayers,” to quote Robert et al. (1991). These
authors characterized it as a “textural” type of interstratifica-
20.3.3  Occurrence of Illite in Soils
tion, which is the same type as that identified by Nadeau et al.
Illites can form in soils by weathering as a result of transforma- (1984) in the context of diagenetic clay minerals in sandstones.
tion, in the solid phase, from micas (Section 20.2.4.3, and also, One of the main conclusions to be drawn from Robert et al.’s
via biota, Section 20.2.5.3) and, like most of the other second- (1991) work is that I–S, as common soil clays, differ significantly
ary minerals, they can also precipitate by neogenesis out of from reference clays. Among their defining characteristics, they
solution. There is little doubt that they most commonly form are always multiphase, their smectitic phase is dominantly dioc-
by transformation from primary micas. The degree of transfor- tahedral, and Al-rich, hence beidellitic (Robert et al., 1991), their
mation they have undergone differs greatly, so that, in younger particles have a very small lateral extension (often 30–50 nm)
and less-weathered soils, especially those in arid environments and a very small number of layers. Furthermore, their smectite
(Section 20.2.5.2), the clay-sized micaceous phases may be component includes partially collapsed layers, and the clays have
mainly a product of comminution of primary micas by physi- a high external surface area, particularly relative to their inter-
cal weathering processes (e.g., Fanning et al., 1989). In this case, nal surface area (Robert et al., 1991). Laird et al. (1991) studied
the secondary phase may be better described as clay-sized mica an I–S mineral that fully occupied fine clay fractions of a soil and
rather than as illite. However, the term illite is used quite widely found that the smectitic layers comprised a high-charge Fe-rich
to describe mica-like clay-size minerals in soils, as already noted montmorillonite. This finding is at odds with several reports of
(Section 20.2.4.3). In all but the youngest or little-weathered soils, soil smectites being more beidellitic, albeit Fe-rich (see Section
the micaceous phase in their clay fraction, hereafter referred to 20.3.5). Laird et  al. (1991) also found that the illitic layers had
as illite, or illitic, contains some expanded layers; hence, some a low, largely tetrahedral charge, and were dioctahedral. Their
degree of interstratification of the K-rich illite layers with vermic- layer charge was more typical of a beidellite than an illite. These
ulite or smectite layers that have become depleted in K through authors speculated that the illitic layers in the I–S could them-
its displacement by hydrated cations. Hence, they are expandable. selves constitute a breakdown product of illite in the coarse clay
Micas, especially muscovite and biotite, are particularly fraction or else they could have formed by the collapse of pre-
abundant in mica schists and some other metamorphic rocks formed beidellite layers, but the evidence available to Laird et al.
(Fanning et  al., 1989). Mica schists are especially abundant (1991) favored neither mechanism. Examination of a fine clay
because they originate from the metamorphosis of argilla- (0.02–0.06 μm) fraction by HRTEM in a later study (Laird and
ceous sediments such as shales and slates (ibid.). According to Nater, 1993) revealed that this was composed of (1) two-layer ele-
Fairbridge and Bourgeois (1978), shales comprise ∼40% to 60% mentary illite particles, which were most abundant, (2) one-layer
of all sedimentary rocks by volume and ∼80% of crustal weath- elementary smectite particles, and (3) rare discrete multilayer
ering products. As relatively soft minerals, micas in the schists illite particles. The elementary illite particles could be separated
are readily broken down during transport and sedimentation. from the smectitic component and were shown  to comprise a
Thence, they become important components of shales and rectorite-like phase with alternate swelling and  nonswell-
slates, the types of sedimentary rocks from which they origi- ing layers except that, in this case, the swelling and nonswelling
nated. Hence, illite may originate by inheritance from micas in layers each had a similar low charge of ∼0.47 per formula unit
underlying or nearby sedimentary shales or slates that may ulti- in contrast to rectorite, with ∼0.35 for the swelling and ∼0.85
mately be recycled by metamorphosis into new mica schists (e.g., for the nonswelling layers (Laird and Nater, 1993). Like Robert
Garrels and Mackenzie, 1971). Illite in soils formed from these et  al. (1991), Laird and coauthors identified this I–S mineral
widespread sedimentary rocks is most abundant in the coarse phase as being characteristic of soils. Whereas it was identified
clay (0.2–2 μm) size fraction (Fanning et al., 1989). as a component of an interstratification with smectite by Laird
20-38 Properties and Processes

et al. (1991), the ease of its separation, together with the lack of a may well be trioctahedral, for example, the regularly interstrati-
1 nm (10 Å) peak for illite in XRD analysis, indicated that the I–S fied phases, hydrobiotite and chlorite–vermiculite, a variety of
phase in this fine clay fraction is a “textural” type of interstrati- structural and composition changes occur within the alumino-
fication, similar to those identified by Nadeau et al. (1984), and, silicate layers alongside the loss of K+ during vermiculitization
in soils, by Robert et al. (1991). (see Section 20.2.4.3). The net result of these changes is the loss of
Illite can also form by neogenesis. Such illites include some Al from the tetrahedral sheet and its gain in the octahedral sheet
that have formed in close proximity of feldspars, most prob- at the expense of Fe2+ and Mg. As a consequence, the layer struc-
ably out of solutions bathing the feldspars (Section 20.2.4.2). In ture becomes more dioctahedral (Wilson, 2004). Nonetheless,
many soils in Australia (Norrish and Pickering, 1983), and also in the North Island of New Zealand, the occurrence of triocta-
in Iran (Mahjoory, 1975) and in some semiarid soils in North hedral vermiculite in a soil derived from a composite of weath-
America (Nettleton et al., 1970), there is a concentration of illite ered tephras was attributed to the presence of biotite, which was
toward the surface of soils, contrary to the trend in soils where known to occur in some of the parent tephras because such teph-
micas are subject to transformation, which leads to increasing ras had been preserved unweathered in layers within sediments
vermiculite and smectite at the expense of illite toward soil sur- in lakes adjacent to the soil (Lowe, 1986).
faces. The trend toward more illite in surface soils than at depth Although dioctahedral micas are much more stable in the
suggests that illite may have formed by neogenesis in these soils. weathering environment than trioctahedral micas, their altera-
Norrish and Pickering (1983) characterized a Fe-rich illite from a tion can also lead eventually to vermiculites, sometimes via reg-
deposit (“Muloorina”) near a seasonally wet and dry central lake ularly interstratified mica–vermiculites, as found in soils formed
in Australia (Lake Eyre) as a product of neogenesis in the lacus- on mica schists in the South Island of New Zealand (Churchman,
trine environment (although it may not be pedogenic) (Wilson, 1980). However, where pHs are moderately acid, that is, between
1999). Its neogenetic origin was suggested by the very uniform about 4.6 and 5.8, organic matter contents are relatively low and
shape and size of its particles, which are almost all ∼0.07 μm in there is frequent wetting and drying—all conditions that are
diameter (see Churchman, 2000, Figure 1.8a). Similarly sized conducive to the vermiculitization of micas—Al-hydroxy species
and shaped particles of illite are also found in a number of soils are deposited, usually as polymeric cations, in the interlayers of
in various parts of Australia (e.g., Willalooka—see Norrish and vermiculites (and also some smectites). As a result, vermiculites
Pickering, 1983). The size, shape, and uniformity of these illites in soils most often occur with incorporated hydroxyl-Al interlay-
are in complete contrast to those originating from micas in ers (see Churchman, 2000; Wilson, 2004).
rocks. They are more similar in their size and shape to the lacus- Only few reports have considered the possibility of a neo-
trine illite from Muloorina (Norrish and Pickering, 1983) than genetic origin for vermiculite. These include those of Smith
to clay-size breakdown products of rock-derived micas. Berkgaut (1962), who observed that vermiculite replaced feldspars in
et al. (1994) found a mineral alongside halloysite in soils formed some Scottish soils of igneous rock origin, and also Barshad and
from pyroclastic layers in a semiarid climate in Israel that com- Kishk (1969), who found dioctahedral micas in soils derived
prised very thin crystallites of a randomly interstratified I–S from rocks containing no mica. Ildefonse et al. (1979) found that
with 70% illite layers and which they considered had formed a vermiculite formed as large (up to 150 μm) crystals by crystal-
authigenically. An authigenic origin for illite/mica in soils in lization from solution, hence by neogenesis, within a weathered
Hawaii that was proposed by Swindale and Uehara (1966) was metagabbro-containing plagioclase and amphiboles, hence no
later discredited when oxygen isotope ratios for the fine quartz micaceous precursor. However, this trioctahedral vermiculite
found alongside the mica in the soils indicated its origin as tro- proved to be unstable within the soil above the weathered rock,
pospheric continental dust (Rex et al., 1969) and it was concluded where it was replaced by a Fe-rich smectite.
by Syers et  al. (1969) that the mica had arrived in the soils in
aerosolic dust along with the quartz. Similar findings have been
20.3.5  Occurrence of Smectite in Soils
made in other countries such as Japan and New Zealand (e.g.,
Mizota and Takahashi, 1982; Stewart et al., 1984; Inoue and Sase, Smectites occur in soils either because they are inherited from
1996; Nagashima et al., 2007; Marx et al., 2009). parent materials, have been formed by neogenesis by crystalli-
zation from solutions of the constituents of rocks, or else they
are the products of the strong, or long-term, transformation of
20.3.4  Occurrence of Vermiculite in Soils
micas and chlorites. They share the possibility of an inherited
Most vermiculites in soils have formed by the transformation origin with most other types of clay minerals. Either (1) pre-
of micas by weathering (Wilson, 1999), although some form by formation in, or prior to, the development of parent materials,
the analogous transformation of chlorites (Wilson, 1999; Velde for example, sedimentary rocks; (2) a detrital origin from other
and Meunier, 2008) (see also Sections 20.2.4.3 and 20.2.4.4). eroded soils or soft sediments; and arguably also (3) preforma-
Dioctahedral vermiculite is much more common in soil clays tion in the soil profile but under previous conditions that differ
than its trioctahedral counterpart (Wilson, 1999). This is from those currently prevailing (Buol, 1965), have been respon-
because, although the first transformation products of triocta- sible for the occurrence of at least a large part of the smectites
hedral biotite (and phlogopite) and also chlorite on weathering found in skeletal soils and soils in arid zones and also in some
Alteration, Formation, and Occurrence of Minerals in Soils 20-39

soils found in strongly leaching climatic regimes (Wilson, 1999). relatively large particles, as already noted, smectites most often
Hence, inheritance may be the main or a major source of smec- are especially fine-grained materials, a feature more consistent
tites in Entisols, Aridisols, and Ultisols and could also have con- with a neogenetic origin. Somewhat confusingly, Boettinger
tributed to soils classified into almost all the other orders of Soil and Southard (1995) found an aluminous dioctahedral smectite
Taxonomy (Wilson, 1999). occurring in each of the sand, silt, and clay fractions of an arid
The possible origin of smectites by the transformation of zone soil. Although the soils also contained biotite, a triocta-
micas and chlorites by acid leaching, and particularly, podzol- hedral vermiculite, and a hydroxyl-interlayered 2:1 Si:Al alumi-
ization, processes was discussed in Sections 20.2.4.3, 20.2.4.4, nosilicate, Boettinger and Southard (1995) considered that the
and 20.2.5.3 (and particularly Section 20.2.5.3.2). The smec- smectite in all size fractions was neogenetic, with the coarser
tites formed in this way, and hence those found in the eluvial particles comprising aggregates of smectite cemented by opaline
horizons of podzols, that is, Spodosols, are beidellitic (Ross silica. A geomorphic and salinity gradient transect in another
and Mortland, 1966; Churchman, 1980; Carnicelli et al., 1997; arid environment contained smectite in both its beidellitic and
Wilson, 1999; April et al., 2004), consistent with the effect of acid montmorillonitic varieties (Reid et al., 1996). These authors con-
leaching in selectively removing structural Mg, especially, from sidered that there were multiple origins for the smectite in the
2:1 Si:Al aluminosilicates, which thereby become more alumi- soils. The beidellites probably originated from shales by trans-
nous. As the products of changes in the solid state they may also formation processes, and, while some montmorillonite was
be expected to occur, like most illites (Section 20.3.3), mainly inherited, the groundwater chemistry was suitable for some
within the coarse clay fractions of soils. having been neoformed. Studying a toposequence of soils sur-
Most typically, however, smectites have been formed in soils rounding an alkaline–saline lake in Brazil, Furquim et al. (2008)
by neogenesis from alkaline solutions that have developed under found smectites in both an upper zone that is largely higher than
poor drainage. Their formation requires high concentrations of lake level and also a lower zone that is submerged seasonally by
Si and basic cations and is therefore favored typically from basic the lake. However, the smectites in the two zones were differ-
parent materials. Concentrations of smectites comprising ben- ent structurally and compositionally, pointing to different ori-
tonite deposits form under similar conditions, most commonly gins for each of them. In the upper zone, a dioctahedral Fe- and
from large bodies of water, for example, lakes or marine lagoons Al-rich ferribeidellite had formed as a result of the transforma-
or shallow-marine embayments into which tephra has fallen or tion of micas whereas in the lower zone, trioctahedral Mg-rich
been deposited fluvially (e.g., Millot, 1970; Chamley, 1989; Naish smectites that were characterized as saponitic or stevensitic had
et  al., 1993; Velde, 1995; Gardam et  al., 2008). Work in New formed, apparently by chemical precipitation from the lake, that
Zealand on detrital glass deposits in shallow-marine Holocene is, by neogenesis (Furquim et al., 2008).
muds showed that the early diagenetic transformation of glass to Most smectites in soils are dioctahedral, including the prod-
smectite occurred as a two-stage process initially with diffusion- ucts of the alteration of Mg-rich serpentinite, where saponite
controlled hydration and dissolution of glass followed by first- might be expected to form (Wildman et  al., 1968). Saponite
order precipitation of smectite (Hodder et al., 1993). Interstitial often does form as a weathering product—for example, within
marine waters of slightly reduced salinity (lower Ca 2+, Na+) and the crystals of altered rocks containing ferromagnesian minerals
higher concentrations of dissolved silica relative to those in (Section 20.2.4.1)—but it can give way to dioctahedral smectites
ocean water played a key role in the smectite formation. Rate in the upper parts of soil profiles (Section 20.2.5.1). Of these, the
constants for both the dissolution of glass and the precipitation beidellitic and montmorillonitic varieties of smectites are most
of smectite were two orders of magnitude greater than those common in soils, although nontronites have been found there
determined for the formation of clay minerals on similar tephra- (Sawhney and Jackson, 1958). Even so, nontronite is thought to be
derived glassy materials in soils (Hodder et al., 1993). particularly susceptible to attack by complexing agents from roots
Some of the knowledge of the conditions for the formation of (Farmer, 1997). Generally, soil smectites have more tetrahedral Al
smectites by neogenesis has come from studies of the conditions and more octahedral Fe than the type of montmorillonite asso-
for their formation in the laboratory (e.g., Harder, 1972, 1977; ciated with most bentonites (Wilson, 1987; Weaver, 1989). There
Siffert, 1978; Farmer, 1997). The requirements for a successful appears to be a tendency toward a ferribeidellite composition for
synthesis of a smectite included pH > 7.5 and some Mg and/or smectites in soils, albeit that a given soil smectite is most probably
Fe in solution. In nature, smectites are often found in calcareous heterogeneous in composition. Petit et  al. (1992) found that the
environments, which provide a high pH, and often also where smectite in a lateritic profile in Brazil could be described as a true
leaching is infrequent or minimal, or where there is an impedi- solid solution between nontronite and beidellite endmembers.
ment to drainage (e.g., Fieldes and Swindale, 1954; Lowe et al., Smectites themselves can be subject to alteration and change
1996). However, smectites can form from many types of rocks within soils. As already discussed (Section 20.3.1), smectites can
or geological deposits and minerals, provided that they can incorporate kaolinite layers to become interstratified kaolinite–
provide a sustained supply of the necessary cations and silica smectites (K–S), most probably following the prior adsorption of
(Churchman, 2000). hydroxyl-Al species into their interlayers (e.g., Ryan and Huertas,
The origin of smectites occurring in soils is not always clear- 2009). Kaolinite appears to be the ultimate product of this process
cut. While smectites formed by transformation may occur in (Section 20.3.1). Nevertheless, Fisher and Ryan (2006), studying
20-40 Properties and Processes

a chronosequence of soils on fluvial fill terraces in tropical Costa been synthesized many times from alkaline solutions with high
Rica, found that there was a transition with age from smectite- activities of Mg, and Si (see, e.g., Churchman, 2000), confirm-
rich to kaolinite-rich soils without any K–S intermediates being ing the conditions for their formation in nature. In nature, the
formed along the way. The smectite was a beidellite and the required Mg may originate in dolomite or Mg-containing cal-
kaolinite was disordered. These authors generalized their results cite. The conversion of high-Mg calcite into low-Mg calcite has
and those of others who had studied this transition by suggesting been observed to accompany palygorskite formation (Singer,
that K–S forms as an intermediate phase in the transition from 1989, 2002). The required Si may derive from the dissolution of
S to K where the MAP is between ∼500 and ∼2000 mm, whereas any silicate mineral, including illite and chlorite (Galán et  al.,
the transition occurs without a K–S intermediate when MAP is 1975; Galán and Castillo, 1984; Dias et al., 1997; Owliaie et al.,
more than ∼3000 mm. The changes may be more subtle, however, 2006), smectites (see Singer, 1989; Bouza et al., 2007; Kadir and
resulting in a change within the composition and structure of the Eren, 2008), and even quartz (Singer, 1989, 2002). It is not sur-
smectite. Thus, a low-charge beidellite inherited from the parent prising that smectites may give rise to palygorskite and/or sepio-
pelitic sediment was converted to a high-change beidellite dur- lite because the chemical conditions of high [Mg], high [Si], and
ing the formation of a Vertisol (Righi et al., 1995). a high pH are shared among these three mineral types. Bouza
et al. (2007) suggested that, as Mg concentration increased with
time in calcic and calcic–gypsic horizons in a weathering pro-
20.3.6  Occurrence of Palygorskite
file in Argentina, smectite gave way to palygorskite. Nor, there-
and Sepiolite in Soils
fore, is it surprising that palygorskites and sepiolites often occur
The fibrous 2:1 Si:Mg clay minerals, palygorskite and sepiolite— together with smectites in soils and may disappear in their favor,
the so-called hormite minerals—undoubtedly occur in the as observed by Paquet and Millot (1972), Khormali and Abtahi
sedimentary parent materials of many soils containing these (2003), Owliaie et al. (2006), and Bouza et al. (2007), for example.
minerals; and, until relatively recently, their inheritance from Paquet and Millot (1972) suggested that this dissolution and ref-
these parent materials was considered to be their source in soils ormation occurs when rainfall rises to a MAP of merely 300 mm.
(Singer, 2002). However, both have since been found to form in Khormali  and Abtahi (2003) found an inverse relationship
soils in many countries, including Israel, Syria, Egypt, Morocco, between the occurrences of palygorskite and smectite with regard
Iraq, Iran, Turkey, Spain, Portugal, China, the United States, to soil available water, measured by the ratio of precipitation to
Mexico, Australia, South Africa, and Argentina (see summaries plant transpiration. Smectite was favored over palygorskite at
in Zelazny and Calhoun, 1977; Singer, 1989, 2002; Churchman, higher values of soil available water. On the other hand, in soils
2000; and reports by Owliaie et  al., 2006; Bouza et  al., 2007; in an irrigated cropping area in India, smectite predominated in
Kadir and Eren, 2008). Even so, they almost invariably form in the rain-fed soils, but irrigation, which exacerbates salinity and
calcareous environments (Singer, 2002) and often in calcretes, sodicity (and attendant waterlogging), had led to the formation
in particular. Verrecchia and Le Coustumer (1996) have listed of palygorskite in just 40–50 years (Hillier and Pharande, 2008).
many reports of their occurrence in calcretes and there are also It appears that evaporative concentration of the irrigation waters
later similar reports (e.g., Kadir and Eren, 2008). The main con- has led to solution conditions more favorable to the formation
ditions under which they form have been summarized as (1) a of palygorskite than smectite. It has also been observed that the
fluctuating saline or alkaline groundwater, (2) strong and con- highly siliceous environment in which palygorskite and sepiolite
tinuous evaporation, and (3) a sharp textural transition (Singer form may give rise to an excess of Si in solution, which results in
and Norrish, 1974; Singer, 1989, 2002). A strong textural transi- deposits of secondary silica upon their formation (Singer, 1989;
tion means that water is likely to accumulate at the transitional Verrecchia and Le Coustumer, 1996). Experiments with nonsoil
boundary, hence maintaining a saturated solution from which palygorskite and sepiolite showed that they were unstable, giv-
the hormite minerals can precipitate, under even arid condi- ing rise to kaolinite, within the rhizospheres of common agri-
tions. Calcretes (or caliches) provide such a transition and, hence, cultural crops (Khademi and Arocena, 2008). In this situation,
these minerals are often found in or below these secondary car- the high acidity of the rhizospheres and the extraction of Mg
bonate concretions. Albeit that palygorskite is most commonly from the minerals by the crops had destabilized them (see also
associated with calcareous soils, gypsiferous soils appeared Section 20.2.5.3).
to contain more palygorskite than calcareous soils within the Palygorskite is much more common than sepiolite in soils
same region in Iran (Khormali and Abtahi, 2003; Owliaie et al., (Singer 1989, 2002). However, Bouza et  al. (2007) found that
2006). It appears that an increase in the concentration of Mg sepiolite formed chronologically after palygorskite within a
that occurred upon the precipitation of gypsum was particularly mature calcrete.
conducive to the neogenesis of palygorskite (Owliaie et al., 2006).
Chemically, the neogenetic formation of both palygorskite
20.3.7  Occurrence of Iron Oxides in Soils
and sepiolite requires considerable magnesium and silicon in a
high pH solution. Palygorskite would also require some Al and Iron oxides and oxyhydroxides (generically known as “iron
Fe (Singer, 1989). Although there had been no reproducible syn- oxides”) occur in almost all soils (Allen and Hajek, 1989). They
thesis of palygorskite, at least up until Singer (2002), sepiolite has are usually the product of the oxidation of Fe(II) occurring
Alteration, Formation, and Occurrence of Minerals in Soils 20-41

either within the structure of primary minerals or upon their in soil solutions to inhibit crystallization of goethite and other
breakdown by weathering, whereupon the newly formed Fe(III) Fe oxides, including lepidocrocite (Churchman, 2000; Bigham
hydrolyzes (e.g., Churchman, 2000). The resulting iron oxides et  al., 2002), and soil ferrihydrites can contain significant
are essentially insoluble at the pH values encountered in soils amounts of Si (Childs, 1992). Nonetheless, ferrihydrite often also
and are mainly remobilized by reduction. As we have seen for occurs in association with goethite and lepidocrocite (Bigham
soils from volcanic materials particularly (Section 20.2.4.6), the et al., 2002). In the laboratory, it has been found that ferrihydrite
specific Fe oxides that occur in a soil depend largely on the envi- is easily converted to hematite (Schwertmann and Taylor, 1989).
ronmental conditions under which they were formed. Nonetheless, ferrihydrite and hematite are rarely found together
Following Schwertmann and Taylor (1989), Cornell and in soils, indicating that the conversion is also rapid in nature.
Schwertmann (1996), Churchman (2000), Bigham et  al. (2002), Even so, Adamo et  al. (1997) found ferrihydrite together with
and Schwertmann (2008), in the main, we can make some gen- both hematite and goethite in the products of weathering of a
eralizations regarding the conditions under which goethite or volcanic rock by lichens. They appear to occupy different micro-
hematite are formed. Goethite, which is yellow to yellowish brown sites in the altering rock.
in color depending partly on particle size, is found in soils almost The formation of lepidocrocite is favored by seasonally anaer-
everywhere. But it is most common in cool and temperate climates obic conditions in noncalcareous soils. It forms when there
and where there are high contents of organic matter. Hematite, is an accumulation of Fe2+ together with a slow rate of oxida-
by contrast, is most common in aerated soils in generally warmer tion (Alekseev et al., 2005). Lepidocrocite is found in ocherous
temperatures in the tropics and subtropics and also in arid and mottles, root mats, and crusts (Cornell and Schwertmann, 1996;
semiarid regions, as well as in xeric (or Mediterranean) climate Churchman, 2000; Bigham et al., 2002). It is often found in asso-
zones. Hematite is characteristically red in color. High organic ciation with goethite. Lepidocrocite was found in all three soils
matter content favors the formation of goethite over hematite, and in a hydromorphic sequence in Ohio (Smeck et al., 2002), but in
it is not uncommon to find soils with yellowish goethitic topsoil different amounts according to ease of drainage. These authors
over red hematitic subsoil. Goethite also tends to be favored at low concluded that the formation of lepidocrocite was favored in
pH, hematite at higher pHs. Laboratory syntheses have shown horizons that were saturated for between 5% and 50% of the part
that from ferrihydrite as a starting material, the most goethite of the year when the soil temperatures were >5°C. Alekseev et al.
was formed at a pH near 4, while the maximum yield of hematite (2005) found that lepidocrocite was concentrated in the bottom
occurred at pHs between 7 and 8. Synthetic work has also shown of the “active” layer immediately above permafrost in Russia.
that hematite is favored over goethite by a high rate of release of Fe The existence of the permafrost below concentrated solutes in
into solution. This finding is consistent with the observed occur- this layer and the low temperature slow oxidation.
rence of hematite in a soil on basalt but not in a nearby soil on Maghemite occurs in soils in the tropics and subtropics, often
shale (Kämpf and Schwertmann, 1982). Hematite is the preferred in association with hematite, and most often in surface soils
phase where the activity of water is low, as in small pores, and (Schwertmann and Taylor, 1989; Churchman, 2000; Bigham
is also the most stable phase thermodynamically in smaller par- et  al., 2002). A common mode of formation of maghemite
ticles (Langmuir and Whittemore, 1971). These latter authors pre- appears to be through the heating of other Fe oxides in the
dicted that goethite would be the stable phase in particles >76 nm presence of organic matter, as occurs in bush and forest fires.
and hematite in smaller particles. While Al substitution for Fe Schwertmann and Taylor (1989) suggested that a temperature
is common in all Fe oxides, synthetic work has shown that goe- of between 300°C and 425°C is conducive to the formation
thite can accommodate more Al in its structure than hematite. of maghemite. It may also form by the oxidation of precursor
Fritsch et al. (2005) explained yellowing toward the surface of a magnetite in parent materials, according to the authors cited
weathering profile on sediments in Brazil by upward changes in herein. However, a completely different, alternative origin for
both the relative amounts of goethite and hematite and also in the this magnetic mineral was suggested by Rivers et  al. (2004) to
extent of Al substitution of goethite. Hematite and Al-poor goe- explain its occurrence in association with hematite in soils on
thite that are remnants of prior weathering of the sediments in a alluvium that has in-filled low-lying areas in Tennessee. These
different climate have dissolved, with Al-rich goethite forming in authors suggested that there had been reduction of Fe(III), either
their place by recrystallization, according to Fritsch et al. (2005). microbial or abiotic, to form magnetite in the hydromorphic
In some tropical soils, the formation of hematite is at the expense soil. Magnetite occurs in many soils but is usually found in the
of goethite when temperatures are high, the aeration good, the pH sand and silt fractions rather than the clay fraction and is gen-
near neutrality, and organic matter is rapidly transformed (Etame erally considered to have been inherited from the parent rock.
et al., 2009). Nonetheless, a partially oxidized form of magnetite was found to
Poorly crystallized or nanocrystalline ferrihydrite is also occur along with hematite in nodules in an Oxisol in Brazil that
widespread in soils, particularly in those formed from tephra, has developed from magnetite-free parent materials, so a pedo-
and also in the illuvial or placic B horizons of podzols (see genic origin has been invoked for the mineral in this soil (Viana
Churchman, 2000, and McDaniel et  al., Section 33.3). Its for- et al., 2006). These authors considered that the magnetite in this
mation is favored by rapid oxidation of Fe and when silicates soil formed under seasonal burning and also that it is becom-
and organic matter, particularly, but also other ions, are present ing converted to hematite by atmospheric oxidation in air. Some
20-42 Properties and Processes

authors (Maher and Taylor, 1988; Geiss and Zanner, 2006) have for the metal associated with organic matter, Table 20.5 shows
considered that some magnetite in soils may have had a bacterial the relative amounts of these forms of Fe and their distribution
origin (see Section 20.2.5.3.5). in relation to aluminosilicate clays in a range of soils, mainly
Other Fe oxides formed in soils include schwertmannite, taken from papers in the most recent literature, which have pre-
from acid sulfate soils (see Section 20.2.5.3.4), and “green rusts,” sented data for both different forms of Fe and also estimates of
found in a highly hydromorphic soil by Trolard et al. (1997). the relative abundance of the phyllosilicates present. The data for
Iron oxides can be extremely labile in the soil environment. They selected horizons within one soil of each type are given in Table
are quickly reduced or oxidized when redox conditions change in 20.5. The soils in Table 20.5 represent a wide range of soil orders
soils, as they can do intermittently over even quite short time peri- and lithologies, and soil horizons are also given for each soil. The
ods (hours to days or weeks) and also seasonally. The activity of table shows that there were substantial proportions of iron oxides
microbes can play a central role in the formation and dissolution and Fe-organic complexes in their various forms in all horizons
of iron oxides. A wide variety of microorganisms are involved in of all the soils examined. They were associated with virtually all
these processes and much remains to be understood about their of the types of phyllosilicates that occur in soils.
operation (Fortin and Langley, 2005). Suffice it to say here that Fe
oxides are often biogenic (see also Section 20.2.5.3). Furthermore,
20.3.8  Occurrence of Manganese
there is widespread recognition that Fe is commonly mobilized
Oxides in Soils
in soils by reduction occurring through the activity of microbes
in anoxic conditions (Robert and Berthelin, 1986; Schwertmann Manganese oxides are a widespread but usually minor com-
and Taylor, 1989; Robert and Chenu, 1992). The ensuing reduction ponent of soils (McKenzie, 1989; Dixon and White, 2002).
occurs along with the oxidation of decomposing biomass. Generally, they occur in soils in small particles, leading to poor
It is a feature of iron oxides in soils that they are most often peaks in XRD. They are more abundant in soils from mafic, that
closely associated with the other components of soils, includ- is, basic, rocks than from siliceous materials (Dixon and White,
ing particularly aluminosilicate clay minerals, which as small- 2002). Because reduced Mn (Mn(II)) is very soluble as a divalent
charged particles attract Fe oxides and other reactive species to cation and is mobile in soils, they commonly form as coatings on
their surfaces and pores. Following the well-accepted convention rocks, on ped surfaces, and on other soil particles, as well as in
that (citrate-) dithionite-extractable Fe represents free, or well- concretions, segregations, pans, and nodules, often with Fe oxides
crystallized oxides, (acid ammonium) oxalate-extractable Fe rep- (McKenzie, 1989; Churchman, 2000; Dixon and White, 2002).
resents poorly crystallized oxides, and pyrophosphate-Fe stands They are characteristically black in color but give a brown streak.

TABLE 20.5  Occurrence of Iron in Oxides and Oxyhydroxides and in Organic Complexes in a Range of Soils
with Different Phyllosilicate Clays

Main Fea (g kg−1)

Soil Subgroup Lithology Horizon pH Fed Feo Fep Fet Phyllosilicates in Clay Fractionb References
Gypsic Gypsiferous Ay 7.6 7.8 n.d. n.d. 16.0 Paly ∼ smec ∼ chl > ill Owliaie et al. (2006)
Haplustept 2By2 7.7 2.1 n.d. n.d. 9.9 Paly > chl ∼ ill > smec
Humic Umbrisol Granite, Ah1 4.0c 22.0 14.0 15.2 51.2 Verm ∼ HIS ∼ HIV > ill = kaol > chl Zanelli et al. (2006)
orthogneiss BC 5.0 6.6 2.2 0.5 9.3 Ill ∼ HIV ∼ (ill-HIV) ∼ allo > verm ∼ chl
Mollic Calcschists, A 6.5 16.6 8.8 3.4 28.2 Chl > ill > serp > talc Scalenghe et al. (2002)
Eutrocryept serpentinites C 8.1 12.3 4.5 0.8 17.8 Chl > ill > serp > talc
Typic Shale, A 3.7 1.4 0.8 1.1 3.3 Ill ∼ kaol ∼ (ill-verm) > verm Pai et al. (2004)
Haplorthod sandstone Bs2 4.8 48.4 16.9 10.1 75.4 Ill ∼ kaol ∼ HIV > (ill-verm) >verm
Ultic Haplorthod Marine E 3.7 37.6 8.4 5.5 51.4 Verm ∼ (i-v) ∼ ill ∼ qtz > kaol ∼ gibb Lin et al. (2002)
sediments Bhs 4.2 59.2 17.7 19.9 86.8 Verm > HIV > ill ∼ kaol ∼ qtz ∼ gibb
Typic Olivine basalt Ap 6.7 26 n.d. n.d. 53 (Kaol-smec 40:60) > (k-s 95:5) >ill Vingiani et al. (2004)
Haploxerert C 8.1 21 n.d. n.d. 96 (K-s 40:60) > kaol ∼ (k-s 95:5) >ill
Andic Rhyolitic ash A1 6.8 3.2 0.5 0.1 3.8 Hall ∼ HIV > allo Takahashi et al. (1993)
Haploxeralf on andesite 2Bt3 6.2 10.1 0.5 0.1 10.7 Hall > gibb ∼ allo
Acrudoxic Andesitic lava Ah1 3.9 2.8 1.7 1.5 6.0 Gibb > kaol > goe > ferr Nieuwenhuyse et al.
Fulvudand BC 5.2 4.1 0.8 0.0 4.9 Allo > goe > ferr (2000)
Orthoxic Olivine basalt Ap 5.9 9.0 n.d. n.d. n.d. Kaol > goe Gallez et al. (1976)
Tropohumult B21t 5.8 10.3 n.d. n.d. n.d. Kaol > goe
a Values of Fe extractable by dithionite (Fed), oxalate (Feo), and pyrophosphate (Fep), also total (Fet).
b Minerals usually given by first three or four letters of their name, except for quartz (qtz) and HIV; interstratified minerals in brackets: their components often
by first letters only; relative amounts of minerals as given in the appropriate reference.
c In CaCl , other pH values in H O.
2 2
Alteration, Formation, and Occurrence of Minerals in Soils 20-43

in low supply. Hence, it occurs under strong leaching. Where

there is a gradation in the extent of leaching, often because of
an altitudinal change, gibbsite may occur in the most heavily
leached soils whereas kaolinite occurs when there is a lesser
degree of leaching. This tendency appeared to be the case for
temperate mountain soils in South Carolina (Norfleet et  al.,
1993), as well as for soils in the humid tropics, where gibbsite
was dominant in the highlands and kaolinite in the low-
lands  (Herbillon  et  al.,  1981). In some Oxisols, gibbsite may
be most abundant in upper horizons but decrease in concen-
tration with depth (Huang et  al., 2002). These authors also
pointed out that, in the tropics, particularly, landscapes may
be extremely old and the occurrence of gibbsite not necessar-
ily related to the present soil environment. This polygenesis
was illustrated in a study by Bhattacharyya et al. (2000), who
4 μM 20 KV 11 451 S found gibbsite occurring alongside mica–vermiculite phases
containing hydroxy-Al interlayers in an acidic tropical soil in
FIGURE 20.11  Scanning electron micrograph of crystals of todorok- India. However, it has long been considered (Jackson, 1963)
ite, with some kaolin minerals, in infill formed as a result of the weath- that the presence of these latter aluminous interlayers pre-
ering of granitic saprolite in Hong Kong. (Photo by Stuart McClure. cludes the formation of gibbsite by the so-called antigibbsite
Reproduced with the permission of the Geotechnical Engineering
effect. Bhattacharyya et  al. (2000) explained the presence of
Office, Civil Engineering Office, Hong Kong.)
gibbsite and these interlayers together by the prior formation
of gibbsite, possibly mainly from sillimanite, in an earlier
Their distinctive appearance, especially in, for example, concre-
neutral to alkaline pH environment. The aluminous inter-
tions and nodules, gives a strong indication of prior oxidation,
layers, by contrast, are products of weathering in the current
including by seasonal drying as noted earlier in this chapter (e.g.,
acidic environment. An apparent contradiction of the “anti-
Birkeland, 1999; Vepraskas et al., 2004). Churchman et al. (2010)
gibbsite” effect was also seen by Jolicoeur et  al. (2000) when
used their occurrence to trace a history of dehydration, leading
they observed each of hydroxyl(-Al) interlayered vermiculite
to the conditions for the formation of kaolinite rather than hal-
(HIV), kaolinite and/or halloysite, and gibbsite occurring
loysite in some saprolites in Hong Kong. Manganese oxides form
together as pseudomorphs after biotite in scanning electron
when conditions favor their oxidation; hence, they are often found
micrographs of saprolites and soils in central Virginia. They
in subsoils with a higher pH than the upper layers and are com-
were considered to coexist because they each occupy their
mon in calcareous soils. Manganese also occurs as a Mn carbonate
own particular microsites and microenvironments of weath-
(rhodochrosite) in calcareous soils (Dixon and White, 2002).
ering, especially in the vicinity of the altering rock material
Among the polymorphs of MnO2, birnessite, especially, and
(Jolicoeur et al., 2000). Gibbsite in soils may also be inherited
lithiophorite have most often been identified in soils. However,
from saprolites (e.g., Huang et  al., 2002; Simas et  al., 2005).
birnessite occurs in soils as poorly developed crystals and the
In these cases, its content decreases toward the surface within
crystals of birnessite produced by biological oxidation of Mn(II)
the soil profile. In another situation, the co-occurrence of
in the laboratory are similarly poorly developed, as are those pre-
both gibbsite and halloysite, together with kaolinite, goethite,
cipitated from solutions with a high Si content (Dixon and White,
hematite, maghemite, quartz, and cristobalite in old soils
2002), suggesting that their formation in soils occurs via micro-
formed on strongly weathered andesite or associated alluvium
biological oxidation or at an early stage of soil formation, or both
in tropical Costa Rica, was studied by Kleber et al. (2007). They
(McKenzie, 1989; Dixon and White, 2002). Todorokite has been
attributed the clay mineral depth-distribution patterns first to
identified in Texas in nodules from a Vertisol and on the surface
intense weathering, with gibbsite increasing with depth as the
of weathered siderite boulders (Dixon and White, 2002) and
end product of prolonged tropical weathering, as noted ear-
appeared in large crystals in saprolite on both granite and volca-
lier. However, the seemingly paradoxical enrichment of kaolin
nic tuff in Hong Kong (Churchman et al., 2010), as seen in Figure
group minerals and quartz near the soil surface was attrib-
20.11, alongside both halloysite tubes and platy kaolinite particles.
uted to ongoing dissolution of Si (quartz being unstable at the
silica concentrations necessary for gibbsite formation, namely
<0.5 ppm) and its vertical redistribution by a plant-based “bio-
20.3.9  Occurrence of Aluminum Hydroxides,
logical resilication mechanism” (Kleber et  al., 2007, and see
Oxyhydroxides, and Oxides in Soils
also Section 20.2.5.3.3).
Gibbsite is the most common of the various hydroxides, Gibbsite may also occur as coatings or infillings of voids in
oxyhydroxides, and oxides of aluminum in soils (e.g., see weathered upper soil horizons (e.g., Huang et al., 2002). Gibbsite
Churchman, 2000). It occurs in soils of any age whenever Si is is also favored if parent materials are rich in Al (e.g., Lowe,
20-44 Properties and Processes

1986), as illustrated by the example of sillimanite within gneiss 20.3.11  Occurrence of Pyrophyllite,
in Bhattacharyya et al.’s (2000) study. Talc, and Zeolites in Soils
Among Al oxyhydroxides, boehmite has been identified,
along with some other poorly ordered, nanocrystalline, and/or Both pyrophyllite and talc are rare in soils (Zelazny and White,
amorphous phases in lateritic profiles, particularly at their sur- 1989; Churchman, 2000; Zelazny et  al., 2002). As minerals
faces, and also in tropical soils (e.g., Churchman, 2000; Huang originating at high temperatures and pressures, they are seldom
et  al., 2002). Some may have resulted from the dehydration of inherited in soils. Pyrophyllite, particularly, is broken down into
gibbsite. Other Al hydroxides, bayerite, nordstrandite, and finer fractions by physical processes (Zelazny et  al., 2002). As
doyleite, have been identified only rarely in soils (Huang et al., with other types of minerals, it is the dioctahedral species, pyro-
2002). The Al oxyhydroxide, boehmite, and the Al oxide, corun- phyllite, that is more stable in the soil environment than its trioc-
dum, have been reported at the surfaces of ferralitic (lateritic) tahedral counterpart, talc (Zelazny et al., 2002). Generally, talc
profiles, whereas corundum has often been seen in the same soils weathers quickly to nontronite or to Fe oxides. Both pyrophyllite
that contain maghemite, for example, in ferralitic duricrusts in and talc have been protected from breakdown by their encapsu-
Western Australia (Anand and Gilkes, 1987), and these authors lation within Fe oxides in some soils (Zelazny et al., 2002).
proposed that it formed from gibbsite and/or boehmite by dehy- Occurrences of zeolites have rarely been reported in soils,
dration in bushfires. A bushfire origin has also been suggested but some may have been overlooked because they are gener-
for maghemite (Section 20.3.7 herein). ally only present in trace amounts (Boettinger and Ming, 2002).
Apart from their inheritance from zeolitic parent materials,
such as through hydrothermal alteration (e.g., Kirkman, 1976),
20.3.10  Occurrence of Phosphate, Sulfide, some zeolites have formed pedogenically (Ming and Mumpton,
and Sulfate Minerals in Soils 1989; Churchman, 2000; Boettinger and Ming, 2002). The most
Phosphate minerals in soils appear to derive mainly by inheri- common pedogenic zeolite is analcime. Along with chabazite,
tance or by alteration through weathering of forms of apatite, mordenite, natrolite, and phillipsite, analcime has been found
namely, fluorapatite and hydroxyapatite, from rocks or other geo- to form in salt-affected, alkaline soils, which contain sodium
logical deposits, or else from reactions between phosphorus fertil- carbonate and have a high pH (Churchman, 2000; Boettinger
izers and soil minerals (Lindsay et al., 1989; Churchman, 2000; and Ming, 2002). These soils were both volcanic and nonvol-
Harris, 2002). The products are various forms of phosphates in canic in origin. A number of zeolites have been found in soils
which the Ca in apatite is substituted, to a greater or lesser degree, in Antarctica that appear to have a secondary origin. These
by other cations. Hence, there are forms of variscite, where the include stilbite, from the weathering of dolerite (Claridge and
major cation is Al, strengite (Fe), also barrandite (Al, Fe), vivi- Campbell, 1968), phillipsite, from tephra dissolved in lakes
anite [Fe(II)], crandallite (Ca, Al), plumbogummite (Pb, Al, and (Claridge and Campbell, 2008), and chabazite, which has been
other elements), gorceixite (Ba, Al), leucophosphite (K and Fe), identified by many workers and which Claridge and Campbell
along with many other variations (Norrish, 1968; Lindsay et al., (2008) suggested is quite widespread as a product of thin saline
1989; Churchman, 2000; Harris, 2002). A hydrated Al hydroxyl films in intergranular spaces in soils. Other zeolites that have
phosphate, wavellite, is the most common Al phosphate in soils been inherited in soils from parent materials include clinoptilo-
derived from phosphoritic marine sediments, which are the most lite, heulandite, gismondine, mordenite, stilbite, and laumontite
extensive phosphate-rich geological materials at the Earth’s sur- (Boettinger and Ming, 2002).
face (Harris, 2002). Nevertheless, phosphates generally occur very
sparsely in soils and have to be either concentrated or examined
20.3.12  Occurrence of Neogenetic
by electron optical methods to be identified (e.g., Norrish, 1968).
Silica in Soils
Sulfide minerals in soils originate ultimately from the bac-
terial reduction of sulfate in seawater (Doner and Lynn, 1989; Because leaching in soil formation results in desilication, silica is
Fanning et al., 2002). They occur in the unoxidized parent mate- often mobilized and then (if not combined with Al for example
rials of soils and are very readily oxidized on exposure to air and to form an aluminosilicate clay) can be reprecipitated deeper
drying. Pyrite is the most common sulfide mineral in the unoxi- in the soil environment. Chemically precipitated overgrowths
dized parent materials. Sulfates, including sulfuric acid, are the of quartz, particularly on carbonates, are relatively common
products of their oxidation. The reaction of the sulfuric acid in soils (Drees et  al., 1989; Churchman, 2000). Quartz appar-
thus produced with silicates leads to hydroxyl Fe sulfate min- ently formed by crystallization out of the dissolution products
erals, especially jarosite and schwertmannite. These, and their of microcline (Estoule-Choux et al., 1995; Section 20.2.4.2). In
variants, occur typically in acid sulfate soils with their attendant soils across two chronosequences on fluvial deposits in arkosic
environmental problems (see also Section 20.2.5.3.4). Gypsum sands in southern California, Kendrick and Graham (2004)
occurs in soils as a result of its inheritance from gypsiferous par- found that the amount of pedogenic, opaline silica (measured by
ent materials (or from agricultural application), while barite, of extraction with tiron) increased with duration of soil develop-
unknown origin, has also been found in some soils, often as a ment from 1.2% to 4.6% of the soil. The loss of Si from primary
white powder (Fanning et al., 2002). minerals approximately equaled the gain of secondary (opaline)
Alteration, Formation, and Occurrence of Minerals in Soils 20-45

silica (Kendrick and Graham, 2004). A number of studies of fine 20.3.13  Occurrence of Titanium
quartz from soils and also shales found a systematic increase in and Zirconium Minerals in Soils
oxygen isotopic ratios with decreasing size, suggesting that the
smallest particles of quartz were authigenic (Sridhar et al., 1975; Although the major forms of titanium oxide, namely, ana-
Churchman et  al., 1976; Clayton et  al., 1978). However, much tase and rutile, and also their polymorph, brookite, as well as
neogenetic silica in soils occurs in other forms besides quartz the Fe–Ti minerals, ilmenite, pseudorutile, titanomaghemite,
(Monger and Kelly, 2002). and others, can all form by neogenesis in intensely weathered
Silica cements are common in hardpans or duripans (Chadwick soils, only anatase and pseudorutile commonly form this way
et al., 1987) and also fragipans (Harlan et al., 1977; Marsan and (Milnes and Fitzpatrick, 1989; Churchman, 2000; Fitzpatrick
Torrent, 1989) in soils and have been seen to coat surfaces of and Chittleborough, 2002). Otherwise, the titanium miner-
primary minerals, for example, micas, and to fill gaps in altered als in soils are inherited from parent materials. Fitzpatrick and
minerals including feldspars and micas (Chadwick et  al., 1987; Chittleborough (2002) leave open the possibility that zircon, the
Singh and Gilkes, 1993). In the extreme, silica forms massive most common Zr-containing mineral, could also form authi-
silcretes in acidic environments (Thiry and Simon-Coinçon, genically in intensely weathered soils. Nevertheless, it is gener-
1996). Secondary silica is sometimes identified as a form of opal, ally inherited from parent materials.
either opal-CT, which is usually inherited from rocks (Munk and Pseudorutile, which occurs widely in soils, is primarily
Southard, 1993), or opal-A, which is biogenic, and includes plant found there as an alteration product of ilmenite (Fitzpatrick
opals. These are common in some Andisols (Drees et  al., 1989) and Chittleborough, 2002). In turn, pseudorutile can dissolve
and may be recycled through the death and regrowth of plants to yield either rutile (Grey and Reid, 1975) or anatase (Anand
(Alexandre et al., 1997). Precipitation of secondary silica may be and Gilkes, 1984). The authigenic formation of titanomaghemite
aided by plant-based processes related to Si uptake and recycling and also ferrian ilmenite may occur by heating Fe–Ti oxides
(Henriet et al., 2008) and by evaporation or freezing of soil water. to high temperatures as occurs in bushfires (Fitzpatrick and
Inorganic silica polymorphs are distinguishable from plant- Chittleborough, 2002). Some Ti4+ can become incorporated in
derived forms of silica, phytoliths, because the latter have more other minerals, notably the Fe oxides goethite and hematite, by
complex shapes inherited from biological cells (Nanzyo, 2007). isomorphous substitution, thereby potentially leading to a rever-
Farmer et al. (2005) concluded from their study on the concen- sal of the charge of the Fe oxides (Fitzpatrick and Chittleborough,
tration and flux of Si in European forest soils (both podzols and 2002). Singer et al. (2004) have also found Ti as an isomorphous
acid brown soils) that phytoliths must be the principal immediate substitute for Al in halloysite (Section 20.3.2).
sink of silica in soil solution (although weathering is the ultimate
source). During the growing season, forest vegetation takes up 20.3.14  Occurrence of Highly Soluble Minerals
most of the Si released through weathering of soil minerals and in Soils
phytolith dissolution and converts it into (new) phytoliths, the lat- The most common minerals that are laid down following their
ter then becoming the main source of Si leached from the soil dur- dissolution from the preformed solid state, whether primary
ing winter rains and spring snowmelt (Farmer et al., 2005). Opals or secondary in origin, and then reprecipitation after evapora-
may be transformed to quartz in duripans in soils and also by tion, include calcium carbonate, mainly as calcite, but also as
diagenesis in fossilized wood and sediments (Drees et al., 1989). aragonite and Mg calcite (Doner and Grossl, 2002). Magnesite
Elsass et al. (2000) examined hard plates in laminar horizons and also dolomite may be formed in that fashion and gyp-
and gray mottles at depth in indurated volcanic soils (“tepetates”) sum probably has a similar origin in arid and semiarid envi-
in Mexico and found strong evidence for the transformation of ronments (Kohut et  al., 1995; Churchman, 2000). Bassanite
halloysite to cristobalite via an amorphous opal-A stage. In this (or hemihydrite) is usually found in surface soils, indicating
case, it appears that the secondary silica phase, first opal-A and its likely evaporative origin (Doner and Grossl, 2002). The
then eventually cristobalite, had formed as a result of subtrac- highly soluble salts, halides, sulfates, and some carbonates
tion of Al from halloysite into solution, rather than through often occur in saline soils and also in arid environments such
addition of Si from solution as in other cases of the occurrence as Antarctica (Section 20.2.5.2), which is where Bockheim
of secondary Si in soils. Other studies, however, have demon- (1997) observed niter (NaNO3) in soils. It is an indication of its
strated that cristobalite in soils is usually of primary volcanic extreme aridity that nitrate, borate, chromate, and perchlorate
origin (e.g., Mizota et al., 1987; Wallace, 1991; Mizota and Itoh, salts have been found in the Atacama desert in Chile (Erickson,
1993). In northern New Zealand, cristobalite isolated from three 1983; Doner and Grossl, 2002).
weathered, halloysitic volcanic soils was identified as alpha cris-
tobalite (opal-C) and was invariably found to be accompanied by
20.3.15  Occurrence of Secondary Minerals
tridymite (Wallace, 1991). SEM and oxygen isotope data, along
in Soils: Summary
with the highly ordered crystal structure and subhedral grain
morphologies, were interpreted to indicate that the cristobalite The main properties of the common types of secondary miner-
and tridymite had formed at high temperature from primary als, and characteristics of their occurrence in soils, are summa-
volcanic sources (cf. Lowe, 1986; Wallace, 1991). rized in Table 20.6.
 20-46
TABLE 20.6  Properties of the Common Types of Secondary Minerals and Characteristics of Their Occurrence in Soils
Specific
Common Soil Surface CEC (cmol+
Group Mineral Chemical Formula Related Phases and Names (m2g−1) kg−1) Characteristics in Soils Soils of Common Occurrence

Silicates
Kaolin Kaolinite Al2Si2O5(OH)4 Dickite, nacrite 6–40 0–8 Very small euhedral Widespread, high in well-
particles, associated with weathered soils
much Fe
Halloysite Al2Si2O5(OH)4 · 2H2O Endellitea, metahalloysitea 20–60 5–10 Generally small tubular or Where humid, especially from
1.0 nm (10 Å) halloysite spheroidal particles, tephra (including volcanic ash)
(= hydrated phase), associated with Fe
0.7 nm (7 Å) halloysite
(= dehydrated phase)
Interstratified Kaolinite–smectite Variable, depending on Halloysite–smectite Unknown 30–70 Moderately drained
kaolin proportions of K:S
Mica Illite K0.6(Ca,Na)0.1Si3.4Al2 55–195 10–40 Widespread, especially weakly
FeIIIMg0.2O10(OH)2 weathered soils
Interstratified mica Illite–vermiculite Variable, depending on Mica–vermiculite Unknown Unknown Usually regular, Eluvial horizons of podzols
proportions of I, V mica–vermiculite
Illite–smectite Variable, depending on Mica–smectite Unknown Unknown Either regular, mica– Regular: eluvial horizons of
proportions of I, S beidellite, or random, poss. podzols
with single layers Random: very widespread, often
in agricultural soils
Interstratified Chlorite– Variable, depending on Corrensite Unknown Unknown At very early stages of weathering
chlorite vermiculite proportions of C, V
Chlorite–smectite Variable, depending on Chlorite-swelling chlorite Unknown Unknown At very early stages of weathering
proportions of C, S
Vermiculite (dioctahedral) K0.2Ca0.1Si3.2Al0.8 Pedogenic chlorite, HIV, Unknown pH-variable Leached, mildly acid soils
(Al1.6Fe0.2Mg0.2) 2:1–2:2 intergrade,
(Al1.5[OH]4)O10(OH)2 chloritized vermiculite
(trioctahedral) M IIx (Mg, Fe)3 50–150 100–210 Early stages of weathering,
(AlxSi4–x) especially below soil zone
O10(OH)2 · 4H2O
Interlayered Pedogenic Variable, depending on HIV, 2:1–2:2 intergrade, Unknown Unknown Intermediate pHs, ∼4.6 to 5.8,

Properties and Processes

chlorite whether layers are chloritized vermiculite with wetting and drying, low
vermiculite or smectite HIS, chloritized smectite organic matter
and interlayered species
Smectite Beidellite M0II.25Si 3.5 Al 2.5 Nontronite, hisingeritea, 15–160 45–160 (all Often occur as More beidellitic in acid-leached
O10(OH)2 saponite Interlayer smectites) ferribeidellites in soils, but horizons; otherwise where
Montmorillonite M0II.25Si 4 Al1.5Mg 0.5O10 (OH)2 Stevensite, hectorite ∼800 (all heterogeneous drainage retarded and pH high
smectites)
(Palagonite) Prob. variable Unknown Unknown Nanocrystalline precursors Early weathering products of
of smectites basaltic volcanic glass
 Alteration, Formation, and Occurrence of Minerals in Soils
Hormite Palygorskite Si8Mg5O20(OH)2 Attapulgitea 140–190 3–30 Fibrous In dry, usually calcareous
(OH2)4 · 4H2O regions, near textural transition
Sepiolite Si12Mg8O30(OH)2 Generally 20–45 Fibrous in profile (both)
(OH2)4 · 8H2O 260–330
Al–Si Imogolite SiO2 · Al2O3 · 2H2O; Si 1500 pH-variable Nanocrystalline: bundles of Limited, mainly from pumice,
tetrahedra within Al very thin hollow threads or also podzol illuvial B horizons
octahedral in tube tubules (nanotubes) and related soil horizons
Allophanes Al:Si 2:1—1:1; variable 700–1500 pH-variable Nanocrystalline: very small From tephra (including volcanic
between imogolite and spherules (nanospheres or ash) and in podzol illuvial B
allophane nanoballs); closely horizons, and in some other
associated with organic materials that are strongly
matter leached
Nonsilicates
Al hydroxide, Gibbsite Al(OH)3 Bayerite, nordstrandite, Unknown pH-variable Hexagonal crystals Where Si low, especially in
oxyhydroxide, doyleite, α, or γ alumina strongly leached soils
oxide trihydrate
Boehmite αAlOOH Diaspore, α, or γ alumina Unknown, pH-variable Strongly weathered soil materials
monohydrate prob. high or soils, ferricrete (laterite),
bauxite
Fe oxyhydroxide, Goethite αFeOOH Limonitea 14–77 pH-variable Yellow to yellow-brown Widespread—most common
oxide color iron “oxide”
Lepidocrocite γFeOOH Akagenéite Unknown, pH-variable Orange color Noncalcareous soils that are
prob. high seasonally anaerobic
Hematite αFe2O3 35–45 pH-variable Bright red color Soils of warmer climates
Maghemite γFe2O3 Titanomagnetite Unknown, pH-variable Ferrimagnetic Tropical and subtropical soils,
prob. high from fires, poss. from bacteria
Ferrihydrite Fe5HO8 · 4H2O Feroxyhite 200–500 pH-variable Nanocrystalline: spherical Widespread, where Fe(II) is
nanoparticles, pinkish to oxidized rapidly
yellowish-red color
Mn oxide Birnessite Na0.7Ca0.3Mn7O14 · 2.8H2O Todorokite, hollandite, Unknown, pH-variable (Blue-) black color Widespread but usually minor
lithiophorite, pyrolusite prob. high component; in concretions,
segregations, pans and nodules
in subsoils
Sulfide Pyrite FeS2 Mackinawite, greigite, Unknown Unknown Coastal regions and from some
pyrrhotite sediments when unoxidized
Sulfate Gypsum CaSO4 Bassanite, anhydrite, Unknown Unknown Often in desert soils
barite (BaSO4)
Jarosite KFe3(OH)6(SO4)2 Natrojaroite, Unknown Unknown Acid sulfate soils or strongly acid
schwertmannite seepages
Phosphate Plumbogummite PbAl3(PO4)2(OH)5 · 2H2O Variscite (Al), strengite Unknown Unknown Rare, from breakdown of rock
(Fe), crandallite (Ca), phosphate
gorceixite (Ba)
Ti oxide Anatase TiO2 Unknown Unknown Widespread, in small amounts
Chloride Halite NaCl Unknown Unknown Seasonally dry saline soils

20-47
a Discredited name.
20-48 Properties and Processes

20.4  Influence of Mode of Formation followed by a journal paper (Hendricks and Fry, 1930), most had
regarded clays, which were largely indistinct in optical micro-
upon Predictions of Properties of scopes, as being amorphous (Cady and Flach, 1997). XRD was
Soils from Their Clay Mineralogy very successful in determining that much of the clay-sized inor-
ganic material in soils was composed of regular crystals like
20.4.1  Introduction: The Role of
those that had been identified in minerals in rocks or other geo-
Mineralogy in Soil Science
logical deposits. Although many other instrumental techniques
Broadly speaking, soils are studied and interpreted either as prod- have been applied to their identification and characterization
ucts of the natural environment, which reflect their environmen- over the intervening years, the search for and refinement of crys-
tal history, or else as useful materials in which to grow plants or tal structures has remained a major pursuit of clay mineralogists
for removing and cleaning wastes and pollutants or providing and XRD has continued to be their major workhorse. Its use,
resources or “environmental services” such as regulating water flow. whether for structural determination or as the major instrument
Minerals, and particularly secondary (clay) minerals, have likewise for the identification of clay-sized minerals in soils, has defined
been regarded and assessed either as indicators of the origin of soils classical clay mineralogy.
and of changes, which have occurred in them through their devel- Among the most useful roles promised for classical clay min-
opment, or else as the most reactive inorganic components of soils. eralogy in soil studies has been that of explaining the abundance
For the latter role, it has often been considered that knowledge of of certain plant nutrients by soils. Probably chief among these
the properties of clay minerals would be useful in predicting the has been potassium, with K-micas apparently providing a labile
agronomic and adsorptive capacities of soils. However, several source of K+ (e.g., Norrish, 1973; Loveland, 1984). Loveland et al.
indicators have suggested that soil mineralogy has come to be (1999), in writing a history of clay mineralogy at the Rothamsted
regarded as less important to practitioners of the discipline of soil Experimental Station from 1934 to 1988, attempted to identify
science in recent years than its other main subdisciplines such as the reasons why considerable effort was put into this area of soil
soil chemistry, soil physics, soil biology, pedology, spatial analysis, science at one of the world’s leading centers of soil research. At
and pedometrics, let alone the major applied aspects of soil fertility its outset in 1934, clay mineralogy was supposed to provide an
and soil pollution, than once was the case. For example, an analysis understanding of the physicochemical behavior of the soil clay
of papers that were published in the first 100 volumes of Geoderma, fraction mainly with respect to “the sorption and desorption of
spanning from 1967 to 2001, showed a sharp decline in those on water and nutrients, with their practical consequence for soil
soil mineralogy, but either a rise or no significant decline in those workability and plant nutrient supply” (Loveland et  al., 1999,
from the other main subdivisions of soil science (Hartemink et al., p. 165). Its most important contributions are judged by these
2001). It appears that mineralogical studies have been able to make authors to have been in the identification of the phenomenon
fewer worthwhile contributions in comparison with those of other of interstratified minerals and the behavior of soil K. Even so,
aspects of soil science than in earlier times. Nonetheless, the sur- in spite of a large number of British studies, at Rothamsted and
vey of the literature for this chapter suggests that a great deal of elsewhere in the United Kingdom, on the influence of clay min-
research continues to be undertaken into the origin of secondary eralogy on the potassium-supplying power of soils, Loveland
minerals in soils and also, to some extent, into their mode of occur- (1984, p. 700) stated that “none were successful in using clay
rence within soils. This new work includes the recognition that the mineralogy as a reasonably exact predictive tool for this prop-
clay fractions of many soils and associated materials contain nano- erty.” Loveland (1984) concluded that (classical) clay mineralogy
minerals (including allophanes and ferrihydrite as discussed ear- related better to geotechnical properties of soils than to their
lier), which confer unique properties and reactivities (Theng and nutrient-supplying power. In apparent contrast, the K-supplying
Yuan, 2008; Waychunas and Zhang, 2008). Nanoscale minerals are power of soils formed from quartzo-feldpathic loess or alluvium
defined as having at least one dimension in the nanorange, that is, and colluvium from sedimentary rocks in New Zealand showed
1–100 nm (Hochella, 2008). Nanoscience is now regarded as being a close relationship to the mica contents of their clay fractions
a critically important new offshoot of more traditional colloid or (Surapaneni et al., 2002). Barré et al. (2008), studying two French
clay mineralogy, and the growth rate of articles being published soils and one from the United States, also found that micaceous
on nanoparticle science (relevant to the geosciences) is around 10% minerals in soil clay-size fractions serve as reservoirs for potas-
per year, about triple the average growth rates of all scientific disci- sium. However, they found that the ability of soils to supply K
plines over a 5-year period (Hochella, 2008). to plants, and also to extract K when it was in excess, through
fertilizer additions, could only be fully understood when the
micaceous minerals were delineated into five different types.
20.4.2  Contributions of Classical Clay
These were a well-crystallized illite, a poorly crystallized illite,
Mineralogy toward Explanations
a highly smectitic interstratification of illite and smectite and
of Soil Properties
its highly illitic counterpart, and a soil vermiculite. These could
Clay mineralogy is a relatively young area of study. Up until be separately determined quantitatively, relative to one another,
1929, with the publication of a pioneering bulletin by Hendricks by decomposition of the XRD peak profile, following Lanson’s
and Fry on the X-ray examination of soil clays that was quickly (1997) procedure. Barré et al. (2008) claimed that the approach
Alteration, Formation, and Occurrence of Minerals in Soils 20-49

could be used to predict the K release potential of soils generally reconcile studies that have found that Fe oxides play a positive
and Velde and Barré (2010) provide many examples of the utility role in aggregation in soils (e.g., Colombo and Torrent, 1991;
of this approach. It may offer a wider applicability than the rela- Oades and Waters, 1991) with others in which Fe oxides do not
tionships developed by Surapaneni et al. (2002) for soils, which appear to affect aggregate stabilities (e.g., Deshpande et al., 1968;
have quite similar origins in just one country. Borggaard, 1983), Duiker et  al. (2003) found that their effect
depended upon their crystallinity. The most poorly crystalline
Fe oxides played an important role along with organic matter in
20.4.3  Potential of Classical Clay Mineralogy
aggregate stabilization and, where organic matter contents were
for Explaining Soil Properties
low, as in B horizons, their contributions to indices of aggrega-
A different mineralogical approach using X-ray fluorescence tion were found to equal or exceed that of organic matter (Duiker
(XRF) analyses of whole soils and also analyses of acid digests of et al., 2003), confirming similar trends seen by Churchman and
soils by inductively coupled plasma mass spectroscopy (ICP-MS) Tate (1987) for the particular case of soils formed on volcanic
was used to determine the normative mineralogies of forest soils ash. However, Al oxides may be more important than Fe oxides
in Finland at the early stages of weathering in order to explore in governing both aggregate stability and also P adsorption in
the availability of reserves of the nutrients Ca and Mg (Starr and some soils. This relationship appeared to hold for Latosols in
Lindroos, 2006). At the earliest stages of weathering, it is the Brazil (Schaefer et al., 2004). In one soil, at least, an amorphous
extent of alteration of primary minerals rather than the nature Al-hydroxy phase appeared to play an important role in both
of any secondary products that is the mineralogical character- aggregation and P adsorption.
istic that best relates to agronomic properties. Clay mineral- One property of soils that particularly demands explanation
ogy per se is of little predictive use when clays have hardly been and, if possible, prediction, at this time is that of the capacity
formed. For soils in most of the world’s agricultural areas, how- of soils to adsorb and retain organic carbon. The momentum
ever, the overwhelming contribution to the surface area of the for work to be done in this area comes from growing commu-
soils, as well as virtually all of their charge, arises from mate- nity concerns about the increased levels of carbon dioxide in the
rial in their clay fraction (e.g., Gilkes, 1990; Churchman, 2006). atmosphere, its links to global warming, and the role that soils
The highly reactive clay-size material includes both organic and may be able to play in sequestering excess carbon and isolating it
inorganic components, and it is the task of soil clay mineralo- from the atmosphere (Amundson, 2001; Kahle et al., 2002a). As
gists to understand the source of the contribution made by the Kahle et al. (2002a) pointed out, many workers have discovered
inorganic components. Gilkes (1990) noted that Norrish and relationships between clay content and carbon content, although
coworkers recognized some time ago that secondary minerals it is noteworthy that not all have found such a link, for reasons
in soils could hold and, when required, supply other important we will discuss herein. Nevertheless, it has long been known (e.g.,
nutrients besides K for plants. These included manganese oxides, Greenland, 1965) that clays and organic matter can be strongly
for cobalt (Adams et  al., 1969), and iron oxides, for phospho- associated in soils. Even so, it has long been appreciated (e.g.,
rus (Norrish and Rosser, 1983). Classical clay mineralogy, using Hamblin and Greenland, 1977) that the links between clays and
XRD, may be capable of detecting the presence of these oxides organic matter can occur through Fe and Al oxides. Mikutta
in soils provided that they are reasonably well crystallized, and et al. (2005) and also Kleber et al. (2005) reported that for acid
that their XRD peaks are not masked by stronger peaks for other subsoils under forest and representing a wide range of parent
minerals. Even so, it is not simply their presence, but rather their rock types and rainfall, poorly crystalline oxides of both Fe and
detailed structural, chemical, and physical characteristics, as Al provided the strongest binding agents for organic matter.
well as their associations with other soil entities that govern the According to Mikutta et al. (2005), poorly crystalline to nano-
reactivities—both chemical and physical—of these and other crystalline Fe oxides such as ferrihydrite were particularly effec-
oxides, hydroxides, and oxyhydroxides, as well as of aluminosil- tive for stabilizing organic C in these soils. It is also significant
icate phases in soils. Furthermore, much evidence points to the that these authors found that none of the factors of clay content,
idea that metal oxides (used generally hereafter to include both namely, the specific surface area of the minerals as determined by
oxyhydroxides and hydroxides) play a role in determining many nitrogen gas adsorption using the BET equation, total iron oxide
of the useful properties of many soils that is out of proportion to content, or the nature of the phyllosilicate clays, was a good pre-
their content in the soils. This status includes the indication from dictor of the ability of the soils to stabilize C. Their results con-
several earlier studies, van Raij and Peech (1972) and also Gallez firmed those of Percival et al. (2000) who correlated the organic
et al. (1976), among them, that the surface charge–pH curves of C contents of 167 New Zealand soils with several soil properties
many tropical soils show the characteristic features of metallic and found they showed significant linear relationships with oxa-
oxides, which have a pH-dependent variable charge. Similarly, late-extractable Si and Al, which together represent allophane
nanocrystalline aluminosilicates such as allophane also make content, and also with pyrophosphate-extractable Al, which
an extremely disproportionate contribution to both the surface represents Al associated with organic matter, that is, “Al-humus
area and reactivity of soils, including through a pH-dependent complexes,” but found no relationship with total clay content.
variable charge, even where only small amounts are present (e.g., Rasmussen et al. (2005), also studying forest soils, came to simi-
Lowe, 1995; McDaniel et al., Section 33.3). In an effort to try to lar conclusions as those of Percival et al. (2000). In a different,
20-50 Properties and Processes

tropical environment, but again studying forest soils on volcanic complexes) may contain as much as ∼30% of C. However, the
ash, Basile-Doelsch et al. (2005) found that organic C in buried residence time of C in soils containing allophane, as measured
horizons was strongly bound in abundant amounts in soils con- by 14C, is much greater than that of other soils (Figure 20.12; also
taining allophane, whereas buried horizons with large amounts see Parfitt, 2009).
of crystalline minerals, including feldspars and gibbsite, had Albeit that the studies by Kleber and coworkers on acid sub-
little capacity for C storage. The studies by Mikutta et al. (2005) soils showed no relationship between stabilized organic C and
and also Kleber et al. (2005), which were on samples devoid of the surface area of minerals in the soils, extent of surface intui-
allophane, showed that it is not the particular occurrence of allo- tively appears likely to be able to explain the capacity of soils for
phane or even of ferrihydrite that is necessary to provide strong organic C, and several workers have proposed such a relation-
links to organic C. Rather it is the capacity of poorly crystalline ship (e.g., Saggar et  al., 1996; Kaiser and Guggenberger, 2000;
or nanocrystalline minerals of both Fe and Al to provide sin- Eusterhues et al., 2005). Indeed, to illustrate the point that differ-
gly coordinated hydroxyl groups that are able to participate in ent soils lead to different generalizations about the relationship
ligand exchange with organic functional groups, which ensures between C content and surface area, and, incidentally, forms of
strong associations with organic C, according to Kleber and Fe in soils, Kahle et al. (2002b) found that a combination of spe-
coworkers in the two related 2005 reports. This generalization cific surface area and total (i.e., dithionite-extractable) Fe oxide
also bears out the results of experiments by Kahle et al. (2004) in content predicted C content almost completely, with an R 2 of 0.96,
which dissolved organic carbon (DOC) was added to soil clays in the topsoils of a set of illitic soils with more or less neutral
that had been depleted of organic C and also to “type” phyllo- pHs that had been farmed since Medieval times. The surface
silicates from nonsoil sources. This experiment showed that soil areas were determined using the sorption of nonreactive nitro-
clays adsorbed much more DOC than the type clay minerals gen gas and hence gave a good measure of external surface (e.g.,
and that the difference appeared to be due to pedogenic oxides, Churchman and Burke, 1991). Using isotopically labeled plant
mainly of Fe, which provide reactive hydroxyl groups for DOC material, Saggar et al. (1996) found that its residence time during
sorption. In the case of some tropical soils, Barthès et al. (2008) its initial decomposition in soils correlated well with the surface
found that organic C content and also aggregate stability were area of the soil as measured by the adsorption of p-nitrophenol. It
promoted when sesquioxides, especially goethite and hematite, is noteworthy that it was this particular (p-nitrophenol adsorp-
in the soils included substitutions by Al, which increased their tion) method that showed a good relationship with organic C
specific surface areas. retained in this case. Like Churchman and Burke (1991), these
One of the common characteristics of Andisols is accumula- authors also tried to explain soil properties (organic C uptake in
tion of relatively large quantities of organic matter, both in the this instance) by the sum of the surface areas from the literature
allophanic (moderate pH) and in the nonallophanic Andisols (low for the mineral components of the soils and also largely failed. By
pH). Allophanic Andisols may contain ∼10% or more C, whereas contrast, consideration of the specific surface areas (SSAs) from
nonallophanic andisols (dominated by Al- and/or Fe-humus N2 sorption of different soil types in relation to those calculated

700
Tokomaru data
(Alfisol) 0–8 cm
600
Egmont data
(Andisol)
500

400 Δ14C atmosphere

Δ14C (per mil)

300
Tokomaru Δ14C model
(RT = 9 years)
200

100 Egmont Δ14C model

(RT = 26 years)
0

–100
1955 1960 1965 1970 1975 1980 1985

FIGURE 20.12  Model showing slower rates of incorporation and turnover of organic C using bomb-derived 14C in an allophanic soil (Egmont
series) compared with those of a soil without appreciable allophane (Tokomaru series) under similar climate and land use in New Zealand. (Based
on Baisden, W.T., R.L. Parfitt, and C.W. Ross. 2010. Radiocarbon evidence for contrasting soil carbon dynamics in an Andisol and non-Andisol pasture
soil comparison. J. Integr. Field Sci. 7:59–64.) RT, residence time of carbon. (Modified diagram from Parfitt, R.L. 2009. Allophane and imogolite: Role
in soil biogeochemical processes. Clay Miner. 44:135–155. With permission of The Mineralogical Society of Great Britain and Ireland.)
Alteration, Formation, and Occurrence of Minerals in Soils 20-51

for their constituent Fe oxides and allophane led Eusterhues held in soils under rainforest and pastures than in those under
et  al. (2005) to conclude that almost all mineral-associated pine plantations. Furthermore, Spielvogel et al. (2008), like many
organic matter in soils is bound to Fe oxides. Churchman and others (e.g., Kleber et al., 2005; Mikutta et al., 2005; Rasmussen
Burke (1991) generally found that the strength of the relation- et al., 2005), examined the causes of OM stabilization in acidic
ship between a soil property and surface area depended upon the forest soils, but arrived at the conclusion that, while Fe and Al
technique chosen to measure surface area (they compared N2 gas oxides, and, particularly, their poorly crystalline to nanocrystal-
sorption, with sorption of polar liquids ethylene glycol mono- line varieties, were responsible for stabilization, they are bound
ethyl ether [EGME] and water) and the relevance of the adsor- to, and stabilize, only a specific fraction of the OM. This frac-
bate to the soil property of interest. A good relationship between tion was concentrated in O/N-alkyl C and microbially derived
a particular soil property and surface area deduced from the sugars compared with the nonstabilized remainder (Spielvogel
sorption of a particular adsorbate shows that the property and et al., 2008).
the capacity of the surface for the adsorbate have similar causes It, therefore, appears likely that the properties of the mineral
but does not show that the property relates to a generic measure fraction, which control the uptake and retention of organic C
of surface area, which most probably does not exist. by soils, vary greatly between soils. Any generalization is likely
To further complicate the nature of the relationship between to founder when applied to a particular case. Indeed, following
minerals and organic C in soils, it is noted that a study of the Kaiser and Guggenberger (2003), Chenu and Plante (2006), Wan
energetics of organic C sorption by Mayer and Xing (2001) et al. (2007), McCarthy et al. (2008), and Richards et al. (2009),
revealed that minerals appeared to be occluded by OM, rather we suggest that it may be that the properties of minerals that
than the OM being adsorbed by minerals, and that micropores are most important are those that enable them to form pores or
were likely to be responsible for some of the associations. Kaiser aggregates for encapsulating OM, and their identification prob-
and Guggenberger (2003) suggested that OM was preferentially ably defies a simple summary. At the most, it can probably be
adsorbed within, or at the mouths of, micropores <2 nm in concluded only that a number of possible characteristics of the
diameter in iron oxides in soils. The results of density fraction- mineral phases are likely to influence the capacity of soils to
ations combined with TEM led Chenu and Plante (2006) to con- stabilize C and it remains for practice to show which are more
clude that most OM was stabilized in soils by close associations important than the others in each instance. A possible list of
with clays in very small microaggregates, either through adsorp- such characteristics is given in Table 20.7. A number of studies
tion or by entrapment. Wan et  al. (2007) mapped organic car- have attempted, like Churchman and Burke (1991) and Saggar
bon along with other elements in different soils using scanning et al. (1996) with specific surface area, to explain soil properties
transmission X-ray microscopy (STXM) and found that OM by the sum of the contributions from their different mineral (and
exists as distinct particles within microaggregates more often also, sometimes, organic) components. Properties that were pro-
than as coatings on minerals. Using small-angle X-ray scattering posed for explanation in this way have included CEC (Seybold
to directly observe pores and their constituents, McCarthy et al. et al., 2005). CECs could be largely explained within mineralogi-
(2008) found that most OM was held within pores, although cal groupings from Soil Taxonomy when organic C was included.
not necessarily very small pores, in formerly cultivated soils Churchman and Burke (1991) also found good relationships
that had been restored to tallgrass prairie. Their main conclu- between CECs and a measure of water retention within mineral-
sion was that OM was encapsulated, rather than adsorbed, by ogical groupings of soils with low carbon contents.
minerals. According to Richards et  al. (2009), it is the occur- Together, these results suggested that the use of classical clay
rence of aggregates, rather than the abundance of oxides of Fe mineralogy to group mineralogically similar soils may be reason-
and Al, that enabled the stabilization of OM in oxide-rich soils ably successful for predicting CECs. In addition, close compari-
in the Australian subtropics. As a result, more organic C was sons of experimental and theoretical titration curves indicated
TABLE 20.7  Characteristics of Mineral Phases That Have Helped to Explain the Capacity of Various Soils
for the Uptake and Retention of Organic Carbon
Most Relevant Mineral Phase and/or Property Soil References
Fe and Al oxides Silty soils Hamblin and Greenland (1977)
Allophane + pyrophosphate–Al 167 soils (from throughout New Zealand) Percival et al. (2000)
Specific surface area + total Fe oxides Neutral illitic topsoils Kahle et al. (2002b)
Pedogenic oxides, mainly of Fe Range of forest and arable soils with range of Kahle et al. (2004)
mineralogy
Fe oxides Cambisol and podzol under forest (acid) Eusterhues et al. (2005)
Poorly crystalline (or nanocrystalline) Fe and Al Acid subsoils under forest Kleber et al. (2005) and
oxides, especially ferrihydrite Mikutta et al. (2005)
Allophane Volcanic ash soils under forest Basile-Doelsch et al. (2005)
Al-substituted Fe oxides Tropical soils Barthès et al. (2008)
Fe and Al oxides Acidic forest soils Spielvogel et al. (2008)
20-52 Properties and Processes

that surface charge densities of some soils from Argentina were varieties of both Al-rich and Si-rich allophanes, while the soils
apparently successfully modeled by the sum of those of their con- also contained many different iron phases, ferrihydrite, hema-
stituent mineral phases when the mineralogical compositions of tite, and also “iddingsite” (see Section 20.2.4.1), among them.
the soils were determined by a Rietveld approach (Taubaso et al., The component additivity modeling approach adopted by
2004). This result suggests further that the charges on soils may Gustafsson (2001) foundered because allophanes and ferrihy-
be largely additive of those on their constituent clay-size miner- drite, as they are found in soils, differ in many important respects
als. Nonetheless, this and earlier work by a group from the same from either natural minerals from nonsoil environments such
laboratory (Torres Sanchez et al., 2001) showed that there was a as the “stream deposit allophane” (Childs et  al., 1990; Parfitt,
mismatch between the point of zero net charge (PZNC) and the 1990) or synthetic minerals of the same name, in the case of
isoelectric point for those soils in which Fe oxides were adsorbed ferrihydrite. They are unique to soils, and they also show varia-
on to phyllosilicate clays. Hence, the diffusion behavior of these tions within their type. A number of other minerals are unique,
soils, which relates to their isoelectric points (IEPs), cannot be or almost unique, to soil environments, and the properties and
simply regarded as additive of their component colloidal miner- reactivities of these, also, cannot be modeled upon those of
als but must account also for their associations with one another. minerals found in nonsoil environments. These include fully or
While there has been some success with the modeling of partially expanded 2:1 Si:Al aluminosilicates with hydroxyl-Al
charge characteristics, both permanent (Seybold et al., 2005) and interlayers (see Section 20.2.4.3), which may show even seasonal
variable (Taubaso et al., 2004) from the mineral composition of changes in the soil biological system (see Section 20.2.5.3). They
soils, mineral composition patently could not describe organic also include interstratified phases in their various manifesta-
matter stabilization by minerals in soils. However, in some tions. Velde and Meunier (2008) have characterized those of
cases, at least (Kahle et  al., 2004; Kleber et  al., 2005; Mikutta illite and smectite as being “peculiar to the soil environment”
et al., 2005; see also Table 20.7), it appears that some functional (Section 20.2.5.3.1), as well as being “the most widespread and
groups, singly coordinated hydroxyl groups in particular, play representative soils clays.” By the same token, smectites found
a crucial role in binding natural organic compounds—albeit in soils have been characterized as being commonly ferribeidel-
perhaps only a fraction of the total soil organic matter, follow- litic in composition and, therefore, are quite different from the
ing Spielvogel et al. (2008). Therefore, the question arises as to bentonites from which typical nonsoil montmorillonites have
whether more accurate descriptions of mineral–organic associa- usually been extracted to serve as models for smectites in soils
tions, and of reactions of other species, for example, anions such (Section 20.3.5).
as phosphates and arsenates with mineral surfaces, might be bet- However, it is not just the particular composition, struc-
ter made on the basis of the amount of the important functional ture, and arrangement of layers of the minerals in soils that
groups present, by an approach that is analogous to that taken by often make them different from so-called typical minerals
modern soil organic matter studies using, for example, 13C-NMR taken from nonsoil sources. They differ from the latter partly
and FTIR spectral analyses (e.g., Baldock and Nelson, 2000). because important physical properties of secondary minerals
Gustafsson (2001) used a “component additivity” approach in soils are generally different from those of nonsoil minerals.
in an attempt to predict, or model the adsorption of arsenate Studies of soil kaolinites from soils on three continents by Singh,
in competition with sulfate, silicic acid, and phosphate on Gilkes, and coworkers (Section 20.3.1), a number of studies of
allophane and also ferrihydrite, and tested the results against soil halloysites (Section 20.3.2), and a study of iron oxides by
experimental data for the adsorption on the spodic horizon of Trakoonyingcharoen et al. (2006) (Section 20.3.7), have focused
a Swedish soil that contained both ferrihydrite and allophane specifically on the sizes and sometimes also surface areas of the
but little organic matter. Although this approach led to results particles. The studies generally concluded that those of the soil
that were qualitatively realistic, Gustafsson (2001) nevertheless particles are almost invariably much smaller than those of their
concluded that the approach is probably impractical, partly, at “reference” nonsoil counterparts with the same mineral names.
least, because it relies on the assumption that the properties of Soil clay minerals also differ from most, at least, of their non-
allophane and ferrihydrite in real soils can be approximated by soil counterparts because of their associations with other species
those of gibbsite and ferrihydrite synthesized in the laboratory. in soils. Apart from their ready association with organic matter
Among many others, Gérard et al. (2007) have shown that this that has already been discussed in this section, they are very com-
assumption is simplistic and unrealistic. In the particular case monly associated also with other minerals. Almost universally,
that these last authors studied, allophane formed on basalt in the they are associated with iron oxides (see Table 20.5 and Section
Azores was found to have an especially complex genesis, lead- 20.3.7) and, often, also with aluminum oxides. While the content
ing to allophanic products with a large range of compositions. of Fe in its various forms varies widely (Table 20.5), it is probably
Gérard et al. (2007) claimed that not all of the allophane formed only in very young soils that it is nearly negligible in affecting
was the product of recrystallization from solution, describing soil properties. The youngest soil in a chronosequence on andes-
some of it as “alteromorphs after lapilli or pumice,” which result itic lava studied by Nieuwenhuyse et al. (2000) contained only
from the leaching of Si and cations from these materials. The 0.4% total Fe in its lowest, CB horizon. This horizon also con-
products encompassed a compositional range from pure alumi- tained 2.2% oxalate-extractable Al and, hence, ∼8% allophane,
nosilicates to Fe- and Ti-enriched aluminosilicates and included but no phyllosilicate minerals  (Nieuwenhuyse  et  al.,  2000).
Alteration, Formation, and Occurrence of Minerals in Soils 20-53

Table  20.5  also shows that soils are almost certainly never monomineralic species described in textbooks” (Gilkes, 1990,
mono-mineralic in their secondary minerals. Only one of the p. 72); and (2) the extent and nature (e.g., charge) of two types of
soils shown there (an Orthoxic Tropohumult) is apparently kaolinites (in different Australian soils) were quite different (op.
monomineralic in phyllosilicates (kaolinite, in this case), but cit., p. 67). Soils are highly heterogeneous in composition and
clearly also contains goethite, at least, in addition. are not simply mixtures of nonassociated entities. In particular,
clay minerals are commonly coated by other minerals or organic
matter, or both, so that the properties of their reactive surfaces
20.4.4  Nature of Soil Minerals and Relationship
reflect the characteristics of the coating material rather than
to Their Mode of Formation
the mineral substrate. For instance, it was found that “without
Clearly, properties of soils relate to properties of clays besides exception, the suspended particles in rivers and gesturing waters
those arising from their particular mineralogical character- were negatively and quite uniformly charged” (R.J. Hunter, 1981,
ization. Properties such as particle size and associations that in Mills, 2003, p. 11). It is almost certain that these particles had
minerals form with other minerals derive from their mode of a soil source. Furthermore, “Since the particles themselves var-
formation. In general terms, minerals with a neogenetic origin ied widely as to composition, Hunter concluded that this was
from solutions in the soil occur in smaller particles than those likely due to a coating of organic matter or metal (iron, alumi-
formed by either transformation in the solid phase from primary num, and/or manganese) oxide” (Mills, 2003, p. 11).
minerals or even those that may be inherited from a source of These observations all suggest that the colloidal “particles”
minerals of authigenic origin from beyond the soil environment, controlling soil properties are generally heterogeneous mix-
for example, hydrothermally formed kaolinite and halloysite, or tures of various types of materials, both inorganic and organic.
smectite in bentonite deposits of marine or lacustrine origins. Predictions of their properties from those of well-crystallized
A dramatic illustration of the differences that are wrought by minerals are likely to fall short of the mark. Grouping of soils by
pedogenesis in comparison with a nonsoil genesis (in this case, their dominant idealized mineral types can generally give only
saprolitic) is given by the observation that the area of the 001 poor, or, at best, only qualitative, predictions of their properties.
faces of kaolinite crystals that formed in the saprolite below 58 m A structural alternative of grouping soils by the nature of their
depth in Brazil were more than five times larger than those that associations of, for example, particular aluminosilicate miner-
formed in the soil above it (Varajão et al., 2001). It is recalled that als, metal oxides, and organic matter together would provide the
Kahle et al. (2002b) found that a combination of specific surface hopeless case of too many categories; indeed, each association
area and total (i.e., dithionite-extractable) Fe oxide content pre- would be very likely unique. A better alternative is suggested by
dicted C content almost completely in a set of illitic soils whereas the example of research into the nature of purely organic col-
explanations of C contents of other soils from mineral proper- loids in soils.
ties were more complex and usually involved poorly crystalline Organic colloids in soils are alternatively known as “humic
or nanocrystalline phases (see also Section 20.4.3). Even though macromolecules.” Hayes et  al. (1989, p. 16) have concluded, on
the land-use history of the illitic soils and their pH may have theoretical grounds, that “it is highly unlikely that there are two
played a role in simplifying the relationships between the inor- humic macromolecules on earth … which are exactly the same.”
ganic (mineral) and organic components of the illitic soils (and, Even so, the field of the chemical and analytical study of organic
incidentally, in altering the course of mineral genesis), it is also colloids in soils is a very active one. It has had continuing success
most likely that the probable formation of the illite in the soils because instead of seeking definitive general structures of inevi-
by transformation rather than neogenesis has led to mineral– tably heterogeneous molecules, it has sought instead to character-
organic relationships that are different from those in soils with ize organic colloids by their “functional groups” (e.g., aromatic,
higher proportions of neogenetic minerals, including poorly carbohydrate, alkyl, carboxyl) —in other words, by their capaci-
crystalline/nanocrystalline metal oxides (e.g., Kleber et al., 2005; ties to participate in reactions with other entities in soils.
Mikutta et  al., 2005). Furthermore, it has been found that the Since a structural characterization of the “ultimate” particles
nature of aggregation within soils dominated by kaolinites in or groupings of minerals would be similarly fraught with difficul-
close associations with Fe and Al oxides differs from that in soils ties as that of organic colloids per se, it may be useful to classify
that are more illitic. Both in a study in which aggregates were bro- soil minerals as contributors to soil properties (mostly via com-
ken down mechanically (Oades and Waters, 1991) and another in plex heterogeneous mixtures) through their characterization and
which they were given the opportunity to build up through plant appropriate grouping according to their most relevant capacities.
growth and inputs of plant residues (Denef and Six, 2005), aggre- These might include (on a weight basis) their surface area—as
gates in the kaolinitic soils were shown to comprise largely self- measured by various techniques, their charge and its variability
associations of minerals, while those in the illitic soils included with pH, their content of plant-available potassium, their shrink–
close associations of minerals with organic matter. swell capabilities, and their concentrations of reactive hydroxyl
The application of analytical techniques with higher resolu- groups. Together, these properties reflect many of the most
tion than XRD, and particularly electron microscopy, has shown important for soil applications and may be correlated with other
that (1) “many clay particles in soils consist of complex inter- properties, for example, their affinity with organic matter and
growths of different structural types rather than being the ideal their capacity to adsorb phosphates or chlorides and other anions.
20-54 Properties and Processes

Nevertheless, selection of a set of useful properties by which Adamo, P., P. Violante, and M.J. Wilson. 2001. Tubular and sphe-
to characterize mineral properties does not provide advances roidal halloysite in pyroclastic deposits of the Roccamonfina
in understanding the origin of these properties. As has always volcano (Southern Italy). Geoderma 99:295–316.
been the case in mineralogical studies, this uncertainty will be Adams, S.N., J.L. Honeysett, K.G. Tiller, and K. Norrish. 1969.
reduced by advances in new instrumental techniques and in Factors controlling the increase of cobalt in plants following
their application to soils. Undoubtedly, electron microscopy at the addition of a cobalt fertilizer. Aust. J. Soil Res. 7:29–42.
higher resolutions, both for viewing and also for quantitative Ahn, J.-H., and D.R. Peacor. 1987. Kaolinization of biotite—TEM
analyses, will be among these. Such techniques of surface analy- data and implications for an alteration mechanism. Am.
sis as XPS might also help. For example, Gerin et al. (2003) were Mineral. 72:353–356.
able to analyze the nature of soil surface coatings, both of organic Aldridge, L.P., and G.J. Churchman. 1991. The role of iron in the
matter and also Fe and Al species, in order to better understand weathering of a climosequence of soils derived from schist.
mineral-organic associations, and they projected more similar Aust. J. Soil Res. 29:387–398.
work with XPS. With the advent of synchrotron radiation, X-ray Alekseev, A., T. Alekseeva, V. Ostroumov, C. Siegert, and
spectroscopic techniques, which include and enhance XPS and B. Gradusov. 2005. Mineral transformations in permafrost-
also XRD and XRF, but also encompass extended X-ray absorp- affected soils, North Kolyma lowland, Russia. Soil Sci. Soc.
tion fine structure (EXAFS), X-ray absorption near-edge struc- Am. J. 67:596–605.
ture (XANES), and other related methods have become available Alexandre, A., J.-D. Meunier, F. Colin, and J.-M. Koud. 1997.
to determine the sites on mineral surfaces that are involved in Plant impact on the biogeochemical cycle of silicon and
interactions with other species (Gates, 2006). related weathering processes. Geochim. Cosmochim. Acta
Continuing developments in instrumental techniques 61:677–682.
undoubtedly enable better descriptions of processes involving Alimova, A., A. Katz, N. Steiner, E. Rudolph, H. Wei, J.C. Steiner,
minerals in soils, but the foregoing discussion nonetheless leads and P. Gottleib. 2009. Bacteria-clay interaction: Structural
us to conclude that in order to be able to provide the best predic- changes in smectite induced during biofilm formation.
tions or explanations of soil behavior from its clay mineralogy, Clays Clay Miner. 57:205–212.
the origins of the clays themselves must be thoroughly under- Allen, B.L., and B.F. Hajek. 1989. Mineral occurrence in soil envi-
stood. The earlier parts of this chapter on the alteration, forma- ronments, p. 199–278. In J.B. Dixon and S.B. Weed (eds.)
tion, and occurrence of minerals in soils thereby gains relevance Minerals in soil environments. 2nd edn. SSSA, Madison, WI.
to the understanding of soils both as useful materials and pro- Alloway, B.V., M.S. McGlone, V.E. Neall, and C.G. Vucetich.
viders of essential ecological and human services. 1992. The role of Egmont-sourced tephra in evaluating the
paleoclimatic correspondence between the bio- and soil-
stratigraphic records of central Taranaki, New Zealand.
Acknowledgments Quat. Int. 13–14:187–194.
Altschuler, Z.S., E.J. Dwornik, and H. Kramer. 1963.
We thank Max Oulton (University of Waikato) for preparing the
Transformation of montmorillonite to kaolinite during
diagrams, Stuart McClure (formerly of CSIRO Land and Water)
weathering. Science 141:148–152.
for the scanning electron micrographs, Balwant Singh (Sydney
Amrhein, C., and D.L. Suarez. 1988. The use of a surface complexation
University) for the prints of the transmission electron micro-
model to describe the kinetics of ligand-promotion dissolution
graphs, Greg Rinder (Adelaide) for their preparation, and Bruce
of anorthite. Geochim. Cosmochim. Acta 52:2785–2793.
Velde (Ecole Normale Supérieure, France) for providing us with
Amundson, R. 2001. The carbon budget in soils. Annu. Rev. Earth
galley proofs of parts of his recent book (with A. Meunier) prior
Planet Sci. 29:535–562.
to its publication. We appreciated very much the comments,
Anand, R.R., and R.J. Gilkes. 1984. Weathering of ilmenite in a
encouragement, and patience of section editor Joseph W. Stucki,
lateritic pallid zone. Clays Clay Miner. 32:363–374.
and very useful comments from Aaron Thompson (University of
Anand, R.R., and R.J. Gilkes. 1987. The association of maghemite
Georgia) as a reviewer. Graham Shepherd, Brent Green, Hiroshi
and corundum in Darling Range laterites, Western
Takesako, Rob Fitzpatrick, and M.S. Skwarnecki are especially
Australia. Aust. J. Soil Res. 25:303–311.
thanked for allowing us to cite unpublished data.
Anand, R.R., R.J. Gilkes, T.M. Armitage, and J.W. Hillyer. 1985.
Feldspar weathering in lateritic saprolite. Clays Clay Miner.
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 21
Phyllosilicates
21.1 Introduction............................................................................................................................ 21-1
21.2 General Structural Features.................................................................................................. 21-1
Ionic Sizes and Coordination Number  •  Polytypes  •  1:1 Layer Type (T–O Type)  • 
2:1 Layer Type (T–O–T Type)  •  2:1:1 Layer Type (T–O–T–O Type)  •  Interstratified Layer
Silicate Group (Mixed-Layer Type)  •  Modulated Layer Silicate Group
21.3 Occurrence of Phyllosilicates.............................................................................................. 21-21
As Rock-Forming Minerals  •  Hydrothermal Origin and the Term “Clay Minerals”   • 
Diagenesis and Low-Grade Metamorphism  •  In Soils, Sediments, and Weathering Products
21.4 Phyllosilicates in Soil Environments................................................................................. 21-24
Introduction  •  Physical Properties  •  Chemical Properties  •  Uses of Clays
21.5 Identification of Soil Phyllosilicates...................................................................................21-30
Introduction  •  X-Ray Diffraction Methods  •  Other Instrumental Methods  •  Quantification
Addendum.........................................................................................................................................21-41
Hideomi Kodama Appendix...........................................................................................................................................21-41
Agriculture and Agri-Food Canada References..........................................................................................................................................21-44

linking together is known as polymerization, and the classified

21.1  Introduction structural units with their compositions are given in Table 21.2.
Phyllosilicates, in other words, layer silicates, occupy one of six
subclasses under the silicates class (Table 21.1). Phyllo- is after 21.2  General Structural Features
the Greek word describing the state of leaves, like a bed or heap
of leaves. Thus in science, often the word is used as a prefix to The crystal structure of phyllosilicates has been determined
express thin layer or paper sheet like in a book. This reflects largely by x-ray diffraction (XRD) methods that were well
general crystal habits and morphological features of the phyl- established within two to three decades of Roentgen’s dis-
losilicates. The silicates are abundant on the earth and of greater covery of x-rays in 1895. The essential features of the mineral,
importance than any other minerals, which is easily understood typified by mica-like minerals, are the continuous 2D tetra-
from the fact that oxygen and silicon constitute nearly 75% of hedral sheets of composition, Si 2O52− , in which SiO4 tetrahe-
the elements in the earth’s crust (Figure 21.1). The fundamental dra (Figure 21.3) are linked by sharing three corners of each
unit in all silicate structures is the silicon–oxygen tetrahedron tetrahedron to form a hexagonal mesh pattern (Figure 21.4a).
(Figure 21.2). As Bragg (1950) stated, the bonds between silicon Frequently Si atoms of the tetrahedra are partially substituted
and oxygen are so strong that the four oxygen atoms are always by Al and, to a lesser extent, by Fe3+. The apical oxygen at the
found at the corners of a tetrahedron of nearly constant dimen- fourth corner of the tetrahedra, which is usually directed nor-
sions and regular shape whatever the rest of the structure may be mal to the sheet, forms part of an adjacent octahedral sheet
like. The Si–O distance is about 0.16 nm, and the O–O distance in which octahedra are linked by sharing edges (Figure 21.5).
0.26 nm. Besides the crustal abundance of these two elements, The junction plane between tetrahedral and octahedral sheets
the ionic radius of Si4+, 0.042 nm, is conveniently accommo- consists of the shared apical oxygens of the tetrahedra and
dated in surroundings with four oxygens to form the funda- unshared hydroxyls that lie at the center of each hexagonal
mental structural unit of all silicates, the tetrahedron having the ring of tetrahedra and at the same level as the shared apical
chemical formula (SiO4)4−. This unit can occur independently oxygen atoms (Figure 21.6). Further details of octahedral con-
with compensating cations like Mg2+ and Fe2+. And also these figurations will be seen in Section 21.2.2, where the explana-
SiO4 tetrahedra may be linked together by having one or more tion of polytypes is given using the phlogopite structure as
oxygen atoms shared in common by neighboring tetrahedra to the example. Common cations that coordinate the octahe-
form indefinitely extended and more complicated structural dral sheets are Al, Mg, Fe3+, and Fe2+; but occasionally, Li, V,
units to cover the existing silicate minerals. This mechanism of Cr, Mn, Ni, Cu, and Zn substitute in considerable amounts

21-1
21-2 Properties and Processes

TABLE 21.1  Six Subclasses under the Silicate Mineral Class

Subclass (Commonly Used) Subclass (in Other Name)
Nesosilicates Orthosilicates
Sorosilicates Disilicates
Cyclosilicates Ring silicates
Inosilicates Chain silicates—Single chain and double
chain
Phyllosilicates Layer silicates
Tectosilicates Framework silicates And Oxygen Silicon

FIGURE 21.3  SiO4 tetrahedra linking to form a hexagonal network.

Oxygen Single tetrahedron is shaded. (From Grim, R.E. 1968. Clay mineralogy.
Silicon McGraw-Hill Book Co. Inc., New York. With permission.)
Aluminum
Iron
Calcium
Sodium
Magnesium
Potassium
Titanium
Hydrogen
Phosphorous
Manganese
0 10 20 30 40 50

FIGURE 21.1  The 12 most abundant elements in the earth’s crust.

(Modified graph from Vanders, I., and P. Kerr. 1967. Mineral recogni-
tion. John Wiley & Sons, Inc., New York.)
(a)

aτ

FIGURE 21.2  Close-packing representation of the SiO4 tetrahedron.

(From Klein, C., and C.S. Hurlbut, Jr., 1985. Manual of mineralogy.
(b)
John Wiley & Sons, Inc., New York.)
FIGURE 21.4  (a) Ideal hexagonal tetrahedral sheet. (b) Contracted
TABLE 21.2  Unit Compositions of Six Subclasses, Mineral Group, sheet of ditrigonal symmetry by rotation of the tetrahedra due to a
and Species Examples dimension misfit between tetrahedral and octahedral sheets. (With
kind permission from Liebau, F. 1985. Structural chemistry of silicates:
Unit Mineral Group Mineral Species
Structure, bonding, and classification. Springer-Verlag, New York.)
Subclass Composition Example Example
Nesosilicates (SiO4)4− Olivin Forsterite into the sheets. If divalent cations (M 2+) are in the octahedral
Sorosilicates (Si2O7)6− Epidote Zoisite
sheets, the composition is M32+ (OH)2 O4 and all the octahe-
Cyclosilicates (Si6O18)12− Tourmaline Elbaite
dra are occupied; if trivalent cations (M 3+), the composition is
Inosilicates
M23+ (OH)2 O4 and two-thirds of the octahedra are occupied,
Single chain (SiO3)2− Pyroxene Diopside
with the absence of the third octahedron. The former type of
Double chain (Si4O11)6− Amphibole Actinolite
octahedral sheet is called trioctahedral (Figure 21.7a) and the
Phyllosilicates (Si2O5)2− Mica Muscovite
latter dioctahedral (Figure 21.7b). This distinction may occa-
Tectosilicates (SiO2)0 Feldspar Albite
sionally be used as a subgrouping for certain mineral groups
Phyllosilicates 21-3

And Hydroxyl Aluminum, magnesium, etc.

FIGURE 21.5  Single octahedron (shaded) and the sheet structure of

b
octahedral units. (From Grim, R.E. 1968. Clay mineralogy. McGraw- (a)
Hill Book Co. Inc., New York. With permission.)

OH

OH OH OH
(b)
OH OH

FIGURE 21.7  Difference in the octahedral sheets of clay miner-

Oxygens Aluminum OH Hydroxyl Silicon
als: (a) trioctahedral, with dots of M2+; (b) dioctahedral, with dots of
M3+. (With kind permission of Liebau, F. 1985. Structural chemistry of
FIGURE 21.6  Structure of 1:1 layer silicate (kaolinite) illustrating the junc- silicates: Structure, bonding, and classification. Springer-Verlag, New
tion between tetrahedral and octahedral sheets. (From Grim, R.E. 1968. Clay York.)
mineralogy. McGraw-Hill Book Co. Inc., New York. With permission.)

(e.g., mica). If all the anion groups are OH in the compositions

of octahedral sheets, the resulting sheets may be expressed
by M 2+(OH)2 and M 3+(OH)3, respectively. Such sheets called
hydroxide sheets occur singly, alternating with silicate lay-
ers in some phyllosilicates, for example, in chlorite minerals.
Brucite, Mg(OH)2 , and gibbsite, Al(OH)3, are typical examples
(a)
of minerals having similar structures.
There are two major types for structural “backbones” of phyllo-
silicates called silicate layers. The unit silicate layer formed by align-
ing one octahedral sheet to one tetrahedral sheet is referred to as a
1:1 silicate layer (Figure 21.8a), and the exposed surface of the octa-
hedral sheet consists of hydroxyls. In another type, the unit silicate
layer comprises one octahedral sheet sandwiched by two tetrahe-
dral sheets, which are oriented in opposite directions and is termed
a 2:1 silicate layer (Figure 21.8b). If hydroxide sheets in the chlorite
structure are treated as a proxy for the octahedral sheet of the sili-
cate layer and denoted as T for the tetrahedral sheet and O for the
octahedral sheet, a majority of the phyllosilicates may be grouped by (b)
T–O type, T–O–T type, and T–O–T–O type, which correspond to FIGURE 21.8  Two basic silicate layer types of phyllosilicates: (a) 1:1
1:1, 2:1, and 2:2 (2:1:1 in some occasions) silicate layers, respectively. or T–O type silicate layer structure, (b) 2:1 or T–O–T type silicate layer
Real structures of phyllosilicates, however, contain substantial structure. (With kind permission of Springer Science + Business media:
crystal strains and distortions, which produce irregularities such Liebau, F. 1985. Structural chemistry of silicates: Structure, bonding,
as deformed octahedra and tetrahedra rather than polyhedra and classification. Springer-Verlag, New York.)
21-4 Properties and Processes

with equilateral hexagonal faces, ditrigonal symmetry modified TABLE 21.3  Relationship between Radius Ratio (Rcation /RO2−)
from the ideal hexagonal surface symmetry, and puckered surface and Coordination Number
instead of the flat plane made up by the basal oxygen atoms of Arrangement of Coordination Crystal
the tetrahedral sheet. One of the major causes of such distortions Radius Ratio Anions around Number of Models Shown
is dimensional “misfits” between the tetrahedral and octahedral (Rcation/Ranion) a Cation Cation in Figure 21.9
sheets. If the tetrahedral sheet contains only silicon in the cationic 0.15–0.22 Corners of an 3 a
site and has an ideal hexagonal symmetry, the longer unit dimen- equilateral triangle
sion within the basal dimension is 0.915 nm, which lies between 0.22–0.41 Corners of a 4 b
the corresponding dimensions 0.86 nm of gibbsite and 0.94 nm of tetrahedron
brucite. To fit the tetrahedral sheet into the dimension of the octa- 0.41–0.73 Corners of an 6 c
octahedron
hedral sheet, alternate SiO4 tetrahedra rotate (up to a theoretical
0.73–1 Corners of a cube 8 d
maximum of 30°) in opposite directions to distort the ideal hex-
1 Closest packing 12 e
agonal array into a doubly triangular (ditrigonal) array (Figure
21.4b). By this distortion mechanism, tetrahedral and octahedral
sheets of a wide range of composition due to ionic substitutions anions for particular radius ratios can be calculated from purely
can link together and maintain silicate layers. Among ionic sub- geometric considerations (Table 21.3) and the corresponding 3D
stitutions, those between ions of distinctly different sizes most coordination models are shown in Figure 21.9. Anions in phyl-
significantly affect geometric configurations of silicate layers. losilicate structures are mostly oxygen ions, O2−, with radius of
0.132 nm. Although to a lesser extent the structures may contain
F− and (OH)−, radii of these anions are similar to that of oxygen.
21.2.1  Ionic Sizes and Coordination Number
Therefore, for phyllosilicates, it is practical to compare the rela-
The arrangement of anions around a cation (as normally anions tionship of coordination number with the size of cation in terms
are larger than cations), defined as the coordination number, of Rcation /RO2− (Table 21.4). The table allows making prediction for
would be expected to be the most symmetrical in the three dimen- the coordination number of a cation in phyllosilicates and for a
sions, that is, 3, 4, 6, 8, and 12 ions would be arranged at the apices possible ionic substitution at a specific structural site.
of an equilateral triangle, regular tetrahedron, octahedron, cube,
and closest packing in order to minimize its overall potential
21.2.2  Polytypes
energy. Pauling (1929) first elucidated that most minerals follow
the principles that are now commonly known as Pauling’s first Because phyllosilicates maintain hexagonal or near-hexagonal sym-
rule to distinguish from his second rule regarding structure sta- metry, the structures allow various ways to stack up atomic planes,
bilization by the sum of the electrostatic strengths between an sheets, and layers, which may be explained by crystallographic
anion and adjacent cations. Thus, as far as geometry is concerned, operations such as translation or shifting and rotation, thereby
the ionic radius ratio, Rcation/Ranion, is the key factor for determin- distinguishing them from polymorphs (e.g., diamond–graphite;
ing a polyhedron suitable for an arrangement of anions around a calcite–aragonite). The former involves 1D variations but the latter
cation for a specific ionic combination. Assuming that ions act as generally 3D ones. With a fixed chemical composition, structural
rigid spheres of fixed radii, the stable arrangements of cations and varieties that are resulted from different stacking sequences are

RA
≈ 0.22–0.15
RX

A
RA
≈ 1
RX
X

(a) (c)

RA
≈ 0.41–0.22 A
RX
X
X X

(b) (d) (e)

FIGURE 21.9  Coordination number (ligancy) See Table 21.3 for further details of each crystal model. (Modified after Bloss, F.D. 1971.
Crystallography and crystal chemistry. Holt, Rinehart and Winston, Inc., New York.)
Phyllosilicates 21-5

TABLE 21.4  Radius of Cations Commonly Present termed polytypes. If such a variety is caused by ionic substitutions,
in Phyllosilicates, Radius Ratio (Rcation /RO2− ), and Predicted which are minor but consistent, they are called polytypoids.
and Observed Coordination Numbers To understand this specific feature of phyllosilicates, consider
Predicted Observed the magnesium mica, phlogopite, as an example. Its silicate layer
Radius Coordination Coordination in terms of a sequence of atom planes is given in Figure 21.10. In
Cation (nm) Rcation /RO2− Number Number the figure, TL represents the atom plane at the level of apical oxy-
gen atoms (•, solid circles) of the lower tetrahedral sheet and at
Cs+ 0.167 1.26 12 12
the same level and hydroxyl (double circles with O and •) fills the
Rb+ 0.147 1.11 12 8, 12
center of a hexagonal array made up by six apical oxygen atoms.
NH4+ 0.143 1.08 12 8, 12 In addition, the projection to the plane of basal oxygen atoms
Ba2+ 0.134 1.02 8 8, 12 (⚪, open circles) of the tetrahedral sheet is also included. OT is
K+ 0.133 1 8 8, 12 the octahedral cation plane where magnesium atoms are repre-
Sr2+ 0.112 0.84 8 8 sented by small solid circles (•). TU corresponds to the atom plane
Ca2+ 0.099 0.75 6 6, 8 of the upper tetrahedral sheet. Unlike TL , the direction of apical
Na+ 0.097 0.73 6 6, 8 oxygen atoms is opposite to that of TL . In TU, the apical oxygen
Mn2+ 0.08 0.6 6 6 atoms, hydroxyls, and the projections of the basal oxygen atoms
Fe2+ 0.074 0.56 6 6 are expressed by an open circle with shaded circle, double circles,
and solid circles, respectively. The lower tetrahedral sheet and the
V3+ 0.074 0.56 6 6
upper tetrahedral sheet having opposing vertices to each other
Zn2+ 0.074 0.56 6 6
are held together by magnesium ions. Each magnesium ion is
Cu2+ 0.072 0.54 6 6
linked to two oxygen anions and one hydroxyl from the lower
Co2+ 0.072 0.54 6 6 tetrahedral sheet and two oxygen anions and one hydroxyl from
Ni2+ 0.069 0.52 6 6 the upper sheet to make a six coordination packing. This packing
Li+ 0.068 0.51 6 6 mechanism requires that the upper tetrahedral sheet be staggered
Ti4+ 0.068 0.51 6 6 by −a/3, where a is the unit cell dimension along the a-axis, rela-
Mg2+ 0.066 0.5 6 6 tive to the lower tetrahedral sheet. The staggering between the two
Fe3+ 0.064 0.48 6 6 sheets, therefore, gives a monoclinic nature to the silicate layer,
Cr3+ 0.063 0.47 4 6 and this nature is common to all the basic silicate layers of phyl-
Al3+ 0.051 0.38 4 4, 6
losilicates. The interlayer atom plane is denoted as I, in which solid
circles represent potassium atoms. At the interlayer position, for
Si4+ 0.042 0.31 4 4
example, between two silicate layers, each interlayer potassium
P5+ 0.035 0.26 4 4
ion keys the two layers without shift by coordinating 12 basal oxy-
B3+ 0.023 0.17 3 3 gens, 6 each from lower and upper tetrahedral sheets. Although
due to the presence of interlayer potassium ions there is no shift
between the two silicate layers, the orientation of the upper one

Interlayer
cation
sheet

I
Tetrahedral
TU sheet
(upper)

OT Octahedral
cation plane
(trioctahedral)

TL

Tetrahedral
sheet
(lower)

FIGURE 21.10  Idealized sketches of mica structure (phlogopite) and its structural segments (atomic planes) at four levels. (After Kodama,
H. 1990. Use of color-coded transparencies for visualizing layer silicate structures, p. 169–175. In V.C. Farmer and Y. Tardy (eds.) Proc. 9th Int. Clay
Conf. 1989. Strasbourg. Sci. Géol., Mém. Strasbourg, France.)
21-6 Properties and Processes

can be changed with respect to the lower one. Because these basal
oxygen planes have a hexagonal or a pseudohexagonal symme-
try, there are six or three possible orientations, which are related
by n × 60° rotations, at maximum six angles: 0°, 60°, 120°, 180°,
240°, and 300°. Among them, angles 60° and 300° are equivalent,
as also are angles 120° and 240°, because the silicate layer itself has
the plane of symmetry, which is parallel to the layer stagger. Thus,
0°, 60°, 120°, and 180° rotation operations lead theoretically to six
simple- ordered-stacking mica layers, and they were depicted by
vectors from one potassium atom to a potassium atom in the next
layer in the direction of increasing height of the mica layers (Smith
and Yoder, 1956). Resulting layer structures having different layer-
stacking sequences are called polytypes. Mica polytypes derived
by them are 1M (0° rotation), 2M1 (a continuous alternation of FIGURE 21.11  Electron micrograph of chrysotile. Most of the fibrils
±120° rotation), 2M2 (a continuous alternation of ±60° rotation), appear “solid,” but a few show the appearance of hollow tubes, and a
3T (±120° rotation), 2Or (±180° rotation), and 6H (±60° rotation), few show “open ends.” (From Gard, J.A. (ed.). 1971. The electron-
as expressed in an adapted simple nomenclature. The first symbol optical investigation of clays. Monograph No 3. Mineralogical Society,
gives the number of layers in the repeat unit (subcell) and the sec- London,  U.K. Reproduced with permission of The Mineralogical
ond in italics gives the symmetry. In case of the same symmetry, Society of Great Britain and Ireland.)
the subscripts 1 and 2 are used for further distinction. Therefore,
1M, 2M, 3T, 2Or, and 6H indicate one-layer monoclinic, two-layer
monoclinic, three-layer trigonal, two-layer orthorhombic, and Mg3Si2O5(OH)4 represent the former, and kaolin minerals with
six-layer hexagonal, respectively. Similar consideration can be Al2Si2O5(OH)4 represent the latter. Among trioctahedral magne-
applied to other types of layer silicates such as T–O and T–O–T–O. sium species, chrysotile, antigorite, and lizardite are commonly
If polytypes are reported in nature, in the glossary of phyllosili- known and their morphology and structure are uniquely dif-
cates given at the end of this chapter (compiled from Blackburn ferent. (Wicks and Whittaker, 1975; Wicks and Zussman, 1975)
and Dennen, 1997, and Lalonde, 2003) a specific mineral name is Electron microscopic observations show that chrysotile crystals
given, for example, Phlogopite-1M, Kaolinite-1Tc, where the letter have a fibril appearance (Figure 21.11), but its cross sections clearly
Tc represents triclinic. The descriptions stated above are based on show cylindrical roll morphology (Figure 21.12a and b); whereas,
the ideal or nearly ideal structure. In practice, however, there are antigorite crystals exhibit lath-shape morphology (Figure 21.13a),
many factors that affect the formation of polytypes, that is, ionic
but the electron-diffraction photograph indicates an alternating
substitutions in the octahedral sheets, ionic substitutions for sili-
con atoms in the tetrahedral sheets, the degree of ordering of these wave structure as shown by the presence of segmental groups
substitutions, the vacancy distributions in the octahedral sheets, of superlattice spots (Figure 21.13b). The structure deduced by
which normally exist in the dioctahedral layer silicates or may be Kunze (1956) consists of curved layers elongated along the a-axis,
caused by the oxidation of Fe2+ to Fe3+ in the sheets. These varia- but the layers change alternately their polarity (or the direction
tions add more complexities to the form of polytypes. of apical oxygens in the tetrahedral sheets) at half a period of the
wave to make up a full periodicity of 4.35 nm, which is the dimen-
21.2.3  1:1 Layer Type (T–O Type) sion of a of antigorite (Figure 21.14). These alternating wave struc-
tural characteristics may be attributed to the degree of fit between
21.2.3.1  General the lateral dimensions of the tetrahedral and octahedral sheets.
The structure of this type is shown in Figure 21.6 (also Figure 21.8), On the other hand, lizardite crystals are platy (Figure 21.15) and
which was used for explaining the junction between tetrahedral and have often a small amount of substitution of Al or Fe3+ for both Si
octahedral sheets. A 2D tetrahedral sheet, made up by sharing three and Mg. This substitution appears to be the main reason for the
corners of each SiO4 tetrahedron, are attached to an octahedral platy nature of lizardite. Obviously, morphology is one of the key
sheet, thereby each cation in the octahedral sheet associates with characteristics to distinguish among serpentine minerals. A few
two apical oxygen atoms and four hydroxyls to make up six coor- selected chemical compositions of serpentine minerals are given
dination binding. Thus, the structure of this type of layer silicate in Table 21.5 for reference. Other than Mg, Fe2+, Ni, and Mn can
consists of tetrahedral and octahedral sheets in which the anions at occupy the octahedral sites and form species such as berthierine,
the exposed surface of the octahedral sheet are hydroxyls. General brindleyite, and kellyite. Chemical compositions of some such
structural formula may be expressed by Y2–3Si2O5(OH)4, where Y varieties are given in Table 21.6. Planar polytypes  of  the  trioc-
are cations in the octahedral sheet such as Al3+ or Fe3+ for dioctahe- tahedral species are far more complicated than those of the
dral species and Mg2+, Fe2+, Mn2+, or Ni2+ for trioctahedral species. dioctahedral ones, owing to the fact that the trioctahedral sili-
cate layer has a higher symmetry because all octahedral cationic
21.2.3.2  Serpentine–Kaolin Group sites are occupied. Polytype structures, such as one-layer trigonal
This group contains two subgroups, trioctahedral and dioc- (1T), one-layer monoclinic (1M), two-layer hexagonal (2H1, 2H2),
tahedral. Serpentine minerals with the ideal formula of two-layer  trigonal  (2T), two-layer orthorhombic (2Or), two-
layer monoclinic (2M1,  2M2), three-layer rhombohedral (3R),
Phyllosilicates 21-7

7.3 Å

C
4.5 Å
B

100 Å 100 Å

(a)   (b)

FIGURE 21.12  Electron micrographs of cross-sectioned chrysotile crystals: (a) The lattice image observed from the direction parallel to the fiber
axis. (From Gard, J.A. (ed.). 1971. The electron-optical investigation of clays. Monograph No 3. Mineralogical Society, London, U.K.) (b) Enlarged
image on crystallites A and B in micrograph (a) showing two kinds of fringe patterns, which correspond to d 001-spacing (0.73 nm) and d 020-
spacing (0.45 nm). (From Gard, J.A. (ed.). 1971. The electron-optical investigation of clays. Monograph No 3. Mineralogical Society, London, U.K.
Reproduced with permission of The Mineralogical Society of Great Britain and Ireland.)

1μ

(a) (b)

FIGURE 21.13  (a) Electron micrograph of antigorite (platy crystals), from Antigorio, Italy. (b) Electron-diffraction pattern from a single crystal
of antigorite, showing the presence of a superlattice structure along the a-axis, with a = ∼3.85 nm. (From Gard, J.A. (ed.). 1971. The electron-optical
investigation of clays. Monograph No 3. Mineralogical Society, London, U.K. Reproduced with kind permission of The Mineralogical Society of
Great Britain and Ireland.)

90°΄
β Q΄ R΄
P΄

(a) C

A
P Q R

FIGURE 21.14  Structure of antigorite as viewed along the y-axis. The curved layers (radius of curvature 7.5 nm) reverse polarity at PP′, RR′,
and near QQ′. (From Gard, J.A. (ed.). 1971. The electron-optical investigation of clays. Monograph No 3. Mineralogical Society, London, U.K.
Reproduced with kind permission of The Mineralogical Society of Great Britain and Ireland.)
21-8 Properties and Processes

1μ

(a) (b)

FIGURE 21.15  (a) Electron micrograph and (b) electron-diffraction pattern of lizardite, from Kennack, Cornwall (platy). (From Gard, J.A. (ed.).
1971. The electron-optical investigation of clays. Monograph No 3. Mineralogical Society, London, U.K. Reproduced with kind permission of The
Mineralogical Society of Great Britain and Ireland.)
TABLE 21.5  Serpentine Mineral Analyses (1)
TABLE 21.6  Serpentine Mineral Analyses (2)
1 2 3 4 5 6
1 2 3 4
SiO2 43.37 41.25 41.65 42.02 42.44 43.45
SiO2 19.08 22.03 27.45 17.6
Al2O3 0 0.54 0.1 0.52 0.64 0.81
Al2O3 26.66 22.91 24.09 28.55
TiO2 0 0.02 nr None None 0.02
TiO2 nr 3.63 0.99 <0.05
Fe2O3 0 1.32 2.88 0.19 0.19 0.88
Fe2O3 4.29 0.46 nr 2.18
FeO 0 0.09 0.16 0.11 0.03 0.69
Cr2O3 nr 0.05 0.17 nr
MnO 0 0.07 0.05 0.03 0.03 None
FeO 34.52 36.68 1.15
MgO 43.64 41.84 41.06 41.44 42.76 41.9
MnO nr 0.04 nr 38.84
CaO 0 0.02 nr None nr nr
MgO 1.55 1.91 3.18 2.97
K2O 0 nr nr 0.49 0.08 0.02
NiO nr nr 30.18 nr
Na2O 0 nr nr 0.36 0.06 0.05
CaO nr 0.07 0.07 nr
H2O+ 12.99 13.68 13.1 14.04 13.58 12.29
K2O nr 0.03 nr nr
H2O− 0 0.97 nr 1.64 0.5 nr
Na2O nr 0.08 nr nr
Total 100 99.8 100.12 99.99 100.31 100.19 H2O total 11.18
Numbers of cations on basis of O10(OH)8 H2O+ nr 10.65 nr nr
Si 4 3.92 3.94 4 3.96 3.99 H2O− nr 0.63 nr nr
Al 0 0.06 0.01 0.04 0.01 Total 99.25 100.05 87.28 90.14
Fe3+ 0 0.02 0.05
Numbers of cations on basis of O10(OH)8
Σtet 4 4 4 4 4 4
Si 2.2 3.23 3.01 1.96
Al 0 0.06 0.03 0.08 Al 1.8 0.77 0.99 2.04
Fe3+ 0 0.07 0.15 0.01 0.01 0.06 Fe3+
Fe2+ 0 0.01 0.01 0.01 0.05 Σtet 4 4 4 4
Mg 6 5.92 5.79 5.88 5.98 5.92
Al 1.84 1.95 2.12 1.72
Σoct 6 6.01 5.95 5.96 5.98 5.92
Fe3+ 0.37 0.03 0.18
Ca 0
Cr3+ 0.01
Na 0 0.01
Fe2+ 3.32 3.09 0.11
K 0 0.01
Mn 3.67
1, Ideal composition based on the structural formula, Mg3Si2O5(OH)4; Mg 0.27 0.29 0.52 0.49
2, lizardite, Transvaal, South Africa (Deer et al., 1962); 3, lizardite, Shetland Ni 2.66
Islands, United Kingdom (Brindley and von Knorring, 1954); 4, chrysotile,
Σoct 5.8 5.36 5.42 6.06
Gila County, Arizona (Faust and Fahey, 1962); 5, chrysotile, Montville,
New Jersey (Faust and Fahey, 1962); 6, antigorite, Mikonui, New Zealand 1, Berthierine (Brindley, 1982); 2, berthierine (Brindley,
(Zussman, 1954). Total includes 0.04% NiO; 0.04% H2O (—). 1982); 3, brindleyite, Marmara karstic bauxite deposits,
Analyses 2–6 are taken from Newman (1987) in which original data Greece (Bish, 1978); 4, kellyite, Bald Knob, North Carolina
for those analyses were referred from respective papers cited above. See (Peacor et al., 1974).
Newman (1987) for original source of each analysis. See Newman (1987) for original source of each analysis.
Phyllosilicates 21-9

TABLE 21.7  Kaolin Mineral Analyses TABLE 21.8  Halloysite Mineral Analyses
1 2 3 4 5 6 1 2 3
SiO2 46.55 46.9 46.77 45.2 46.43 46.22 SiO2 40.09 46.2 44.7
Al2O3 39.49 37.4 37.79 37.02 39.54 39.92 Al2O3 35.38 39.84 28.1
TiO2 0 0.18 nr 1.26 Nil 0 TiO2 nr 0.02
Fe2O3 0 0.65 0.45 0.27 0.15 0 Fe2O3 tr 0.17 12.8
FeO 0 nr 0.11 0.06 nr 0 FeO nr nr nr
MgO 0 0.27 0.24 0.47 0.17 0 MgO tr 0.02 0.1
CaO 0 0.29 0.13 0.52 Nil 0 CaO 0.77 0.34 tr
K2O 0 0.84 1.49 0.49 0.02 0 K2O tr 0.02 tr
Na2O 0 0.44 0.05 0.36 0.03 0 Na2O 0.1 0.01 1.7
H2O+ 13.96 12.95 12.18 13.27 14.2 13.86 H2O total
H2O− 0 nr 0.61 1.56 nr 0 H2O+ 15 14 13.7
Total 100 99.92 99.82 100.47 100.54 100 H2O− 8.61
Numbers of cations on basis of O10(OH)8 Total 100.51 100.62 100.7
Si 4 3.982 3.969
Numbers of cations on basis of O10(OH)8
Al 0 0.018 0.031
Si 3.907 3.957 4.029
Σtet 4 4 4
Al 0.093 0.043
Al 4 3.979 4.01 Fe3+
Fe3+ 0 0.01
Σtet 4 4 4.029
Fe2+ 0
Al 3.971 3.978 2.985
Mg 0 0.022
Ti 0.001
Σoct 4 4.011 4.01
Fe3+ 0.011 0.868
1, Ideal composition based on the structural formula, Al2Si2O5(OH)4; Mg 0.003 0.013
2,  kaolinite, Zettlitz, Czechoslovakia; 3, kaolinite, St. Austell, England; Σoct 3.971 3.993 3.866
4, kaolinite, Macon, Georgia; 5, dickite, Barkly East, Cape Province, South
Africa; 6, nacrite, Eureka Tunnel, St. Peter’s Dome, Colorado. Ca 0.08 0.031 0
Analyses 1, 5, and 6 are taken from Newman (1987) in which original data K 0 0.002 0
for analyses 5 and 6 (recalculated after subtracting impurity) were referred Na 0.019 0.002 0.297
from Schmidt and Heckroodt (1959) and Blount et al. (1969), respectively.
Analyses 2, 3, and 4 are taken from Grim (1968) in which original data for 1, Hydrated halloysite (halloysite—1 nm), Wagon
the analysis 2 is referred from Ross and Kerr (1931) and analyses 3 and 4 Wheel Gap, Colorado (Larsen and Wherry, 1917); 2,
from Kerr et al. (1950). For these references, see Grim (1968). halloysite (halloysite—0.7 nm), Djebel Debar, Morocco
(Garrett and Walker, 1959); 3, iron-rich hydrated hal-
three-layer trigonal (3T), six-layer hexagonal (6H), and six-layer loysite, Hokkaido, Japan (Wada and Mizota, 1982).
rhombohedral (6R) are reported (Bailey, 1969, 1980, 1988). See Newman (1987) for original data.
For the dioctahedral subgroup, kaolin minerals include kaolin-
ite (one-layer triclinic, 1Tc), dickite (two-layer monoclinic, 2M),
and nacrite (two-layer monoclinic, 2M), which are in polytypic
relation. Examples of the chemical composition of kaolin minerals
are given in Table 21.7. Kaolinite has triclinic symmetry. Oxygen
atoms and hydroxyl ions between the layers are paired with hydro-
gen bonding. Because of this weak bonding, random displacements
between the layers are quite common and result in a poor symme-
try rather than distinctive triclinic kaolinite. Dickite and nacrite
are polytypic varieties of kaolinite. Both of them consist of a double
1:1 layer and have monoclinic symmetry but distinguish them-
selves by different stacking sequences of the two 1:1 silicate layers.

21.2.3.3  Halloysite—Hydrated Halloysite Group

Halloysite has a composition close to that of kaolinite (Table 21.8)
and is characterized by its tubular nature (see Figure 21.27) in 1μ
contrast to the platy nature of kaolinite particles. Although tubu-
lar forms are the most common, other morphological varieties FIGURE 21.16  Electron micrograph of halloysite (with spherical
are also known: prismatic, rolled, pseudospherical (Figure 21.16), structure), altered from glassy tuff. (From Sudo, T. 1959. Mineralogical
and platy forms. The structure of halloysite is believed to be study on clays of Japan. Maruzen Co. Ltd., Tokyo, Japan.)
21-10 Properties and Processes

similar to that of kaolinite, but no precise structure has been TABLE 21.9  Talc and Pyrophyllite Analyses
revealed yet. Halloysite has a hydrated form with composition 1 2 3 4 5 6
of Al2Si2O5(OH)4 · 2H2O. This hydrated form irreversibly changes
SiO2 63.37 62.67 63.9 63.57 66.04 66.7
to a dehydrated variety at relatively low temperatures (60°C) or
Al2O3 tr 0.03 29.25 28.15 28.3
upon being exposed to conditions of low relative humidity. The
TiO2 nr 0.1 0.04 nr
dehydrated form has a basal spacing about the thickness of a
Fe2O3 nr 0.21 0.1 0.64
kaolinite layer (approximately 0.72 nm), and the hydrated form
FeO 2.46 nr 0.12 nr
has a basal spacing of about 1.01 nm, the difference of 0.29 nm
MnO 0.01 nr None nr
is approximately the thickness of one molecular layer of water.
MgO 31.88 30.22 31.49 0.37 0.04
Consequently, in the hydrated form of halloysite, its silicate lay-
CaO nr 0.08 0.38 0.01
ers are separated by monomolecular water layers that are lost
K2O nr 0.01 0.02 nr
during dehydration.
Na2O nr 0.02 tr 0.04
H2O+ 4.75 4.72 4.86 5.66 5.27 5
21.2.4  2:1 Layer Type (T–O–T Type) H2O− 0.66
Total 100 100.02 100.7 100.17 100.19 100
21.2.4.1  General
Numbers of cations on basis of O10(OH)2
As seen in Figure 21.8b, the unit silicate layer of T–O–T type Si 4 3.99 4.01 3.89 3.975 4
comprises one octahedral sheet sandwiched by two tetrahedral Al 0 0.11 0.025
sheets, which are oriented in opposite directions and may be Fe3+ 0
termed a 2:1 layer type. A majority of phyllosilicates hold a back- Σtet 4 3.99 4.01 4 4 4
bone of this type for their structures. This type includes talc,
Al 0 1.99 1.975 2
pyrophyllite, micas, brittle micas, vermiculite, and smectite.
Fe3+ 0 0.01 0.005 0.03
Fe2+ 0 0.13 0.005
21.2.4.2  Talc–Pyrophyllite Group
Mg 3 2.87 2.94 0.035 0.005
Minerals of this group have the simplest form of 2:1 layer with
Σoct 3 3 2.95 2.036 2.01 2
its unit thickness of approximately 0.92–0.96 nm—that is, the
Ca 0 0.005 0.025
structure consists of an octahedral sheet sandwiched by two
Na 0 0.005
tetrahedral sheets. Talc and pyrophyllite represent the triocta-
K 0
hedral and dioctahedral members, respectively, of the group.
In the ideal case, the structural formula of talc is expressed by 1, Ideal composition, Mg3Si4O10(OH)2; 2, talc, Muruhatten, Northern
Sweden (Du Rietz, 1935); 3, talc, Manchuria (Brindley et al., 1977);
Mg3Si4O10(OH)2 and pyrophyllite by Al2Si4O10(OH)2. Selected
4, pyrophyllite, pale blue, Honami mine, Nagano Prefecture, Japan (Iwao
analyses are given in Table 21.9. Figure 21.17 shows these two and Udagawa, 1969); 5, pyrophyllite, Ibitiara Bahia, Brazil (Lee and
structures as an extended crystal model, where the staggering Guggenheim, 1981); 6, ideal composition, Al2Si4O10(OH)2.
between tetrahedral sheets above and below and the difference Analysis 2 is referred from Deer et al. (1962). Analyses 3, 4, and 5 are
in octahedral sheets between talc and pyrophyllite is clearly taken from Newman (1987). See Newman (1987) for original source of
each analysis except analyses 1 and 2.
seen. Each 2:1 layer of these minerals is electrostatically neutral;
therefore, van der Waals forces hold the silicate layers together. in this case, which has an ideal formula of NaAl2(Si3Al)O10(OH)2.
One-layer triclinic and two-layer monoclinic forms are known Various polytypes of the micas are known to occur. Among them
for polytypes of pyrophyllite and talc. The ferric iron analog of one-layer monoclinic (1M), two-layer monoclinic (2M including
pyrophyllite is called ferripyrophyllite. 2M1 and 2M2), and three-layer trigonal (3T) polytypes are the
most common. The majority of clay-size micas are dioctahedral
21.2.4.3  True Mica Group aluminous species; those similar to muscovite are called illite
Mica has a basic structural unit of 2:1 layer type, like pyrophyl- (Bailey et al., 1984). The illites are different from muscovite in
lite or talc, but some of the silicon atoms (ideally one-fourth) that the amount of substitution of aluminum for silicon is less,
are always replaced by aluminum atoms. This results in a charge sometimes only one-sixth of the silicon ions are replaced. This
deficiency that is balanced by potassium ions between the reduces a net unbalanced charge deficiency from 1 to about 0.65
unit layers (Figure 21.18). The sheet thickness (basal spacing per chemical formula unit. As a result, the illites have a higher
or dimension along the direction normal to the basal plane) is silica-to-alumina molecular ratio and lower potassium content
fixed at about 1 nm. Typical examples are muscovite, KAl2(Si3Al) than the muscovites (Graf von Reichenbach and Rich, 1975;
O10(OH)2 for dioctahedral species and phlogopite, KMg3(Si3Al) Fanning et al., 1989). To some extent, octahedral aluminum ions
O10(OH)2, and biotite, K(Mg,Fe)3(Si3Al)O10(OH)2, for trioctahe- are replaced by magnesium (Mg2+) and iron ions (Fe2+, Fe3+).
dral species. Formulas rendered may vary slightly due to pos- In the illites, stacking disorders of the layers are common, but
sible substitution within certain structural sites. The interlayer their polytypes are often unidentifiable. Celadonite and glauco-
cation can be sodium instead of potassium, notably paragonite nite are ferric ion-rich species of dioctahedral micas. The ideal
Phyllosilicates 21-11

(a) (b)

FIGURE 21.17  Extended crystal structure models of (a) talc and (b) pyrophyllite.

OH

OH

OH

Oxygens OH Hydroxyls Aluminum Potassium

And Silicons (one-fourth replaced by aluminums)

FIGURE 21.18  The structure of muscovite. (From Grim, R.E. 1968. Clay mineralogy. McGraw-Hill Book Co. Inc., New York. With permission.)

composition of celadonite may be expressed by K(Mg,Fe3+) micas (Table 21.12) are given for reference. Comprehensive reviews
(Si4−xAl x)O10(OH)2, where x = 0–0.2. Glauconite is a dioctahedral on true micas are available (Bailey, 1984; Fleet, 2003).
mica species with tetrahedral Al substitution greater than 0.2
and octahedral Fe3+ or R3+ (total trivalent cations) greater than 21.2.4.4  Brittle Mica Group
1.2. Unlike illite, a layer charge deficiency of celadonite and glau- Brittle micas are distinguished from true micas in having a layer
conite arises largely from the unbalanced charge due to ionic charge of ∼2.0 per formula unit, which arises entirely within
substitution in the octahedral sheets. Some chemical analyses of the tetrahedral sheet or partly within the tetrahedral sheet and
dioctahedral micas (Tables 21.10 and 21.11) and of trioctahedral partly octahedral sheet. The tetrahedral composition varies
21-12 Properties and Processes

TABLE 21.10  Dioctahedral Mica Analyses (1)

1 2 3 4 5 6 7 8
SiO2 45.26 45.87 45.24 42.63 44.94 48.42 51.19 55.61
Al2O3 38.4 38.69 36.85 20.87 27.56 27.16 9.23 0.79
TiO2 0.01 0.45 0.98 0.87 0.13
Cr2O3 0.24 4.75
V2O3 13.72
Fe2O3 0.09 6.57 18.15 17.19
FeO 0 0.02 3.76 1.07 0.81 1.78 4.02
MnO 0 0.12 0.23 0 0.01 0.09
MgO 0.1 0.08 2.34 2.34 0 3.34 7.26
CaO 0 0.01 0 0 0.58 0.21
BaO 0.95 6.42 0.07
K2O 11.82 10.08 10.08 10.16 7.44 11.23 7.98 10.03
Na2O 0.64 0.64 0.06 0.27 0.35 0.02 0.19
Cs2O 0.2
Rb2O 0.93 0.19
Li2O 0.49
F 0.91
Cl
H2O+ 4.52 4.67 4.12 4.31 5.21 4.88
H2O− 0.7 0.09 0.19 1.95
OΞF,Cl 100 100.05 100.24 95.21 95.77 100.17 99.67 100.27
−0.38
Total 100 100.05 99.86 95.21 95.77 100.17 99.67 100.27
Numbers of cations on basis of O10(OH)2
Si 3 3.009 3.024 3.061 3.136 3.297 3.71 3.995
Al 1 0.991 0.976 0.939 0.864 0.703 0.29 0.005
Fe3+ 0
Σtet 4 4 4 4 4 4 4 4
Al 2 2.001 1.927 0.827 1.403 1.477 0.505 0.065
Cr 0.262 0.045
Fe3+ 0 0.005 0.005 0.337 0.99 0.93
Fe2+ 0 0 0.001 0.226 0.062 0.046 0.24
Mg 0 0.01 0.008 0.25 0.243 0.36 0.775
Li 0.132 1.06
Other M 0.008 0.051
Σoct 2 2.011 2.081 2.132 2.021 1.905 1.965 2.015
Ca 0 0.005 0.001 0.045 0.015
Ba 0.027 0.176 0.002
Na 0 0.081 0.008 0.037 0.046 0.005 0.025
Rb 0.008
K 1 0.844 0.931 0.662 0.976 0.735 0.92
ΣInt 0.925 0.875 1.032 0.785 0.965
1, Ideal muscovite composition, KAl2(Si3Al)O10(OH)2; 2, muscovite, Methuen Township, Ontario
(Hurlbut, 1956); 3, muscovite (rose), Rociada, New Mexico (Heinrich and Levinson, 1953); 4, muscovite
(vanadian), Hemlo gold deposit, Ontario (Pan and Fleet, 1992); 5, muscovite (barian–chromian), Hemlo-
Heron Bay (Pan and Fleet, 1991); 6, phengite (high-silica muscovite), Morar, Inverness-shire (Lambert,
1959); 7, glauconite, Praha-Prosek (Cimbalnikova, 1971); 8, celadonite, Reno, Nevada (Hendricks and
Ross, 1941).
Analyses 2–6 are taken from Fleet (2003). Analyses 7 and 8 are from Newman 1987 and recalculated.
See Fleet (2003) or Newman (1987) for original source of each analysis.
Phyllosilicates 21-13

TABLE 21.11  Dioctahedral Mica Analyses (2) from SiAl3 to nearly Si3Al and this is supplemented by octahe-
1 2 3 dral sheet charges that range from +1.0 to 0 to nearly −1.0. As the
layer charge is higher than that of true micas, divalent interlayer
SiO2 48.34 41.79 38.54
cations are required for compensation, instead of monovalent.
Al2O3 37.87 18.98 25.61
Clintonite is a trioctahedral species of ideal composition,
TiO2 0.3 0.21 0
Ca(Mg2Al)(SiAl3)O10(OH)2. Because high Al content in the tetra-
Cr2O3 0.29
hedral sheet and Al atomic radius size is larger than Si, the hex-
V2O3 17.55
agonal symmetry of the tetrahedral sheet is modified to ditrigonal
Fe2O3 1.02
(Figure 21.4b) by a tetrahedral rotation of 23° to match the lateral
FeO 1.15 2.44
dimensions of the octahedral sheet. The reported polytypes are
MnO 0.08 0.07
1M, 2M1, and 3T. Margarite is a known sole dioctahedral species
MgO 0.11 2.18 1.78
in the brittle mica group, having ideal composition CaAl2(Si2Al2)
CaO 0 0 0.01
O10(OH)2, and with a 2M1 structure. Other species belonging to
BaO 3.29
the group include kinoshitalite (1M and 2M1), with ideal formula
K2O 3.25 9.76 0.53
Na2O 0 0.16
BaMg3(Si2Al2)O10(OH)2; anandite (2Or), with Ba(Fe,Mg)3(Si3Fe3+)
Cs2O 25.29
O10(OH)S; and bityite (2M1), with BaLiAl2(Si2AlBe)O10(OH)2.
Rb2O 0.25
Polytypes in brackets are only of high abundance. Analyses of
Li2O 0.44
representative brittle micas are given in Table 21.13.
NH4 3.85
F 1 21.2.4.5  Vermiculite Group
H2O+ 4.96 3.27
The vermiculite unit structure consists of talc-like 2:1 silicate lay-
H2O− 0.31
ers separated by two molecular layers of water (approximately
OΞF,Cl 100.01 95.44 99.23 0.48 nm thick). Substitutions of aluminum (Al3+) for silicon (Si4+)
0 0 −0.42 in tetrahedral sheets constitute the chief charge imbalance, but
Total 100.01 95.44 98.81 the net-charge deficiency may be partially balanced by other
Numbers of cations on basis of O10(OH)2 substitutions within the 2:1 silicate layer; but a residual net-
Si 3.078 3.047 3.161 charge deficiency always exists, commonly in the range 0.6–0.8
Al 0.922 0.953 0.839 per O10(OH)2. This charge deficiency is satisfied with interlayer
Fe3+ cations, which are closely associated with the water molecules
Σtet 4 4 4 between the silicate layers (Figure 21.19); Mathieson and Walker,
1954. As the net-charge deficiency is higher than smectites, in ver-
Al 1.92 0.679 1.637
miculites interlayer water molecules are better coordinated with
Ti 0.014 0.012
interlayer cations. In macroscopic vermiculites of hydrothermal
Cr 0.017
origin, unlike those in soils, the balancing cation is mostly mag-
V 1.026
nesium (Mg2+), sometimes associated with a small amount of
Fe3+ 0.049
calcium (Ca2+). The interlayer cation, however, is readily replaced
Fe2+ 0.07 0.167
by other inorganic and organic cations. A number of water mol-
Mn 0.005 0.005
ecules are related to the hydration state of cations located at
Mg 0.01 0.237 0.218
the interlayer sites. Therefore, the basal spacing of vermiculite
Li 0.145
changes from about 1.05 to 1.57 nm, depending upon its crystal
Other M size, relative humidity, and the kind of interlayer cation. If potas-
Σoct 1.993 2.046 2.172 sium or ammonium ions are not present in the interlayer sites, in
Ca 0.001 some extreme cases, heating vermiculite to temperatures as high
Na 0.081 as 500°C drives the water out from between the silicate layers, but
K 0.264 0.844 0.055 the mineral quickly rehydrates at room temperature to maintain
Rb 0.013 its normal basal spacing of approximately 1.4–1.5 nm. Special
Cs 0.885 care would, therefore, be required to examine the dehydration–­
NH4 0.566 rehydration temperature of a vermiculite mineral in question.
ΣInt 0.83 0.925 0.954 If complete and irreversible dehydration occurs, the basal
1, Tobelite, Horo deposit, Toyosaka Hiroshima Prefecture, spacing becomes 0.902 nm. Figure 21.20 illustrates various
Japan (Higashi, 1982); 2, roscoelite, Hemlo gold deposit, hydration states of vermiculite. Note, however, that these states
Ontario, Canada (Pan and Fleet, 1992); 3, nanpingite, are affected by crystal size of the sample. Some dioctahedral
Nanping pegmatite field, Fujian, China (Yang et al., 1988). analogs of vermiculite have also been reported to occur in soils
Analyses 1, 2, and 3 are taken from Fleet (2003). See Fleet
(2003) for original source of data.
(Brown, 1953).
21-14 Properties and Processes

TABLE 21.12  Trioctahedral Mica Analyses

1 2 3 4 5 6 7 8
SiO2 43.21 42.98 39.17 36.05 33.96 35.21 50.31 45.51
Al2O3 12.2 12.9 11.24 14.2 13.1 9.96 19.95 20.59
TiO2 0.33 2.23 4.38 3.55 0.87 0.22 0.24
Fe2O3 0.91 1.86 6.24 3.06 6.57 0.49 1.51
FeO 2.7 16.58 13.35 32.04 42.11 2.55 9.2
MnO 0.08 0.89 0.23 0.65 2.63 0.53
MgO 28.99 25.93 13.51 12.23 0.97 0.02 0.3
CaO 0.06 0.2 0.42 0 0.27
BaO 0.05
K2O 11.29 10.63 9.29 9.36 8.47 9.2 10.14 9.68
Na2O 0.25 0.62 0.14 0.27 0.49 0.6
Cs2O 0.06
Rb2O 0.97
Li2O 0.18 0.02 5.39 3.66
F 6.04 3.46 0.82 7.65 7.45
Cl 0.41 0.34
H2O+ 4.31 1.7 1.64 3.21 2.5 3.52 0.88 1.9
H2O− 0.7 0.09 0.66 1.21
OΞF,Cl 100 105.21 101.28 100 100.37 100 102.41 102.65
0 −2.54 −1.48 −0.09 −0.43 −3.22 −3.14
Total 100 100.67 99.8 99.91 99.95 100 99.19 99.51
Numbers of cations on basis of O10(OH)2
Si 3 2.985 3.024 2.742 2.812 3.297 3.71 3.285
Al 1 1.015 0.976 1.258 1.188 0.703 0.29 0.715
Fe3+ 0
Σtet 4 4 4 4 4 4 4 4
Al 2 0.04 1.927 0.015 0.091 1.477 0.505 1.035
Cr 0.045
Fe3+ 0 0.05 0.005 0.357 0.191 0.337 0.99 0.08
Fe2+ 0 0.155 0.001 0.861 2.219 0.046 0.555
Mg 0 2.685 0.008 1.387 0.12 0.36 0.03
Li 0.132 0.006 1.06
Other M 0.02 0.008 0.051
Σoct 2 2.95 2.081 2.892 2.888 1.905 1.965 2.81
Ca 0 0.005 0.005 0.037 0.045 0.02
Ba 0.027 0.002
Na 0 0.035 0.021 0.079 0.046 0.005 0.085
Rb 0.008
K 1 0.94 0.908 0.895 0.976 0.735 0.89
ΣInt 0.98 0.929 1.011 1.032 0.785 0.995
1, Ideal phlogopite composition, KMg3(Si3Al)O10(OH)2; 2, phlogopite, Ontario (Newman, 1987);
3, biotite, North Burgers, Ontario (Rausell Colom et al., 1965): Total includes 0.12% Cl and 0.05%
Rb2O; 4, biotite, Valle Vercelli, Northwestern Italy (Brigatti and Davoli, 1990); 5, annite, Pikes Peak
granite, Colorado (Hazen and Burnham, 1973); 6, ideal annite composition KFe23+ (Si 3 Al)O10 (OH)2 ;
7, lepidolite, Wakefield, Quebec, Canada (Steven, 1938; Backhaus, 1983); 8, zinnwaldite, Cinovec,
Czechoslovakia (Rieder, 1970).
Analyses 2, 3, and 8 are taken from Newman 1987. Analyses 4, 5, and 7 are from Fleet (2003). See
Newman (1987) or Fleet (2003) for original source of each analysis.
Phyllosilicates 21-15

TABLE 21.13  Brittle Mica Analyses

1 2 3 4 5 6
SiO2 15.84 24.58 30.34 29.9 24.59 33.37
Al2O3 44 20.06 49.8 25.9 0.8 36.51
TiO2 nr 0.16 0.12 0.08
V2O4 5.4 1.14 Å
V2O3 18.3
Fe2O3 2.04 0.71 0.35 0.4 21.15 2.76 Å
FeO nr 0.04 0.51 22.7 0.55 Å
c/2 1.67 Å
BeO 7.3
Mn2O3 3.24 (a) 1.06 Å
MnO nr 7.38 0.01 0.92 σ
MgO 20.33 16.6 0.59 1.6 2.89 0.04 Unfilled Mg2+ sites
CaO 13.01 0.05 11.43 0.01 14.42 Filled Mg2+ sites
BaO 17.85 9.35 23.05
Li2O 0.28 2.39 Unfilled sites
K2O 0.19 3.3 0.27 0.7 0.24 0.04 Upper H2O sheet
Filled sites
Na2O 0.26 0.68 1.95 1.32 0.06 0.29
F 0.21
H2O+ 4.56 2.9 4.65 6 5.27 5.72 Unfilled sites
H2O− 0.2 1.1 Lower H2O sheet
Filled sites
OΞF −0.09

Total 100.23 99.87 100.3 99.97 99.38 99.98

Numbers of cations on basis of O10(OH)2 (b)
Si 1.108 2.052 2.012 2.192 2.507
Al 2.892 1.948 1.988 1.808 0.096
Fe3+ 0 1.397 O2,3
Σtet 4 4 4 4 4 Si, Al
Al 0.734 0.222 1.903 0.431 O1
Ti 0.01 0.006 0.006 b Mg, Fe, Al
V4+ 0.287
V3+ 1.076
(c) a
Fe3+ 0.107 0.045 0.017 0.022 0.225
Fe2+ 0 0.003 0.028 1.935 FIGURE 21.19  The crystal structure of Mg-vermiculite; (a) projection
Mn3+ 0.206 0.037 normal to ac plane, (b) projection normal to ab plane, showing inter-
Mn2+ 0.522 0.001 0.042 layer region, and (c) projection normal to ab plane, showing one-half of
Mg 2.119 2.066 0.058 0.175 0.439 a silicate layer (z = 0 to c/8). (From Brown, G. (ed.). 1961. The X-ray iden-
Li 0.075 tification and crystal structures of clay minerals. Mineralogical Society,
Σoct 2.96 3.074 2.088 1.991 2.684 London, U.K. Reproduced with kind permission of The Mineralogical
Society of Great Britain and Ireland.)
Ca 0.975 0.004 0.812
Ba 0.584 0.269 0.921
Na 0.035 0.11 0.251 0.188 0.012 21.2.4.6  Smectite Group
K 0.017 0.351 0.023 0.065 0.031 The structural units of smectite (Figure 21.21) can be derived from
Σint 1.027 1.029 1.086 0.522 0.964 the structures of pyrophyllite and talc. Unlike pyrophyllite and talc,
1, Clintonite, Zlatoust, Shishim Mts., Ural, Russia (Forman et al., 1967); the 2:1 silicate layers of smectite have a slight negative charge owing
2, kinoshitalite, Nodatamagawa mine, Japan (Yoshii et al., 1973); 3, margarite, to ionic substitutions in the octahedral and tetrahedral sheets. The
Chester, Massachusetts (Storre and Nitsch, 1974); 4, chernykhite, Karatau net-charge deficiency is normally smaller than that of vermicu-
Mts., Kazakhstan (Ankinovich et al., 1972); 5, anandite, Wilagedera, Sri
lite from ∼0.2 to 0.6 per O10(OH)2 and balanced by the interlayer
Lanka (Filut et al., 1985); 6, bityite, Londonderry, Australia (Anthony et al.,
1995). cations as in vermiculite (Table 21.14). This weak bond offers an
Bityite: ideally CaLiAl2(AlBeSi2)O10(OH)2. Analyses 1–5 are taken from excellent cleavage between the layers. The distinguishing feature of
Fleet (2003). See Fleet (2003) for original source of each analysis. the smectite structure from the other types is that water and other
21-16 Properties and Processes

(a) (b) (c) (d) (e)

FIGURE 21.20  Various hydration states of Mg-vermiculite. Projections normal to the ac plane in the mineral at the various stages of hydration,
showing the silicate layer relationships: (a) 1.481 nm phase, (b) 1.436 nm phase, (c) 1.382 nm phase, (d) 1.159 nm phase, and (e) 0.902 nm phase (key
as for Figure 21.19). (From Brown, G. (ed.). 1961. The X-ray identification and crystal structures of clay minerals. Mineralogical Society, London,
U.K. Reproduced with kind permission of The Mineralogical Society of Great Britain and Ireland.)

OH

OH

OH

Exchangeable cation
nH2O

Oxygen OH Hydroxyl
Aluminum, iron, magnesium

Silicon, occasionally aluminum

FIGURE 21.21  The structure of smectite. (From Grim, R.E. 1968. Clay mineralogy. McGraw-Hill Book Co. Inc., New York. With permission.)

polar molecules (in the form of certain organic substances) can, by (OH)2 . nH2O, with 0.2 ≤ x + y ≤ 0.6, where M+ is the interlayer
entering between the unit layers, cause the structure to expand in exchangeable cation expressed as a monovalent cation and x and
the direction normal to the basal plane. Thus, this dimension may y are the amounts of tetrahedral and octahedral substitutions,
vary from about 0.96 nm, when no polar molecules are between the respectively. The smectites with y > x are called montmorillonite
unit layers, to nearly complete separation of the individual layers. and those with x > y are known as beidellite. In the latter type of
The structural formula of dioctahedral aluminous smec- smectites, those in which ferric iron is a dominant cation in the
tites may be represented by M x + y + (Al 2 − y Mg y 2 + )(Si 4 − x Al x ) O10 octahedral sheet instead of aluminum and magnesium are called
Phyllosilicates 21-17

TABLE 21.14  Smectite and Vermiculite Analyses

1 2 3 4 5 6 7 8
SiO2 59.6 66.32 59.3 42.4 53.88 51.4 45.56 43.07
Al2O3 22.17 22.42 36.11 5.6 4.47 9 15.82 16.92
TiO2 0.09 0.25 0.38 0.68
Fe2O3 4.32 3.3 0.5 32.53 0.6 5.4 1.4 11.75
FeO 4.8 0.95
MnO Tr 0.13 0.36
MgO 2.73 4.07 0.1 0.32 31.61 26.1 29.66 22.63
CaO 0.14 0.03 0.02 0.38 0.01 3.2 6.86 4.66
K2O 0.03 0.06 0.11 5.14 0.05 0.12 0.17 0.03
Na2O 3.18 3.68 3.98 0.01 0.04 0.06
H2O+ 6.02 9.28
Total H2O 14.03
Total 100.17 99.88 100.12 100.02 100.15 100 99.98 101.11
Numbers of cations on basis of O20(OH)4
Si 7.68 7.86 6.97 6.91 7.23 6.6 5.79 5.57
Al 0.32 0.14 1.03 0.77 0.71 1.36 2.21 2.43
Fe3+ 0 0.32 0.06 0.04
Σtet 8 8 8 8 8 8 8 8
Al 3.05 2.99 3.98 0.29 0.16 0.14
Ti 0.04 0.07
Fe3+ 0.42 0.04 3.67 0.03 0.48 0.13 1.14
Fe2+ 0 0.29 0.52 0.1
Mn 0.01 0.04
Mg 0.52 0.72 0.02 0.04 5.97 5 5.62 4.36
Σoct 4 4 4.04 4 6 6 5.96 5.85
Ca 0.02 0.025 0.44 0.93 0.65
Mg 0.35
Na 0.8 0.85 0.91 0 0.01
K 0 0.01 0.02 1.13 0.01 0.02 0.03 0.02
ΣInter. charge 0.84 0.86 0.93 1.13 0.71 0.91 1.89 1.32
1, Montmorillonite, Clay Spur, Wyoming: Total includes 0.02% P2O5; 2, montmorillonite, Camp
Berteau, France, ignited weight basis (Weir, 1965); 3, beidellite, Black Jack Mine, Owyhee County,
Idaho (Weir, 1965); 4, nontronite, Garfield, Washington (Besson et al., 1983); 5, saponite,
Krugersdorp, Transvaal, South Africa (Schmidt and Heystek, 1953); 6, saponite, Kozakov,
Czechoslovakia (Suquet et al., 1975); 7, vermiculite, Llano County, Texas; 8, vermiculite, Ypung
River, Western Australia.
See Newman (1987) for original source of each analysis.

nontronite or ferruginous smectite. Although less frequent, similar amounts of net-charge deficiency as those of other smec-
chromium (Cr3+) and vanadium (V3+) also are found as domi- tites. Typical examples are (Mg3−y□y) for stevensite and (Mg3−yLiy)
nant cations in the octahedral sheets of the beidellite structure; for hectorite, respectively, where □ denotes a vacancy site in the
in the case of chromium, the mineral is named volkonskoite. structure. In stevensite, therefore, y sites out of three are vacant.
The ideal structural formula of trioctahedral ferromagnesian The structure of smectites described above is based on their
smectites, the series saponite through iron-saponite, is given by ideal model. Their actual structures are more or less distorted and
M +x(Mg,Fe2+)3(Si4−xAlx)O10(OH)2 · nH2O. Tetrahedral substitution is show different physical appearances due to various circumstances.
responsible for the net-charge deficiency in the smectite minerals of Electron optical diffraction examinations are most effective for
this series. Besides magnesium and ferrous iron, zinc, cobalt, and their characterization. According to the accounts of Méring and
manganese are known to be dominant cations in the octahedral his colleagues (Méring and Brindley, 1967; Méring and Oberlin,
sheet. Zinc-dominant species are called sauconite. In other types 1967, 1971; Méring, 1975), three types of layer-stacking arrange-
of trioctahedral smectites, the net-charge deficiency arises largely ment have been observed and classified. Particles of smectites
from ionic substitution or a small number of cation vacancies in the are composed of a stacking of elementary layers, in which on
octahedral sheets, or from both. Ideally x is 0, but most often it is the average 10–20 elementary layers are stacked together, and
less than 0.15. Thus, the octahedral composition varies to maintain their arrangements are ordered, semiordered, or turbostratic.
21-18 Properties and Processes

The ordered arrangement should give a clear hexagonal net (spots) (Fe52 + Al)(Si 3Al)O10 (OH)8 (chamosite)
pattern by the electron microdiffraction diagram. In semiordered
arrangement, the mutual orientation of the elementary layers is (Mn5Al)(Si 3Al)O10 (OH)8 (pennantite)
defined by arbitrary multiples of 60°. Therefore, the stacking is no
longer a triperiodic crystal but maintains “hexagonal” symmetry.
(Ni 5Al)(Si 3Al)O10 (OH)8 (nimite)
If disorientation is defined by rotations about the c*-axis (normal
to the basal plane of smectites), layer stacking is called turbostratic. The unbalanced charge of the silicate layer is compensated by an
With the disorientation, diffraction spots of hk become diffuse excess charge on the hydroxide sheet caused by the substitution of
and elongated, and the extent of those effects are related to the trivalent cations (Al3+, Fe3+, etc.) for divalent cations (Mg2+, Fe2+,
degree of disorientation. Turbostratic arrangements are unique to etc.). Chlorites, with an aluminous dioctahedral silicate layer and
smectite minerals and no other phyllosilicates with such structure an aluminum hydroxide sheet are called donbassite and have the
are known. Typically montmorillonite, hectorite, and nontronite ideal formula of Al4.33(Si3Al)O10(OH)8 as an end-member for the
show turbostratic structure. Beidellite and saponite are, on dioctahedral chlorite. However, in many cases, the octahedral
the other hand, known to possess relatively ordered structures. Al ions are partially replaced by magnesium, as in magnesium-
rich aluminum dioctahedral chlorites, which are called sudoite.
21.2.5  2:1:1 Layer Type (T–O–T–O Type) Cookeite is another type of dioctahedral chlorite, in which lithium
21.2.5.1  Chlorite Group (Li) substitutes for aluminum in the octahedral sheets. Selected
chemical analyses are listed in Table 21.15. The symmetry of chlo-
The structure of the chlorite minerals consists of alternate mica-
rite structures is variable due to the kind and amount of substitu-
like layers and brucite-like hydroxide sheets about 1.4 nm thick
tions within the hydroxide sheet and within the tetrahedral and
(Figure 21.22). Structural formulas of most trioctahedral chlo-
octahedral sites of the 2:1 silicate layer, the orientation of successive
rites may be expressed by four end-member compositions:
octahedral and tetrahedral sheets, and the way of the stacking of
(Mg 5Al)(Si 3Al)O10 (OH)8 (clinochlore) successive chlorite units. Specifically, as the chlorite unit contains
hydroxide layers, the way of stacking between the basal oxygen
atoms of the tetrahedral sheet and the hydroxyls in the first atomic
plane of the hydroxide sheet is unique for chlorite. According to
Shirozu and Bailey (1965), among six possible polytypes four are
known to naturally occur and they are denoted as Ia, Ib (β = 97°),
Ib (β = 90°), and IIb, respectively. Type I and Type II are distin-
guished by a difference in the shifting direction of the silicate layer
OH with respect to that of the successive hydroxide sheet. Designation
a indicates the case in which two-thirds of cations in the hydroxide
sheet locate above tetrahedral cations and the remaining octahedral
OH
cations occupy at the center of the hexagonal rings, whereas desig-
OH nation b is the case in which cations of the hydroxide sheet distrib-
ute symmetrically upon projecting them onto the hexagonal ring.
An overwhelmingly common polytype in nature is the single-layer
monoclinic structure designated as IIb. A majority of trioctahedral
chlorites including sudoite takes this polytype, while Ib (β = 97°)
OH
OH
OH
OH OH and Ib (β = 90°) polytypes are abundant in iron-rich chlorites. The
OH OH
OH
Ia polytype is often realized in cookeite and donbassite. Chlorite
structures are relatively thermally stable compared to kaolinite,
OH OH OH vermiculite, and smectite minerals. Due to this, the presence of the
OH OH OH
OH OH XRD peak at 1.4 nm after heat treatment at 500°C–700°C is widely
used for the identification of chlorite minerals.

21.2.6  Interstratified Layer Silicate Group

(Mixed-Layer Type)
As seen from the foregoing discussion, structures of phyllo-
silicates are strikingly similar except for sheet sequence such as
Oxygen OH Hydroxyl Silicon T–O and T–O–T and layer thickness. Because of similarity as
such, nature finds that a layer silicate of one kind interstratifies
FIGURE 21.22  The structure of chlorite. (From Grim, R.E. 1968. Clay with that of another kind to make up a new structure that differs
mineralogy. McGraw-Hill Book Co. Inc., New York. With permission.) from either component layer.
Phyllosilicates 21-19

TABLE 21.15  Chlorite Analyses

1 2 3 4 5 6 7 8
SiO2 33.83 26.65 21.29 27.27 33 33.31 35.36 34.4
Al2O3 12.95 16.14 19.07 15.21 35.69 44.16 47.35 51.85
TiO2 tr
Fe2O3 2.25 6.69 6.67 2.74 1.72 0.52
FeO 3.02 34.43 2.78 0.24 1.69 0.07
MnO 0 0.07 39.82 0.06 0.28 0.18
ZnO 0.97
NiO 29.49
CoO 0.38
MgO 34.94 4.47 41.06 10.13 14.07 0.37 0.67
Li2O 3.4
CaO 0.38 0 0.45
K2O 0 0.67
Na2O 0.7
H2O+ 13.11 11.42 12.11 10.48 13.83 13.19 14.28 13.75
H2O− 0 0.08 0.27 0.46
Total 100.1 99.88 100.12 100.8 100.03 99.85 99.1 100
Numbers of cations on basis of O10(OH)8
Si 3.21 3.05 2.59 3.01 3.01 2.975 3.155 3
Al 0.79 0.95 1.41 0.99 0.99 1.025 0.845 1
Fe3+
Σtet 4 4 4 4 4 4 4 4
Al 0.65 1.23 1.31 0.98 2.84 3.625 4.13 4.33
Fe3+ 0.16 0.6 0.36 0.19 0.115 0.035
Fe2+ 0.24 3.87 0.26 0.02 0.125
Mn 4 0.02 0.015
Ni 2.62
Co 0.04
Zn 0.09
Mg 4.94 0.76 1.68 1.91 0.05 0.09
Li 1.22
Σoct 5.99 5.86 6 5.96 4.98 5.15 4.26 4.33
1, Clinochlore, Zillertal, Austria; 2, chamosite, Schmiedefeld, Germany: Total Fe as
Fe2+ in numbers of cation; 3, pennantite, Ushkatyn deposit, Kazakhstan; 4, nimite,
Barberton, South Africa: Total octahedral cation number includes 0.04 Ca; 5, sudoite,
(di, trioctahedral chlorite) Venn-Stavelot Massif, Ardennes, Belgium (Fransolet and
Bourguignon, 1978); 6, cookeite, Northwestern USSR (Cerny, 1970); 7, donbassite,
Novaya Zemlya, Russia (Drits and Lazarenko, 1967); 8, ideal donbassite composition,
Al4.33(Si3Al)O10(OH)8.
Analyses 1–4 and 8 are taken from Anthony et al. (1995). Analyses 5–7 are taken
from Newman (1987) and modified to fit with the table. For original data source, see
Anthony et al. (1995) or Newman (1987).

The most striking examples of interstratified structures are hydrobiotite (trioctahedral mica/­vermiculite), aliettite (talc/­
those having a regular AB AB … type structure, where A and B saponite), and kulkeite (talc/chlorite). Analyses of selected sam-
represent two different component layers. The interstratified ples of those regular interstratifications are shown in Table 21.16.
minerals of this type show a long periodicity along the c*-axis Other than the AB AB … type with equal numbers of the two-
(normal to the basal plane) of the structure, which is the sum of component layers in a structure, a variety of modes of the layer-
the two individual periodicities of the component layers A and B. stacking sequence is possible from nearly regular to completely
Several minerals are known to have structures of this type, that random. The following interstratifications of two components are
is, rectorite (dioctahedral mica/montmorillonite), tosudite (dioc- reported in these modes in addition to those given above: Illite–
tahedral chlorite/smectite), corrensite (trioctahedral ­vermiculite/ smectite, glauconite–smectite, dioctahedral mica–­chlorite, dioc-
chlorite) in two types with high- and low-layer charge vermiculite, tahedral mica–vermiculite, and kaolinite–smectite. As the mixing
21-20 Properties and Processes

TABLE 21.16  Interstratified Layer Silicates (Two Components ratio (proportion of the component layers) of the two-component
with 1:1 Ratio and Regular Sequence) layers varies, the number of possible layer-stacking modes increases
1 2 3 4 5 6 7 greatly. Theoretically, any number of the kinds of component layers
can form interstratified structures. In practice, however, a maxi-
SiO2 46.21 53.15 36.77 35.2 36.96 41.25 54.11
mum of three-component layers have been positively identified.
Al2O3 14.44 3.48 11.6 14 32.09 36.48 40.38
Interstratified structures consisting of illite–chlorite–smectite and
TiO2 tr 0.34 0.07 0.01
illite–vermiculite–smectite have been reported so far. Because cer-
Fe2O3 3.48 8.19 3.48 1.57 0.67 0.15
tain interstratified structures are known to be stable under relatively
FeO 0.98 2.9 tr
limited conditions, their occurrence may be used as a geothermom-
MnO 0.03 0.08 tr 0
eter or other geoindicator. On the other hand, Nadeau (1985) and
MgO 37.85 27.4 20.04 28.5 8.2 1.27 0.78
Nadeau et al. (1984a, 1984b) proposed the fundamental particle
CaO 0.07 1.1 1.94 0.93 2.21 3.97 0.52
theory, which argues that interstratified structures may be consid-
K2O 0.06 3.84 tr 0.23 3.87
ered as artifacts of sample preparation. Extra caution is required to
Na2O 1.18 0.12 tr 0.16 0.29
describe interstratified layer silicates correctly.
H2O total 10.18
H2O+ 6.69 10.6 12.71 7.19
H2O− 7.8 4.28 6.12 6.99 21.2.7  Modulated Layer Silicate Group
Total 100.1 100 99.93 99.89 100.59 99.72 100.24 21.2.7.1  General
Anion basis A B C D E F G Guggenheim and Eggleton (1988) defined modulated layer silicates
Si 13.14 14.66 5.77 6.062 12.5 5.85 12.84 as those minerals that contain a periodic perturbation to the basic
Al 2.86 1.13 2.14 1.938 3.5 2.15 3.16 layer silicate structure. The basic structure involves 1:1 or 2:1 layer
Fe3+ 0.21 0.09 configurations. Thus, as the severity of the modulations increases,
Σtet 16 16 8 8 16 8 16 2D continuous layer-like qualities diminish. The octahedral sheet
of a modulated layer silicate is invariably a ­brucite-like (trioctahe-
Al 1.98 0.897 9.29 3.92 8.12
dral) sheet. Palygorskite, sepiolite, greenalite, minnesotaite, caryo-
Ti 0.09 0.01 0
pilite, zussmanite, stilpnomelane, ganophyllite, bementite, etc. are
Fe3+ 0.51 0.88 0.45 0.4 0.07 0.03
known to be mineral species belonging to this group. Strictly speak-
Fe2+ 0.13 0.416
ing, antigorite may also be treated as one of the modulated 1:1 layer
Mn 0.01 0.01 0
silicates. In this chapter the “phyllosilicate” antigorite is thought to
Mg 16.05 11.26 4.68 7.362 4.13 0.15 0.09
be represented in comparison with its other counterparts.
Σoct 18.03 11.78 5.82 9.125 13.91 4.15 8.24

Total Ca 0.02 0.33 0.34a 0.172 0.8 0.59 0.14

21.2.7.2  Sepiolite–Palygorskite Group
Total K 0.02 0.77 0.1 0.15 0.09 Sepiolite and palygorskite are papyraceous or fibrous hydrated
Total Na 0.76 0.63 0.04 0.11 0.27 1.78 magnesium silicate minerals (Figure 21.23) and are included in
Σ 0.8 0.96 1.15 0.172 1.01 2.01

Exch. Ca 0.29
Exch. K 0.01
Exch. Na 0.13
Exch. Mg 0.16
Σcharge 0.32 0.72

Anion basis: A = E [O40(OH)20]; B = G [O40(OH)8]; C = F [O20(OH)4]; and

D [O20(OH)10].
1, Kulkeite, chlorite-talc, Derrag, Tell Atlas, Algeria (Schreyer et al.,
1982); 2, aliettite, talc-saponite, Nure Valley, Piacenza Province, Italy (Alietti
and Mejsner, 1980); 3, hydrobiotite, biotite–vermiculite, Rainy Creek, near
Libby, Montana (Boettcher, 1966): Total includes 0.27% Cr2O3, 0.01% NiO,
0.01% SrO, 0.19% BaO, 0.0158% Rb2O, 0.0005% Cs2O and 0.06% P2O5;
4, corrensite, trioctahedral chlorite–vermiculite (or smectite) Sharbot Lake,
Ontario, Canada (De Kimpe et al., 1987); 5, tosudite, chlorite–smectite,
Niida, Akita Prefecture, Japan (Sudo and Shimoda, 1978); 6, rectorite, dioc-
tahedral mica (Ca)–smectite, Sano mine, Nagano Prefecture, Japan
(Matsuda et al., 1997); 7,  rectorite, dioctahedral mica (Na)–smectite, Fort FIGURE 21.23  Electron micrograph of palygorskite from Nawton,
Sandeman, Baluchistan, Pakistan (Kodama, 1966): Total includes exchange- near Thirsk, Yorkshire. (From Gard, J.A. (ed.). 1971. The electron-
able Ca, Mg, and Sr. optical investigation of clays. Monograph No 3. Mineralogical Society,
See Newman (1987) for original data source of each analysis. London, U.K. Reproduced with kind permission of The Mineralogical
a Ba is included. Society of Great Britain and Ireland.)
Phyllosilicates 21-21

A D

A D
a
13.4 Å

B C B C
A b 26.8 Å

A΄ D΄
A΄ D΄
a sin β
12.9 Å

B΄ C΄
B΄ C΄
B b 18.0 Å
Octahedral cation Hydroxyl
Bound water (OH2) Zeolitic water (H2O)

FIGURE 21.24  Structural sketches of palygorskite and sepiolite. (Reprinted from Sudo, T., S. Shimoda, H. Yotsumoto, and S. Aita. 1981. Electron
micrographs of clay minerals. Developments in sedimentology. Vol. 31. Elsevier Scientific Publishing Co., New York. With permission from Elsevier.)

the phyllosilicates because they contain a continuous 2D tetra- larger than the latter and having a domain size of about 2 nm.
hedral sheet of composition Si2O5. They differ, however, from Minnesotaite has a continuous octahedral sheet (Guggenheim
the other layer silicates because they lack continuous octahedral and Bailey, 1982). Adjacent tetrahedral are present on either side
sheets. The structures of sepiolite and palygorskite are alike and of this sheet to form an approximate 2:1 layer. However, in contrast
can be regarded as consisting of narrow strips or ribbons of 2:1 to talc, strips of linked hexagonal rings of tetrahedra are formed
layers that are linked stepwise at the corners (Figure 21.24). One only parallel to y (Figure 21.25; Guggenheim and Eggleton,
ribbon is linked to the next by inversion of the direction of the 1986). Some analyses of greenalite and minnesotaite are listed in
apical oxygens of SiO4 tetrahedra, in other words, an elongated Table 21.18, in which an analysis of caryopilite, as a mangan spe-
rectangular box consisting of a continuous 2:1 layer is attached cies of serpentine-like mineral, is included for comparison.
by the nearest boxes at their elongated corner edges. Therefore,
channels or tunnels due to the absence of the silicate layers
occur on the elongated sides of the boxes. The elongation of the 21.3  Occurrence of Phyllosilicates
structural element is related to the fibrous morphology of the
21.3.1  As Rock-Forming Minerals
minerals and parallel to the a-axis. Since the octahedral sheet
is discontinuous, some octahedral magnesium ions are exposed Known established species of phyllosilicates are no more than
at the edges and hold bound water molecules (OH2). In addition 100 (see Appendix). Although this is a rather small portion of
to the bound water, variable amounts of zeolitic (i.e., free) water the total mineral kingdom of some 3700 species, the occurrence
(H2O) are contained in the rectangular channels. The major dif- of phyllosilicates is spread to a wide variety of geological envi-
ference between the structures of sepiolite and palygorskite is ronments. Among those described in the previous sections, per-
the width of the ribbons, which is greater in sepiolite than in haps biotite is the most; it is found in igneous rocks varying from
palygorskite. The width determines the number of octahedral granitic pegmatites, to granites, to syenites, to diorites, and to
cation positions per formula unit. Thus, sepiolite and palygor- gabbros and peridotites. It also occurs in felsic volcanic rocks
skite have the ideal compositions Mg8Si12O30(OH)4(OH2)4(H2O)8 such as dacites, rhyolites, trachyte, and phonolites. In metamor-
and (Mg,Al, □)5Si8O20(OH)2(OH2)4(H2O)4, respectively. Some phic rocks, including contact-metamorphosed rocks, biotite is
of Mg in sepiolite may be replaced by Al, Fe3+, or Fe2+. Selected formed under a wide range of temperature and pressure condi-
analyses of this mineral group are given in Table 21.17. tions. Muscovite is also a widespread and common rock-­forming
mineral, especially in pegmatites and granitic rocks. It is often
21.2.7.3  Greenalite, Minnesotaite, and Caryopilite found in metamorphic rocks as mica schists and as green schists
Greenalite was once expected to be a near iron end-member of with chlorite. Phlogopite occurs in metamorphosed magne-
serpentine. Guggenheim et al. (1982) showed that its structure sium limestones, dolomites, and ultrabasic rocks. Lepidolite is
is composed of coherent intergrowths of a trigonal polytype an uncommon mineral, found in lithium-rich pegmatites. Some
and a monoclinic polytype, with volume wise the former being brittle micas occur in regional contact-metamorphosed rocks.
21-22 Properties and Processes

TABLE 21.17  Palygorskite and Sepiolite Analyses Z

1 2 3 4
SiO2 55.03 53.75 52.5 52.36
Al2O3 10.24 10.23 0.6 0.23
Fe2O3 3.53 1.83 2.99 0.4 Si
FeO 0.26 0.7
Fe
MnO 0.01
(a) a = 28 Å X
MgO 10.49 9.39 21.31 22.6
CaO 2.29 0.47 0.83
K2O 0.47 0.02
Na2O tr
H2O+ 10.13 12.04 9.21 9.34
H2O− 9.73 10.16 12.06 13.85
Total 99.62 99.97 99.84 99.62 y

Numbers of cations on basis of

b
A B
Si 7.8 7.82 11.81 11.95
Al 0.2 0.18 0.16 0.05
Fe3+ 0.03
Σtet 8 8 12 12 x
(b) o a
Al 1.51 1.57 0.01
Fe3+ 0.38 0.2 0.47 0.07 FIGURE 21.25  Structural sketches of minnesotaite: (a) Perspective
Fe2+ 0.03 0.13 view of the idealized structure in which the interlayer tetrahedra share
Mg 2.22 2.04 7.14 7.69 corners to form a chain parallel to Y and (b) in the (001) plane drawing.
Ni (From Guggenheim, S., and S.W. Bailey. 1982. The superlattice of min-
Σoct 4.11 3.84 7.74 7.77 nesotaite. Can. Mineral. 20:579–584.)

Ca 0.36 0.11 0.2 rocks, shales, and mudstone, while talc is formed from mag-
K 0.09 nesium silicates, such as olivines, pyroxenes, and amphiboles.
Na Generally speaking, near-neutral hydrothermal solutions gen-
Σ charge 0.09 0.72 0.22 0.4 erate rock alteration, including the formation of illite, chlorite,
A: O20(OH)4(OH2)2 for anion basis of palygorskite; and smectite, whereas acid hydrothermal solutions generate the
B: O30(OH)4(OH2)4 for anion basis of sepiolite. formation of kaolinite.
1, Palygorskite, Attapulgus, Georgia (Bradley, 1940); Most phyllosilicates of hydrothermal origin hold properties
2, palygorskite, Kuzu District, Tochigi Prefecture, Japan defined by the term “clay.” The term “clay” is generally applied
(Imai et al., 1969); 3, sepiolite, Ampandrandava,
Maagascar (Caillère and Hénin, 1961); 4, sepiolite, Kuzu
to the following: (1) a natural material with plastic properties,
District, Tochigi Prefecture, Japan (Takahashi, 1966). (2) an essential composition of particles found in a very fine-size
Analyses are taken from Newman (1987). fraction, which is customarily defined as particles smaller than
2 μm, and (3) a composition of very fine mineral fragments or
particles that are mostly hydrous layer silicates of aluminum
21.3.2  Hydrothermal Origin and the or occasionally containing magnesium and iron (Grim and
Term “Clay Minerals” Kodama, 1997). Although, in a broader sense, clay minerals can
include virtually any minerals in the clay-size fraction, the defi-
In hydrothermal deposits or wall-rock alteration zones, many of
nition adopted here is restricted to the hydrous layer silicates,
phyllosilicates except palygorskite and sepiolite have been found
which are conveniently used to distinguish themselves from
as alteration products associated with hot springs and geysers
macroscopic phyllosilicates. In other words, the term “clay min-
and as aureoles around metalliferous deposits. Frequently a
erals” is a synonym of microcrystalline phyllosilicates.
zonal arrangement of phyllosilicates, normally as very fine-
grained clayey materials, is observed around the source of the
alteration. The zonal arrangement varies with the type of parent
21.3.3  Diagenesis and Low-Grade
rocks and the nature of hydrothermal solution. Extensive clay
Metamorphism
zones formed in close association with “kuroko” deposits con- Analyses of many ancient sediments in many parts of the world
tain mica (illite), chlorite, tosudite, smectite, and mica–smectite indicate that very old argillaceous (clay-rich) sediments (physi-
interstratifications. Pottery stones that consist of kaolinite, illite, lites) are largely composed of illite and chlorite. These clay min-
and pyrophyllite occur as alteration products of acidic volcanic erals are also found in carbonate rocks (calcretes). Smectite is a
Phyllosilicates 21-23

TABLE 21.18  Modulated Layer Silicate Analyses chlorites are often major components in metamorphic rocks.
1 2 3 4 Smectites are known to occur in sediments of pyroclastic mate-
rials as the result of devitrification of volcanic ash in situ. Much
SiO2 33.58 36.5 35.4 51.29
discussion appears to favor marine origin for glauconite and
Al2O3 0.16 2.38 0.61
nonmarine origin for celadonite (Dunoyer de Sagonzac, 1970;
TiO2 0.04
Weaver, 1989; Vielde, 1992).
Fe2O3 11.16 nr nr 2
FeO 45.19 33.66
Total Fe as FeOa 46.7 0.95 nr 21.3.4  In Soils, Sediments, and
MnO 1.5 49.2 0.12 Weathering Products
MgO 4.53 1.23 6.26
The formation of the clay minerals by weathering processes is
CaO 0.02 0.16 0
determined by the nature of the parent rock, climate, topography,
K2O 0.03 0.03
vegetation, and the time period during which these factors have
Na2O 0.16 0.08
operated. Climate, topography, and vegetation influence weath-
H2O total 10.07
H2O+ 5.54
ering processes by their control of the character and direction of
H2O− 0.24
movement of water through the weathering zone. When the domi-
nant movement of water is downward through the alteration zone,
Total [100] 89.41 89.4 99.87
any alkaline or alkaline-earth elements tend to be leached and
Anion basis O5(OH)3.28 O10(OH)8 O10(OH)8
primary minerals containing these components are first degraded
Si 2.18 4 4 3.95
and then broken down. If the leaching is intense, then after the
Al 0.05
removal of the alkalis and alkaline earths, the aluminum or silica
Fe3+
may be removed from the alteration zone. This will depend on
Σtet 2.18 4 4 4
the pH of the downward-seeping waters. The pH of such water
Al 0.02 0.32 is determined, in turn, by the climate and cover of vegetation.
Fe3+ 0.45 Under warm and humid conditions, with long wet and dry peri-
Fe2+ 2.34 4.28 0.09 2.28 ods, the surface organic material tends to be completely oxidized.
Mn 0.14 4.7 0.01 The downward-seeping waters, therefore, are neutral or perhaps
Mg 0.74 0.21 0.72 slightly alkaline and silica will be removed, whereas aluminum
Σoct 2.79 5.18 5.32 3.01 and iron will be left behind and concentrated. The result is a lat-
1: Greenalite, Mesabi Range, Minnesota. Recalculated to 100% after eritic type of soil. Under more temperate conditions, the surface
reduction of SiO2 and other impurities. Anion basis: O5(OH)3.28; 2: green- organic material is not completely oxidized and the downward-
alite, Sokoman iron formation, Knob Lake, Labrador, Canada; 3: caryopi- seeping water contains organic acids. In this case, aluminum and
lite, Hurricane Claim, Olympic Peninsula, Washington; 4: Minnesotaite,
Mesabi district, Minnesota.
iron oxides are leached and the silicon is left behind; podzolic
Analyses 1 and 4 are taken from Anthony et al. (1995). Analyses 2 and types of soils will develop. Under these conditions, mica and chlo-
3 are taken from Newman (1987). rite tend to be transformed into expandable clay minerals such
For original data source of each analysis, see Anthony et al. (1995) or as vermiculite and smectite or their intergrades as interstratifica-
Newman (1987). tions. Allophane and imogolite may be present as newly formed
clay minerals. In andosols, which are the soils developed on vol-
common component of many shales of Mesozoic and younger canic ash, allophane and imogolite as well as hydrated halloysite
ages. As temperature and pressure increase with the progression and halloysite are dominant components. (Wada and Greenland,
of diagenesis, clay minerals in sediments under these circum- 1970) Smectite is usually the sole dominant component in vertisols,
stances change to those stable under given conditions. Therefore, which are clayey soils. Smectite and illite, with occasional small
certain sensitive minerals may serve as indicators for various amounts of kaolinite, occur in mollisols and prairie chernozemic
stages of diagenesis. Typical examples are the crystallinity of soils. Illite, vermiculite, smectite, chlorite, and interstratified clay
illite (Kubler, 1966), illite and chlorite polytypes, and the conver- minerals occur in podzolic soils. The alkaline and alkaline-earth
sion of smectite to illite. The data reported indicate that smectite elements remain close to the surface and the dry grassland soils
was transformed into illite through interstratified illite–smectite (chernozem) containing illite, chlorite, and smectite, will develop.
mineral phases as diagenetic processes advanced. Much detailed In dry areas, the dominant movement of water is not downward
work has been devoted to the conversion of smectite to illite in and leaching does not take place. In extreme dry desert areas (des-
the lower Cenozoic–Mesozoic sediments because such a con- ert soils, some aridsols), where the concentration of magnesium
version appears to be closely related to oil-producing processes is particularly high, the formation of palygorskite–sepiolite min-
(Burst, 1969). In the very low-grade metamorphic zone, which is erals has been reported. Kaolinite is the dominant component in
considered to be an intermediate zone between diagenetic and laterite soils (oxisols). Clay minerals other than those mentioned
metamorphic zones, the occurrence of rectorite, kulkeite, pyro- above usually occur in various soils as minor components inher-
phyllite, and talc has been reported. Well-crystallized micas and ited from the parent materials of those soils (cf. Kittrick, 1985).
21-24 Properties and Processes

In general, the process of transportation and sedimentation little soils and which belong to the category above include hydrated
affects the weathering products. However, in lagoon–estuary halloysite, halloysite, kaolinite, micas, chlorites, vermiculites,
areas, some mineral transformations are possible because envi- smectites, and their interstratified minerals. Allophane and imo-
ronments change from nonmarine to marine and vice versa. As golite are often associated. The occurrence of clay minerals other
burial sedimentation and compaction continues, temperature than these in soils is either uncommon or rare. Because of fine
and pressure increase. Weathering products in sediments change particles, until relatively recently no appropriate analytical tech-
accordingly. The weathering products are transformed into other niques were available by which to determine the precise nature,
clay minerals or decomposed completely to provide constituents composition, and structure of clays. Therefore, clays had long
required for the neoformation of clay minerals, depending on the been believed to be noncrystalline “colloidal” substances before
chemical environments of the sedimentation and the types of clay XRD techniques developed in the 1920s, followed a few years
minerals present in sediments prior to diagenesis. later by improved microscopic and thermal procedures, which
In soils, we observe the alteration of phyllosilicates by weather- established that clays are composed of a few groups of crystalline
ing action, as in a notable case like the transformation of micas into minerals (Bradley and Grim, 1948). The introduction of electron
vermiculite, smectite, or randomly interstratified layer silicates microscopic methods was very useful to determine characteris-
(mica–vermiculite, mica–smectite, mica–vermiculite–­smectite). tic shape and size of clay minerals. Relatively modern analyti-
On the other hand, we also notice the formation of chloritic miner- cal techniques such as infrared absorption, neutron diffraction,
als from vermiculite or montmorillonite by precipitating hydrox- Mössbauer spectroscopy, and nuclear magnetic resonance have
ide sheets between the silicate layers, is also noticed as a results been applied to advance our knowledge of crystal chemistry of
of accretion. Other observations have supported some systematic clay minerals (Greenland and Hayes, 1978; Wilson, 1992).
weathering patterns: Kaolinite is formed from aluminum silicates,
particularly feldspar. Chlorite is found in igneous rocks as an alter- 21.4.2  Physical Properties
ation product from Mg–Fe silicates such as olivines, pyroxenes,
amphiboles, and biotite micas, and serpentine is also found in the 21.4.2.1  Optical Index, Specific Density,
manner similar to chlorite. In meteorites, the occurrence of iron- and Particle Shape and Size
rich serpentines in carbonaceous chondrites is reported. Clay mineral particles are commonly too small for the measure-
Weathering and subsequent transportation result in the accu- ment of optical properties. Oriented aggregates that are large
mulation of sediments at the bottom of lakes, rivers, and oceans. enough for optical measurements can, however, be prepared by
In the Mississippi River system, for example, smectite, illite, and allowing the flake-shaped clay mineral particles to settle from a
kaolinite are the major components in the upper Mississippi and clay water suspension on a horizontal surface. The particles settle
Arkansas Rivers, whereas chlorite, kaolinite, and illite are the with one flake on top of another so that their basal plane sur-
major components in the Ohio and Tennessee Rivers. This is faces are essentially parallel. Refractive indices of clay minerals
the case for nonmarine conditions. Under marine conditions, at generally fall within a relatively narrow range from 1.47 to 1.68.
the Gulf of Mexico, for example, smectite, illite, and kaolinite are This range may be subdivided into several groups represented by
found to be the major clay mineral composition and their compo- major mineral species: 1.47–1.52 (allophane, hydrated halloysite);
sitions vary from place to place. In some limited regions, it is note- 1.53–1.58 (kaolinite minerals, vermiculite); 1.58–1.65 (nontronite,
worthy that these compositions are significantly altered by other glauconite, celadonite); and 1.57–1.68 (trioctahedral chlorites).
factors such as airborne effects. The high-kaolinite concentration All remaining clay minerals have refractive indices ranging from
off the west coast of Africa near the equator reflects this effect. 1.54 to 1.63, except that smectite minerals have a range from 1.48
In a supergene enrichment process, the formation of nickel to 1.61. In general, iron-rich species show high refractive indices,
deposits at New Caledonia is well known, where Ni–serpentine whereas water-rich porous mineral species have lower refractive
minerals occur in serpentine and peridotite rocks. indices. Specific densities are as follows: 2.5–2.7 g · cm−3 (kaolinite-
group minerals); 2.5–2.9 (pyrophyllite, talc, clay micas); 2.6–3.3
(chlorite minerals); 2.6–3.0 (vermiculite); 2.5–2.8 (smectite); ∼2
21.4  Phyllosilicates in Soil (palygorskite–sepiolite group); 1.7–2.4 (bulk); and 2.6–2.8 (par-
Environments ticle) for imogolite and allophane. Table 21.19 lists density, crystal-
lographic units, and optical data of major clay minerals.
21.4.1  Introduction
The size and shape of clay minerals have been determined by
In the foregoing section in which phyllosilicates of hydrothermal electron micrographs. Well-crystallized kaolinite occurs as well-
origin were discussed, the term “clay minerals” was introduced formed six-sided flakes (Figure 21.26), frequently with a promi-
and the term can be the synonym of phyllosilicates of clay size. The nent elongation in one direction. Particles with maximum surface
number of phyllosilicate species that occur either in clay size or in dimensions of 0.3 to about 4 μm and thickness of 0.05–2 μm are
a wide range of particle sizes from macroscopic to microscopic is common. The flakes of disordered kaolinite have poorly devel-
rather limited. Although the numbers of species are small, their oped hexagonal outlines. Halloysite commonly occurs as tubu-
quantities are huge. Hence, clay components have great impact lar units with an outside diameter ranging from 0.04 to 0.15 μm
on soil environments. The phyllosilicates commonly found in (Figure 21.27). Electron micrographs of smectite frequently show
 Phyllosilicates
TABLE 21.19  Crystallographic, Specific Gravity, and Optical Data of Some Selected Phyllosilicates
Crystallographic Data Optical Data
D (g mL )
−3 a b c α β γ Z α β γ 2V
Halloysite 2.55–2.265 0.514 0.89 1.49 101.9° [4] nd
Kaolinite 2.61–2.68 0.515 0.895 0.739 91.8° 104.5°–105° 90° [2] Biaxial (−) 1.553–1.566 1.559–1.569 1.560–1.570 23°–50°
Dickite 2.6 0.515 0.894 1.4424 96°44′ 4 Biaxial (+) 1.560–1.561 1.561–1.563 1.566–1.567 52°–80°
Nacrite 2.5–2.7 0.8909 0.5146 1.5697 113°42′ 4 Biaxial (−) 1.557–1.560 1.562–1.563 1.563–1.566 40°–90°
Lizardite 2.55 0.5325 0.7259 2 Uniaxial (−) 1.538–1.554 1.546–1.560 1.546–1.560 Small
Chrysotile ≈2.55 0.535 0.925 0.733 94.2° 1.532–1.544 1.545–1.553 Small
Antigorite 2.65 4.353 0.9259 0.7263 91°8.4′ 16 Biaxial (−) 1.558–1.567 1.565 1.562–1.574 37°–61°
Talc 2.58–2.83 0.5287 0.9158 1.895 99.30° 4 Biaxial (−) 1.539–1.55 1.589–1.594 1.589–1.60 0°–30°
Pyrophyllite 2.65–2.9 0.516 0.8966 0.9347 91.18° 100.46° 89.64° 2 Biaxial (−) 1.534–1.556 1.586–1.589 1.596–1.601 53–62°
Muscovite 2.77–2.88 0.519 0.904 2.008 95°30′ 4 Biaxial (−) 1.552–1.576 1.582–1.615 1.587–1.618 30°–47°
Glauconite 2.4–2.95 [0.527] [0.914] [1.009] ≈100° 2 Biaxial (−) 1.592–1.610 1.614–1.641 1.614–1.641 0°–20°
Celadonite 2.95–3.05 0.523 0.906 1.013 100°55′ 2 Biaxial (−) 1.606–1.625 nd 1.579–1.661 5°–8°
Phlogopite 2.78–2.85 0.53078 0.91901 1.01547 100.08° 2 Biaxial (−) 1.530–1.590 1.557–1.637 1.558–1.637 0°–15°
Biotite 2.7–3.3 0.53 0.92 1.02 100° 2 Biaxial (−) 1.565–1.625 1.605–1.696 1.605–1.696 0°–25°
Clinochlore 2.60–3.02 0.535 0.9267 1.427 96.35° 2 Biaxial (±) 1.571–1.588 1.571–1.588 1.576–1.597 0°–50°
Chamosite 3.0–3.4 0.5373 0.9306 1.4222 97°53′ 2 Biaxial (−) 1.595–1.671 1.599–1.684 1.599–1.685 0°–30°
Donbassite 2.63 0.5174 0.8956 1.426 97.83° [2] Biaxial (+) 1.728 1.729 1.735 52°
Vermiculite 2.2–2.6 0.524 0.917 2.86 94°36′ 4 Biaxial (−) 1.520–1.564 1.530–1.583 1.530–1.583 0°–15°
Montmorillonite 2–3 0.517 0.894 0.995 nd 1 Biaxial (−) 1.492–1.503 1.513–1.534 1.513–1.534 10°–25°
Beidellite 2–3 0.5179 0.897 1.757 ≈90° nd Biaxial (−) 1.494 1.536 1.536
Nontronite 2.2–2.3 [0.525] [0.91] [1.53] ≈90° nd Biaxial (−) 1.567–1.600 1.604–1.632 1.605–1.643 25°–68°
Saponite 2.24–2.30 0.53 0.914 1.69 ≈97° nd Biaxial (−) 1.48–1.54 1.50–1.58 1.50–1.58 0°–40°
Greenalite 2.85–3.15 0.554 0.955 0.744 104°20′ 2
Minnesotaite 3.01 0.5623 0.9419 0.9624 85.21° 95.64° 90.00° 4 Biaxial 1.580–1.592 nd 1.615–1.632 Small
Palygorskite >1.0–2.6 1.278 1.786 0.524 95.78° 4 Biaxial (−) 1.522–1.528 1.530–1.546 1.553–1.548 30°–61°
Sepiolite >2 0.521 2.673 1.35 4 Biaxial (−) 1.515–1.520 nd 1.525–1.529 0°–50°
Source: Adapted from Yong, R.N., and B.P. Warkentin. 1975. Soil properties and behaviour. Developments in geotechnical engineering 5. Elsevier Scientific Publishing Co., Amsterdam, the
Netherlands.
Unit cell: a, b, and c are in nanometers. Z is the number of formula units per unit cell and [Z] is estimated one. Compilation by Kodama.

21-25
21-26 Properties and Processes

FIGURE 21.26  Electron micrograph of kaolinite, from Mont

Megantic, Quebec. Quick freeze–dry and Pt shadowing. The longer side
edge of the photograph equals about 2 μm. FIGURE 21.28  Electron micrograph of illite, from Eldorado,
Saskatchewan. Although outline is irregular, it appears as a single crystal
(about 1–1.5 μm across). (From Kodama, H., and R.S. Dean. 1980. Illite
from Eldorado, Saskatchewan. Can. Mineral. 18:109–118.)

Frequently, the individual laths are many microns in length and

5–10 nm in width. Sepiolite occurs in similar lath-shaped units,
but the laths are somewhat thicker and shorter than the palygor-
skite. As mentioned earlier in the structures, allophane occurs in
very small spherical particles (3–5 nm in diameter), individually
or in aggregated forms, whereas imogolite occurs in long thread-
like tubes of several microns in length. One of the interesting
features of layer silicate minerals is their modes of particle associ-
ation. When a clay suspension of flaky particles flocculates, three
different modes of particle association may occur: face-to-face,
edge-to-face, and edge-to-edge. These modes are determined by
the electrostatical interaction energy between particles, which
is influenced by the kind of salt and salt concentration in the
medium as well as the surface conditions of the particles.
FIGURE 21.27  Electron micrograph of halloysite, in a paleosol
21.4.2.2  Clay–Water Relations
from Gaspe, Quebec. Pt shadowing. The scale indicates 1 μm. (From
Ross, G.J., H. Kodama, C. Wang, J.T. Gray, and L.B. Lafreniere. 1983. Clay minerals contain water in several forms. The water may be
Halloysite from a strongly weathered soil at Mont Jacques Cartier, held in pores and may be removed by drying under ambient condi-
Quebec. Soil Sci. Soc. Am. J. 47:327–332.) tions. Water also may be adsorbed on the surface of clay mineral
structures and in smectites, vermiculites, hydrated halloysite, sepi-
broad undulating mosaic sheets. In some cases, the flake-shaped olite, and palygorskite; this water may occur in interlayer positions
units are discernible but frequently they are too small or thin or within structural channels. Finally, the clay mineral structures
to be seen individually without special attention (Oberlin and contain hydroxyls that are lost as water at elevated temperatures.
Méring, 1962). Illite occurs in poorly defined flakes commonly The water adsorbed between layers or in structural channels may
grouped together in irregular aggregates (Figure 21.28). Many further be divided into zeolitic (free) and bound waters. The latter
of the flakes have a diameter 0.1–0.5 μm and the thinnest flakes is bound to exchangeable cations or directly to the clay mineral
are approximately 3 nm thick. Although sizes vary more widely, surfaces. Zeolitic and bound waters may be removed by heating
vermiculite, chlorite, pyrophyllite, talc, and serpentine miner- to temperatures on the order of 100°C–200°C and in most cases,
als except for chrysotile are similar in character to the illites. As except for hydrated halloysite, is regained readily at ordinary tem-
shown in Figure 21.11, chrysotile occurs in slender tube-shaped peratures. Exceptions include those minerals like K-saturated
fibers with an outer diameter of 10–30 nm. Their lengths com- vermiculite in which the interlayer K atoms do not associate with
monly reach several microns. Electron micrographs show that zeolitic water. The bound water is generally agreed to have a struc-
palygorskite occurs as elongated laths, singly or in bundles. ture that is different from bulk water, being more ice-like in its
Phyllosilicates 21-27

TABLE 21.20  Cation-Exchange Capacity and Specific Surface TABLE 21.21  Consistency Data of Representative Clay Minerals
Area Data of Representative Clay Minerals, Including Including Allophane
Imogolite and Allophane
Plastic
Cation-Exchange Plastic Limit Liquid Limit Index (PI)
Capacity at pH 7 Specific Surface
Kaolinite–Na 26 52 26
(cmolc kg−1) Area (m2 g−1)
Kaolinite–Ca 26 73 37
Kaolinite 3–5 5–40 Illite–Na 34 61 27
Hydrated halloysite 40–50 ∼1100 Illite–Ca 40 90 50
Illite 10–40 10–100 Montmorillonite–Na 97 700 603
Chlorite 10–40 10–55 Montmorillonite–Ca 63 177 114
Vermiculite 100–150 ∼760 Palygorskite–sepiolite 145 171 26
Smectite 80–120 40–800 Allophane (undried) 136 231 95
Palygorskite–sepiolite 3–20 40–180 Allophane (dried) 78 85 7
Imogolite 20–30 ≈1540
Source: Adapted from Yong, R.N., and B.P. Warkentin. 1975. Soil proper-
Allophane 30–135 ∼2200
ties and behaviour. Developments in geotechnical engineering 5. Elsevier
Scientific Publishing Co., Amsterdam, the Netherlands.
structure, even though still liquid. As the thickness of the adsorbed PI = liquid limit − plastic limit. Numerical figures are expressed in dag kg −1.
water increases outward from the surface, the nature of the bound
liquid water changes abruptly or gradually from ice-like to that of depending on the composition and structure of the clay miner-
bulk water. Ions and molecules adsorbed on the clay mineral sur- als. In the presence of fluxes, such as iron or potassium, fusion
face exert a major influence on the thickness of the adsorbed water may follow dehydroxylation very quickly. In the absence of such
layers and on the nature of this water. The bound liquid water with components, particularly for aluminous dioctahedral miner-
ice-like characteristics may extend out from the clay mineral sur- als, a succession of new phases may be formed at increasing
faces as much as 6–10 nm. Hydroxyl ions are driven off by heating temperatures prior to fusion. Thus, in the case of kaolinite, the
clay minerals to temperatures of 400°C–700°C. The rate of loss of first high-temperature phase formed is a silica–alumina spinel
the hydroxyls and the energy required for their removal are specific or γ-alumina plus amorphous silica that is followed at a higher
properties characteristic of the various clay minerals. The reaction temperature by the development of mullite and cristobalite prior
for dioctahedral minerals such as kaolinite is abrupt, whereas the to fusion. In general terms, the first high-temperature phases
loss takes place rather gradually in trioctahedral minerals. This are a consequence of the original structure of the clay mineral,
dehydroxylation process results in the oxidation of Fe2+ to Fe3+ in whereas the later phases are more in accord with the chemical
ferrous-iron-bearing clay minerals. The amount of the adsorbed composition. Information on high-temperature-phase change of
water is closely related to the surface area of clay minerals that is, the clay minerals has been obtained by the use of an x-ray diffrac-
of course, determined by their particle size and shape as well as the tometer to which a small high-temperature furnace is attached.
type of clay minerals. The range of measured surface areas of some This unit provides x-ray data, while the sample is at an elevated
clay minerals is given along with that of cation-exchange capaci- temperature. Information concerning high-temperature reac-
ties in Table 21.20. The capacity of water retention of clay minerals tions is important for ceramic science and industry.
is generally proportional to the extent of their surface area (e.g.,
Ross, 1978). As the water content increases, clays become plas- 21.4.3  Chemical Properties
tic and then change to a near-liquid state. The amounts of water
21.4.3.1  Layer Charge and Ion Exchange
required for the two states are defined by the plastic and liquid
limits. These limits vary with the kind of exchangeable cations and Depending upon deficiency in the positive or negative charge bal-
the salt concentration in the adsorbed water. The plastic and liq- ance (locally or overall) of mineral structures, clay minerals are
uid limits for different clay minerals are given in Table 21.21. The able to adsorb certain cations and anions and retain them around
plasticity index (PI), the difference between the two limits, gives the outside of the structural unit in an exchangeable state, gener-
a measure for the rheological (flow) properties of clays. A good ally without affecting its basic silicate structure. These adsorbed
example is a comparison of the PI of montmorillonite with that of ions are easily exchanged by other ions. The exchange reaction
allophane or palygorskite. The former is considerably greater than differs from simple sorption because it has a quantitative rela-
the latter, indicating that montmorillonite has a prominent plas- tionship between reacting ions. The range of the cation exchange
tic nature. Such rheological properties of clay minerals have great capacities of the clay minerals is given in Table 21.20 along with
impacts on building foundations, highway construction, chemical specific surface areas. Exchange capacities vary with particle size,
engineering, and soil structure in agricultural practice. perfection of crystallinity, and nature of the adsorbed ion; hence,
a range of values exists for a given mineral rather than a single
21.4.2.3  High-Temperature Reactions specific capacity. With certain clay minerals—such as imogolite,
When heated at temperatures beyond dehydroxylation, the allophane, and to some extent ­kaolinite—that have hydroxyls
clay mineral structure may be destroyed or simply modified, at the surfaces of their structures, exchange capacities also vary
21-28 Properties and Processes

with the pH of the medium, which greatly affects dissociation of in the solution, the more hindered the extraction of the element.
the hydroxyls. The ion-exchange charge created as such is called In alkaline solutions, a cation exchange reaction first takes place
pH-dependent charge or variable charge to distinguish it from the and then the silica part of the structure is attacked. The reaction
permanent layer charge originating by the ionic substitution in the depends upon the same variables as those stated for acid reactions.
structure that is independent from pH. The rate of ion exchange
varies with clay mineral type and the nature and concentration of 21.4.3.3  I nteractions with Inorganic
the ions. In general, the reaction for kaolinite is most rapid, being and Organic Compounds
almost instantaneous. It is slower for smectites and for sepiolite Smectites, vermiculites, and other expansible clay minerals can
and palygorskite and requires even long time, perhaps hours or accommodate relatively large and multivalent inorganic cations
days, to reach completion for illites. Under a given set of condi- between the layers. Because of this multivalency, the interlayer
tions, the various cations are not equally replaceable and do not space is only partially occupied by such inorganic cations, which
have the same replacing power. Calcium, for example, will replace are distributed in the space-like islands. Hydroxy polymers of alu-
sodium more easily than sodium will replace calcium. Sizes of minum, iron, chromium, zinc, and titanium are known examples
potassium and ammonium ions are similar, and the ions are fit- of such interlayering materials. Most of these are thermally stable
ted in the hexagonal cavities of the silicate layer. Vermiculite and and stand as pillars to allow a porous structure in the interlayer
vermiculitic minerals preferably and irreversibly adsorb these space. The resulting complexes, often called pillared clays, exhibit
cations and fix them between the layers. Such a preference of one attractive properties as catalysts—namely, large surface area, high
exchangeable cation over another, so-called ion selectivity, may porosity, regulated pore size, high solid acidity. Cationic organic
be a tool to exploit layer-charge characteristics of clay minerals molecules, such as certain aliphatic and aromatic amines, pyri-
in question. Heavy metal ions such as copper, zinc, and lead are dines, and methylene blue, may replace inorganic exchangeable cat-
strongly attracted to the negatively charged sites on the surfaces ions present in the interlayer of expansible minerals. These organic
of 1:1 layer minerals, allophane and imogolite, which is caused by compounds contain nitrogen atoms, which are able to be positively
the dissociation of surface hydroxyls of these minerals. charged. Polar organic molecules may replace adsorbed water on
The ion exchange properties of the clay minerals are extremely external surfaces and interlayer positions. Ethylene glycol and glyc-
important because these properties determine their physical erol are known to form stable specific complexes with smectites
characteristics and economic use. The availability and retention and vermiculites. The formation of such complexes is frequently
of fertilizer in soils, the adsorption and release of toxic elements utilized for the identification of these minerals. On the other hand,
in soil and aquatic environments, plasticity, and other clay prop- potassium acetate can penetrate between kaolin-type silicate layers,
erties depend to a great extent on ion exchange in general and on which are neutral and held together by hydrogen bonds, and the d001
the identity of the exchange cation. of the mineral expands to 1.42 nm (Wada, 1959, 1961); if dimethyl
sulfoxide, DMSO, is used, the expansion is to 1.12 nm (Camazano
21.4.3.2  Solubility and Garcia, 1966); if formamide, to 1.0 nm (Weiss et al., 1963). These
The solubility of the clay minerals in acids varies with the nature intercalations with organic compounds are often utilized for the
of the acid, the acid concentration, the acid to clay ratio, the tem- characterization of kaolin minerals. However, experimental results
perature, the duration of treatment, and the chemical composi- are not always consistent. Caution is required for firm conclusions.
tion of the clay mineral to be attacked. It also varies as a function As organic molecules coat the clay mineral surfaces, the nature
of heating of the clay minerals and the firing temperatures prior of clay particle surfaces changes from hydrophilic to hydrophobic,
to the acid attack. In general, ferromagnesian clay minerals are thereby losing its tendency to bind water. Consequently, the affinity
more soluble in acids than the aluminum counterparts. Basset of the material for oil increases, so that it can react with additional
(1960) considered that hydroxyl orientation may be an important organic molecules. As a result, the surface of such clay minerals
factor for mica alteration, because in trioctahedral micas hydro- can accumulate organic materials. Some of the clay minerals can
gen atoms are oriented directly toward the interlayer K atoms, but serve as catalysts, promoting reactions in which one organic sub-
in dioctahedral micas, they are tilted away from the interlayer stance is transformed to another on the mineral’s surface. Some of
cation. Incongruent dissolutions may result from reactions in a these organic reactions develop particular colors, which may be of
low acid concentration medium where the acid first attacks the diagnostic value in identifying specific clay minerals. Organically
adsorbed or interlayer cations and then the components of the clad clay minerals are used extensively in paints, inks, and plastics.
octahedral sheet of the clay mineral structure. Frequently with
aluminous clay minerals in particular, the tetrahedral silica sheets
21.4.4  Uses of Clays
are not attacked and the morphology of the clay minerals may be
retained after solution of all components except silica. In the case Clays are perhaps the oldest materials of which man has manufac-
of higher acid concentration, such stepwise reactions may not be tured various artifacts. The making of fired bricks possibly started
recognizable and the dissolution appears to be congruent. One of some 5000 years ago and was probably the second earliest industry
the important factors controlling the rate of dissolution is the con- of mankind next to agriculture. The use of clays (probably smectite)
centration in the aquatic medium of the elements extracted from as soaps and absorbents was reported in Natural History by a Roman
the clay mineral—the greater the concentration of an element author, Pliny the Elder (AD 77). Clays composed of kaolinite are
Phyllosilicates 21-29

required for the manufacture of porcelain, whiteware, and refrac- palygorskite–sepiolite and smectite clays are used as carriers for
tories. The absence of iron in this clay mineral gives it a white burn- insecticides and herbicides. Smectite clays are used as plasticiz-
ing color, and the absence of alkalis and alkaline earths gives it a ing agents and kaolinite clays are used as extenders and fillers in
very high fusion temperature that makes it refractory. Whiteware a large number of organic and inorganic bodies. Kaolinite and
bodies frequently contain talc, pyrophyllite, feldspar, and quartz in smectite clays also are used in a variety of pharmaceutical and
addition to the kaolinite clay, in order to develop desirable shrink- medical preparations. For cosmetic products, kaolinite, talc,
age and burning properties. If the kaolinite is poorly crystalline, the mica, and smectite clays are used. Smectite and kaolinite clays
clay will have higher plastic and bonding properties. can be coated with organic molecules for use in many organic
Clays composed of a mixture of clay minerals, in which illite is systems. Often such organic-clad clays are tailor-made to fit a
most abundant, are used in the manufacture of brick, tile, stone- particular organic system, and thus become an integral part of
ware, and glazed products. Small proportions of smectite in such the system rather than simple diluents. Typical examples are their
clays provide good plastic properties, but in large amounts, smec- application to printing inks, oil paints, and lubrication greases.
tite is undesirable because it causes too great a degree of shrink- Table 21.22 gives a glimpse of industrial uses of kaolinite, smec-
age. Besides the ceramic industry, kaolinite is used as an extender tite, and palygorskite–sepiolite minerals.
in aqueous-based paints and as filler in natural and synthetic
polymers. Smectitic clays (bentonite) are used primarily in the TABLE 21.22  Industrial Uses of Clay Minerals
preparation of muds for drilling oil wells. This type of clay, which
Kaolinite Smectite Palygorskite–Sepiolite
swells to several times its original volume in water, provides
desirable colloidal and wall-building properties. Palygorskite and Paper coating Drilling mud Drilling fluids
sepiolite clays also are used because of their resistance to floccula- Paper filling Foundry bond clay Paint
tion (grouping or clustering of individual grains or flakes) under Extender in paint Pelletizing iron ores Paper
high salinity conditions. Certain clay minerals, notably palygor- Ceramic raw material Sealants Ceramics
skite, sepiolite, and some smectites, possess substantial ability to Filler in rubber Animal feed bonds Asphalt emulsions
remove color bodies from oil. These so-called Fuller’s earths are Filler in plastics Bleaching clay Cosmetics
used in processing many mineral and vegetable oils. Because of Extender in ink Industrial oil absorbents Sealants
their large absorbing capacity, Fuller’s earths are also commer- Cracking catalysts Agricultural carriers Adhesives
cially used for preparing animal litter trays and oil and grease Fiberglass Cat box absorbents Pharmaceuticals
absorbents. Acid treatment of some smectite clays increases their Foundries Beer and wine Catalyst supports
clarification
decolorizing ability. Much gasoline is manufactured by using cat-
Desiccants Medical formulations Animal feed
alysts prepared from either smectite-type or kaolinite–halloysite-
Cement Polishing and cleaning Petroleum refining
type clay minerals. The preparation may be by acid treatment to agents
modify the structure or by the use of kaolinite and halloysite as Pencil leads Detergents Anticracking agent
a source of alumina and silica for the synthesis of new zeolite- Adhesives Aerosols Reinforcing fillers
type structures. Large tonnages of kaolinite clays are used as a Tanning leather Adhesives Cat box absorbents
paper filler and a paper coating to give sheen and carry pigments. Pharmaceuticals Pharmaceuticals Suspension fertilizer
The coating clays are washed to free them from grit and then are Enamels Food additives Agricultural carriers
processed by physical and chemical techniques to improve their Pastes and glues Deinking of paper Industrial floor
whiteness and viscosity. In general, well-crystallized kaolinite that absorbents
cleaves easily into thin flakes is desired. Palygorskite–sepiolite Insecticide carriers Tape-joining Mineral and vegetable
minerals and acid-treated smectites are used in the preparation of compounds oil
carbonless carbon paper because of the color they develop during Medicines Emulsion stabilizer Refining
reactions with certain colorless organic compounds. Large ton- Sizing Crayons Tape-joint compounds
nages of bentonite are used as bonding agents in foundry sands Textiles Cement Environmental
for casting metals. Some poorly crystallized illites and kaolin- absorbents
ites are also used for this purpose. Bentonite is combined with Food additives Desiccants
Bleaching Cosmetics
lime and coke to pelletize finely ground iron ore, which renders
Fertilizers Paints
it suitable for use in blast furnaces. Because many clay minerals
Plaster Paper
have aluminum oxide contents on the order of 30%–40%, they
Filter aids Fillers
are potential ores for aluminum. A variety of processes have been
Cosmetics Ceramics
developed to extract this element from clays but clays are not yet
Crayons Catalysts
competitive with bauxite as a source of aluminum. Extremely
Detergents Pencil leads
large tonnages of reasonably pure clays, preferably of the kaolinite
Roofing granules
type, would be required for this purpose. Clays have a tremen-
Linoleum
dous number of miscellaneous uses and for each use a particular
Polishing compounds
type of clay with particular properties is important. For example,
21-30 Properties and Processes

21.5  Identification of Soil Phyllosilicates where

the constant factor includes all the basic electronic terms,
21.5.1  Introduction which arises from the fundamental x-ray scattering
process
Clay mineralogical analysis is a very important first step to eluci-
Lp is the Lorentz-polarization factor
date soil behavior, because the clay fraction of soil is most active
F is the structure factor that is related to number, kind, and
and influential to the physical, chemical, and biological reac-
array fashion of the atoms on a lattice plane and the factor
tions of soil. X-ray diffraction is a universally accepted method
can be a positive or negative number
for identifying crystalline mineral components (Brindley, 1951;
G is the Laue function that determines diffraction peak pro-
Brown, 1961; Brindley and Brown, 1980). Unlike the case where
file (Kodama et al., 1971) and, therefore, provides infor-
only pure crystalline substances are dealt with, soils are complex
mation about the distribution of crystallite sizes and
mixtures of various minerals with a wide range of crystallinity
shapes and their crystal imperfections
and compositions. Because of these complexities, we often have
to compromise with identification and quantification of mineral
Figure 21.29 illustrates XRD patterns from oriented samples of
group rather than mineral species, and the estimation of rela-
muscovite and phlogopite for comparison. They show a series
tive amounts of minerals may often be the best for a given cir-
of basal reflections, which can be traced down to at least fifth
cumstance. Nevertheless, such data provide useful information
order. The two minerals have a similar structure except for their
about mineral translocations and transformations that might
octahedral cations, aluminum in muscovite and magnesium
have taken place in the soil profiles in question.
in phlogopite. This difference affects the IFI2 value and reflects
on the diffraction pattern. Thus, the ratio (I001/I002)phlogopite:
21.5.2  X-Ray Diffraction Methods (I001/I002)muscovite may be used as one of the criteria for identifica-
21.5.2.1  Basics tion. Similarly, this approach is also useful for the determination
of chlorite species (Petruk, 1964; Bailey, 1972). If mineralogical
X-ray diffraction techniques provide a set of reflections from data accumulation is the main purpose, more reflections should
crystalline substances with various diffraction intensities as a be observed. Figure 21.30 illustrates differences in diffraction
function of diffraction angle. The simplest is, therefore, to take patterns from random and oriented powder specimens of a mus-
standard diffraction diagrams of the principal clay minerals and covite. To determine polytypes, not only are the basal reflections
of the most commonly occurring impurities and to make direct required, but the b unit cell dimension from the d060 reflection
comparison with the diffraction diagrams of unknown clays. and impurities must also be known.
For this purpose, Mineral Powder Diffraction File Data Book
published by JCPDS (Joint Committee on Powder Diffraction 21.5.2.2  Distinguishing among Soil Phyllosilicates
Standards) is handy and useful. X-ray reflection takes place from As mentioned earlier, the types of phyllosilicates occurring in
lattice planes with indices, hkl, according to the Bragg law, soils (and particularly in its clay fraction) are limited to only
nλ = 2dhkl sin θ (21.1) several layer silicate structures (Figure 21.31), and interstrati-
fied layer silicates can also be considered as a combination of
two or three basic structures. Obviously from Figure 21.31, the
where
identification of those basic layer structures is due to determina-
dhkl is lattice spacing for planes hkl
tion of respective layer thickness (distance normal to the basal
λ is the wavelength
plane), which is obtained by XRD as d001-spacing. By choosing
θ is the glancing angle of reflection
effective and critical conditions under which basic layer units
n is the order of the reflection
are clearly distinguished, criteria for the identification of clay
minerals by XRD can be set up (Bradley, 1945). For example, the
The latter two are often called Bragg’s angle and the order of
distinction between smectite and vermiculite is made as follows:
Bragg’s reflection, respectively. Thus, diffraction experiments
Mg-saturation and treated with glycerol expand the d001-spacing
measure the quantity from
of smectite to 1.7–1.8 nm but do not change the d001-spacing at
dhkl λ 1.4 nm of vermiculite (Walker, 1949). With the same treatment,
= chlorite, mica, and kaolinite do not change their d 001-spacings
n 2sin θ (21.2)
at 1.4, 1.0, and 0.72 nm, respectively. On heating at 550°C, how-
ever, the structure of kaolinite is destroyed. The d001-spacing at
and this is the lattice spacing for nth-order reflection, which
about 1.0 nm of hydrated halloysite contracts to 0.72 nm on heat-
is readily understood by introduction of the reciprocal space
ing at 100°C, therefore easily distinguishable from mica. The
concept. The Bragg equation gives no intensity information.
distinction between vermiculite and chlorite is based on the heat
Diffraction intensities are generally expressed by the relation
treatment at 550°C or saturation with K+, either of which causes
the reduction of the d001-spacing at 1.4–1.0 nm in vermiculite
I = const.(Lp) IFI 2G (21.3)
but no change in chlorite. These diagnostic criteria are based on
Phyllosilicates 21-31

(a)

(b)

FIGURE 21.29  XRD patterns of preferred oriented samples: (a) muscovite and (b) phlogopite.

(a)

(b)

FIGURE 21.30  XRD patterns of muscovite: (a) random sample and (b) oriented sample.
21-32 Properties and Processes

8
7
W W 6
W W 5

15.4 Å
K

14.2 Å
14.4 Å
4 W

10.1 Å
10 Å
3
9Å

7.2 Å
2
1
A B C D E F G

2:1 Layer type 1:1 Layer type

Octahedral cation Exchangeable cation Hydroxyl

W Plane of water molecules K Potassium

FIGURE 21.31  Diagrammatic representation of principal clay mineral structures, comparing the relative layer thickness of the unit structures.
A, Talc–pyrophyllite; B, mica; C, smectite; D, vermiculite; E, chlorite; F, serpentine–kaolinite; and G, hydrated halloysite (halloysite—1.0 nm). In
this presentation, tetrahedral and octahedral anions and tetrahedral cations are omitted. (From Sudo, T., S. Shimoda, H. Yotsumoto, and S. Aita.
1981. Electron micrographs of clay minerals. Developments in sedimentology. Vol. 31. Elsevier Scientific Publishing Co., New York.)

generally accepted specific properties of each mineral group for (Mooney et al., 1952). These forms expand to 1.8 nm upon
its definition, which may be categorized as follows: solvation with glycerol. Heating to 550°C causes a reduc-
tion of the basal spacing to 1.0 nm. It collapses further to
• Mica. A 1.0 nm basal spacing and integral series of higher
0.96 nm at 700°C, accompanied by its third-order peak at
order reflections do not shift upon either hydration or
0.32 nm. This behavior is also a characteristic of vermicu-
glycerol salvation or heating at 550°C and 700°C.
lite, but nonexpandable clay minerals like mica retain
• Kaolinite. Characterized by a series of basal reflections at
their third-order peak at 0.333 nm.
0.72, 0.36 nm, and so forth, which do not shift upon either
hydration or solvation with glycerol but disappear upon After clay mineral components are distinguished at a level of
heating at 550°C. the mineral group category, and if circumstances allow, the pro-
• Chlorite. An integral series of basal reflections associ- cedure of identification continues to determination at the level
ated with the largest spacing of 1.4 nm; does not expand of mineral subgroup and finally mineral species. To reach the
by glycerol sorption and does not shift upon heating at final stage of identification, most likely further tests are needed.
550°C. On heating at 700°C, the intensity of the 1.4 nm For the distinction between montmorillonite and beidellite, for
peak is enhanced in comparison with those of other example, the so-called Greene-Kelly test (Greene-Kelly, 1953,
peaks. One should bear in mind that the basal intensity 1955) based on the Hofmann–Klemen effect (Hofmann and
ratio varies with chemical composition. The higher order Klemen, 1950) is often applied. For apparently chloritic minerals
reflections such as third- and fourth-order reflections at derived from vermiculite by acquiring hydroxide sheets between
0.473 and 0.355 nm, respectively, may also be used for the vermiculite silicate sheets, the interlayered vermiculite can be
distinction of chlorite from kaolinite. distinguished from chlorite by complexing with sodium citrate
• Vermiculite. According to the conventional definition, its to remove the interlayer material. Further information may be
Mg form maintains the 1.44 nm basal spacing upon solva- obtained from XRD data if complexities due to the combination
tion with glycerol and hydration, but the spacing collapses of clay mineral components themselves and associated impurity
to 1.0 nm upon heating to 550°C, whereas the K form gives are relatively limited.
the contracted spacing of 1.0 nm without heating. Although Ideally, any pretreatment would be avoided to obtain infor-
its Ca form also shows symptoms similar to those of the Mg mation about mineral components of soil as they are. However,
form, in some cases, the symptoms become less definite, that cases are often unavoidable. An extreme example is given in
is, some of the Ca forms expand beyond 1.44 nm on glycerol Figure 21.32, where only a pretreatment of the clay fraction by
solvation depending upon their layer-charge characteristics. Tiron improves XRD patterns because masking substances are
• Smectite. Under intermediate humidity (about 50%), the mainly amorphous silica. Many soils cannot disperse without
Na form of smectite shows an expansion of its basal spac- treatment for fractionation. Organic matter, carbonate, and
ing to 1.24 nm, and the Ca (also Mg) form to 1.54 nm iron oxide removal are often prerequisite. Another example
Phyllosilicates 21-33

82–151
(<2 μm)
Ultrasonic

Before tiron treatment DCB

50 cps

0.334
0.319
1.44

NaOH
0.84

After tiron treatment Qtz

Tiron
0.319
1.44

Fsp Chl Mi
Amph
0.334 0.324

0.32 0.35 0.43 0.5 0.7 0.8 1.0 1.4

Nanometers (nm)
0.281
50 cps

FIGURE 21.33  XRD patterns of a Mg-saturated and glycerol-solvated

clay sample after four separate pretreatments. After organic matter
0.71

removal, <2 mm fraction was collected from the Whatcom Bf horizon

and dispersed by an end-to-end shaker and then the clay fraction was
2 10 20 30 40 obtained by sedimentation. (From Wang, C., H. Kodama, and N.M.
Degree 2θ, CoK α Miles. 1981. Effect of various pretreatments on X-ray diffraction patterns
of clay fractions of podzolic B horizons. Can. J. Soil Sci. 61:311–316.)
FIGURE 21.32  XRD patterns (in nm) of a soil clay before and after
tiron treatment, exemplifying any suitable chemical pretreatments are and expandable. Chlorites gradually experience a mild attack on
often required to obtain decent XRD patterns of soil clays for identifica- their hydroxide sheets to alter toward vermiculite-like miner-
tion. (From Kodama, H., and G.J. Ross. 1991. Tiron dissolution method als. Vermiculites may undergo further ion exchange and hydra-
to remove and characterize inorganic components in soils. Soil Sci. Soc. tion with their interlayer cations to alter toward smectites. On
Am. J. 55:1180–1187.)
the contrary, in a lower horizon of the soil profile, an accretion
process such as acquiring interlayer substances may take place.
represents effects of various treatments on XRD patterns (Figure By this process, the following transformation routes are also
21.33). After fractionation, subsamples (from a clay fraction possible: smectites through vermiculites to chlorites, vermicu-
of podzolic B horizon) were subjected to various treatments. lites to chlorites, micas to chlorites, smectites through vermicu-
After destruction of organic matter, the <2 mm size fraction lites to micas, vermiculites to micas, and so on. As these actions
was dispersed in water by shaking overnight on an end-over- constantly work on minerals in soil, encountering a phyllosili-
end shaker, and the clay fraction was collected by sedimenta- cate mineral that cannot be correctly identified with a defini-
tion, saturated with Mg2+, and freeze-dried. This illustrates the tive soil phyllosilicate is no surprise. For example, although a
necessity of pretreatments for amorphous substances, which soil phyllosilicate indicates a nature similar to vermiculite or
mask crystalline components. A quick reference to major chem- smectite, positive identity as either entity may be impossible.
ical dissolution methods is given in Table 21.23. Details of pre- This is due to the fact that the soil phyllosilicates possess an
treatments may be consulted with appropriate manuals (Bear, intermediate nature. We have observed such cases in the series
1964; Jackson, 1967; Thorez, 1975; McKeague, 1976; Klute, 1986; mica–vermiculite, vermiculite–chlorite, ­smectite–chlorite, etc.
Dixon and Weed, 1989; Carter, 1993). One of the notable accretion processes in soils is the reaction of
hydroxyl-Al ions with 2:1 phyllosilicates. Aluminum ions solu-
21.5.2.3  Soil Phyllosilicates of Intermediate Nature bilized from minerals hydrolyze readily and are polymerized
In soil environments, especially of the temperate climate to form precipitates between expandable silicate layers like ver-
region, a majority of the weathering actions on phyllosilicates miculite or smectite to form a chlorite-like mineral. They can be
includes hydration, ion exchange, selective depletion, and par- referred to as hydroxyl-Al interlayered vermiculite or hydroxyl-
tial decomposition of the minerals. As a whole, the actions are Al interlayered smectite, respectively. These names have been
considered to be gentle ones. Under these circumstances, micas shortened to the acronyms HIV and HIS for which Barnhisel
partially loose their interlayer cations to become hydrated and Bertsch (1989) proposed to standardize the terminology.
21-34 Properties and Processes

TABLE 21.23  Major Chemical Dissolution Methods

Category Chemical Reagents Used for Dissolution Selected References
(a) Alkaline NaOH Foster (1953), Hashimoto and Jackson (1960)
Na2CO3 Mitchell and Farmer (1962), Follett et al. (1965)
(b) Acid HCl Deb (1950)
(a) + (b) alkaline + acid NaOH/HCl Segalen (1968)
(c) Complexing H4C2O4, acetic acid method Chester and Hughes (1967)
H2C2O4, oxalic acid method Ball and Beaumont (1972)
(NH4)2C2O4/H2C2O4, acid NH4–oxalate method Tamm (1922), Schwertmann (1959)
Na2C2O4/H2C2O4, acid Na–oxalate method Henmi and Wada (1976)
C6H4Na2O8S2, alkaline tiron method Biermans and Baert (1977)
Na4P2O7, Na–pyrophosphate method McKeague (1967)
K4P2O7, K–pyrophosphate method Ball and Beaumont (1972)
(d) Reducing NH2OH · HCl/HCl, hydroxylamine method Chao and Zhou (1983), Ross et al. (1985)
(c) + (d) Reducing + complexing Na2C6H5O7/NaHCO3/Na2S2O4 sodium–dithionite method Mehra and Jackson (1960)
K2C2O4/H2C2O4/Mg, Jeffries’ method Jeffries (1946)
(NH4)2C2O4/H2C2O4/Na2S2O4, combined oxalate method Duchaufour and Souchier (1966)

21.5.2.4  Interstratified Layer Silicates sheets between silicate layers of these minerals results in chlorite.
As mentioned earlier in the structure of interstratified layer sili- Therefore, interstratifications among those minerals are expected
cates, due to the structural similarities of the clay minerals, inter- to be common, as in fact they are. Figure 21.34 gives a graphic
stratified minerals can exist in which individual crystallites are presentation for each of the clay minerals as an elementary com-
composed of elementary layers of two or more types. Such mixed ponent, which is known to be composed of an interstratified
structures, in some cases, do not show characteristic features of structure with another elementary component.
each of the component layers but possess their own identity. They The most striking interstratifications occurs when two-compo-
show more or less intermediate nature of the component layers, nent layers A and B alternate regularly to make an interstratified
they are thus called intergrades. Therefore, this intermediate structure, AB AB … type, having a long d001-spacing = d001-spacing
nature may be useful to identify component layers. Table 21.24 (layer A) + d001-spacing (layer B). Let PAB be the probability that B
gives an example of diagnostic criteria. Interstratified, or mixed succeeds A given that the first layer is A, perfect regularity must
layer, clay minerals represent a special case of intergrowths, in satisfy the conditions PAB = 1 and PAA = 0. As the evaluation of such
relation to a genetic relationship between components. Neglecting conditions is not always possible, a practical measure is recom-
all questions regarding interlayer cations, ionic substitution, and mended by the Clay Minerals Society Nomenclature Committee
layer charge, montmorillonites and vermiculites, for instance, (Bailey et al., 1982). This is based on a statistical test on a well-
are essentially hydrated varieties of mica having interlamel- defined series of at least 10 00-­summation spacings (dAB = dA + dB),
lar water molecules. Instead of water, introduction of hydroxide for which the suborders are integral. The  coefficient of variation

TABLE 21.24  Diagnostic Criteria for Interstratified Minerals in Soils

Humid, Air-Dry, Very Dry,
Type of Interstratificationa Glycerol >95% RH 45% RH <3% RH 110°C 550°C
Mica–vermiculite b b 1.0–1.4 1.0–1.15 1.0–1.15 1
Mica–chlorite b b 1.0–1.4 b b 1.0–1.4
Mica–smectite 0.9–1.0 or ≈1.8 Expansion 1.0–1.55 1.0–1.15 1.0–1.15 1
Vermiculite–chlorite b b 1.4 1.15–1.4 1.15–1.4 1.0–1.4
Vermiculite–smectite 1.4–1.8 Expansion 1.4–1.54 1.15 1.15 1
Chlorite–vermiculite 1.4–1.8 Expansion 1.4–1.54 1.15–1.4 1.15–1.4 1.0–1.4
Mica–vermiculite–chlorite b b 1.0–1.4 Contraction Contraction 1.0–1.4
Mica–vermiculite–smectite Expansion Expansion 1.0–1.54 Contraction Contraction 1
Vermiculite–chlorite–smectite Expansion Expansion 1.4–1.54 Contraction Contraction 1.0–1.4
Source: Modified after Kodama, H., and J.E. Brydon. 1968a. A study of clay minerals in podzol soils in New Brunswick, eastern
Canada. Clay Miner. 7:295–309.
Expansion and contraction mean shift of the original first-order reflection (air-dry) toward large and small spacing sides, respectively.
a As Ca-saturated specimens.

b Indicates that the basal spacing is unchanged from air-dry.

Phyllosilicates 21-35

Smectite

Vermiculite

Chlorite

Mica
Hydrated
halloysite

Talc

Pyrophyllite

Halloysite

Kaolinite

FIGURE 21.34  Diagrammatic representation of layer silicate type combination found in nature as interstratified clay minerals. = frequent ▪
▫
occurrence; = less-frequent occurrence. (Modified after Sudo, T., S. Shimoda, H. Yotsumoto, and S. Aita. 1981. Electron micrographs of clay
minerals. Developments in sedimentology. Vol. 31. Elsevier Scientific Publishing Co., New York.)

(CV) of the d00-values should be less than 0.75 to demonstrate ade- of the Xi values, and n is the number of observed Xi values. In Table
quate regularity of alternation. The CV is defined as CV = 100s/X, 21.25, an example is shown using the case of rectorite–Ca, which is
where the standard deviation for a small sample is s = [Σ(Xi − X)2/ a regularly interstratified mineral, smectite–Ca mica. The observed
(n − 1)]1/2, Xi is an individual observed − x d00-value, X is the mean long d001-spacing is 2.8 nm on glycolation. This agrees with the
summation of 1.8 nm for smectite and 1.0 nm for mica when they
TABLE 21.25  Example of the CV Test for Evaluating are glycolated. The XRD data of the rectorite show observable basal
Regularity of Interstratifications reflections up to the 20th in that recording range. The d × ℓ values
Rectorite–Ca, Sample # 1820 in the table correspond to observed − x d00-values (Xi). Calculations
for this rectorite result in 2.751 nm for the average (X) and 0.463 for
00ℓ d (Å) I d (Å) × ℓ
the CV value that is much smaller than the recommended value
1 28.09 847 28.09a of 0.75. The majority of interstratified layer silicates is not well
2 14.01 174 28.02a ordered, so they do not show basal reflection of a long spacing
3 9.267 84 27.8 (dAB = dA + dB) nor a rational integral series of basal reflections.
4 6.923 40 27.69
Characterization requires:
5 5.495 7 27.47
6 4.588 31 27.53 1. Determination of component layers A and B (or, and C)
7 3.933 23 27.53 2. Evaluation of the mixing ratio for the component layers
8 3.442 33 27.54 A and B, that is, A:B = m:(1 − m), where 0 < m < 1
9 3.065 42 27.58 3. Probability for layer-stacking sequence as expressed by
10 2.723 4 27.23 PAA, PAB , etc
11 2.503 7 27.53
12 — — — The determination of component layers can be done by choosing
13 — — — appropriate diagnostic tests for them. A relatively simple method
14 1.963 6 27.48 is available to evaluate the mixing ratio of two components
15 1.832 5 27.48 in an irregularly interstratified structure. The principle of the
16 — — — method is based on the peak migration due to the interference
17 1.615 3 27.46 phenomenon of x-rays (Méring, 1949). According to Méring’s
18 1.527 3 27.49 idea, Figure 21.35 is constructed to explain the principle, using
19 1.443 2 27.42
0 S1 2S1 3S1 4S1 5S1 6S1 7S1
20 1.372 3 27.4 2 sin θ
Average 27.51 λ
S2 2S2 3S2 4S2 5S2 6S2 7S2 8S2
CV 0.463
Source: After Matsuda, T., H. Kodama, and A.-F. Yang. FIGURE 21.35  Demonstration of Méring’s method, in which peak
1997. Ca-rectorite from Sano mine, Nagano prefecture, migration is used for evaluating the mixing ratio of two-component
Japan. Clays Clay Miner. 45:773–780. layers in an interstratified clay mineral. S1: Na-saturated rectorite,
a Excluded from CV calculations. S2: Ca-saturated rectorite.
21-36 Properties and Processes

modified rectorite samples. Sodium (Na)-saturated rectorite SMJ 1 AAAAA

A AAAA + ABC
(S1) and Ca-saturated rectorite (S2) were prepared separately.
AAA + + ABC
Because the hydration state of Na-saturated smectite differs from AA AAAB
AC BC AAC
that of Ca-saturated smectite under relative humidity at 50%, + BBC
B AB
S1 gives d001 at 2.24 nm and S2 at 2.54 nm. In this figure, the 00ℓ AAAC
C AAB
reciprocal lattice rows of reciprocal spacing S1 = 1/d1 and S2 = 1/d2
are given and the heavy lines, such as between S2 and S1, indicate
the regions in reciprocal space where reflections are predicted to
appear as two-component peaks merging together when the two
are mixed coherently (in respect with x-rays) without physical
segregation and do not constitute a regularly interstratified struc-
ture. The assumption is that the peaks move linearly from the
position for one pure component toward the nearest position of
AAAA
the other component as the proportions of the components alter.

W (R)
SMJ 9 + ABC
This may not be rigorously correct, but information obtained
this way is quite useful. This estimation should be performed by AAA AAAAA
A B AC + AABC
inspecting the peak migrations in as many regions as possible. + BC
As the next step, it is desirable to determine the probability of C AB AAAB
layer-stacking sequence. A direct Fourier transform method devel- AA
AAC
+ BBC
oped by MacEwan and Wilson (1980) and MacEwan et al. (1961)
has been applied widely. With mathematical approximation,
MacEwan formulates the equation as

⎛ a⎞
WR = ⎜ ⎟ Σi(s)cos(μ S R) (21.4)
⎝ π⎠

with 10 20 30 40 50
R (Å)
Is
i( s ) =
Θ s IFs I 2 FIGURE 21.36  Example of direct Fourier transform method by

MacEwan on soil clays. (From Kodama, H., and J.E. Brydon. 1968a.
A study of clay minerals in podzol soils in New Brunswick, eastern
where
Canada. Clay Miner. 7:295–309.)
WR is the distribution function defined as the probability of
finding another layer at the distance R measured perpen- the observed allow the probability coefficients to be estimated
dicularly from any layer from the results of the Fourier transform. The direct method is
μS , Is, Θs, and IFsI2 are values at the position of the intensity applicable to any interstratifications but caution should be paid
maximum to the precision of the results obtained by the Fourier method,
μS = 2 sin θ/λ which may be affected by premature termination of basal reflec-
Is is the integrated intensity tion series and assessing the baseline for the obtained occurrence
Θs is the operational function probability curve. Thus, preliminary information concerning the
IFsI 2 is the layer structure factor mixing ratio and layer-stacking sequence is acquired and diffrac-
tion patterns can be simulated by computer calculations. Several
Therefore, a Fourier transform on a series of basal reflections simulation approaches are available (Kakinoki and Komura,
of unknown mixed-layer mineral gives the probability of find- 1952, 1954; Sato, 1965, 1973; Reynolds, 1980; Moore and
ing layer B succeeding layer A (PAB) and so on. An application Reynolds, 1989; Yuan and Bish, 2010) for further refinement of
to soil minerals is shown in Figure 21.36. This case happened to the structure of interstratified layer silicates, if cases allow.
be a tertiary system, smectite–vermiculite–mica. The first three
peaks (hA, hB , hC) correspond to the probabilities of occurrence
of the fundamental component layers, A (smectite), B (vermic- 21.5.3  Other Instrumental Methods
ulite), and C (mica), respectively. Obviously PA + PB + PC = 1,
therefore, PA = 0.53, PB = 0.27, and PC = 0.20 were obtained from 21.5.3.1  X-Ray Diffraction Photograph Methods
the observed heights for sample SMJ 1. Knowing the relation Undoubtedly x-ray diffractometer methods are dominating to
between peak heights and occurrence frequencies (for instance, collect diffraction data nowadays. However, in the case where
hAA = PAPAA, hAB = PAPAB + PBPBA, etc.), calculating heights for only a limited quantity of sample is available, classical photo-
all possible layer sequences and comparing the calculated with graphic methods by the Debye–Scherrer camera is still useful
Phyllosilicates 21-37

to obtain maximum information on a mineral in a fraction of goniometer head itself rotating around an axis tilted 45° to the
milligram. This camera method can avoid preferred orienta- central rotating axis. With this camera, a single-mineral crystal,
tion to which phyllosilicates have a strong tendency. The deter- or grain, or aggregate, in a fraction of millimeter size, is suffi-
mination of polytypes requires details of nonbasal reflections. cient to provide adequate powder diffraction patterns without
Therefore, the use of camera techniques is beneficial. Gandolfi grinding. Examples are presented in Figure 21.38b. Wilson and
camera is one type of a modified Debye–Scherrer x-ray powder Clark (1978) developed a method for identifying minerals on
diffraction camera. In this camera (Figure 21.37a), the mounted thin sections by a combination of optical observations and XRD
sample rotates around two axes, that is, the sample stage arm analysis. This is an interesting area to be explored further for
rotating around the center of the camera and the sample on a routine application.

1 cm

(a) (b)

FIGURE 21.37  An application of Gandolfi diffraction camera method to a small grain of mineral for collecting data without pulverizing the
sample. (a) Shows the mounted sample rotating around two axes. (b) XRD patterns obtained. A, Phlogopite; B, corrensite; C, calcite; and D, graph-
ite. A, B, C, and D correspond to those locations in the weathered phlogopite crystal piece where samples were taken. (Modified after De Kimpe,
C.R., N. Miles, H. Kodama, and J. Dejou. 1987. Alteration of phlogopite to corrensite at Sharbot Lake, Ontario. Clays Clay Miner. 35:150–158.)

20–10 μ
10–5 μ

20–10 μ 5–2 μ
–dw/dT (DTGA)

2–1 μ
Weight loss

10–5 μ
ΔT (DTA)

20–10 μ
10–5 μ 5–2 μ 1–0.5 μ
5–2 μ
2–1 μ
2–1 μ
1–0.5μ
1% 1–0.5 μ
0.5–0.2 μ
0.5–0.2 μ

200 400 600 800 1000 200 400 600 800 1000 1200
(a) Temperature °C (b) Temperature °C

FIGURE 21.38  (a) TGA curves and (b) DTGA (solid lines) and DTA (dashed lines) curves of the fractionated samples of a naturally occurring micro-
crystalline muscovite. (From Kodama, H., and J.E. Brydon. 1968b. Dehydroxylation of micro-crystalline muscovite. Trans. Faraday Soc. 64:3112–3119.)
21-38 Properties and Processes

21.5.3.2  Methods for Specific Characterization method, the application of 29Si (and 27Al) magic-angle spinning,
As discussed in the section on crystal structures, the 1:1 type solid-state nuclear magnetic resonance spectroscopy was intro-
structures possess hydroxyls in two different octahedral envi- duced into the research in this line (Herrero et al., 1985). The
spectra are obtained as chemical isomer (in this case 29Si) shift
ronments, that is, one locates inside at the interface between
(ppm), which is influenced by the chemical environment of the
the octahedral and tetrahedral sheets, and another is exposed
nucleus. The range where resonance spectra appear as a func-
to the outside of the octahedral sheet. This is one of the unique
tion of polymerization (if true mica, denoted as Q3 for Si3Al1)
characteristics of the 1:1 layer silicates, which may be used for
and analysis of spectra provides information about Si and Al
their identification. Infrared absorption spectroscopy can pro-
ordering in the tetrahedral sheet, including the number of next-
vide details of the OH-stretching bonds in the region of 4000–
neighbor Si in layer silicates. Conversely, using the 27Al nucleus,
3000 cm−1 in terms of its orientation against the basal plane
spectra acquired supply information regarding Al and Si order-
and its bond distance (O–H . . . O) as affected by octahedral
ing and the number of next-neighbor Al in layer silicates (Sans
environments, including elemental compositions (Tuddenham
and Serratosa, 1984). Data can be used to compliment each other.
and Lyon, 1959; Nakamoto, 1963). The orientation is known
The origin of the total layer charge in phyllosilicates is due to
to depend on octahedral cation vacancies; therefore, a simi-
ionic substitutions by atoms of lower valence for those of higher
lar view can be extended to the difference in dioctahedral and
valence like Al3+ → Si4+, Fe2+ → Fe3+, Mg2+ → Al3+. The way in
trioctahedral 2:1 type structures as well (Serratosa and Bradley,
which layer charge is distributed in the structure of a specific
1958). A number of papers have been published along these lines
phyllosilicate appears to closely relate to the course of weather-
(only selected ones: Vedder and McDonald, 1963; Vedder, 1964;
ing or alteration, which the mineral might take in nature. We
Farmer, 1974; Robert and Kodama, 1988).
often believe that phyllosilicates behave erratically, but this is
Dealing with iron-bearing phyllosilicates, the actual amount
because we normally treat them as if they were totally “struc-
of iron incorporated structurally; the Fe2+:Fe3+ ratio as oxidation
turally homogenous.” For instance, when smectite is suspended
state; structural configuration, like distribution of these cations
in water containing Na+ and Ca 2+, a demixing phenomenon is
between cis- and trans-octahedral sites; the amount of Fe3+ in tet-
observed (Glaeser and Méring, 1954; Glaeser, 1958). Certain
rahedral sites; and occasionally their role in the magnetic nature
phyllosilicates behave as if the distribution of their layer charge
of the minerals are sought. In the presence of organic matter, the
is not symmetrical, in other words, the layer charge distribution
determination of Fe2+ is impossible by wet-chemical methods.
in the structure has a polarity. In this connection, the n-alkyl-
Application of the Mössbauer effect under these situations is very
ammonium exchange method developed by Lagaly and Wiess
appropriate. The 57Fe Mössbauer spectroscopy provides param-
(1969) is useful for estimating interlayer charge and character-
eters such as isomer shift, IS (mm s−1), quadrupole splitting, ΔEQ
izing expandable layer silicates by making complexes with the
(mm s−1), and internal magnetic hyperfine field, H (in kOe), if
surface of the expandable layer silicates, then the d001-spacings
magnetic ordering is present. Most key information is foiled in
of the complexes are measured. The magnitude of the spacing
the quadrupole doublets. Spectra are recorded at temperatures
is related to the size and tilt angle (α) of the n-alkylammonium
ranging from 4 to 298 K (liquid He to room temperature) to iden-
intercalated between the expandable silicate layers. The tilt angle
tify the oxidation state, coordination environment, and magnetic
(α), that is, the angle between the alkyl chain and the basal plane
exchange interactions occurring in the constituent minerals.
of the clay, is related to the layer charge. To evaluate layer charge
The parameters allow the identification of Fe in various (oxy-
irregularity, peak positions and profiles of higher order basal
hydr)oxide and phyllosilicate phases in mixed mineral systems.
reflections may need to be inspected in detail (Lagaly, 1979,
Analysis of Mössbauer spectra is carried out by computer using a 1982; Ghabru et al., 1989) Vali and Koster (1986) developed a
least-squares minimization fitting routine for obtaining the best method that allows us to make the alkylammonium ion treat-
peak profile. Spectral parameters obtained after refinement may ment of clay minerals in ultrathin sections for high-resolution
give answers to the questions above (Stucki et al., 1988; Coey, transmission electron microscope (HRTEM) observations. The
1988; Murad, 1988; Murad and Cashion, 2004). Among minerals method proved promising and awaits further applications, espe-
having a chlorite structure, the distinction between iron atoms cially studies on microenvironments.
in the octahedral sheet and iron atoms in the hydroxide sheet The task of distinguishing and quantifying the various types
has yet to succeed. Murad and Wagner (1991, 1994) succeeded of water, that is, physically adsorbed, zeolitic, interlayer, and
in obtaining detailed characterization of kaolinite minerals and structural, is not easy. Thermoanalytical methods including
illite by the application of Mössbauer spectroscopy. thermogravimetric analysis (TGA), differential TGA (DTGA),
The distribution of aluminum atoms that substitute for silicon and differential thermal analysis (DTA) are often applied for this
atoms in the tetrahedral sheet is an interesting subject from a crys- purpose. Although TGA is indispensable for obtaining weight
tallographic point of view (Loewenstein, 1954). Investigations by loss, DTGA is helpful to evaluate a critical temperature for dis-
x-ray methods were performed as done for muscovite by Gatineau tinguishing between water of two different types. The features
(1964). Because the data needed for this purpose require tedious in a TGA curve are generally too broad to pinpoint precisely
recording and collection of non-Bragg reflections, only special- the temperatures over which a dehydration reaction occurs (see
ized laboratories can afford such experiments. Besides the x-ray Figure 21.38).
Phyllosilicates 21-39

Water retention is one of the key properties of clay mineral sur- where
faces, as already mentioned. This is due in part to the small par- ρi and �i* are the density and mass absorption coefficient of
ticle size and large surface area of the clay minerals, as illustrated the component i, respectively
by the fact that a handful of clay provides enough surface area to Ki depends upon the nature of component i and the geometry
cover an area the size of a football field. Among clay minerals, of the apparatus employed
expandable minerals possess greater surface area than nonex-
pandable minerals, because in the former surfaces both internal By regarding the mixture of n components as if it consisted of
and external to the particles contribute to the total surface area. just two components, component 1 to be analyzed and the sum
Surface area measurements by N2 gas adsorption, notably using of the other components designated as matrix, Equation 21.5
the Brunnauer, Emmett, and Teller (BET, method (Brunauer may be extended to a very useful form:
et al., 1938), are often applied for evaluating external surface area.
For total surface area (=external + internal) measurements, gly- K1x1
I1 = (21.6)
col retention method (Diamond and Kinter, 1958), ethylene glycol {ρ1[x1(μ1* − μ *M ) + μ *M ]}

monoethyl ether (EGME) method (Carter et al., 1965), a modi-
fied EGME method (Eltantawy and Arnold, 1973), and methylene where �*M is the mass absorption coefficient of the matrix.
blue method (Hang and Brindley, 1970) are often applied. Equation 21.6 is the basic relationship underlying quantitative
Recent developments in analytical instrumentation enable us analysis of multicomponent mixtures with the x-ray diffractom-
to explore objects in much smaller domains as they exist without eter (Alexander and Klug, 1948; Klug and Alexander, 1954). The
separation, that is, almost in situ observations (e.g., Tessier, 1990). diffraction intensity of component 1 is thus related to its concen-
Perhaps, studies of clay minerals in soil aggregates and in the tration in the mixture and to relative mass absorption coefficients
rhizosphere are certainly interesting. Ideas and concepts regard- of the component and matrix. Because of this relationship, except
ing mineral alteration mechanisms have long been speculated for the case where μ1* = μ *M , that is, the case of a mixture consisting
since Keller and Frederickson (1952) followed by Mortland et al. of only polymorphic substances, the intensity–concentration rela-
(1956). This appears recently to revive and improve with modern tion is generally not linear. Since mass absorption coefficients are
technologies (Robert and Berthelin, 1984; April and Keller, 1990; functions of the chemical composition of the absorber and of the
Hinsinger et al., 1992; Hinsinger and Jaillard, 1993). Approaches wavelength of x-rays irradiated, it is readily understood that the
from different perspectives were attempted by Kodama et al. choice of radiation to be employed is important. Practical solutions
(1994) for the role of clay minerals in the rhizosphere and by to Equations 21.5 and 21.6 are discussed in the following section.
Monreal and Kodama (1997) for the role of clay minerals as soil
21.5.4.2  Intensity–Concentration Calibration Curve
aggregates in microbial activity.
Interactions with microbes have received a great deal of atten- For general analytical purposes, one possible solution of
tion. Huang and Schnitzer (1986) summarized an achievement Equation 21.6 is to establish intensity–concentration working
of the workshop organized for interactions of soil minerals curves from multicomponent standard synthetic mixtures that
with natural organics and microbes. Reviews until 1997 can be simulate a natural system in question. This approach has been
seen in Geomicrobiology (Banfield and Nealson, 1997). Tazaki attempted for the quantitative estimation of clay minerals by
and Asada (2007) provided transmission electron micrographs Talvenheimo and White (1952) among others. However, numer-
showing intimate association where clay particles attached ous combinations of mineral associations occur in nature, so to
to a thick wall covering the bacteria. They explained that clay cover all possible cases by preparing synthetic standard mixtures
particles and the thick wall, a kind of cellular polymeric sub- is not practical. Thus, this approach is necessarily restricted to
stance, are able to protect bacteria from toxic elements such as simple systems. One of the more practical solutions to the analy-
Hg. The research was performed by an appropriate application sis of complicated multicomponent systems may be to compare
of energy-filtering transmission electron microscopy, scanning intensities of two components in a multicomponent mixture and
transmission microscopy equipped with energy dispersive x-ray to relate them to their weight proportions. By introducing the
spectroscopy, optical and fluorescence microscopy, XRD, and average mass absorption coefficient, μ*, for the mixture, we can
atomic absorption spectrometry. simplify Equation 21.5 to

⎡ x ⎤
21.5.4  Quantification I i = K iʹ ⎢ i ⎥ (21.7)
⎣ (ρi μ*) ⎦
21.5.4.1  Basic Theory
Then a comparison between intensities of the ith and jth compo-
Alexander and Klug (1948) showed that the XRD intensity (Ii)
nents produces the relation independent of μ* (Brindley, 1961)
from  the ith component in a multicomponent mixture can  be
as follows:
related to the weight fraction of the component (xi) by the equation,
K i(xi /ρi ) Ii K iʹ xiρ j ⎛x ⎞
Ii = (21.5) = = K ʹʹ ⎜ i ⎟ (21.8)
(Σμ*i xi ) I j (K ʹj x jρi ) ⎝ xj ⎠

21-40 Properties and Processes

j , ρi, and ρj, for two min-

where K″ includes all constants, K i�, K � μ* of Equation 21.7 by this addition can be neglected, then the
eral components i and j. Equation 21.8 suggests a linear relation- ratio (I1�: I1) of intensities of component 1 being analyzed before
ship between the intensity ratio (Ii:Ij) and the ratio of weight (I1) and after (I1�) should be directly proportional to the ratio of
fractions (xi:xj) for the two mineral components. Therefore, if weight fractions as follows (Brindley and Udagawa, 1960):
the K″ is evaluated experimentally by synthetic mixtures, the
relative weight fractions in unknowns can be determined from I1ʹ (x1 + x1ʹ )
= (21.11)
measurements of intensity ratios. In a multicomponent system, I1 [x1(1 + x1ʹ )]

the weight fraction of each mineral component can be estimated
by integration of the results on mineral pairs, which cover all
where the right-hand term is the weight fraction of the compo-
mineral species in the sample. This method was applied to clay
nent after the addition of the component to the sample. It should
minerals by Theisen and Bellis (1964).
be borne in mind that the optimum amount of the pure mineral
21.5.4.3  Internal Standard Method added depends upon the initial amount of the mineral compo-
nent in the sample. As a general guide, 25%–100% of the initial
The use of an internal standard also permits quantitative analy-
amount may be recommended.
sis without any direct knowledge of the mass absorption coef-
ficients of components (�i*), since the method is based on a 21.5.4.5  External Standard Method (Direct Method)
relation similar to Equation 21.8. Suppose that a known and
constant amount of an internal standard, which will be desig- This method requires mass absorption coefficient measurements
nated by the subscript “s” is added to an unknown mixture. Then and has been applied by Williams (1959), Norrish and Taylor
the weight fraction of component 1 (x1) in the original mixture is (1962), and others. Such measurements are, however, rather
changed to x1�, which is expressed by the relation, x1 = x1ʹ /(1 − x S ) . time-consuming and the method has only limited application to
This relation can be derived as follows: since wS/xS = (w + wS), complicated mineral mixtures in soils.
where w and wS are the total sample weight before the addition of
21.5.4.6  Estimation Based on Intensity Factor Ratios
the standard and the weight of the standard added, respectively;
thus, 1 − xS = w/(w + wS). On the other hand, x1ʹ = w1 /(w + wS ) The diffraction intensity, Ihkl, of the hkl reflection is proportional
and x1 = w1/w, therefore x1 = x1ʹ /(1 − x S ). Taking the intensity to the square of the structure factor, Fhkl, thus, Ihkl ∼ KIFhklI 2,
ratio of I1 to IS in a manner similar to Equation 21.8, we obtain where K depends upon experimental conditions and the value
the relation of F is related to the numbers and kinds of atoms involved in the
reflection plane hkl of a mineral structure. Consider a mixture
I1 K1x1ʹ ρS [K1ʹ x1(1 − x S )ρS ] consisting of two minerals A and B with equal amounts and let
= = (21.9) IA and IB be the diffraction intensities from any reflection planes
IS K S x Sρ1 K S x Sρ1
of minerals A and B, respectively. The ratio IB:IA should be con-
stant regardless of the absolute amounts of both minerals, and
All components but x1 in the right-hand term of Equation 21.9
this constant factor, k, may be expressed by IFBI 2/IFAI 2, where FA
are regarded as constant; Equation 21.9 can, therefore, be
and FB are the structure factors for the corresponding reflections
arranged to
of minerals A and B, respectively. The IA is, therefore, equal to
IB/k. If the amounts of minerals A and B are not the same, they
⎛I ⎞ would be proportional to IA/1 and IB/k, respectively. This is the
x1 = k ⎜ 1 ⎟ (21.10)
⎝ IS ⎠ basic concept for the quantification method based on the inten-
sity factor ratios. The concept can be extended easily to multi-
Thus, the concentration of component 1 is proportional to the component systems.
intensity ratio I1:IS alone and independent of mass absorp- The preferred orientation method is widely applied to iden-
tion coefficients of a specific mineral and matrix. This method tify clay minerals. It is, therefore, very convenient and practical
has been applied to clays and related minerals using internal that the basal reflections are used for quantification. The basal
standards such as fluorite (CaF2) (Alexander and Klug, 1948), intensity factor ratios may be obtained (a) directly from struc-
boehmite (AlOOH) (Brindley and Kurtossy, 1961), Zn(OH)2 ture factor calculations or (b) by graphical approximation from
(Mossman et al., 1967), and pyrophyllite (Mossman et al., 1967). squared moduli of layer structure factors prepared by Bradley
(1953), MacEwan et al. (1961), and Cole and Lancucki (1966)
21.5.4.4  Standard Additional Method (Spike Method) for various types. By these approaches, Johns et al. (1954) first
As described by Brindley and Udagawa (1960), this method attempted the quantification of clay minerals and many inves-
involves an addition of a known amount of a pure mineral tigators followed (e.g., Weaver, 1958; Schultz, 1960, 1964; Dell,
component to a sample in which the mineral component is to be 1973). Another way to evaluate the factors is by an experimen-
analyzed. The method is useful if the characteristics of the min- tal determination based upon synthetic standard mixtures. The
eral component in the sample closely resemble those of the pure advantage of the latter is that the factors evaluated can include
mineral component to be added. If the change in the average all necessary correction factors due to experimental conditions
Phyllosilicates 21-41

as well as the intensity factor. Therefore, the factors can be Appendix

applied immediately to estimate quantities of clay minerals, as
long as the experimental conditions are the same as those for the Glossary of Phyllosilicates
synthetic standard mixtures from which the factors were evalu-
Notes:
ated. In general practice for the quantification of clay minerals,
intensity factors are determined using a series of binary mineral 1. Every valid mineral species names are listed in bold face.
systems, like minerals A and B, with equal amounts at several 2. Mineral group names are in italic.
different levels. Similar experiments should be extended to other 3. Majority of interstratified minerals listed here are given
binary systems like minerals A and C, or A and D, and so on. in a form of binary system expressed by mineral group
Obviously, the intensity factors of mineral A are expected for names (mica–smectite, vermiculite–smectite, etc.).
normalization for the whole. The mineral illite is often chosen
for this purpose due to various merits. This approach was chosen A
by Oinuma et al. (1961). Most clay minerals vary in crystallin- Aliettite  1:1 regular interlayering of talc–trioctahedral
ity and composition, which greatly affect their basal reflection ­smectite-group mineral, Interstratified Layer Silicate Group
intensities. Because of this, quantitative estimations made from Allevardite = Rectorite
these intensity factor methods are crude in comparison with Alurgite = magnesian manganiferous Muscovite
those done by methods described in previous sections. In view Amesite  Mg2Al(Si,Al)O5(OH)4, Serpentine–Kaolin Group
of difficulties due to variations in clay minerals, however, such Amesite-2H
an approach is believed to be the best compromise. Amesite-6R
Anandite  Ba,K(Fe2+,Mg)3(Si,Al,Fe3+)4O10(O,OH)2, Brittle Mica
21.5.4.7  General Outline for Soil Mineral Group
Quantification Anandite-2M1
Anandite-2Or
Since soils are complex mixtures of substances of varying Anauxite = mixture of kaolinite and amorphous silica
degrees of crystallinity ranging from amorphous to strongly Annite  K(Fe2+)3(AlSi3)O10(OH,F)2, True Mica Group
crystalline, achieving quantitative analysis with a comparable Antigorite  (Mg,Fe)3Si2O5(OH)4, Serpentine–Kaolin Group
precision for all mineral components at the same time is almost Aphrosiderite = ferroan Clinochlore
impossible. Although a major emphasis should be put on clay Aspidolite = sodium Phlogopite
minerals that usually constitute a large portion of crystalline Attapulgite = Palygorskite
substances in the clay-size fraction of soils, depending upon the
type of minerals involved, a more precise estimation may be
made by choosing a suitable method for a specific case. Thus, the B
general outline adapted in our laboratory for the soil mineral Baileychlore  (Zn,Fe2+,Al,Mg)6(Si,Al)4O10(OH)8, Chlorite Group
quantification is a combination of methods as follows (Kodama Bannisterite  KCa(Fe,Mn,Zn,Mg)20(Si,Al)32O76(OH)16 · 4–12H2O,
et al., 1977): Modulated Layer Silicate Group
Baumite = zirconian Caryopilite, zirconian Greenalite
1. The method using intensity factor ratios for clay minerals Bementite  Mn7Si6O15(OH)8, Modulated Layer Silicate Group
(phyllosilicates) in general Beidellite  (Na,Ca)0.3(Al)2(Si,Al)O10(OH)2 · nH2O, Smectite Group
2. The intensity–concentration calibration method for quartz Bentonite = (a) impure Montmorillonite, (b) Beidellite
3. The internal standard method for hematite and goethite Berthierine  (Fe2+,Fe3+,Mg)2–3(Si,Al)2O5(OH)4, Serpentine–Kaolin
4. A combination of the intensity–concentration and inter- Group
nal standard methods for feldspars and amphiboles Berthierine-1M
5. The standard addition method for minerals such as cal- Biotite  K(Mg,Fe2+)3(Al,Fe3+)Si3O10(OH,F)2, True Mica Group
cite, dolomite, gypsum, serpentine minerals, talc, pyro- Bityite  CaLiAl2(AlBeSi2)O10(OH)2, Brittle Mica Group
phyllite, and jarosite, which occur less frequently in soils Bowingite = Saponite
and whose crystallinities do not vary much so that a stan- Bramallite = sodian Muscovite (Illite)
dard representing the mineral to be analyzed in a sample Brandisite = Clintonite
is easily available Brindleyite  (Ni,Mg,Fe2+)2Al(Si,Al)O5(OH)4, Serpentine–Kaolin
Group
Brunsvigite = Chamosite
Addendum
After the preparation of this chapter, the author received a C
copy of the following manuscript: The Mica Group, In Kluwer Cardenite = ferrian Saponite
Encyclopaedia of Mineralogy by A.E. Lalonde, 90 pp with nine Carlosturanite  (Mg,Fe2+,Ti)21(Si,Al)12O28(OH)34, Modulated Layer
figures. This appears to be available online. Silicate Group
21-42 Properties and Processes

Caryopilite  (Mn2+,Mg)3Si2O5(OH)4, Modulated Layer Silicate F

Group Falcondoite  (Ni,Mg)4Si6O15(OH)2 · 6H2O, a nickeloan variety
Celadonite  K(Mg,Fe2+)3(Fe3+,Al)Si4O10(OH)2, True Mica Group of Sepiolite, Sepiolite–Palygorskite Group
Cerolite = (a) talc; (b) mixture of serpentine and Stevensite Ferriannite (Ferri-annite)  K(Fe2+,Mg)3(Fe3+,Al)Si3O10(OH,F)2,
Chamosite  (Fe2+,Mg,Fe3+,Al)5Al(Si3Al)O10(OH,O)8, Chlorite Group True Mica Group
Chamosite-7Å Ferriphlogopite = ferrian Phlogopite
Chernykhite  (Ba,Na)(V3+,Al)2(Si,Al)4O10(OH)2, True Mica Ferripyrophyllite  Fe23+ Si4O10(OH)2, compare Pyrophyllite
Group Fraipontite  (Zn,Al)3(Si,Al)2O5(OH)4, Serpentine–Kaolin
Chlorite  A mineral group, with general structural formula, Group
(Mg,Fe2+,Fe3+,Li,Al,Mn,Ni,Zn)4−6(Si,Al,B,Fe3+)4O10(OH,O)8
Chlorite–mica  See Mica–chlorite
Chlorite–smectite  Interlayering of chlorite and smectite min- G
erals with various mixing ratio and layer-stacking sequence Ganophyllite  (K,Na)2(Mn,Al,Mg)8(Si,Al)12O29(OH)7 · 8−9H 2
of the two components, Interstratified Layer Silicate Group O, Modulated Layer Silicate Group
Chlorite–talc  See Talc–chlorite Garnierites = general term for hydrous nickel silicates, mainly
Chlorite–vermiculite  Interlayering of chlorite and vermiculite Népouite, Falcondoite
minerals with various mixing ratio and layer-stacking sequence Ghassoulite = Hectorite
of the two components, Interstratified Layer Silicate Group Glauconite  (K,Na)(Fe3+,Al,Mg)2(Si,Al)4O10(OH)2, True Mica
Chloropal = Nontronite Group
Chrysocolla  (Cu2+,Al)2H2Si2O5(OH)4 · nH2O, Serpentine– Gonyerite  (Mn2+,Mg)5Fe3+(Si3Fe3+)O10(OH)8, Modulated Layer
Kaolin Group Silicate Group
Chrysolite  Mg3Si2O5(OH)4, Serpentine–Kaolin Group Greenalite  (Fe2+,Fe3+)2−3Si2O5(OH)4, Modulated Layer Silicate
Chrysolite-1Mcl Group
Chrysolite-2Mcl Griffithite = ferroan Saponite
Chrysolite-2Orcl Grovesite = Pennantite
Clinochlore  (Mg,Fe2+)5Al(Si3Al)O10(OH,O)8, forms a series
with Chamosite, Chlorite Group
Clinochrysotile = Chrysolite-1Mcl H
Clintonite  Ca(Mg,Al)3(Al3Si)O10(OH)2, Brittle Mica Group Halloysite  Al2Si2O5(OH)4, Serpentine–Kaolin Group
Clintonite-1M Halloysite-7 Å  Al2Si2O5(OH)4
Clintonite-2M Halloysite-10 Å  Al2Si2O5(OH)4 · 2H2O
Cookeite  Li,Al4(Si3Al)O10(OH)8, Chlorite Group Halloysite—hydrated halloysite  Interlayering of halloysite-7 Å
Corrensite  1:1 Regular interlayering of trioctahedral chlorite– and halloysite-10 Å, with various mixing ratio and stacking
smectite or vermiculite-group mineral, with approximate sequence of the two components, Interstratified Layer Silicate
structural formula (Mg,Fe,Al)9(Si,Al)8O20(OH,O)10 · nH2O, Group
Interstratified Layer Silicate Group Hectorite  Na0.3(Mg,Li)3Si4O10(F,OH)2, Smectite Group
Corundphilite = ferroan Clinochlore Hendricksite  K(Zn,Mg,Mn2+)3(Si3Al)O10(OH)2, True Mica
Cronstedtite  Fe32+ Fe3+(Si,Fe3+)2O5(OH)4, Serpentine–Kaolin Group
Group Hydrated halloysite = Halloysite-10 Å
Cronstedtite-1H Hydrobiotite  1:1 Regular interlayering of biotite and vermicu-
lite, Interstratified Layer Silicate Group
D Hydromicas  K-poor and H2O-rich Muscovite (illite); altered
Daphnite = manganoan Chamosite Muscovite
Delessite = magnesian Chamosite or ferrous Clinochlore Hydromuscovite = Hydromicas
Deweylite = mixture of Chrysotile or Lizardite and
Stevensite
Diabantite = ferroan Clinochlore, Chamosite I
Dickite  Al2Si2O5(OH)4, polymorphic relationship with kaolin- Illite  (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,H2O], True Mica
ite and nacrite, Group
Donbassite  Al4−5(Si3Al)O10(OH)8, Chlorite Group Illite–chlorite  Compare Mica–chlorite, Interstratified Layer
Silicate Group
E Illite–smectite  Compare Mica–smectite, Interstratified Layer
Eastonite = (a) Biotite, (b) Vermiculite, (c) Phlogopite Silicate Group
Endellite = (a) Hydrated halloysite, (b) Halloysite Illite–vermiculite  Compare Mica–vermiculite, Interstratified
Ephesite  NaLiAl2(Al2Si2)O10(OH)2, Brittle Mica Group Layer Silicate Group
Phyllosilicates 21-43

K Muscovite  KAl2(Si3Al)O10(OH,F)2, True Mica Group

Kämmererite = chromian Clinochlore Muscovite-1M
Kaolin  A general term for kaolin minerals, with Serpentine Muscovite-2M1
forms Serpentine–Kaolin Group Muscovite-2M2
Kaolin–smectite  Interlayering of kaolin and smectite minerals Muscovite-3T
with various mixing ratio and various stacking sequence of
the two components, Interstratified Layer Silicate Group N
Kaolinite  Al2Si2O5(OH)4, Serpentine–Kaolin Group Nacrite  Al2Si2O5(OH)4 polymorphic relationship with Dickite,
Kellyite  (Mn2+,Mg,Al)3(Si,Al)2O5(OH)4, Serpentine–Kaolin Group Halloysite, and Kaolinite, Serpentine–Kaolin Group
Kerolite  (a) Mixture of serpentine and stevensite; (b) talc Nanpiningite  Cs(Al,Mg,Fe2+,Li)2(Si3Al)O10(OH,F)2, True Mica
Kinoshitalite  (Ba,K)(Mg,Mn,Al)3(Si,Al)4O10(OH,F)2, Brittle Group
Mica Group Népouite  Ni3Si2O5(OH)4, Serpentine–Kaolin Group
Kotschubeite = ferroan Clinochlore Nimite  (Ni,Mg,Fe2+)5Al(Si3Al)O10(OH)8, Chlorite Group
Kulkeite  (Na0.4Mg8Al(Al,Si7)O20(OH)10, a 1:1 interlayering of Nontronite  Na 0.3Fe23 + (Si, Al)4 O10 (OH)2 . nH2O, Smectite Group
talc and trioctahedral chlorite, Interstratified Layer Silicate Norrishite  KLiMn23+Si 4O12, True Mica Group
Group
O
L Odinite  (Fe3+,Mg,Al,Fe2+)2.5(Si,Al)2O5(OH)4, Serpentine–Kaolin
Lepidolite  K(Li,Al)3(Si,Al)4O10(F,OH)2, True Mica Group Group
Lepidolite-1M Odinite-1M
Lepidolite-2M1
Lepidolite-2M2 P
Lepidolite-3T Palygorskite  (Mg,Al)2Si4O10(OH) 4H2O, Sepiolite–Palygorskite
Leptochlorite = iron-rich Chlorite, mainly Chamosite Group
Leuchtenbergite = iron-deficient Clinochlore Paragonite  NaAl2(Si3Al)O10(OH)2, True Mica Group
Lizardite  Mg3Si2O5(OH)4, Serpentine–Kaolin Group Parsettensite  (K,Na,Ca)(Mn,Al)7Si8O20(OH)8 · 2H2O, Modulated
Lizardite-1T Layer Silicate Group
Lizardite-2H Pecoraite  Ni3Si2O5(OH)4, dimorphic relationship with
Lizardite-6T népouite, Serpentine–Kaolin Group
Pennantite  Mn25 + Al(Si 3Al)O10 (OH)8, Chlorite Group
M Penninite = Clinochlore
Manganopyrosmalite  Modulated Layer Silicate Group Phengite  KAl1.5(Mg,Fe2+)0.5(Si3.5Al0.5)O10(OH,F)2, True Mica Group
Margarite  CaAl2(Al2Si2)4O10(OH)2, Brittle Mica Group Phlogopite  K(Mg,Fe2+)3Si3AlO10(F,OH)2, True Mica Group
Margarite-2M Polylithionite  KLi2AlSi4AlO10(F,OH)2, True Mica Group
Masutomilite  K(Li,Al,Mn2+)3(Si,Al)4O10(F,OH)2, True Mica Preiswerkite  Na(Mg2Al)(Si2Al2)O10(OH)2, True Mica Group
Group Prochlorite = ferroan Clinochlore
Medomontite = mixture of Chrysocolla and mica or hydromica Pseudophite = Clinochlore
Metahalloysite = Halloysite-7 Å, dehydrated halloysite Pyrophyllite  Al2Si4O10(OH)2, Talc–Pyrophyllite Group
Mica  A mineral group, with general structural formula, Pyrophyllite-2M
(Ba,Ca,Cs,H3O+,K,Na,NH4)(Al,Cr,Fe2+,Fe3+,Li,Mg,Mn2+,Mn3+, Pyrophyllite–smectite  Interlayering of pyrophyllite and smectite
V,Zn)2−3(Al,Be,Fe3+,Si)4O10(OH,F)2 minerals with various mixing ratio and layer-stacking sequence
Mica–chlorite  Interlayering mica and chlorite minerals with of the two components, Interstratified Layer Silicate Group
various mixing ratio and layer-stacking sequence of the two
components, Interstratified Layer Silicate Group R
Mica–smectite  Interlayering of mica and smectite minerals Rectorite  (Na,Ca)Al4(Si,Al)8O20(OH)4 · 2H2O, a 1:1 interlayering
with various mixing ratio and layer-stacking sequence of the of dioctahedral mica and dioctahedral smectite and rectorite
two components, Interstratified Layer Silicate Group may further be distinguished into the following:
Mica–vermiculite  Interlayering of mica and vermiculite min- Ca–Rectorite = the mica-like layer whose composition is similar to
erals with various mixing ratio and layer-stacking sequence that of margarite
of the two components, Interstratified Layer Silicate Group Na–Rectorite = rectorite in which its nonexpandable layer is
Minnesotaite  (Fe2+,Mg)3Si4O10(OH)2, Modulated Layer Silicate similar to paragonite
Group K–Rectorite = the mica-like layer whose composition is similar to
Montdorite = aluminum-deficient Biotite that of muscovite
Montmorillonite  (Na,Ca) 0.3 (Al,Mg) 2 Si 4 O10 (OH) 2  · nH 2 O, Ripidolite = ferroan Clinochlore, magnesian Chamosite
Smectite Group Roscoelite  K(V3+,Al,Mg)2(Si,Al)4O10(OH)2, True Mica Group
21-44 Properties and Processes

S V
Saponite  (Ca,Na)0.3(Mg,Fe2+)3(Si,Al)4O10(OH)2 · 4H2O, Smectite Vermiculite  A majority of this mineral are trioctahedral and
Group with a sample composition, (Mg,Ca)0.3(Mg2.5Fe0.5)(Al1.2Si2.8)
Iron saponite = saponite with Fe > Mg in its octahedral sheet O10(OH)2 · 4H2O, Vermiculite Group
Sauconite  Na0.3Zn3(Si,Al)4O10(OH)2 · 4H2O, Smectite Group Vermiculite  A group name for minerals with the general for-
Sepiolite  Mg4Si6O15(OH)2 · 6H2O, Sepiolite–Palygorskite mula, (Mg,Ca)0.35(Mg,Fe,Al)3(Al,Si)4O10(OH)2 · 4H2O
Group Vermiculite–mica  See Mica–vermiculite
Septechlorite = amesite, antigorite, berthierine, chrysotile, cron- Vermiculite–chlorite  See Chlorite–vermiculite
stedtite, lizardite, etc., trioctahedral kaolinite–serpentine Vermiculite–smectite  Interlayering of vermiculite and smectite
minerals minerals with various mixing ratio and layer-stacking sequence
Sericite = (a) Muscovite (illite); (b) fine-grained mica-like of the two components, Interstratified Layer Silicate Group
minerals Volkonskoite  Ca0.3(Cr3+,Mg)2(Si,Al)4O10(OH)2 · 4H2O, Smectite
Serpentine = a group name for minerals with the general for- Group
mula, (Mg,Fe,Ni)3Si2O5(OH)4
Seybertite = Clintonite
Sheridanite = aluminum Clinochlore, ferroan Clinochlore W
Shirozulite  KMn32 + (Si, Al)4 O10 (OH)2 , True Mica Group Wonesite  (Na,K)(Mg,Fe,Al)6(Si,Al)8O20(OH,F)4, True Mica
Siderophyllite  KFe22 + Al(Al 2Si 2 )4 O10 (F, OH)2, True Mica Group Group
Smectite  represent the smectite-group minerals, with general
formula X0.3Y2–3Z4O10(OH)2 · nH2O where X = Ca, Li, Na; X
Y = Al, Cr, Cu, Fe2+, Fe3+, Li, Mg, Ni, Zn; Z = Al, Si, Smectite Xanthophyllite = Clintonite
Group
Smectite–chlorite  See Chlorite–smectite
Smectite–illite  Compare Mica–smectite Z
Smectite–kaolin  See Kaolin–smectite Zinnwaldite  KLiFe2+Al(AlSi3)O10(F,OH)2, True Mica Group
Smectite–mica  See Mica–smectite Zussmanite  K(Fe2+,Mg,Mn2+)13(Si,Al)18O42(OH)14, Modulated
Smectite–pyrophyllite  See Pyrophyllite–smectite Layer Silicate Group
Smectite–talc  See Talc–smectite
Smectite–vermiculite  See Vermiculite–smectite References
Stevensite  Ca0.15Mg3Si4O10(OH)2, Smectite Group
Stilpnomelane  K(Fe2+,Mg,Fe3+)8(Si,Al)12O10(O,OH)27, Modulated Alexander, L., and H.P. Klug. 1948. Basic aspects of X-ray absorp-
Layer Silicate Group tion in quantitative diffraction analysis of powder mixtures.
Sudoite  Mg2(Al,Fe3+)3Si3AlO10(OH)8, Chlorite Group Anal. Chem. 20:886–889.
Swinefordite  (Ca,Na) 0.3(Li,Mg)2(Si,Al) 4 O10 (OH,F)2 · 2H 2O, Anthony, J.W., R.A. Bideaux, K.W. Bladh, and M.C. Nichols. 1995.
Smectite Group Handbook of mineralogy. Vol. II. Silica, silicates. Parts I and
II. Mineral Data Publishing, Tucson, AZ.
T April, R., and D. Keller. 1990. Mineralogy of the rhizosphere in
Taeniolite  K(LiMg2)Si4O10(F,OH)2 forest soils of the eastern United States. Mineralogical stud-
Talc  Mg3Si4O10(OH)2, Talc–Pyrophyllite Group ies of the rhizosphere. Biogeochemistry 9:1–18.
Talc–chlorite  Interlayering of talc and chlorite minerals with Bailey, S.W. 1969. Polytypism of trioctahedral 1:1 layer silicates.
various mixing ratio and layer-stacking sequence of the two Clays Clay Miner. 17:355–371.
components, Interstratified Layer Silicate Group Bailey, S.W. 1972. Determination of chlorite compositions by X-ray
Talc–saponite  Compare Talc–smectite spacings and intensities. Clays Clay Miner. 20:381–388.
Talc–smectite  Interlayering of talc and smectite minerals with Bailey, S.W. (ed.). 1984. Micas: Reviews in mineralogy. Vol. 13.
various mixing ratio and layer-stacking sequence of the two Mineralogical Society of America, Chelsea, MI.
components, Interstratified Layer Silicate Group Bailey, S.W. (ed.). 1988. Hydrous phyllosilicates (exclusive of
Tarasovite  A regular interstratified mineral of illite (I) and micas). Reviews in mineralogy. Vol. 19. Mineralogical
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Interstratified Layer Silicate Group Bailey, S.W., G.W. Brindley, D.S. Fanning, H. Kodama, and
Thuringite = ferrian Chamosite R.T.  Martin. 1984. Report of the CMS Nomenclature
Tobelite  (NH4,K)Al2(Si3Al)O10(OH)2, True Mica Group Committee for 1982 and 1983. Clays Clay Miner. 32:239.
Tosudite  A 1:1 interlayering of chlorite and a smectite- Bailey, S.W., G.W. Brindley, H. Kodama, and R.T. Martin. 1982.
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(OH,F)12 · 5H2O, Interstratified Layer Silicate Group CMS Nomenclature Committee for 1980–1981. Clays Clay
Trilithionite  K(Li1.5Al1.5)(Si3Al)4O10(F,OH)2, True Mica Group Miner. 30:76–78.
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 22
Oxide Minerals in Soils
22.1 Introduction............................................................................................................................22-1
22.2 Iron Oxides..............................................................................................................................22-1
Mineral Phases  •  Occurrence and Formation  •  Influence on Soil Properties  •  Identification
22.3 Manganese Oxides..................................................................................................................22-9
Nestor Kämpf Mineral Phases  •  Occurrence and Formation  •  Influence on Soil Properties  •  Identification
Universidade Federal do 22.4 Aluminum Oxides................................................................................................................22-16
Rio Grande do Sul Mineral Phases  •  Occurrence and Formation  •  Influence on Soil Properties  •  Identification
22.5 Silicon Oxides........................................................................................................................22-19
Andreas C. Scheinost Mineral Phases  •  Occurrence and Formation  •  Influence on Soil Properties  •  Identification
Institute of Radiochemistry
22.6 Titanium and Zirconium Minerals...................................................................................22-23
Darrell G. Schulze Mineral Phases  •  Occurrence and Formation  •  Influence on Soil Properties  •  Identification
Purdue University References..........................................................................................................................................22-25

22.1  Introduction 22.2.1  Mineral Phases

Oxide minerals or oxides comprise the oxides, hydroxides, The structures of most Fe oxides can be described in terms of
oxyhydroxides, and hydrated oxides of Fe, Mn, Al, Si, and Ti. close-packed arrays of O and OH ions, with Fe occupying inter-
They commonly occur in soils, particularly those in advanced stitial octahedral sites. Structures based on hexagonal close
stages of weathering where they can sometimes account for as packing (hcp) of the anions are called α-phase, and those with
much as 50% of the total soil mass. In the discussion to follow, cubic close packing (ccp), γ-phase (note that this convention is
a polyhedral approach will be used to introduce the mineral not necessarily followed for oxides of other elements). Both hcp
species and highlight their major differences and similarities and ccp structures also contain tetrahedral interstices. In two
(Figure 22.1). For additional structural details, the reader is minerals, magnetite and maghemite, Fe is present in some of
referred to the literature cited. Thereafter, their occurrence and these tetrahedral sites as well. The basic structural unit for most
formation in soils and their influence on soil properties will be of the Fe oxides, however, is an octahedron in which each Fe
discussed, concluding with the major techniques for identify- atom is surrounded either by six O or by both O and OH ions.
ing these minerals in soils. The various Fe oxides differ mainly in the arrangement of these
octahedra and in how they are linked.

22.2.1.1  Oxyhydroxides
22.2  Iron Oxides
Goethite (α-FeOOH) consists of double chains of edge-shared
Iron oxide minerals are ubiquitous in soils and sediments. All octahedra that are joined to other double chains by shar-
of the Fe oxide minerals are strongly colored and, when finely ing corners and by hydrogen bonds (Figure 22.1; Cornell and
dispersed throughout the matrix, even small amounts impart Schwertmann, 1996). Lepidocrocite (γ-FeOOH) also contains
bright colors to soils. Iron oxides often cement other soil miner- double chains of octahedra, but they are joined by shared edges,
als into stable aggregates, and when they reach massive propor- resulting in corrugated sheets of octahedra. These corrugated
tions, such cementations are called laterite or ferricrete. Because sheets are stacked one on top of the other and are held together
iron oxide surfaces have a strong affinity for the oxyanions of by hydrogen bonds (Figure 22.1; Ewing, 1935a, 1935b; Fasiska,
phosphorus and some transition metals, they play a signifi- 1967). Akaganéite (β-FeOOH) consists of double chains that
cant role in the environmental cycling of these elements. A list share corners with adjacent chains to give a 3D structure con-
of the Fe oxides is given in Table 22.1. Recent comprehensive taining tunnels 0.5 nm in cross section (Figure 22.1). These
reviews include Schwertmann and Taylor (1989), Cornell and tunnels contain Cl− ions that stabilize the structure (Post
Schwertmann (1996, 2003), and Bigham et al. (2002). and Buchwald, 1991). Schwertmannite (Fe8O8(OH)6(SO4)) is

22-1
22-2 Properties and Processes

c a1
a2
Mn: Pyrolusite, MnO2
c b
Manganite, γ-MnOOH
Ti: Rutile, TiO2 a
Mn: Romanechite, Ba0.66(MnIVMnIII)5O10 . 1.3H2O

c b
a c
Fe: Goethite, α-FeOOH
Mn: Ramsdellite, MnO2 a b
Groutite, MnOOH
Al: Diaspore, α-AlOOH Mn: Todorokite,
(Na,Ca,K)0.3–0.5(MnIVMnIII)6O12 . 3.5H2O

b
B c
c a
a1 a2

A
Fe: Lepidocrocite, γ-FeOOH
Al: Boehmite, γ-AlOOH Fe: Feroxyhyte, δ΄-FeOOH (A = B = Fe)
Mn: Buserite (A = B = Mn)
Lithiophorite, (Li,Al) (MnIII,MnIV)O2(OH)2
(A = Mn,Co; B = Al,Li,Ni,Cu,Zn)
Asbolane, (Co,Li)MnO2 (OH)2
(A = Mn; B = Co,Ni)
Al: Gibbsite, bayerite, nordstrandite, Al(OH)3
(A = B = Al)

c
b
a

Fe: Akaganéite, β-FeOOH

Schwertmannite, Fe8O8(OH)6(SO4)
Mn: Hollandite, Bax(MnIVMnIII)8O16, x = 1
c
Cryptomelane, Kx(MnIVMnIII)8O16, x = 1.3–1.5 b a
IV III
Coronadite, Pbx(Mn Mn )8O16, x = 1.0–1.4
Fe: Green rust, FeII4 FeIII
2
(OH)12(Cl,SO4,CO3)

FIGURE 22.1  (See color insert.) Structural schemes for oxide minerals in soils.
Oxide Minerals in Soils 22-3

a2 a1 a1
a2 c

Mn: Chalcophanite, ZnMn3O7 . 3H2O

Birnessite, (Na,Ca,MnII) Mn7O4 . 2.8H2O Si: α-Cristobalite, SiO2

a2 a1
a2 a1

Fe: Hematite, α-Fe2O3 c

Al: Corundum, α-Al2O3
Ti: Anatase, TiO2
Ti,Fe: Ilmenite, FeTiO3

b
c a

Ti: Brookite, TiO2

a2 a3 a1

Fe: Magnetite, Fe3O4

Maghemite, γ-Fe2O3
Mn: Hausmannite, Mn3O4
Ti,Fe: Titanomagnetite, Fe3–xTixO4
c b
Titanomaghemite, Fe2–xTixO3
a

Ti,Fe: Pseudobrookite, FeIII

2
TiO5

c a2
Ti,Fe: Pseudorutile, FeIII
2
Ti3O8(OH)2
a1
Si: α-Quartz, SiO2

FIGURE 22.1 (continued)

22-4 Properties and Processes

TABLE 22.1  Iron Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Crystal System, Unit-Cell Six Most Intense Diffraction Lines
Mineral Chemical Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesa
Goethite α-FeOOH Orthorhombic, a = 4.608 4.183 2.450 2.693 1.719 2.190 2.253 29-0713
Pbnm b = 9.956 100 50 35 20 18 14
c = 3.021
Lepidocrocite γ-FeOOH Orthorhombic, a = 3.07 6.260 3.290 2.470 1.937 1.732 1.524 Cornell and
Cmcm b = 12.53 100 90 80 70 40 40 Schwertmann
c = 3.88 (2003); 08-0098
Akaganéite β-FeOOH Monoclinic, a = 10.56 3.333 2.550 7.467 2.295 1.643 5.276 Post and
I2/m b = 3.031 100 5 40 35 35 30 Buchwald
c = 10.483 (1991); 34-1266
β = 90°63′
Schwertmannite Fe8O8(OH)6SO4 Tetragonal, a = 10.66 2.55 3.39 4.86 1.51 2.28 1.66 Bigham et al.
P4/m c = 6.04 100 46 37 24 23 21 (1994)
Feroxyhite δ′-FeOOH Hexagonal, a = 2.93 2.545 2.255 1.685 1.471 4.610 1.271 Cornell and
P3ml c = 4.56 100 100 100 100 20 20 Schwertmann
(1996); 13-0087
Ferrihydrite Fe5HO8 . 4H2O Hexagonal a = 5.08 2.50 2.21 1.96 1.48 1.51 1.72 Towe and Bradley
c = 9.4 100 80 80 80 70 50 (1967); 29-0712
Hematite α-Fe2O3 Hexagonal, R3c a = 5.034 2.700 2.519 1.694 1.840 3.684 1.486 33-0664
c = 13.752 100 70 45 40 30 30
Magnetite Fe3O4 Cubic, Fd3m a = 8.3967 2.532 1.484 2.967 1.616 2.099 1.093 19-0629
100 40 30 30 20 12
Maghemite γ-Fe2O3 Cubic, Fd3m a = 8.35 2.518 2.953 1.476 1.607 2.088 1.704 Goss (1988);
100 40 30 20 15 10 39-1346
Bernalite Fe(OH)3 Orthorhombic, a = 7.544 3.784 1.692 2.393 2.676 1.892 1.545 Birch et al. (1993)
Immm b = 7.560 100 17 16 15 10 9
c = 7.558
Fougerite (Fe2+,Mg)6 Trigonal– a = 3.125 7.97 2.692 3.97 2.027 1.563 1.595 http://webmineral.
Fe3+ .
2 (OH)18  4H2O hexagonal, c = 22.5 100 34 32 19 10 9 com
R3m
Fe(OH)2 Fe(OH)2 Hexagonal, a = 3.262 4.597 2.403 2.817 1.782 1.629 1.535 Miyamoto (1976)
P3ml c = 4.596 vsb vs s s s w
Green rust I Fe(OH)2Fe(OH)3Cl Rhombohedral a = 3.198 8.02 4.01 2.701 2.408 2.037 1.487 Bernal et al.
(variable) c = 24.21 vs s m m w w (1959)
Green rust II Fe(OH)2Fe(OH)3SO4 Hexagonal, a = 3.174 10.92 5.48 3.65 2.747 2.660 2.459 Bernal et al.
(variable) R3/m b = 10.94 vs s s m ms ms (1959)
a Numbers of the format XX-XXXX indicate ICDD file number (ICDD, 1994).
b vs, very strong; s, strong; ms, moderately strong; m, moderate; w, weak.

isostructural with akaganéite, but instead of Cl−, SO2− 4 occupies many sites vacant and more OH− and H2O and less Fe3+ than in
the tunnels (Figure 22.1; Bigham et al., 1990, 1994). Feroxyhite hematite (Cornell and Schwertmann, 1996).
(δ′-FeOOH) consists of sheets of edge-sharing octahedra (Figure
22.1), with the presence of face-sharing octahedra (Manceau 22.2.1.2  Hydroxides
and Combes, 1988; Drits et al., 1993a; Manceau and Drits, 1993). Green rusts are a group of Fe2+–Fe3+ hydroxy salts with a struc-
In naturally occurring feroxyhite, Fe3+ ions are randomly dis- ture consisting of sheets of edge-shared Fe2+(OH)6 octahedra in
tributed over the octahedral sites, while in synthetic δ-FeOOH, which some of the Fe2+ is replaced by Fe3+, creating a positive
the Fe3+ ions are orderly distributed over half of the octahe- layer charge. The charge is balanced by anions such as Cl−, SO2− 4 ,
dral sites (Waychunas, 1991). Ferrihydrite (Fe5HO8 · 4H2O) is a and CO2−3 located between the octahedral sheets (Figure 22.1;
poorly ordered Fe oxide, with a variable degree of ordering. The Brindley and Bish, 1976; Taylor and McKenzie, 1980). Bernalite,
structure is still being investigated (Drits et al., 1993b; Manceau Fe(OH)3 · nH2O (Birch et al., 1993), is a rare Fe hydroxide and has
and Drits, 1993; Manceau and Gates, 1997) but can be visual- not been found in soils. Fougerite, (Fe2+Mg)6 Fe3+ 2 (OH)18 · 4H 2O,
ized as a defective hematite structure containing both edge- and has recently been identified as a green rust mineral in soils
face-sharing octahedra (Towe and Bradley, 1967). The Fe3+ ions (Trolard et al., 2007), whereas the Fe(OH)2 compound has not
are randomly distributed over the octahedral interstices, with been found as a mineral (Cornell and Schwertmann, 1996).
Oxide Minerals in Soils 22-5

22.2.1.3  Oxides Other metallic cations with an ionic diameter similar to

Hematite (α-Fe2O3) consists of sheets of edge-shared octahe- Fe3+ (Al, Ni, Ti, Mn, Co, Cr, Cu, Zn, V) may replace the Fe ion
dra with two-thirds of the available octahedral sites filled with in the structure of various Fe oxides. Isomorphous substitution
Fe3+ ions. The unoccupied sites are regularly arranged to form of Al3+ for Fe3+ occurs most frequently and to the greatest extent
sixfold rings of occupied octahedra analogous to dioctahedral (Schwertmann and Carlson, 1994). In addition to M3+ cations, M2+
phyllosilicate sheets (Chapter 21) and are stacked along the and M4+ cations may also enter Fe3+ oxide structures, but the uptake
c-axis. Each plane of O is shared by two adjacent dioctahedral is usually less than 0.1 mol−1 (Cornell and Schwertmann, 1996).
sheets. Each octahedron shares three edges with three neighbor- The typical shapes of well-crystallized Fe oxide samples are
ing octahedra in the same sheet and a face and six corners with listed in Table 22.2. These shapes, usually observed in samples
nine octahedra in adjacent sheets (Figure 22.1; Blake et al., 1966; from synthetic preparations, rocks, ferricretes, and bauxites, are
Maslen et al., 1994). Magnetite (Fe3O4), which differs from most frequently less well expressed by soil Fe oxides. Soil hematites
other Fe oxides in that it contains both Fe2+ and Fe3+ ions, has usually have a granular texture, and goethites show almost no
an inverse spinel structure consisting of octahedral and mixed acicularity (Figure 22.2), particularly in highly weathered soils
tetrahedral/octahedral layers stacked along the [111] plane, with (Schwertmann and Kämpf, 1985; de Brito Galvão and Schulze,
Fe3+ occupying tetrahedral sites and both Fe2+ and Fe3+ in octa- 1996). Thus, morphology alone is unreliable for distinguishing
hedral sites (Figure 22.1). Titanomagnetites (Fe3−xTi xO4) are solid these minerals by transmission electron microscopy (TEM)
solutions of magnetite with ulvöspinel (Fe2TiO4), with Ti4+ occu- (Anand and Gilkes, 1987a; Singh and Gilkes, 1992), although
pying only octahedral sites (Wechsler et al., 1984). Maghemite soil lepidocrocites often appear as thin laths, very similar to syn-
(γ-Fe2O3) has the chemical composition of hematite but has a thetic lepidocrocites (Cornell and Schwertmann, 1996). Soil Fe
structure analogous to magnetite (Figure 22.1). Most or all of oxides may range from a few to several hundred nanometers in
the Fe occurs as Fe3+ and cation vacancies preserve charge bal- length, but data are scarce because of their tendency to occur as
ance caused by the oxidation of Fe2+ to Fe3+. The cations are microaggregates (Schwertmann, 1988).
randomly distributed over the tetrahedral and octahedral sites.
The vacancies are also randomly distributed but are confined
22.2.2  Occurrence and Formation
to the octahedral sites. Titanomaghemites are oxidation prod-
ucts of titanomagnetites, but their structure needs clarification The concentration of Fe oxides in soil ranges between <1 and
(Waychunas, 1991). Maghemite–magnetite solid solutions are >500 g kg−1 and is related to parent material, degree of weathering,
formed by varying degrees of oxidation of magnetite. and pedogenic accumulation or depletion processes. Iron oxides

TABLE 22.2  Diagnostic Criteria for Iron Oxide Minerals

Magnetic Hyperfine Field (kOe)
Color and Munsell Typical Crystal IR Bands
Mineral Hues Range Shape DTA Events (°C) (cm−1) 295 K 77 K 4 K
Goethite Strong brown to Needles, laths Endotherm, 280–400 890, 797 382 503 506
yellowish brown,
7.5YR–2.5Y
Lepidocrocite Reddish yellow Laths Endotherm, 300–350 1026, 1161, 753 458
(“orange”), 5YR–7.5YR Exotherm, 370–500
Akaganéite Strong brown to reddish Spindle-shaped rods 489/478/473
yellow, 2.5YR–7.5YR
Schwertmannite Reddish yellow to yellow, Fibers Endotherm, 100–300, 3300, 1634, 456
5YR–10YR 650–710 1186, 1124,
Exotherm, 540–580 1038, 976, 608
Ferrihydrite Dark red to strong Spherical Endotherm, 150 470/500
brown, 2.5YR–7.5YR
Feroxyhite Dark red to dark reddish Fibers, needles Endotherm, 250 1110, 920, 790, 420 530 535
brown, 1.5YR–5YR 670
Hematite Dusky red to dark red, Hexagonal plates Nil 345, 470, 540 518 542/535a 542/535a
5R–2.5YR
Maghemite Dark reddish brown, Cubes Exotherm, 600–800 400, 450, 570, 500 526
2.5YR–5YR 590, 630
Magnetite Black Cubes b 400, 590 491/460c
a With and without Morin transition, respectively.
b Magnetite converts via maghemite or directly to hematite, depending on particle size.
c For tetrahedral and octahedral Fe, respectively.
22-6 Properties and Processes

exudates, organic compounds) able to keep a low Fe3+ activity

in solution will favor goethite. Thus, the formation pathways of
hematite and goethite are different but competitive.
Environmental conditions that favor the formation of ferri-
hydrite and its subsequent transformation to hematite are high
Fe content in the parent rock (resulting in higher Fe release
rate), near neutral pH (pH of minimum solubility of ferrihy-
drite), higher temperature or lower water activity (favoring the
dehydration step) (Torrent et al., 1982), and rapid turnover of
biomass (low Fe complexation) (Schwertmann, 1988). Such envi-
ronmental conditions are usually related to climate (Kämpf and
40 nm
Schwertmann, 1983), landscape (Curi and Franzmeier, 1984;
Schwertmann and Latham, 1986), landscape associated with
drainage (Macedo and Bryant, 1987; da Motta and Kämpf, 1991;
FIGURE 22.2  Transmission electron micrograph of the <0.2 μm Peterschmitt et al., 1996; Fritsch et al., 2007), and soil depth
fraction of a Rhodic Hapludox showing a goethite or hematite particle (Bigham et al., 1978; Kämpf and Schwertmann, 1983).
(arrow) surrounded by clean kaolinite particles. (Modified from de In soils, the transformation rate of ferrihydrite to hematite
Brito Galvão, T.C., and D.G. Schulze. 1996. Mineralogical properties of is probably very rapid, whereas that of ferrihydrite to goethite,
a collapsible lateritic soil from Minas Gerais, Brazil. Soil Sci. Soc. Am. J.
which proceeds through dissolution–recrystallization, is slower.
60:1969–1978.)
This explains the widespread association of ferrihydrite–­goethite,
may occur evenly distributed in the matrix or concentrated as fer- while that of ferrihydrite–hematite has been rarely found (Parfitt
ricretes, layers, bands, horizons, nodules, mottles, plinthite, etc. et al., 1988). There is no pedogenic indication for a solid-state
Iron, present as Fe2+ in primary minerals (mainly silicates) of transformation of goethite to hematite by simple dehydration,
most rocks, is released during weathering through protolysis and nor the inverse by simple hydration. However, high tempera-
oxidation processes, hydrolyzes in contact with water, and then tures caused by forest or bush fires may transform goethite into
forms Fe3+ oxides. In most aerobic environments, the Fe oxides hematite and lepidocrocite into maghemite (Stanjek, 1987; see
are evenly distributed resulting in homogeneous soil color. maghemite below).
Under anaerobic conditions, however, Fe oxides may be reduced Both hematite and goethite have a similarly low solubility
and dissolved, thus leading to a heterogeneous distribution of Fe (Lindsay, 1979). Under moderately reducing conditions, how-
oxides and color (redoximorphic features; Schwertmann, 1993). ever, a transformation of red into yellow soils (yellowing or
The formation of each of the Fe oxide minerals requires specific xanthization) may take place due to a preferential dissolution of
conditions that have been established for soils by laboratory and hematite over goethite (Macedo and Bryant, 1989; Jeanroy et al.,
field observations (Schwertmann and Taylor, 1989). 1991; Peterschmitt et al., 1996; Fritsch et al., 2005). The increased
In aerobic environments, goethite and hematite are the most resistance of goethite to dissolution is explained by a higher
common Fe oxides due to their high thermodynamic stability. Al for Fe substitution (Torrent et al., 1987; Trolard and Tardy,
Their formation pathway starts with Fe2+ released by weather- 1987). The solubility and dissolution of Fe oxides is reviewed
ing and its immediate oxidation to Fe3+ or by any other source by Schwertmann (1991). When Fe oxides are reduced in higher
of Fe3+ (e.g., dissolution of Fe oxides), which precipitates as fer- landscape positions, the soluble Fe2+ may be transported to lower
rihydrite or goethite, depending on which of the solubility prod- landscape positions and reprecipitate as Fe oxides (Schwarz,
ucts is exceeded first (ferrihydrite, Ksp ~ 10−39 or goethite, 10−44 < 1994). In aquic environments with prolonged waterlogging, the
Ksp  <  10−41). Hematite forms from its necessary precursor, fer- complete removal of Fe oxides may take place, resulting in soil
rihydrite, through a solid-state reaction in which individual bleaching (chroma < 2) (da Motta and Kämpf, 1991; Peterschmitt
hematite crystals nucleate and grow within individual ferrihy- et al., 1996). The bleached color is due to the matrix minerals
drite aggregates by a dehydration and rearrangement process. All (phyllosilicates, quartz, etc.) in the absence of Fe oxides.
of the iron in each individual hematite crystal is derived from Many species of microorganisms, mainly anaerobic bacteria,
a single-ferrihydrite aggregate (Cornell and Schwertmann, 1996). are capable of reducing Fe oxides (Lovley, 1995). As heterotro-
The transformation of ferrihydrite to goethite, however, proceeds phic organisms, they depend on available biomass for metabolic
via a dissolution–precipitation process. The presence of face-sharing oxidation so that reduction in soils is most intense in the upper
Fe(O,OH)6 octahedra in ferrihydrite, as in hematite, prevents the horizons. The process usually involves enzymatic transfer of
direct solid-state transformation of ferrihydrite into goethite, electrons by microorganisms from the decomposing biomass to
which consists only of edge- and corner-sharing octahedra. Thus, Fe3+ (Ghiorse and Ehrlich, 1992; Lovley, 1992, 1995).
the transformation of ferrihydrite to goethite requires the break- Some Fe and Mn oxides may be formed by microorganisms
down of the oxo-bridges of face-sharing octahedra (Combes et al., in a biologically induced form outside the cell, or matrix medi-
1989). Goethite forms from Fe3+ ions in solution via a nucleation– ated, by internal cellular precipitation (Ghiorse and Ehrlich,
crystal growth process. Hence, any Fe source (minerals, biological 1992). The most common occurrence of biotic formation of
Oxide Minerals in Soils 22-7

Fe oxides is Fe ochre in field drains (Houot and Berthelin, 1992), 2010a, 2010b), and in an acid alpine stream draining a pyritic
the Fe plaque in the root zone of wetland plants (Weiss et al., schist (Schwertmann et al., 1995a). Most of these occurrences
2003), and the Fe precipitate, yellow boy, in acid mine drainages reflect acid environments where bacteria catalyze the oxidation
(Bigham et al., 1992). Aspects of biomineralization of Fe and Mn of FeS2 releasing Fe3+ and SO4 2− that, in the pH range 2.8–4.0,
in soils are reviewed in Skinner and Fitzpatrick (1992). precipitate as schwertmannite (Bigham et al., 1992, 1996b). At
The typical Fe oxides of seasonally reduced soil environments lower pH, jarosite is favored, while at higher pH values, goethite
are goethite, lepidocrocite, and ferrihydrite, formed by abiotic and ferrihydrite form (Bigham et al., 1996a). Schwertmannite
or biotic processes. Therefore, goethite and lepidocrocite are is metastable and converts to goethite over time. Bigham et al.
widely associated in reductomorphic soils, whereas hematite is (1992) proposed a biogeochemical model for the precipitation
restricted to mottles and nodules (Schwertmann and Kämpf, of jarosite, schwertmannite, and ferrihydrite, and their conver-
1983; Fitzpatrick et al., 1985; Wang et al., 1993; dos Anjos et al., sion to goethite. The model considers the oxidation of Fe2+ by
1995). While goethite can form from either Fe2+ or Fe3+ ions in Thiobacillus ferrooxidans or oxygen, the concentration of SO4 2−,
solution, lepidocrocite in soils seems to require the presence of the pH, and the presence of other cations (K, Na) in the system.
Fe2+ ions (Schwertmann and Taylor, 1989). Thus, lepidocrocite, Magnetite in soils is usually inherited from the parent rock
recognized by its bright orange color, indicates prevailing reduc- (lithogenic), but both biologically (Fassbinder et al., 1990) and
tomorphic conditions in a soil profile leading to the formation of abiotically formed magnetite (Maher and Taylor, 1988) has been
Fe2+. Factors that favor the formation of goethite over lepidocroc- reported. The alteration of magnetite to hematite via solid-state
ite, however, are a higher partial pressure of CO2, normally found transformation, with no evidence for maghemite development,
closer to roots, the presence of HCO3 − or CO32−, an increasing rate is described by Gilkes and Suddhiprakarn (1979) and Anand
of oxidation, and the presence of Al in the system (Schwertmann and Gilkes (1984a). In laboratory studies, particle size deter-
and Taylor, 1989; Carlson and Schwertmann, 1990). mines whether hematite or maghemite forms when magnetite
Ferrihydrite has been reported in ochreous precipitates from is oxidized below 220°C (Egger and Feitknecht, 1962; Gallagher
the oxidation of emerging, Fe2+-containing waters (Schwertmann et al., 1968). Particles less than 300 nm in diameter transform to
and Fischer, 1973; Carlson and Schwertmann, 1981; Schwertmann maghemite, while larger particles oxidize to hematite. This may
and Kämpf, 1983), in bog and lake Fe ores (Schwertmann et al., explain why soil maghemites typically occur in the clay fraction.
1982), in podzol B horizons (Adams and Kassim, 1984), in placic Maghemite is common in many different soils, especially
horizons (Campbell and Schwertmann, 1984), in Andepts (Parfitt in the tropics and subtropics, occurring dispersed or concen-
et al., 1988), in soil iron pans (Childs et  al., 1990), and in con- trated in concretions (Taylor and Schwertmann, 1974; Curi and
structed wetlands for acid drainage treatment (Karathanasis Franzmeier, 1984; Anand and Gilkes, 1987a; Fontes and Weed,
and Thompson, 1995). These occurrences reflect an environ- 1991). The two major possible pathways for maghemite formation
ment where Fe2+ is rapidly oxidized (abiotically or biotically) in in soils are the aerial oxidation of lithogenic magnetite (Fontes
the presence of high concentrations of organic matter and/or Si. and Weed, 1991) and the transformation of other pedogenic Fe
These compounds and possibly others hinder the immediate for- oxides by heating (between 300°C and 425°C) in the presence
mation of FeOOH phases and the subsequent transformation of organic compounds (Schwertmann and Fechter, 1984; Anand
of ferrihydrite to more stable Fe oxides (Schwertmann, 1966; and Gilkes, 1987b; Stanjek, 1987).
Cornell, 1987). In contrast, in tropical soils, the concentration Akaganéite and feroxyhite are both rare minerals. Akaganéite
of ferrihydrite is very low because of low interference of Si and has been found in environments with high chloride concen-
organics. The presence of ferrihydrite together with FeOOH trations (e.g., 0.1 M), low pH (e.g., 3–4), and high temperature
phases may indicate that environmental conditions are not favor- (e.g., 60°C), as found in some hot springs and volcanic depos-
able for crystal development or that the formations are relatively its (Schwertmann and Fitzpatrick, 1992) and has only recently
young, as in paddy soils (Wang et al., 1993) and constructed been reported in soils (Fitzpatrick et al., 2008; Gao and Schulze,
wetlands (Karathanasis and Thompson, 1995). 2010a, 2010b). Laboratory synthesis showed that chloride is
Reductomorphic soils often display greenish-blue colors that essential for the crystallization of akaganéite (Shah Singh and
change rapidly to yellowish brown on exposure to the air. These Kodama, 1994). The mechanism of feroxyhite formation in
colors are indicative of the presence of green rusts, recently nature is unknown. It has been observed in rusty precipitates,
identified as fougerite (Trolard et al., 2007). Iron-reducing bac- formed in the interstices of sand grains from rapidly flowing
teria appear as the main factor involved in green rust forma- Fe2+-containing water, which was quickly oxidized (Carlson and
tion (Berthelin et al., 2006). Green rusts occur under reducing Schwertmann, 1980). A possible association with dominant fer-
and weakly acid to weakly alkaline conditions as intermediate rihydrite in some typic Hydrandepts of Hawaii is reported by
phases in the abiotic formation of goethite, lepidocrocite, and Parfitt et al. (1988). The similarity of the x-ray diffraction (XRD)
magnetite (Schwertmann and Fechter, 1994). patterns of feroxyhite and ferrihydrite makes it extremely dif-
Schwertmannite has been found in strongly acid, sulfate- ficult, however, to distinguish these minerals in natural samples
rich waters associated with mining activities (Bigham et al., (Carlson and Schwertmann, 1981).
1990, 1992, 1994, 1996b; Fanning et al., 1993), a Histosol that The different types of Fe oxides may show a partial replace-
received runoff from lead smelting activities (Gao and Schulze, ment of Fe by other cations. This substitution is conditioned
22-8 Properties and Processes

by the availability of cations that, in turn, makes it representa- Landscape  sequences of red soils (hematite and goethite) on
tive of specific environments of the Fe oxide formation, like a well-drained hilltops, through yellow soils (goethite) on mod-
­mineralogical–pedochemical signature. So far, such relation- erately drained midslopes, to mottled and gray soils in poorly
ships have been established for Al substitution in goethites and drained valleys are examples of Fe oxides acting as indica-
for V3+ in goethite and hematite (Schwertmann and Pfab, 1994, tors of aerobic and anaerobic environments (Peterschmitt
1996). Medium to high Al substitution (0.15–0.33 mol frac- et al., 1996). Localized accumulations of Fe oxides (mottling,
tion) is usually observed in goethites from environments with plinthite) and bleached matrix colors (chroma < 2), indicative
low Si and high Al activity, found in highly weathered tropical of seasonal to permanent waterlogged soil environments, are
and subtropical soils, bauxites, and saprolites (Fitzpatrick and used as diagnostic criteria for redoximorphic features and aquic
Schwertmann, 1982; Curi and Franzmeier, 1984; Schwertmann regimes (Chapter 2).
and Kämpf, 1985; Anand and Gilkes, 1987a; Fontes et al., 1991; The aggregating effect of Fe oxides in soils is indicated by
Singh and Gilkes, 1992; Muggler, 1998), whereas goethite with significant correlations between the fraction of water-stable
low substitution (0–0.15 mol fraction) prevails in slightly acidic, aggregates or related structural properties, and the content of Fe
eutrophic soils and in redoximorphic soils (Fitzpatrick and oxides (see Schwertmann and Taylor, 1989; Barthès et al., 2008),
Schwertmann, 1982). The occurrence of goethites with highly by electron microscopy (EM) observations of Fe oxide deposits
contrasting Al substitution indicates changes in the weather- on kaolinite platelets (Fordham and Norrish, 1979), and by the
ing rate or soil redox conditions (da Motta and Kämpf, 1991; dispersion of aggregated soils after removal of their Fe oxides
Muggler, 1998). The presence of V3+ in goethite and hematite with a reducing agent (McNeal et al., 1968). Although an aggre-
may be used as an indicator for former anoxic environments gating effect of the Fe oxides in soils is generally accepted, the
(Schwertmann and Pfab, 1996). exact mechanism remains obscure. Thin sections and scanning
electron microscopy (SEM) observations of nodules, concre-
tions, and ferricretes suggest that cementation develops through
22.2.3  Influence on Soil Properties
the growth of Fe oxide crystals in place between matrix particles,
Crystals of Fe oxides in soils are often extremely small, some- leading to a very stable, nondispersible association of matrix par-
times as small as 5 nm in diameter for poorly crystalline miner- ticles (Shafdan et al., 1985). Aggregates, on the other hand, seem
als like ferrihydrite or as small as 150 nm in diameter for better to form through an attraction between positively charged Fe
crystalline minerals like goethite and hematite. Structural disor- oxide particles and negatively charged matrix particles, mainly
der is common. Fe oxides, therefore, exhibit a large specific sur- clay-sized phyllosilicates. A typical example of aggregation is the
face area (70–250 m2 g−1). They usually occur in higher amounts highly stable microaggregates (coffee powder structure) found
in comparison to Mn and Al oxides, they have a high point of in Oxisols. Because these aggregates are not dispersible in water,
zero charge (PZC; pH 7–9) and a pH-dependent surface charge. they have a significant influence on the water-holding capacity
All these factors explain the substantial influence of Fe oxides on and the hydraulic conductivity of these soils (van Wambeke,
the physical and chemical properties of soils. 1992). On the other hand, these aggregates can be dispersed by
Significant correlations have been found between the sorption organic ligands (oxalate, citrate) without solubilizing much iron
of heavy metals (Cu, Pb, Zn, Cd, Co, Ni, Mn), anions (PO4, SO3, (Pinheiro-Dick and Schwertmann, 1996).
MoO4, AsO4, Se4O, S4O, and organic anions), and the content
and mineralogy of Fe oxides (Chapter 17).
The Munsell color ranges for the various Fe oxides are listed 22.2.4  Identification
in Table 22.2. Detailed aspects of that subject are reviewed by
22.2.4.1  Field Techniques
Schwertmann (1993) and Cornell and Schwertmann (1996).
The iron oxides may show a variation of color with their crys- Fe oxides show striking colors, ranging between yellow and red.
tal size and the isomorphous substitution of Fe by foreign ions Particular colors are typical of the various forms and are help-
(Schwertmann, 1993). Basically, reddish soil color (Munsell ful for their identification in the field (Table 22.2). Correlations
hues 5YR and redder) is due to the presence of hematite (and have been established between Munsell hue and a redness or yel-
maghemite in some tropical soils), masking the presence of goe- lowness index based on hematite/goethite ratios and hematite
thite. Thus, the hematite content determines the redness of a content in soils (Torrent et al., 1983). Color alone is, however,
soil (Torrent et al., 1983), while the yellow color due to goethite not sufficient to unequivocally identify specific Fe oxide min-
(Munsell hue between 7.5YR and 2.5Y) is expressed only in the erals. The presence of the magnetic Fe oxides, magnetite, and
absence of hematite. The presence of lepidocrocite is indicated maghemite, can be easily detected in soils with a hand magnet
by an orange color, normally restricted to mottles or localized (Schulze, 1988).
spots in aquic environments. In surface soils, the colors due to Fe
oxides may be masked by black organic compounds. Information 22.2.4.2  Chemical Dissolution Techniques
about aeration and soil drainage can be inferred from the distri- Chemical dissolution procedures for Fe oxides, initially pro-
bution or absence of different Fe oxide minerals in soils, accord- posed to eliminate their interference in the examination of
ing to their specific formation  conditions  described  above. phyllosilicates, were later developed to dissolve, and thus
Oxide Minerals in Soils 22-9

to quantify, specific phases (see reviews by Borggaard, 1988; 22.2.4.3  X-Ray Diffraction and Other
Parfitt and Childs, 1988). However, the identity of the dis- Spectroscopic Techniques
solved phases must be determined by noninvasive techniques, The identification of the various Fe oxides requires physical
such as XRD and Mössbauer spectroscopy. Potassium or Na methods, like XRD, differential thermal analysis (DTA), infra-
pyrophosphate solutions have been used for estimating Fe red spectroscopy (IR) (Cambier, 1986), Mössbauer spectroscopy
(and Al) organic complexes (McKeague, 1967; Bascomb, 1968). (Murad, 1988, 1996), electron microscopy (EM) (Boudeulle and
The soil is usually shaken for 16 h with 0.1 M pyrophosphate Muller, 1988; Eggleton, 1988), or magnetic measurements (Coey,
at pH 10, but the extraction and clarification procedures are 1988). A review of characterization methods for Fe oxides is
highly technique dependent (Schuppli et al., 1983; Loveland given by Cornell and Schwertmann (1996) and Schwertmann
and Digby, 1984). For the extraction of short-range order Fe and Taylor (1989). The most important diagnostic criteria are
oxides (predominantly ferrihydrite), a 2 (Schwertmann, 1964) summarized in Tables 22.1 and 22.2. XRD patterns for the major
or 4 h (McKeague and Day, 1966) extraction with 0.2 M ammo- soil Fe oxides are shown in Figure 22.3.
nium oxalate at pH 3 in the dark is widely used. This technique For powder XRD, unless one uses a monochromator, CoKα or
also extracts Fe from organic complexes and poorly crystalline FeKα radiation should be employed to avoid the high-fluorescence
lepidocrocite (Ohta et al., 1993), whereas some magnetites are background that results when Fe-rich samples are irradiated
partly dissolved. Feroxyhite is more resistant to the 2 h oxalate with CuKα radiation. The sensitivity of XRD is improved by
treatment than ferrihydrite (Carlson and Schwertmann, 1980), using a differential XRD method (Schulze, 1981) and selective
and for schwertmannite, a 15 min treatment is used (Murad dissolution treatments (Wang et al., 1993). Due to the low con-
et al., 1994; Bigham et al., 1996b). According to Wang et al. centration of Fe oxides in soils, concentration techniques may
(1993), a shorter oxalate treatment (~10–30 min) is more appro- be necessary (Schulze, 1988), like particle-size separation, mag-
priate to measure ferrihydrite in <2 μm reductomorphic soil netic separation (Schulze and Dixon, 1979), and, for goethite and
fractions than the much longer treatments commonly used for hematite in kaolinitic soils, a 5 M NaOH treatment (Norrish and
soils. For the complete dissolution of the pedogenic Fe oxide Taylor, 1961; Kämpf and Schwertmann, 1982a). A quantitative
minerals, without dissolution of other minerals, a treatment determination of Fe oxide minerals in soils is generally possi-
with sodium dithionite–citrate–bicarbonate (DCB) is used. ble using the intensities of selected x-ray lines, DTA peaks, or
The extraction is carried out for 15 min at 75°C (Mehra and Mössbauer hyperfine sextets. Suitable standards with the same
Jackson, 1960) or by shaking for 16 h with a dithionite–citrate characteristics may be isolated from soils or can be synthesized.
solution at room temperature (Holmgren, 1967). However, as The accuracy of the quantification can be controlled by compari-
dissolution is affected by particle size, crystallinity (particu- son with the chemically determined total amount of Fe oxides
larly for lithogenic magnetite and hematite) and high Al sub- (Fed) (Kämpf and Schwertmann, 1982b).
stitution (goethite and hematite), several DCB treatments may The Al substitution in goethite can be calculated from the
be required. unit-cell c-dimension by Al (mole fraction) = 17.30−57.20c (nm)
The ratio of oxalate-extractable Fe (Feo) to DCB-extractable (Schulze, 1984). The c value is obtained from the XRD positions
Fe (Fed) quantifies the proportion of the more and less active d(110) and d(111) by c = [1/d(111)2 − 1/d(110)2]−1/2, with all goethite
fractions, respectively. A high Feo/Fed ratio and a loss in red- data based on space group Pbnm (Table 22.1). In hematite, Al sub-
ness after oxalate treatment give first indication of ferrihydrite stitution is given by Al (mole fraction) = 31.09−61.71a (nm), where
in a sample. Additionally, it is a useful parameter for character- a = d(110)2, or, preferably, a = d(300)2√3 (Schwertmann et al., 1979).
izing soil properties (e.g., P sorption) and pedogenic processes
(McKeague and Day, 1966; Blume and Schwertmann, 1969). The
ratio of Fed to Fet (total Fe content by HCl or HF digestion) quan- 22.3  Manganese Oxides
tifies the proportion of Fe in primary silicate minerals, which
has been released by weathering and precipitated as Fe3+ oxides, Manganese oxides are usually minor components in soils but
hence estimating Fe sources for potential Fe oxide formation with a significant influence on the soil chemical properties.
and/or soil weathering stage. Advanced soil weathering stages, While Mn is a micronutrient essential for plants and animals, it
indicated by Fed/Fet ratios > 0.8, are usually shown by Oxisols is the only plant essential element that also frequently occurs in
and Ultisols. toxic concentration in acid soils. The mineralogy of Mn oxides is
A field test for the presence of Fe2+ ions and ferric-organic complicated by the large number of minerals and the lack of pre-
complexes in reductomorphic soils can be performed with a cise knowledge of some of their structures, leading to uncertain-
solution of α,α′-dipyridil (Childs, 1981; Kennedy et al., 1982) or ties as to whether certain forms should be regarded as distinct
with a solution of 1:10-phenanthroline (Richardson and Hole, mineral species, or merely as variants, or mixtures of other min-
1979). Lovley and Phillips (1987) proposed the use of hydrox- eral forms (McKenzie, 1989; Post, 1992). The poor crystallinity
ylamine hydrochloride to determine whether Fe3+ is available and low concentration of these minerals in most soils is a fur-
for microbial reduction. The amount of reducible Fe in natural ther challenge for their characterization. A list of Mn oxides is
wetlands and rice paddies is highly correlated to the labile and given in Table 22.3. More information can be found in McKenzie
stabile Fe3+ oxides (van Bodegom et al., 2003). (1989), Graham et al. (1988), and Dixon and White (2002).
22-10 Properties and Processes

110 110
Six-line ferrihydrite
112
300
Goethite, well crystalline 115
114 113
111
221 130 110
104
121 Two-line ferrihydrite
300

020
Goethite, poorly crystalline
Schwertmannite

031 104
120 110
051, 200
Lepidocrocite Hematite 116 021
024 113
231 002 151 300
214

211 310
110
301 311
Akaganeite 522 400
200
Magnetite
411
541 600 440 220
400
511
422 111
100
Feroxyhite
101
110
102 Maghemite

210
213 113
°2 θ Co Kα
80 60 °2 θ Co Kα 40 20 80 60 40 20

0.15 0.2 0.3 0.5 1.0 0.15 0.2 0.3 0.5

d value (nm) d value (nm)

FIGURE 22.3  XRD patterns for the major soil iron oxide minerals (Co Kα, peaks are labeled with their Miller indices). (From Cornell, R.M.,
and U. Schwertmann. 1996. The iron oxides. Wiley-VCH Verlag, Weinheim, Germany.)

22.3.1  Mineral Phases as chain structures because they do not contain tunnels but are
included in the group of tectomanganates because of their struc-
Manganese oxides consist mainly of Mn in octahedral coordina- tural similarity to the channel or tunnel structure members.
tion. The various minerals differ in the arrangement and linkage Pyrolusite, MnO2 , consists of single chains of edge-sharing
of the octahedra. The Mn oxides may be placed into three groups: MnO6 octahedra linked by sharing corners to form 1 × 1 pseu-
(1) Tectomanganates or tunnel structures, (2) phyllomanganates dotunnels (Figure 22.1; Baur, 1976). The single rows of unoc-
or layer structures, both groups with mainly tetravalent Mn, and cupied octahedral sites are not wide enough to accommodate
(3) the trivalent oxides or lower oxides. foreign ions or water molecules. High-resolution transmission
electron microscopy (HRTEM) of pyrolusite crystals showed
22.3.1.1  Tectomanganates (Tunnel Structures) lamellae with the structure of ramsdellite (Yamada et al., 1986).
Tectomanganates are formed from single, double, or wider Ramsdellite, MnO2, consists of double chains of MnO6 octahe-
chains of MnO6 octahedra that are linked into a framework, dra forming 1 × 2 tunnels (Figure 22.1; Post, 1992), that possibly
thus forming tunnels (or channels) through the structures. contain water molecules (Potter and Rossman, 1979). Nsutite
These tunnels are occupied by large foreign cations and water has a structure formed by the intergrowth of pyrolusite-like
molecules. Pyrolusite, ramsdellite, and nsutite are also referred single chains and ramsdellite-like double chains of octahedra
 Oxide Minerals in Soils
TABLE 22.3  Manganese Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Mineral (Synthetic Crystal System, Unit-Cell Six Most Intense Diffraction Lines
Equivalent)a Chemical Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesb
Pyrolusite; MnO2 Tetragonal, P42/mnm a = 4.398 3.11 2.407 1.623 1.306 1.304 2.110 Baur (1976); 24-0735
(β-MnO2) c = 2.873 100 55 55 20 20 16
Ramsdellite MnO2 Orthorhombic, Pnma a = 9.27 4.06 1.647 2.438 2.344 1.660 1.906 39-0375
b = 2.866 100 57 49 46 34 31
c = 4.533
Nsutite (γ-MnO2) Mn4+Mn3+ (O,OH)2 Hexagonal, P a = 9.65 1.635 4.00 2.33 2.42 2.13 1.60 Zwicker et al. (1962); 17-0510
c = 4.43 100 95 70 65 45 45
Hollandite Bax(Mn4+Mn3+)8O16 (x=1) Monoclinic, I2/m a = 10.026 3.10 3.14 3.172 2.412 3.069 3.459 Post et al. (1982); 38-0476
(α-MnO2) b = 2.8782 100 88 40 37 32 23
c = 9.729
β = 91°03′
Cryptomelane Kx(Mn4+Mn3+)8O16 (x=1.3–1.5) Monoclinic, I2/m a = 9.956 2.40 3.122 3.09 2.41 4.852 7.01 Post et al. (1982); 44-1386
b = 2.8705 100 51 45 40 32 30
c = 9.706
β = 90°95′
Coronadite Pbx(Mn4+Mn3+)8O16 (x=1–1.4) Monoclinic, I2/m a = 9.938 3.124 3.491 2.209 2.409 6.98 1.548 Post and Bish (1989); 41-0596
b = 2.8678 100 30 18 17 7 6
c = 9.834
β = 90°39′
Romanèchite Ba0.66 (Mn4+Mn3+)5O10 · 1.34H2O Monoclinic, C2/m a = 13.919 2.408 2.188 3.481 6.96 2.366 2.882 Turner and Post (1988);
b = 2.8459 100 85 60 55 50 40 14-0627
c = 9.678
β = 92°39′
Todorokite (Na,Ca,K)0.3−0.5 Monoclinic, P2/m a = 9.764 9.55 2.399 2.388 2.355 4.77 2.345 Post and Bish (1988); 38-0475
(Mn4+Mn3+)6O12 · 3.5H2O b = 2.8416 100 36 25 24 24 25
c = 9.551
β = 94°06′
Chalcophanite ZnMn3O7 · 3H2O Trigonal, R3 a = 7.533 6.93 2.228 4.07 1.590 3.507 2.550 Post and Appleman (1988);
c = 20.794 100 40 29 23 19 17 45-1320
(continued)

22-11
 22-12
TABLE 22.3 (continued)  Manganese Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Mineral (Synthetic Crystal System, Unit-Cell Six Most Intense Diffraction Lines
Equivalent)a Chemical Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesb
Birnessite (Na,Ca,Mn2+)Mn7O4 · 2.8 H2O Monoclinic, C2/m Na: a = 5.175 7.14 3.57 2.519 2.429 2.154 2.222 Post and Veblen (1990);
b = 2.850 100 27 14 13 7 5 43-1456
c = 7.337
β = 103°18′
Vernadite MnO2 · nH2O (Pseudo) tetragonal a = 9.866 2.39 3.11 2.15 1.827 1.537 1.422 Chukhrov et al. (1980);
(δ-MnO2) I4/m c = 2.844 100 60 60 40 40 40 15-0604
Rancieite (Ca,Mn)Mn4O9 · nH2O Hexagonal, P a = 8.68 7.49 3.74 2.463 2.342 1.425 2.064 22-0718
c = 9.00 100 14 10 6 4 2
Buserite Na4Mn14O27 · 21H2O Orthorhombic a = 17.5 10.1 5.01 3.34 1.46 2.56 2.47 32-1128
b = 30.7 100 70 50 50 30 30
c = 10.2
Lithiophorite LiAl2Mn24+Mn3+O6(OH)6 Trigonal, R3m a = 2.924 4.71 9.43 2.371 1.880 3.143 1.453 Post and Appleman (1994);
c = 28.169 100 68 24 14 7 4 41-1378
Groutite MnOOH Orthorhombic, Pbnm a = 4.560 4.20 2.81 2.67 2.30 1.695 2.38 Glasser and Ingram (1968);
(α-MnOOH) b = 10.70 100 70 70 60 50 40 12-0733
c = 2.870
Manganite MnOOH Monoclinic, a = 8.88 3.40 2.64 1.782 2.417 1.672 2.414 Dachs (1963); in Bricker
(γ-MnOOH) pseudoorthorhombic, b = 5.25 100 24 21 17 17 16 (1965); 41-1379
B21m c = 5.71
β = ~90°
Feitknechtite MnOOH Tetragonal, P a = 8.6 4.62 2.635 2.36 1.96 1.55 1.50 Bricker (1965); 18-0804
(β-MnOOH) c = 9.30 100 50 20 10 1 1
Hausmannite Mn3O4 Tetragonal, I41/amd a = 5.7621 2.847 2.768 1.544 3.089 4.924 1.799 Bricker (1965); 24-0734
c = 9.4696 100 85 50 40 30 25
Manganosite Mn2+O Cubic, Fm3m a = 4.4448 2.223 2.568 1.571 1.34 0.994 0.907 Sasaki et al. (1980); 7-0230
100 60 60 20 18 16
Bixbyite (Fe,Mn)2O3 Cubic, Ia3 a = 9.4091 2.716 1.663 3.842 2.352 1.418 1.845 Geller (1971); 41-1442

Properties and Processes

(α-Mn2O3) 100 28 16 14 13 9
a Designation commonly used in the literature for a synthetic compound with the same crystal structure as the natural mineral are given in parentheses.
b Numbers of the format XX-XXXX indicate ICDD file number (ICDD, 1994).
Oxide Minerals in Soils 22-13

in random fashion (Zwicker et al., 1962; Potter and Rossman, structure similar to birnessite, with Ca 2+ as the main interlayer
1979; Turner and Buseck, 1983). Inclusions of todorokite cation and interlayer water molecules (Bardossy and Brindley,
have also been found in nsutite (Turner and Buseck, 1983). 1978; Potter and Rossman, 1979; Chukhrov et al., 1980). The
Hollandite, cryptomelane, and coronadite, sometimes grouped structure and existence in nature of buserite, also known as
as α-MnO2 , consist of double chains of edge-sharing MnO6 10 Å manganite, are still unresolved. Buserite appears to have a
octahedra linked to form 2 × 2 tunnels (Figure 22.1; Post et al., layer structure similar to birnessite, with the larger, 10 Å layer
1982; Post and Burnham, 1986; Post and Bish, 1989). These spacing probably due to interlayer water (Waychunas, 1991).
minerals have the general formula A0−2(Mn4+,Mn3+)8(O,OH)16. Lithiophorite has a layer structure comprising sheets of edge
The tunnels contain water molecules along with the A cation, and corner-sharing MnO6 octahedra alternating with sheets
which is primarily Ba 2+ in hollandite, K+ in cryptomelane, and of (Al,Li)(OH)6 octahedra (Figure 22.1; Post and Appleman,
Pb2+ in coronadite. Natural samples usually contain a variety 1994). The cation sites in the Mn–O octahedral sheet are fully
of cations in the tunnels. These large cations are located at spe- occupied, 2/3 with Mn4+ and 1/3 with Mn3+. In the (Al,Li)–OH
cific tunnel sites, and their presence is necessary to prevent the octahedral sheet, 2/3 of the sites are occupied by Al and 1/3 by
structure from collapsing (Giovanoli, 1985a). The charges of Li cations. Lithiophorites with only traces of Li and others with
the tunnel cations are balanced by the substitution of Mn4+ by wide variations in Ni, Co, Cu, and Zn concentrations inversely
Mn3+ ions. Romanèchite consists of double and triple chains related to the Al content have been found (Ostwald, 1984a).
of edge-sharing octahedra that share corners to form a frame- According to Manceau et al. (1987, 1990), Co can occur within
work containing 2 × 3 tunnels. The tunnels contain Ba 2+ (and a the octahedral Mn sheets, while Ni and Cu are located in the
variety of other large cations, such as Na, K, Sr) and water mol- (Al,Li)–OH octahedral sheet, probably replacing Li, whereas
ecules (Figure 22.1; Turner and Post, 1988). The charges of the in asbolane, Ni builds partial Ni(OH)2 sheets. Manceau et al.
tunnel cations are balanced by the substitution of Mn4+ by Mn3+ (1987) also found evidence for mixed layering between lithio-
ions. HRTEM images show that intergrowths of romanèchite phorite and asbolane, as observed by Ostwald (1984a). Asbolane
and hollandite are common and are produced by the sharing has a layer structure with alternating sheets of Mn4+–O octa-
of the double chains common to both minerals with double or hedra and Co–Ni–OH octahedra (Figure 22.1; Chukhrov
triple chains occurring at random (Turner and Buseck, 1979). and Gorshkov, 1981). The Co–Ni sheet may be discontinuous
While romanèchite has also been called psilomelane, McKenzie (island-like). The positive charge of the Mn4+ sheets is balanced
(1989) used psilomelane for a structural type and Waychunas by the negative charge of the Co–Ni sheets. Hydrogen bond-
(1991) for mixtures of Mn oxide minerals. Todorokite, which ing occurs between the oxygen atoms of the Mn sheets and
had its structure and existence as a single mineral questioned the hydroxyl groups of the Co–Ni sheets. Most asbolanes are
until recently (Burns et al., 1985; Giovanoli, 1985b), consists fine-grained, poorly crystalline minerals. Vernadite has been
of triple chains of edge-sharing MnO6 octahedra linked to considered a disordered birnessite, lacking regular stacking in
form large 3 × 3 tunnels (Post and Bish, 1988) containing Na, the c-axis. However, according to Chukhrov et al. (1980) and
Ca, K, Ba, Sr, and water molecules (Figure 22.1). The octahe- Chukhrov and Gorshkov (1981), it is a distinct mineral spe-
dra at the edges of the triple chains are larger than those in cies with a disordered structure that has some similarity to that
the middle and, therefore, probably accommodate the larger, of birnessite, represented by layers of hexagonal close-packed
lower-valence cations (Mg 2+, Mn3+, Cu 2+, Ni 2+, etc.) found in O and water molecules in which less than half of the octahe-
todorokite samples (Post and Bish, 1988). The occurrence of dra are occupied by Mn ions. Diffraction patterns of vernadite
variable tunnel widths (3 × 2, 3 × 3, 3 × 4, and 3 × 5) observed have only two d-spacings at ~2.4 and ~1.4 Å, whereas birnes-
in HRTEM images suggests that todorokite represents a family site yields additional reflections at 7.0–7.2, 3.5–3.6 Å, and other
rather than a single mineral (Turner and Buseck, 1981). spacings (Chukhrov et al., 1980).

22.3.1.2  Phyllomanganates (Layer Structures) 22.3.1.3  T rivalent Manganese Oxides

Chalcophanite has a layer structure composed of sheets of and Oxyhydroxides
edge-sharing MnO6 octahedra alternating with planes of Zn Groutite (α-MnOOH) is isostructural with goethite and rams-
cations (but also Mn 2+, Ba, Ca, Mg, K, Pb, Cu, etc.) and water dellite (Figure 22.1; Glasser and Ingram, 1968). Feitknechtite
molecules (Figure 22.1; Ostwald, 1985; Post and Appleman, (β-MnOOH) has a structure similar to lepidocrocite (Figure
1988). One of every seven octahedral sites in the Mn–O sheet 22.1), but its structure has not been refined (Waychunas, 1991).
is vacant, and the Zn cations are situated above and below the Manganite (γ-MnOOH) is similar to pyrolusite and rutile (Figure
vacancies. The other phyllomanganates are structurally analo- 22.1; Huebner, 1976). Hausmannite (Mn3O4) has a disordered
gous to chalcophanite, with Na+, Ca 2+, K+, and Mn 2+ as inter- spinel structure analogous to magnetite (Figure 22.1; Huebner,
layer cations. Birnessite, consists of a layer structure analogous 1976). Manganosite has the NaCl structure and is of limited
to chalcophanite but with fewer vacancies in the octahedral occurrence in nature (Huebner, 1976). Bixbyite (α-(Fe,Mn)2O3)
sheets and with Na, K, or Mg replacing the Zn cations (Figure has an anion-deficient fluorite structure (Geller, 1971), while
22.1; Post and Veblen, 1990). The interlayer region contains pure (synthetic) α-Mn2O3 is orthorhombic (Huebner, 1976;
water molecules as in chalcophanite. Rancieite has a layer Waychunas, 1991).
22-14 Properties and Processes

22.3.2  Occurrence and Formation

Many studies have been made on the synthesis of Mn oxides
(McKenzie, 1971; Hem and Lind, 1983; Giovanoli, 1985a) and
the transformation of one form to another (Faulring et al., 1960;
Bricker, 1965; Glasser and Smith, 1968; Rask and Buseck, 1986).
Some of these studies, even if more applicable to diagenetic and
hydrothermal conditions and to the formation of ore deposits,
may be extrapolated to soil environments. Of the variety of Mn
oxides found in terrestrial environments, only a few have been
positively identified in soils. For example, nsutite and pyrolusite
are common in Mn ore deposits (Zwicker et al., 1962; Varentsov,
1982) but have not been found in soils. Synthesis studies show 2 μm
that large amounts of foreign ions prevent the formation of
nsutite, while even small amounts of foreign ions prevent the
FIGURE 22.4  Scanning electron micrograph of the fractured sur-
formation of pyrolusite. In soils, the foreign ions released by
face of a nodule from a Tropeptic Eutrustox showing crystals of the
mineral weathering probably limit the formation of these Mn Mn oxide mineral lithiophorite. (From Golden, D.C., J.B. Dixon, and Y.
oxides, whereas in ore deposits, the abundance of Mn would aid Kanehiro. 1993. The manganese oxide mineral, lithiophorite, in an Oxisol
in the removal of foreign ions, thus allowing the formation of from Hawaii. Aust. J. Soil Res. 31:51–66.)
nsutite and pyrolusite (McKenzie, 1989). According to Ostwald
(1984b), the mineral associations birnessite–montmorillonite, Manganese oxides are commonly of authigenic origin in
chalcophanite–kaolinite, and lithiophorite–gibbsite observed soils, formed by direct chemical or biochemical precipitation
in Australian Mn ore deposits may represent special cases of from solution and by crystallization of poorly organized colloi-
metasomatic replacements of clay minerals by phyllomanganate dal sols. However, little is known about the processes involved
minerals, whereas the occurrence of vernadite in a wide range in their pedogenic formation. In most soils, Mn oxides occur as
of substrates is explained by its formation as a product of rapid finely dispersed particles but may also be found as discontinu-
microbial oxidation of Mn2+ (Chukhrov and Gorshkov, 1981). ous black–brown coatings of ped surfaces (mangans), as pore
Laboratory experiments show that Mn3O4 (hausmannite) is fillings, and as concretions and nodules (Figure 22.4). Their
the initial product of the chemical oxidation of aqueous Mn2+ at presence and concentration are more likely in soil environments
25°C in moderately alkaline solutions (pH 8.5–9.5). It converts with alternate reducing and oxidizing conditions, which affect
to β-MnOOH (feitknechtite) and then to γ-MnOOH (manga- the mobility and the precipitation of Mn (White and Dixon,
nite) by aging in solution (Hem and Lind, 1983; Murray et al., 1996). Thus, higher accumulations of Mn oxides are more fre-
1985). At 0°C, the initial product is feitknechtite, which converts quent in soils with restricted drainage such as the aquic subor-
to MnO2, identified as ramsdellite or birnessite (Hem and Lind, ders (Aqualfs, Aquolls, Aquults, etc.), and intergrades (Aquic
1983). The formation and transformation of Mn oxides through Hapludalfs, Aquic Dystrochrepts, etc.), and are also commonly
successively increasing oxidation states are compatible with the found in saprolites. However, Mn accumulations in a soil are not
common distribution of Mn oxides observed in supergene Mn necessarily an indication of a present redox environment but
ores (Bricker, 1965) and in lateritic weathering sequences (Parc may reflect former wetter conditions (Allen and Hajek, 1989).
et al., 1989). Minor inversions of that Mn oxidation sequence Mn and Fe oxides are usually associated in nodules with
occur, however, due to the presence of foreign ions, thus pro- dominant silicates (quartz, clay minerals) that probably act as
moting the formation of cryptomelane and lithiophorite instead primary templates for the Mn and Fe oxidation and precipita-
of pyrolusite (Parc et al., 1989). The influence of microorganisms tion (Schwertmann and Fanning, 1976). Golden et al. (1986)
and organic compounds additionally increases the complexity of demonstrated experimentally that Mn4+ oxide minerals can
Mn oxide formation in soil environments. also act as oxidizing agents of Fe2+ ions in solution, causing the
Manganese is one of the first elements released during weath- precipitation of Fe3+ oxides in association with Mn oxides. The
ering of primary minerals, which explains its common accumu- crystal growth and progressive cementation of the nodules can
lation in saprolites. Mobile in solution as Mn2+, its oxidation to be explained by an autocatalytic oxidation of Mn2+ adsorbed
Mn3+ and Mn4+ and its subsequent precipitation is often acceler- onto the formed Mn (and Fe) oxides (McBride, 1994). Thus, abi-
ated by microorganisms (Ghiorse, 1988). Most of the Mn oxides otic oxidation accelerates in response to the increased surface
found in surface environments are compounds of Mn4+ with available for selective adsorption of Mn2+. The overall process,
some Mn3+. The typical fine-grain size and poor crystallinity of of Mn oxidation and nodule formation, may also be promoted
the Mn oxides in soils are probably related to seasonal moisture by Mn-oxidizing bacteria (Robbins et al., 1992; Ehrlich, 1996;
changes, the presence of interfering organic and inorganic com- Leinemann et al., 1997) and fungi (Thompson et al., 2005, 2006).
ponents in the soil solution, and the presence of multiple Mn Furthermore, microorganisms may indirectly control local
oxidation states. environments, through elevation of pH and Eh, which favor
Oxide Minerals in Soils 22-15

oxidation of Fe and Mn (Ghiorse and Ehrlich, 1992). Models of related to the crystallinity, specific surface areas, and the PZC of
biotic oxidation of Mn (and Fe) are described by Ghiorse and the oxides. In contrast to other transition elements, Cr toxicity
Ehrlich (1992), Ehrlich (1990), and Tebo et al. (2004). and mobility increase with its oxidation state. Thus, the presence
In soil samples from Australia, the abundance of Mn oxides of Mn oxides, as oxidizing agents for Cr3+ in soil systems, should
decreased from birnessite and lithiophorite, over hollandite, to be considered in disposal studies (Fendorf et al., 1992).
only one occurrence of each of pyrolusite and todorokite (Taylor Manganese and Fe oxides also act as final electron acceptors
et al., 1964). A high frequency of birnessite was also found in soils oxidizing organic compounds and are conversely dissolved in the
of other regions (Taylor, 1968; Ross et al., 1976). Todorokite for- process. Organic compounds that form inner-sphere complexes
mation from Mn released by the weathering of Mn-substituted with the oxide surface (e.g., catechol) dissolve the Mn oxide more
siderite in lignite overburden was reported by Senkayi et al. quickly than those compounds that form outer-sphere complexes
(1986). Birnessite, lithiophorite, and lattice fringes attributed (e.g., hydroquinone) (Stone and Morgan, 1984a, 1984b; McBride,
to todorokite were observed in nodules of a Vertic Argiustoll, 1987). Lovley and Phillips (1988) found evidence that microorgan-
while lithiophorite only was found in a Rhodic Paleudult isms can obtain energy for growth by coupling the oxidation of
(Uzochukwu and Dixon, 1986). Romanèchite was identified in organic matter to the dissimilatory reduction of Fe3+ and Mn4+.
nodules of a Typic Ochraquult (Robbins et al., 1992), and verna- They proposed a microbial food-chain model, in which fermen-
dite associated with feroxyhite was identified in a Scottish Gleyic tative organisms initially metabolize complex organic matter,
Cambisol (Birnie and Paterson, 1991). Chukhrov and Gorshkov and in the next stage, a separate group of bacteria oxidizes the
(1981), as cited by McKenzie (1989), reported that the most fermentation products to CO2 while reducing Fe3+ and Mn4+. The
common Mn oxide in soils was vernadite, followed by birnes- overall process may be an important degradative pathway for
site, cryptomelane, todorokite, and hausmannite. Chukhrov organic compounds and the formation of humic material, while
and Gorshkov (1981) reported the presence of hausmannite in the reduction and dissolution of Mn oxides increases the Mn
unspecified soils with pH ~ 8.2. mobility and bioavailability to organisms. Hui et al. (2003), for
example, showed that aromatic amines are oxidized by soil Mn
oxides resulting in the release of Mn2+ to solution.
22.3.3  Influence on Soil Properties
The wide range of PZC values reported for synthetic samples
22.3.4  Identification
of Mn oxides (Healy et al., 1966; Crowther and Dillard, 1983;
Oscarson et al., 1983), from 1.5–3.5 for birnessite to 2.8–4.6 Accumulations of Mn oxides in soils are readily identified by
for the hollandite group and 6.4–7.3 for pyrolusite, is probably their characteristic black–brown coloration. The effervescence
related to the synthesis conditions. In general, most Mn oxides observed with the addition of H2O2 is a usual field criterion
have a PZC at a pH < 4.0, a high negative charge, a large range of that helps to confirm the presence of these minerals. The small
surface area (5–360 m2 g−1), and show a strong specific adsorp- amount of Mn oxides in soils, the diffuse nature of the x-ray
tion of cations. patterns of some of the minerals, and the coincidence of diag-
A high sorption capacity of Mn oxides for metal ions has been nostic lines with those of associated matrix minerals can make
found by many authors (see Murray, 1975; McKenzie, 1989). In their identification by XRD difficult. Thus, XRD, preferably with
general, metal ions are sorbed in the increasing order Mg < Ca < Fe Kα radiation, can be used only where natural segregations
Sr < Ba < Ni < Zn < Co < Mn < Cu < Pb (Murray, 1975), leading of the minerals occur, such as nodules, veins, or coatings. Even
to the accumulation of relatively high concentrations of heavy then, a concentration pretreatment may be necessary. Powder
metals (Childs, 1975; Sidhu et al., 1977) and actinides in the Mn XRD patterns for some of the more important Mn oxide miner-
oxides (Means et al., 1978; Cerling and Turner, 1982). als are shown by Post (1992) and the most intense XRD lines of
Manganese oxides are strong inorganic oxidants, thus affect- the major minerals are listed in Table 22.3. Because of the lower
ing the availability or the hazard of particular metals. In the case crystallinity, soil Mn oxides may, however, show some devia-
of Co adsorption onto the birnessite surface at pH <7, Co2+ is tion from these patterns. A selective dissolution of Mn oxides
oxidized to Co3+ by Mn4+, with formation of Mn2+ in the process with acidified hydroxylamine hydrochloride was proposed by
(Crowther and Dillard, 1983). The strong adsorption mechanism Chao (1972), whereas Tokashiki et al. (1986) characterized Mn
has a significant influence on the availability of Co to plants oxides by using successive sodium hydroxide, hydroxilamine
(Adams et al., 1969; McKenzie, 1978). hydrochloride, and DCB treatments. Concentration procedures
The Mn oxides have a major influence on the toxicity and bio- for Mn oxides, selective chemical treatments, and identification
availability of As and Cr in terrestrial and aquatic environments. by XRD and thermal methods are also reported by Uzochukwu
The reduced species As3+, which is more toxic, more soluble, and Dixon (1986). A comprehensive compilation of IR powder-
and more mobile than the oxidized As5+ species, is effectively absorption spectra of synthetic and naturally occurring Mn
adsorbed and oxidized by Mn4+ oxides at pH <6 (Oscarson et al., oxides is given by Potter and Rossman (1979).
1983; Thanabalasingam and Pickering, 1986; Scott and Morgan, Crystal structure and crystal chemistry refinements have
1995). However, the ability to deplete the concentration of As3+ been performed with HRTEM, electron-microprobe analy-
in solution varies between different types of Mn oxides and is sis, electron diffraction, powder XRD with Rietveld analysis
22-16 Properties and Processes

(Post and Appleman, 1988; Post and Bish, 1988; Post and structures can be described in terms of the arrangement and
Veblen, 1990), and x-ray absorption spectroscopy (Manceau linkage of Al-containing octahedra.
et al., 1987, 1992a, 1992b; Manceau and Combes, 1988).
HRTEM has led to the discovery of complex intergrowths of 22.4.1.1  Hydroxides
variable lattice periodicities in some Mn oxides (Turner and
Gibbsite (γ-Al(OH)3) consists of sheets of edge-shared octahedra
Buseck, 1979, 1981, 1983; Yamada et al., 1986).
with two-thirds of the available octahedral sites filled with Al3+
ions. The occupied octahedral sites form sixfold rings, analo-
22.4  Aluminum Oxides gous to the dioctahedral sheet of phyllosilicates. The octahedral
Of six different Al oxide minerals, gibbsite and, less commonly, sheets are stacked along the c-axis, and the OH groups in one
boehmite form under soil conditions. Nordstrandite and bayer- sheet reside directly above those in the next, rather than  in
ite have only been identified in restricted geologic environments. the position of closest packing. The interlayer attractions are
Diaspore and corundum are occasionally found in bauxite weak and are dominated by hydrogen bonding (Figure 22.1;
deposits but are rare in soils. The relative rarity of Al oxide min- Hsu, 1989). Bayerite, a second polymorphic form of Al(OH)3,
erals in soils, which is in contrast to their structural Fe analogs, is analogous to gibbsite except that the OH groups of one sheet
may be explained by the competitive formation of aluminosili- reside in the depressions between the O atoms of the next sheet
cates and by the difficulty of identifying small amounts of these and are in the close-packing position (Figure 22.1; Hsu, 1989).
minerals by XRD (Taylor, 1987). More information on Al oxides Nordstrandite, a third polymorphic form of Al(OH)3, has a struc-
is given by Hsu (1989) and Huang et al. (2002). ture in which the stacking of the octahedral sheets alternate
between the gibbsite and bayerite arrangements (Hsu, 1989). In
addition to these crystalline phases, amorphous Al(OH)3 may
22.4.1  Mineral Phases
occur in soils (Süsser and Schwertmann, 1991). Doyleite, a fourth
Crystallographic properties for the Al oxide minerals likely to polymorphic form of Al(OH)3, has a structure of sheets of edge-
occur in soils are listed in Table 22.4. Aluminum occurs exclu- sharing octahedra (Chao et al., 1985) and is a rare hydrothermal
sively in octahedral coordination in the Al oxides, and the mineral not found in soils.

TABLE 22.4  Aluminum Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Chemical Crystal System, Unit-Cell Six Most Intense Diffraction Lines
Mineral Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesa
Gibbsite γ-Al(OH)3 Monoclinic, P21/n a = 8.6552 4.85 4.371 2.385 4.32 2.45 2.05 33-0018
b = 5.0722 100 70 55 50 40 40
c = 9.7161
β = 94°607′
Nordstrandite Al(OH)3 Triclinic, P1 a = 5.082 4.79 2.27 4.32 2.393 2.016 1.902 24-0006
b = 5.127 100 30 25 25 25 20
c = 4.980
α = 93°40′
β = 118°55′
γ = 70°16′
Bayerite Al(OH)3 Monoclinic, P21/a a = 5.062 2.222 4.71 4.35 1.723 3.20 1.333 20-0011
b = 8.671 100 90 70 40 30 18
c = 4.713
β = 90°27′
Doyleite Al(OH)3 Triclinic, P/1 or P1 a = 5.00 4.794 2.36 1.972 1.857 1.842 4.29 Chao et al. (1985)
b = 5.17 100 40 30 30 30 20
c = 4.98
α = 97.5°
β = 118.6°
γ = 104.74°
Diaspore α-AlOOH Orthorhombic, Pbnm a = 4.396 3.99 2.317 2.131 2.077 1.633 2.558 05-0355
b = 9.426 100 56 52 49 43 30
c = 2.844
Boehmite γ-AlOOH Orthorhombic, Amam a = 3.70 6.11 3.164 2.346 1.86 1.85 1.453 21-1307
b = 12.227 100 65 55 30 25 16
c = 2.868
Corundum α-Al2O3 Rhombohedral, R3c a = 4.7592 2.086 2.551 1.60 3.48 1.374 1.74 43-1484
c = 12.992 100 98 96 72 57 48
a Numbers of the format XX-XXXX indicate ICDD file number (ICDD, 1994).
Oxide Minerals in Soils 22-17

22.4.1.2  Oxyhydroxides in turn, is affected by rainfall, temperature, parent rock, topog-

Diaspore (α-AlOOH) is isostructural with goethite (Figure raphy, groundwater table, vegetation, and time. Environments
22.1; Ewing, 1935a, 1935b; Busing and Levy, 1958). Boehmite with warm temperatures, high rainfall, and free drainage favor
(γ-AlOOH) has the same structure as lepidocrocite (Figure desilication and leaching of ions, as well as mineralization of
22.1). Poorly crystalline boehmite, formerly also called pseudo- organic matter. Oxisols and laterites found in these environ-
boehmite, has a restricted number of unit cells along the b-axis ments may have significant amounts of gibbsite associated with
(Tettenhorst and Hofmann, 1980). kaolinite and Fe oxides (Curi and Franzmeier, 1984; Macedo and
Bryant, 1987). Gibbsite is frequently a minor component in ulti-
22.4.1.3  Oxides sols, which are widespread in humid tropical, subtropical, and
Corundum (α-Al2O3) is isostructural with hematite (Figure 22.1; temperate regions (Allen and Hajek, 1989). High amounts of
Maslen et al., 1993). gibbsite may be found under temperate climates in deeper parts
of soil profiles submitted to higher leaching rates (Norfleet et al.,
1993; Ogg and Baker, 1999). The porosity of the soil parent mate-
22.4.2  Occurrence and Formation
rial is important in determining whether or not gibbsite forms.
Aluminum is a common element in primary silicate miner- In Kenya, for example, soils formed in porous volcanic ash on
als, from which it may be released by weathering. Depending the slopes of Mt. Kenya contain considerably more gibbsite than
on the environmental conditions, the free Al hydrolyzes and soils from western Kenya formed from hard igneous and meta-
precipitates as Al hydroxide or oxyhydroxide, and then crys- morphic rocks (Obura, 2008).
tallizes. The reason this fails to occur in many soils is because Nordstrandite has been found in nature as crystals radiating
aluminum usually binds to silicon to form aluminosilicate clay into solution cavities in limestone from Guam (Hathaway and
minerals. Only in the most intense leaching environments is the Schlanger, 1965) and as small pellets in a limestone soil from
Si concentration low enough that gibbsite may form. However, Borneo (Wall et al., 1962). Bayerite found in calcareous material
the detailed chemistry of Al oxide formation in soils remains in Israel probably formed under hydrothermal conditions (Gross
obscure, mainly because of the uncertainties in the formation and Heller, 1963). The apparent rarity of bayerite and nordstran-
and the type of hydroxy polymers involved. dite in soils may reflect identification difficulties, due to their
Synthesis studies have, so far, given an approximate outline of low concentration and/or masking by the presence of gibbsite.
the probable processes of Al-hydroxide formation. The develop- The same factors may be responsible for the rare reports of
ment of Al-hydroxide polymorphs appears to be related to the boehmite in soils (Taylor, 1987). Boehmite has been identified
rate of precipitation, pH of the system, clay mineral surfaces, and in lateritic materials (Gilkes et al., 1973) and together with dia-
the nature and concentration of inorganic and organic anions spore in bauxites (Vgenopoulos, 1984). Boehmite often occurs
(Huang, 1988; Hsu, 1989). Only synthesis experiments related in bauxite deposits in association with gibbsite, from which it is
to pedogenic environments are summarized here. At room tem- considered to form through partial dehydration by diagenesis or
perature, gibbsite forms in acid solutions (pH < 6) under slow hydrothermal alteration. Hughes et al. (1994) identified boehm-
hydrolysis, nordstrandite in neutral to alkaline solutions (pH > 7), ite in native American artifacts from an Ordovician-age paleo-
and bayerite in alkaline solutions under fast hydrolysis (Hsu, sol in northwestern Illinois. The formation of poorly crystalline
1966; Schoen and Roberson, 1970). These conditions agree with boehmite has been attributed to the presence of foreign ions dur-
the natural occurrence of gibbsite in highly weathered acidic ing crystallization (Hsu, 1967). Since poorly crystalline boehm-
soils, whereas nordstrandite and bayerite have been found in ite alters to crystalline Al(OH)3 polymorphs on removal of the
association with limestone materials. Thermodynamically, foreign ions from the environment, the occurrence of crystalline
gibbsite is the most stable of the three Al(OH)3 polymorphs boehmite in soils, other than those derived from bauxite, may be
(Hemingway et al., 1991). less common than believed (Taylor, 1987).
Anions that have strong affinity for Al3+, such as SO4 2− , CO32− , Diaspore in association with minor amounts of goethite has
PO4 4 − , and SiO32−, may interfere with the crystallization of been identified as a surface weathering product formed by the
Al(OH)3 (Huang, 1988; Hsu, 1989). Organic ligands like citric, desilication of a kaolinitic clay in Missouri (Keller, 1978). The
malic, tannic, aspartic, and fulvic acids block the coordination possible influence of Fe in diaspore formation is supported by
sites of polynuclear Al ions and restrain the hydrolysis, inhibiting synthesis experiments and natural rock weathering and baux-
the crystallization of Al(OH)3 and influencing the nature of the ite occurrences (Taylor, 1987). The formation of Fe-substituted
precipitated compound (Kodama and Schnitzer, 1980; Violante diaspore is, however, unlikely because the large Fe3+ does not
and Violante, 1980; Violante and Huang, 1985; Singer and Huang, fit into the diaspore structure, in contrast to the substitution
1990). This explains why little or no gibbsite is found in the A hori- of the smaller Al3+ in the larger goethite structure (Davies and
zon of acidic soils high in organic matter and exchangeable Al, Navrotsky, 1983). In confirmation, Fe in a diaspore crystal has
while it is found in greater quantities in deeper horizons. been identified as a hematite-like cluster (Hazemann et al., 1992).
The pathway for gibbsite formation by direct desilication Corundum occurs in pegmatites and other rocks associ-
of primary Al silicates or through clay mineral intermediates ated with nepheline syenites, in high-grade aluminous meta-
(Jackson, 1964) is conditioned by the intensity of leaching, which, morphic rocks, in aluminous xenoliths in igneous rocks, in
22-18 Properties and Processes

metamorphosed bauxitic deposits, and as a detrital mineral in

sediments (Deer et al., 1992). Reports of corundum in soils are
scarce, but because of its high resistance to weathering, it can
be found as a residual mineral of igneous or thermally meta-
morphosed rocks, like in lateritic bauxites of Australia (Taylor
et al., 1983) and in Brazilian Oxisols (Macedo and Bryant, 1987).
In some Australian soils derived from corundum-free rocks, the
presence of corundum is attributed to the heating of the soil by
bush fires (Wells et al., 1989). The corundum may have formed in
association with hematite by the dehydroxylation of Al-goethite.
The associated crystallization of isostructural hematite may
have acted as a template for the nucleation of corundum, thereby
reducing the activation energy and enabling its formation at
relatively low temperature via the epitaxial growth on hematite. 5 μm

FIGURE 22.5  Scanning electron micrograph from a bauxitic zone

22.4.3  Influence on Soil Properties
in a deep lateritic profile from the Jos plateau, Nigeria, showing hema-
Because of the high surface area (100–220 m2 g−1), high PZC tite crystal aggregates on large euhedral gibbsite crystals. (From
(pH 5–9), and a variable surface charge, Al oxides favorably che- Zeese, R., U. Schwertmann, G.F. Tietz, and U. Jux. 1994. Mineralogy
misorb heavy metals (Cu, Pb, Zn, Ni, Co, Cd) and anions (PO4 4 −, and stratigraphy of three deep lateritic profiles of the Jos plateau (central
Nigeria). Catena 21:195–214.)
SiO32−, MoO4 2−, SO4 2−, catechols) (Hingston et al., 1974; McBride
and Wesselink, 1988; McBride, 1989). The adsorption is related to plane (Schoen and Roberson, 1970; Violante and Jackson, 1981;
the reactive (singly coordinated OH− groups at crystallite edges) Hsu, 1989). Synthetic nordstrandite shows rectangular plates,
rather than the total surface area. The high P retention in Oxisols elongated parallelograms, ill-defined ovoidal particles, or clus-
and Ultisols is usually related to the content of gibbsite, in addi- ters of acicular crystals (Shoen and Roberson, 1970; Violante and
tion to that of Fe oxides (Juo, 1981; van Wambeke, 1992). Synthesis Jackson, 1979, 1981; Violante et al., 1982; Tait et al., 1983). With
studies have shown the effectiveness of Al(OH)3 precipitates in the exception of gibbsite, many of these crystal shapes seem to
improving the physical properties of soils and clay minerals (see occur only in synthetic Al oxides.
Hsu, 1989). Aluminum oxides, mainly gibbsite, in addition to Fe
22.4.4.1  X-Ray Diffraction
oxides, are strongly associated with the aggregation of Oxisols
and Ultisols, but the mechanism of aggregation is unclear. The main XRD peaks of the Al oxides are listed in Table 22.4. For
specimens with poor crystallinity, these diffraction peaks may not
be completely resolved. Gibbsite in soils can be quantified by XRD,
22.4.4  Identification
but it will not be detected if its content is below about 50 g kg−1
Crystalline Al oxides can be identified and quantified by XRD, (Jackson, 1969). The strongest peak for boehmite is the d(020) at
thermal analysis, IR, and EM with a combination of several 6.11 Å, while very fine boehmite particles show a broadening and
methods being necessary. Currently, no selective dissolution an apparent line shift of the d(020) peak to larger d-spacings due
methods are known for the specific dissolution of crystalline and to a diffraction effect (Tettenhorst and Hoffman, 1980).
noncrystalline Al forms in soil samples, but acid NH 4 + oxalate
treatment (Schwertmann, 1964) is frequently used to estimate 22.4.4.2  Thermal Analysis
the content of undefined, poorly crystalline Al forms in soils. DTA is frequently used for the identification of Al hydroxides
The problems inherent in the identification of poorly crystal- and oxyhydroxides (Mackenzie, 1970, 1972; Karathanasis and
line Al oxides in the presence of clay minerals are illustrated by Harris, 1994). The presence of 10 g kg−1 gibbsite can be detected
Violante and Huang (1994). By XRD analysis, the detection limit by DTA, and its amount can be estimated by comparing the
of poorly crystalline boehmite in samples containing kaolinite 300°C–330°C endothermic peak with those of standards. The
or montmorillonite was approximately 30%–40%. When both peak temperature for bayerite is only slightly lower than that
kaolinite and montmorillonite were present, however, the iden- for gibbsite, so that their differentiation in natural samples is
tification by DTA, IR, or TEM often failed even for concentra- impossible (Karathanasis and Harris, 1994). In soil samples, the
tions of boehmite as high as 50%–80%. 300°C–330°C peak may overlap with that of goethite, requir-
Under the electron microscope, well-crystallized gibbsite ing an additional DTA curve after the removal of goethite with
occurs as hexagonal plates (Hsu, 1989) or as elongated hexago- sodium dithionite (Jackson, 1969). Diaspore yields an endother-
nal rods in synthetic crystals (Tait et al., 1983). Euhedral gibbsite mic peak at 540°C, whereas boehmite has a peak that occurs in
crystals from a bauxite zone in a deep lateritic weathering profile the range of 450°C–580°C depending on crystallinity and par-
are shown in Figure 22.5. Bayerite frequently occurs as a trian- ticle size. The overlap with the kaolinite peak at 550°C limits the
gular pyramid, with its long direction perpendicular to the basal identification of these oxyhydroxides.
Oxide Minerals in Soils 22-19

22.4.4.3  I nfrared Absorption Analysis oxides can be found in Drees et al. (1989), Heaney et al. (1994),
Characteristic OH-stretching absorption spectra have been and Monger and Kelly (2002).
used to identify Al(OH)3 and AlOOH polymorphs in monomin-
eralic samples. Gibbsite shows three absorption bands and
22.5.1  Mineral Phases
another doublet, with reported bands for well-crystallized natu-
ral gibbsites at 3622, 3627, 3460, 3396, and 3384 cm−1. Each of The Si oxides are tectosilicates. The repeating unit is a SiO4
the absorption bands may shift slightly to lower wave numbers tetrahedron in which each O is linked to Si atoms of adjacent
with decreasing crystallinity (Elderfield and Hem, 1973). The tetrahedra, forming a 3D framework structure. This contrasts
3622 cm−1 absorption band is coincident with that of kaolinite with the Fe, Al, Mn, and Ti oxides in which the basic unit is
and micaceous clays (Farmer and Russel, 1967), thus precluding a cation in octahedral coordination. The pattern of the tetra-
its use for the identification of gibbsite. Boehmite and diaspore hedral linkage is different for each Si oxide polymorph, and
each show two OH-stretching bands, boehmite at 3087 and this difference is reflected in their structural, physical, and
3283 cm−1 and diaspore at 2922 and 2990 cm−1 (Ryskin, 1974). chemical properties. The structures of the α-phases are closely
Raman microprobe spectroscopy offers an alternative procedure related to those of their high-temperature β-phase equivalents.
in characterizing Al(OH)3 polymorphs in soils (Rodgers, 1993). Quartz consists of paired helical chains of corner sharing SiO4
tetrahedra that spiral along the Z-axis (Heaney, 1994). The
22.5  Silicon Oxides intertwined chains produce open channels parallel to c (Z)
that appear hexagonal in projection (Figure 22.1). In tridymite
The Si oxides occurring in soils are given in Table 22.5. In nature, and cristobalite, the idealized fundamental module consists of
the SiO2 polymorphs (quartz, tridymite, and cristobalite) occur a sheet containing six-member rings of SiO4 tetrahedra, with
as both higher temperature or β-phases and lower temperature or the tetrahedra alternately pointing above and below the plane
α-phases. In soils, however, only the α-phases are usually found. defined by the basal oxygen atoms (Heaney and Banfield, 1993).
Opal is a hydrated form of Si of both biogenic and inorganic ori- Tridymite and cristobalite are differentiated by a different
gin. Microcrystalline quartz, or microquartz, occurs in the form stacking arrangement of this tetrahedral sheet. In tridymite,
of chalcedony and chert (Heaney, 1994). Microcrystalline fibrous the sheets are stacked such that the hexagonal rings (ditrigo-
α-quartz, in the form of chalcedony, usually occurs as a second- nal and oval rings in α-tridymite structures) lie directly over
ary infilling of seams and cavities within rocks, sometimes cre- one another, creating continuous tunnels normal to the sheets
ating concentrically banded agates or geodes. An intergrowth of (Figure 22.1). These tunnels account for the lower density of
authigenic microcrystalline α-quartz grains, which range in size tridymite (2.26 g cm−3) as compared to quartz (2.65 g cm−3). In
from <1 to 50 μm, occurs in highly silicified sedimentary rocks cristobalite, the stacking involves three sheets that are trans-
in the form of chert (Knauth, 1994). More information about Si lated relative to one another such that the hexagonal rings

TABLE 22.5  Silicon Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Crystal
Chemical System, Unit-Cell Six Most Intense Diffraction Linesa
Mineral Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesb
α-Quartz SiO2 Trigonal, a = 4.912 3.342 4.257 1.818 1.542 2.457 2.282 Will et al. (1988, in
P3121 c = 5.403 100 22 14 9 8 8 Heaney, 1994);
33-1161
α-Tridymite SiO2 Monoclinic, a = 10.04 4.08 4.28 3.80 3.24 2.48 2.382 Heaney (1994);
C2221 b = 17.28 100 93 68 48 35 21 42-1401
c = 8.20
β = 91°50′
α-Cristobalite SiO2 Tetragonal a = 4.969 4.04 2.487 2.841 3.136 2.467 1.929 Schmahl et al. (1992,
P41212 c = 6.925 100 13 9 8 4 4 in Heaney, 1994);
39-1425
Opal (natural) 4.08 2.51 2.86 3.14 1.937 1.878 38-0448
100 30 10 9 5 5
Opal-C ~α-Cristobalite + 4.3 Drees et al. (1989)
Opal-CT 4.10 4.29 2.50 3.34 3.18 2.85 Drees et al. (1989)
vs s s w w w
Opal-A 4.1 2.0 1.5 1.2 Drees et al. (1989)
sb wd wd wd
a vs, Very strong; s, strong; w, weak; sb, strong broad; wd, weak diffuse.
b Numbers of the format XX-XXXX indicate ICDD file number (ICDD, 1994).
22-20 Properties and Processes

(oval rings in α-cristobalite) do not superimpose (Figure 22.1). in soils developed from volcanic materials, opal may be a signifi-
Thus, cristobalite lacks the continuous tunnels normal to the cant component of soils, but tridymite occurs only rarely.
layers as in tridymite, but tunnel structures are formed parallel Quartz in soils is mainly a primary mineral, inherited from
to the layers. Thus, the density of cristobalite is only slightly the parent material. The higher stability of quartz compared to
higher than that of tridymite (2.32 g cm−3). other silicate minerals is explained by its crystallization from
magma closer to present earth-surface conditions. The higher
Opal is classified into three structural groups based on XRD
stability of quartz relative to the other Si oxide polymorphs is
powder patterns: Opal-C (well-ordered α-cristobalite), opal-
due to a denser packing of the crystal structure and a higher
CT (disordered α-cristobalite, α-tridymite), and opal-A (highly
energy required to break the Si–O–Si bond. Quartz in chert
disordered, nearly amorphous) (Jones and Segnit, 1971; Deer
forms through a diagenetic transformation from opal-A via
et al., 1992), in a sequence of decreasing structural order. In
opal-CT and opal-C (Hesse, 1988). As demonstrated experi-
opal-C, the stacking is predominantly cristobalitic, which is
mentally, quartz may also precipitate directly (Mackenzie and
revealed by weak superstructure XRD reflections characteris-
Gees, 1971). Authigenic quartz in the form of chemical precipi-
tic of α-cristobalite. Opal-CT consists of random stackings of
tations and grain overgrowths frequently occurs in sediments
α-cristobalite- and α-tridymite-like arrangements, yielding a
(carbonates, sandstones) and is believed to form in soils, too
disordered crystal structure. The microstructure of opal-CT is
(Drees et al., 1989).
composed of small spheres less than 5 μm in diameter, called
Quartz is generally concentrated in the sand and silt frac-
lepispheres, which consist of an interpenetrative growth of tiny
tions of soils, with a lower frequency in the coarse-clay fraction
cristobalite and tridymite blades (Hesse, 1988; Graetsch, 1994).
(0.2–2 μm). The depth distribution of quartz is a function of
Opal-A is a noncrystalline hydrous Si polymorph (SiO2 · nH2O)
parent material and degree of weathering (Drees et al., 1989).
differing from the crystalline polymorphs in that it lacks long-
In  relatively undifferentiated soils (Entisols and Inceptisols),
range atomic order. The microstructure of opal-A shows the clos-
distributions of quartz reflect mainly variations in parent
est packing of spheres of Si with diameters ranging from 10 to
material. Quartz may comprise >90% of the inorganic frac-
50 nm (Greer, 1969) with water filling the interstices (Graetsch,
tion of Quartzipsamments. In Aridisols, quartz is generally
1994). The specific gravity of biogenic opal from soils and plants
abundant due to restricted weathering, while in moderately
varies continuously over the range 1.5–2.3, with modal values
weathered soils (Spodosols, Alfisols, Mollisols, and Ultisols),
from 2.10 to 2.15 g cm−3 (Drees et al., 1989). The broad range is a
the eluvial horizons are enriched in quartz relative to the par-
function of the submicron opal structure, H2O content, occluded
ent material due to the weathering and removal of less resistant
organic matter, and microscopic voids.
minerals. Conversely, illuvial horizons have lower quartz con-
Quartz is one of the purest minerals known, and due to its more tents than eluvial horizons or parent materials due to the dilu-
closed structure, it is purer than the other Si oxide polymorphs tion by silicate clays, carbonates, or oxides. Highly weathered
(Drees et al., 1989). Nevertheless, common trace elements in quartz, and leached Oxisols have only very low amounts of quartz left
either interstitial or as substitutions, occur and include Al, Ti, Fe, in the clay fraction.
Na, Li, K, Mg, Ca, OH. Both cristobalite and tridymite, which are Opal-CT, opal-C, and α-cristobalite are usually limited to
also the major structural constituents of opal-CT, may accom- specific geographic regions and rock-stratigraphic units. Opal-C
modate more impurities than quartz because of their more open and α-cristobalite have been reported in Andepts and other soils
framework structure. The predominant impurity is Al, with lesser derived from volcanic material in South America, New Zealand,
amounts of Fe, Ti, K, Na, Ca, and Mg. Opal-A contains 850–950 g Central America, and Japan. Opal-CT has been identified in
kg−1 of SiO2, 40–90 g kg−1 of bound H2O, and significant amounts bentonites, siliceous shales, and indurated silicates. As a con-
of occluded, chemisorbed, or solid-solution impurities of Al, Fe, Ti, sequence, soils developed in these materials commonly contain
Mn, P, Cu, N, C, alkalies, and alkaline earths (Drees et al., 1989). opal-CT. It is also a primary constituent of many cherts, por-
celanites, fossil wood, silcretes, and some duripans (Drees et al.,
1989). According to synthesis experiments and evidence from
22.5.2  Occurrence and Formation
diagenetic environments, opal-A transforms to opal-CT and
Quartz is a common constituent in many igneous, sedimentary, quartz by a series of dissolution–precipitation reactions (Kastner
and metamorphic rocks, and also occurs as a secondary min- et al., 1977; Williams and Crerar, 1985; Williams et al., 1985,
eral, forming cementing materials in sediments. Tridymite is a Cady et al., 1996). The conversion is dependent on temperature,
typical mineral of acid volcanic rocks together with cristobalite pressure, pH, pore solution chemistry, and specific surface area.
that also occurs in basaltic rocks. Tridymite is also a common As the transformation is mediated by clays, oxides, and carbon-
constituent of highly metamorphosed impure limestones and ates, it is assumed to occur in soils (Drees et al., 1989).
arkoses adjacent to basic igneous intrusions, while cristobalite Opal-A may form by both organic and inorganic processes
occurs in metamorphosed sandstones and sandstone xenoliths in pedogenic environments. Biogenic opal-A originates from Si
in basic rocks. Opal is found in sedimentary, volcanic, and accumulated by plants and aquatic organisms, and thus occurs
marine environments (Deer et al., 1992). Thus, quartz is the under a wide range of environmental conditions (Jones and
most abundant Si oxide in soil environments, cristobalite occurs Beavers, 1964; Wilding and Drees, 1971).
Oxide Minerals in Soils 22-21

composition, and the presence of a disrupted surface layer. For

both crystalline and amorphous Si polymorphs, it is essentially
constant between the pH limits of 2 and 8.5, increasing rapidly
above pH 9 due to the ionization of monosilicic acid.
The presence of organic molecules greatly enhances the dis-
solution rates of Si oxides. The dissolution of biogenic opal and
quartz increases as particle size decreases due to the increase in
surface area (Drees et al., 1989). Chemisorption of metallic ions
such as Al, Fe, Mg, Ca, Cu, Pb, and Hg to Si surfaces reduces the
dissolution rates of Si due to the formation of relatively insoluble
Si coatings (Drees et al., 1989), thus increasing the stability of
Si oxides. Oxides of Fe and Al, by acting as a soluble Si sink,
greatly increase the dissolution rates of amorphous Si oxides and
reactive uncoated quartz surfaces. Dissolution (weathering) of Si
oxides is induced by the reduction of Si levels in soil solution by
leaching and plant uptake. Dissolution of quartz initiates below
10 μm approximately 3 mg of Si L−1 (Kittrick, 1969).

22.5.3  Influence on Soil Properties

FIGURE 22.6  Scanning electron micrograph of an opal phytolith
isolated from a forest soil. (From Drees, L.R., L.P. Wilding, N.E. Smeck, Noncemented soils comprised dominantly of quartz are non-
and A.L. Senkayi. 1989. Silica in soils: Quartz and disordered silica poly- plastic due to the weak cohesion (van der Waals forces) that
morphs, p. 913–974. In J.B. Dixon and S.B. Weed (eds.) Minerals in soil develops between Si particles and show low water-retention
environments. 2nd edn. SSSA, Madison, WI.)
capacity and high hydraulic conductivity. Duripans, cemented
by even small amounts of Si, are hard to extremely hard when
Biogenic opal is a minor but nearly ubiquitous constituent dry, have high unconfined compressive strength, and resist dis-
of soils, with opal phytoliths (Figure 22.6) representing the persion in Na hexametaphosphate (Flach et al., 1974).
major form in nonaquatic environments, while sponge spic- Due to their essentially uncharged, poorly hydrated surface,
ules, diatoms, and radiolaria are the main opal form in aquatic crystalline Si oxides have relatively small effects on the physi-
environments and limestone residuum (Jones and Beavers, cochemical activity affecting the soil–plant relationship and act
1964; Wilding and Drees, 1971). Amounts of opal phytoliths in as a diluent to the much more reactive clay minerals and oxides
soils commonly range from <1 to 30 g kg−1, usually occurring of Fe, Al, and Mn. Silica is not essential for the growth of most
in the 5–20 and 20–50 μm size fractions and decreasing with plants, but orthosilicic acid, H4SiO4, has a beneficial effect on
soil depth (Drees et al., 1989). Phytoliths are recognized as the the growth of some plants (Jones and Handreck, 1967). Rice and
principal sink and source of Si in soil solutions (Lucas, 2001; sugarcane, for example, often respond to fertilization with very
Farmer et al., 2005). soluble Si sources such as Si slag.
Opal-A, which forms when the conditions favor supersatura- Due to its ubiquity, abundance, resistance to weathering,
tion of Si in soil solution (Jones and Handreck, 1967), occurs and immobility, quartz has been often used as an index min-
as nodules and as a primary cement for indurated soil horizons eral for weathering and soil formation (Barshad, 1964; Sudom
(duripans) and silcretes. Such soils usually have pH and mois- and St. Arnaud, 1971). Extensive leaching may, however, dras-
ture regimes favoring solubilization and translocation of Si to tically increase the solubility of primary quartz (Little et al.,
lower positions in the soil profile. Geographically, duripans are 1978; Asumadu et al., 1988; Pye and Mazzullo, 1994), and authi-
restricted to materials that provide soluble Si, such as pyroclas- genic (Breese, 1960) as well as biogenic quartz may form in soils
tics and intermediate and basic igneous rocks (Flach et al., 1969; (Wilding and Drees, 1974), thus restricting the use of quartz as
Soil Survey Staff, 1975). According to Flach et al. (1969), pedo- an index mineral.
genic transformation of opal to quartz is believed to occur in The isotopic composition of quartz (18O), which depends on
duripans and in Si-cemented soils. Silica released by weather- the temperature of formation, has been used to identify eolian
ing of silicate minerals may precipitate as amorphous SiO2 on additions to soils (Clayton et al., 1972; Mizota and Matsuhisa,
soil particles, forming bridges between mineral grains, leading 1995) and the formation of authigenic opaline Si in volcanic ash
to the hardness and brittleness of fragipans (Franzmeier et al., soils (Mizota et al., 1991).
1989; Karathanasis, 1989). Opal phytoliths have been used to trace the origin of collu-
At ambient temperature and neutral pH, the solubility of vial sediments (Lutwick and Johnston, 1969) and to identify sur-
amorphous Si in soils is approximately 50–60 mg Si L−1 and face horizons of paleosols (Dormaar and Lutwick, 1969). Depth
that of quartz is commonly 3–7 mg Si L−1. The solubility of Si distributions of sponge spicules may be useful to identify litho-
oxides is a function of temperature, pH, particle size, chemical logical discontinuities, and opal of aquatic organisms (diatoms,
22-22 Properties and Processes

sponge spicules, and siliceous shells) provides direct evidence

0.410 nm
that the parent material of the soil is of marine or lacustrine ori-

0.403
gin (Jones and Beavers, 1963, 1964; Wilding and Drees, 1968,
1971). Biogenic opal has been extensively used to reconstruct
the vegetative history of soils (Drees et al., 1989; Fisher et al.,
1995; Staller, 2002). The 13C/12C isotope ratio of C occluded in
opal phytoliths was used to establish the succession of C3 and Opal-A
C4 grasses, providing a quantitative method for monitoring cli-

0.429
matic changes (Kelly et al., 1991).

0.250
0.318

0.285
0.334
22.5.4  Identification
Opal-CT
Silica oxides can be identified by XRD, SEM, microprobe analy-
sis, IR, and light microscopy. Opal-CT and opal-A may need to

0.404
be concentrated by particle-size fractionation, specific gravity,
and/or differential dissolution. Counting particle size separates

0.249
under the light microscope is the simplest method of quantify-

0.284
0.313
ing Si oxides but is limited in resolution (5–10 μm) (Drees et al.,
1989). A review of methodologies for extraction of amorphous Si Synthetic
from soils and aquatic sediments is given by Sauer et al. (2006) christobalite
and Sacconne et al. (2007).

0.426

0.246
22.5.4.1  Crystal Form, Habit, and Color
In soils, quartz generally occurs as anhedral grains, rarely exhib-
iting the characteristic prismatic habit of macrocrystals. Angular Quartz
grains are generally the result of mechanical fracturing, while
rounding is a result of physical attrition during both transport and 16 20 24 28 32 36
solution. Overgrowths on quartz grains may suggest long-term 2θ (degrees)
stable environments. Particles <100 μm are commonly shaped
like flat plates due to cleavage (Drees et al., 1989). Thus, quartz FIGURE 22.7  XRD patterns for quartz, synthetic cristobalite, opal-
grain surface morphology may be used to elucidate mineral ori- CT, and opal-A (Cu Kα radiation, peak position in nanometers).
gin and past and/or present chemical and physical environment. (Modified from Drees, L.R., L.P. Wilding, N.E. Smeck, and A.L. Senkayi.
Opal-CT is commonly observed in sediments as small 1989. Silica in soils: Quartz and disordered silica polymorphs, p.  913–
(<10 μm) lepispheres. The morphology of opal-A of biogenic ori- 974. In J.B. Dixon and S.B. Weed (eds.) Minerals in soil environments.
2nd edn. SSSA, Madison, WI.)
gin is closely related to the biological cell or structure in which
it originates: opal of forest origin consisting of cellular incrus-
tations with numerous thin-sheet structures (Figure 22.6); opal assemblages. The accuracy of the quantitative determination
of grass consisting of solid polyhedral structures resulting from of quartz depends on sample preparation and the diffraction
the silicification of the entire cell; and opaline microfossils of peak used (Rowse and Jepson, 1972). For well-ordered or
sponge spicules, diatoms, and shells (Drees et al., 1989). α-cristobalite, the 4.04 Å peak is the main clue in mixed samples
Pure Si oxides are colorless but chemical impurities may provided that no feldspars are present. Opal-C gives a pattern
impart various colors. Quartz is usually colorless and trans- resembling that of α-cristobalite, except for slight line broaden-
parent, or white, with a vitreous luster. Cristobalite is white to ing and minor evidence of tridymite stacking. Opal-CT usually
milky white and ranges from translucent to opaque. The color exhibits broad cristobalite peaks at about 4.1 and 2.5 Å and a
and degree of translucency of opal-CT seem to depend on the peak at 4.3 Å, which is attributed to tridymite. The wide varia-
aggregation of lepispheres. For opal-A, color is not a diagnos- tions in the intensity and line profiles make its quantification by
tic criterion because it is strongly affected by occluded chemical XRD difficult. The short-range order in opal-A produces a dif-
impurities and light interference and scattering. In transmitted fuse, broad x-ray hump centered at about 4.0 Å.
light, biogenic opal isolated from soils ranges from colorless or
light tan to various shades of brown or black (Drees et al., 1989). 22.5.4.3  Thermal Properties
Quartz exhibits a sharp endothermic DTA peak at about 570°C
22.5.4.2  X-Ray Diffraction (Drees et al., 1989), which may not be evident for microcrystal-
The diagnostic parameters for Si oxides are presented in Figure line quartz (<0.05 μm). Well-ordered synthetic cristobalite has a
22.7 and Table 22.5. Quartz is easily identified by its most characteristic endothermic peak at about 260°C, whereas opal-CT
intense reflections at 4.26 and 3.34 Å, even in mixed mineral and opal-A do not yield a characteristic endotherm below 600°C.
Oxide Minerals in Soils 22-23

According to Rowse and Jepson (1972), DTA is better than either 22.6.1  Mineral Phases
XRD or chemical techniques for detecting small quantities of
quartz in clay materials. Titanium occurs primarily in octahedral coordination, and like
the Fe and Mn oxides, the structures of the various Ti oxide min-
22.5.4.4  I nfrared Spectroscopy erals can be described in terms of the different arrangement of
All tectosilicates are characterized by Si–O–Si stretching vibrations the Ti-containing octahedra (Lindsley, 1976; Waychunas, 1991;
between 950 and 1200 cm−1 and by O–Si–O bending vibra- Heaney and Banfield, 1993).
tions between 400 and 550 cm−1. Quartz is distinguished from Rutile (TiO2) is isostructural with pyrolusite and manga-
the other Si polymorphs by a distinctive absorption band at nite, consisting of single chains of edge-sharing TiO6 octahedra
692 cm−1 and two strong doublets, one at 395 and 370 cm−1 and (Figure 22.1; Heaney and Banfield, 1993). Anatase consists of
the other at 800 and 780 cm−1 (Drees et al., 1989). The latter dou- TiO6 octahedra that share four O–O edges, two at the top and
blet has been used also for the quantification of quartz (Chester two at right angles at the bottom. The octahedra outline a 3D
and Green, 1968). This method is, however, restricted to samples framework, rather than distinct chains (Figure 22.1; Waychunas,
<1 μm in particle size and free of other Si polymorphs. 1991). Schwertmann et al. (1995b) reported the substitution of
The disordered Si polymorphs, opal-C, opal-CT, and opal-A, Ti4+ by Fe3+ up to 0.1 mol fraction in pedogenic and synthetic
have a single band around 800 cm−1 in common. Well-ordered anatase. Charge compensation is achieved by the incorpora-
cristobalite and opal-C show additional bands at 620 and tion of structural OH. Brookite has a more complex structure
380 cm−1. Opal-A of biogenic origin is characterized by much than rutile or anatase, consisting of deformed TiO6 octahe-
weaker and broader absorption bands at 460 and 1100 cm−1 as dra sharing three O–O edges to form staggered, cross-linked
compared to the better crystallized polymorphs and an addi- chains that are oriented along the c-axis (Figure 22.1; Lindsley,
tional weak band at 965 cm−1 (Drees et al., 1989). 1976). Ilmenite (FeTiO3) is almost isostructural with hematite,
with one-half of the Fe atoms replaced by Ti, so that the Fe3+–
O3–Fe3+ units in hematite become Fe2+–O3–Ti4+ units in ilmenite
22.6  Titanium and Zirconium Minerals (Figure 22.1; Lindsley, 1976). Pseudobrookite (ideally Fe2TiO5)
has strongly distorted octahedra but can be described in terms
Of all Ti and Zr compounds in soil and weathered materials, of an ideal cubic close packing anion arrangement (Figure 22.1;
the Ti oxides (rutile, anatase, and ilmenite) and the Zr silicate Waychunas, 1991). The two types of octahedral sites are M1 and
(zircon) are the most ubiquitous. The principal Ti and Zr min- M2 in the ratio 1:2, ideally occupied by Fe3+ and Ti4+, respec-
erals are listed in Table 22.6. Additional information about Ti tively. Pseudorutile (Fe2O3 · nTiO2 · mH2O; 3 < n < 5 and 1 < m < 2)
and Zr minerals can be found in Milnes and Fitzpatrick (1989), is a structurally disordered and poorly characterized mineral
Lindsley (1976, 1991), and Fitzpatrick and Chittleborough formed by the alteration of ilmenite. Its structure is based on a
(2002). Titanomagnetite and titanomaghemite are described in hexagonal closest packing of O2− anions and has been described
Section 22.2. as an intergrowth of a rutile-type structure with a goethite-type

TABLE 22.6  Titanium and Zr Oxide Minerals: Crystallographic Properties and d Values for the Six Most Intense Diffraction Lines
Chemical Crystal System, Unit-Cell Six Most Intense Diffraction Lines
Mineral Formula Space Group Dimensions (Å) d Value (Å), Relative Intensity Referencesa
Rutile TiO2 Tetragonal, P42/mnm a = 4.5933 3.247 1.687 2.487 2.188 1.624 1.36 21-1276
c = 2.9592 100 60 50 25 20 20
Anatase TiO2 Tetragonal, I41/amd a = 3.7853 3.52 1.892 2.378 1.70 1.666 1.481 21-1272
c = 9.5139 100 35 20 20 20 14
Brookite TiO2 Orthorhombic, Pbca a = 5.4558 3.152 2.90 3.465 1.893 1.66 2.476 29-1360
b = 9.1819 100 90 80 30 30 25
c = 5.1429
Ilmenite Fe2+TiO3 Hexagonal, R3 a = 5.0884 2.754 2.544 1.726 1.868 1.468 3.737 29-0733
c = 14.093 100 70 55 40 35 30
Pseudobrookite Fe23+ TiO5 Orthorhombic, a = 9.7965 3.486 2.752 4.90 2.458 1.865 2.407 41-1432
Bbmm b = 9.9805 100 77 42 23 23 22
c = 3.7301
Pseudorutile FeIII2Ti3O8(OH)2 Hexagonal, P6322 a = 14.486 3.50 2.66 2.51 1.687 3.67 3.23 Waychunas
c = 4.467 100 90 80 70 40 30 (1991)
Ulvöspinel Fe2TiO4 Cubic, Fd3m a = 8.393–8.536 2.573 1.509 3.018 1.642 2.134 1.742 34-0177
100 39 33 33 19 10
Zircon ZrSiO4 Tetragonal, I41/amd a = 6.604 3.30 4.434 2.518 1.712 2.066 1.908 6-266
c = 5.979 100 45 45 40 20 14
a Numbers of the format XX-XXXX indicate ICDD file number (ICDD, 1994).
22-24 Properties and Processes

structure (Figure 22.1; Grey et al., 1983). Zircon (ZrSiO4) is an Because ilmenite and zircon are generally very resistant in
orthosilicate with a structure consisting of chains of alternat- soils, they may be used as reference minerals in weathering and
ing edge-sharing SiO4 tetrahedra and [ZrO8] triangular dodeca- soil genesis studies (Bleeker, 1972; Mitchell, 1975; Claridge and
hedra. The chains are joined laterally by dodecahedra-sharing Weatherhead, 1978; Tejan-Kella et al., 1991). The immobility of
edges in an arrangement that produces unoccupied octahedral these minerals must, however, be previously assured (Colin et al.,
voids (Speer, 1982). 1993; Anda et al., 2009).

22.6.4  Identification
22.6.2  Occurrence and Formation
As Ti and Zr minerals can occur in different particle-size frac-
Rutile, anatase, ilmenite, and less frequently brookite are found tions and exhibit variable crystallinity, a variety of techniques
as accessory minerals in many igneous and metamorphic may be necessary to identify and characterize them. Optical
rocks and as detrital minerals in sediments, although anatase microscopy is a useful technique for examining and identifying
is often also of authigenic origin (Deer et al., 1992). The Ti and these minerals, both in undisturbed form in thin sections and
Zr minerals in soils may be residual minerals inherited from as components separated by physical or chemical techniques
the parent material, formed through weathering of Ti- and (Mitchell, 1975). A combination of XRD, IR absorption, DTA,
Zr-bearing minerals, or authigenic (Milnes and Fitzpatrick, and electron microprobe techniques is useful for identifying the
1989). Rutile, anatase, ilmenite, and zircon are commonly Ti and Zr minerals in the sand and silt fractions of soils but may
residual minerals occurring in the sand and silt fractions of be less satisfactory for the clay fractions due to the interference
a variety of soils. Ilmenite may weather to pseudorutile and of layer silicates (Milnes and Fitzpatrick, 1989). TEM along with
mixtures of rutile, anatase, and Fe oxides. Some evidence indi- energy-dispersive x-ray analysis of individual particles can be
cates that anatase and ilmenite weathering occurs by organic used to identify Ti oxide crystals in soil clay fractions (Figure
acids in A horizons of Scottish podzols (Berrow et al., 1978), 22.8). Titanium oxides may be concentrated in kaolinitic soils by
and weathering features were observed on the surface of zir- dissolution of clay minerals in boiling 5 M NaOH alone (Norrish
con and rutile grains of Australian Spodic Quartzipsamments and Taylor, 1961) or by a combination of boiling 5 M KOH and
(Tejan-Kella et al., 1991). DCB treatments (Zeese et al., 1994). Amorphous Ti oxides can
Many examples of secondary Ti oxides formed through be separated from more crystalline forms by extraction in acid
weathering of primary minerals are found in saprolites and in ammonium oxalate (Fitzpatrick et al., 1978). Minor amounts
soils. The data on the secondary or authigenic formation of Zr of anatase (>0.02%) can be identified by Raman spectroscopy
minerals are, however, controversial (Milnes and Fitzpatrick, (Murad, 1997). Tejan-Kella et al. (1991) described an SEM method
1989). The alteration of ilmenite under oxidizing conditions to characterize microtextural features of zircon and rutile grains.
leads to the formation of pseudorutile (Grey and Reid, 1975; In XRD of the clay fraction, the strong, sharp anatase peak at 3.52 Å
Anand and Gilkes, 1984b) but, at this stage, there is no clear (Table 22.6) is often clearly resolved after the interfering 3.59 Å
evidence that it also takes place under pedogenic conditions kaolinite line has been eliminated by heating at 550°C.
(Berrow et al., 1978). Authigenic formation of poorly crystal-
line anatase as an alteration product of sphene was observed in
peaty podzols from Scotland (Berrow et al., 1978). In conclu-
sion, basic aspects of the Ti and Zr minerals, such as whether
the minerals are relict or pedogenic, and the conditions respon-
sible for their weathering and formation in soils, are still unre-
solved (Taylor, 1987; Milnes and Fitzpatrick, 1989).

22.6.3  Influence on Soil Properties

Because of their generally low concentrations in soils, there
is little evidence of the effect of Ti and Zr minerals on soil
reactivity. Only in tropical soils where their concentrations 1 μm
are much higher some effects may be expected. The broken-
edge bonds of anatase are hydroxylated and can exhibit vari-
FIGURE 22.8  Transmission electron micrograph of the 2–0.2 μm
able charge characteristics (Fitzpatrick et al., 1978). The rutile fraction of a Rhodic Hapludox showing an anatase or rutile particle
and anatase surface has hydroxyl groups with different reac- (arrow) surrounded by kaolinite and iron oxide particles. (Modified
tivities (Tanaka and White, 1982) that can adsorb and retain from de Brito Galvão, T.C., and D.G. Schulze. 1996. Mineralogical prop-
phosphate and arsenate (Cabrera et al., 1977; Fordham and erties of a collapsible lateritic soil from Minas Gerais, Soil Sci. Soc. Am.
Norrish, 1983). J. 60:1969–1978.)
Oxide Minerals in Soils 22-25

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Anand, R.R., and R.J. Gilkes. 1984a. Mineralogical and chemical Fe(II) in mine drainage. Catena Suppl. 1:219–232.
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of manganese(III) and manganese(IV) oxides by organ- Gaeumannomyces graminis var. tritici. Phytopathology
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Stone, A.T., and J.J. Morgan. 1984b. Reduction and dissolution of oxide analysis in soils by combined x-ray diffraction
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2. Survey of the reactivity of organics. Environ. Sci. Technol. 50:1079–1084.
18:617–624. Torrent, J., R. Guzman, and M.A. Parra. 1982. Influence of rela-
Sudom, M.D., and R.J. St. Arnaud. 1971. Use of quartz, zirconium tive humidity on the crystallization of Fe(III) oxides from
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Tait, J.M., A. Violante, and P. Violante. 1983. Coprecipitation Torrent, J., U. Schwertmann, H. Fechter, and F. Alferez. 1983.
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18:95–99. content. Soil Sci. 136:354–358.
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Trolard F., G. Bourrié, M. Abdelmoula, P. Refait, and F. Feder. Violante, P., A. Violante, and J.M. Tait. 1982. Morphology of nor-
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51:945–957. Waychunas, G.A. 1991. Crystal chemistry of oxides and oxy-
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 23
Poorly Crystalline
Aluminosilicate Clay Minerals
23.1 Structure of Poorly Crystalline Materials...........................................................................23-1
Definition of Short-Range Ordered Materials  •  Structure of Imogolite  • 
Structure of Allophane
23.2 Identification and Synthesis of Allophane and Imogolite................................................23-5
Imogolite Identification and Synthesis  •  Allophane Identification and Synthesis
23.3 Occurrence of Imogolite and Allophane in Natural Environments..............................23-5
23.4 Surface Charge Characteristics of Short-Range Ordered Aluminosilicates
and Variable-Charge Soils.................................................................................................... 23-6
Surface Charge Determination  •  Interaction with Anions and Cations
23.5 Interaction of Allophane and Imogolite with Other Soil Constituents.........................23-8
James Harsh Organic Matter and Iron Oxides  •  Water
Washington State University References..........................................................................................................................................23-10

This chapter covers the poorly crystalline aluminosilicate environment of the atoms. The atoms are arranged in a variety
materials, commonly known as allophane and imogolite. With of states and structures where bond lengths, coordination, and
dimensions generally less than 50 nm, allophane and imo- geometry vary from site to site. Poorly crystalline materials fall
golite are naturally occurring nanoparticles. Their solubility, in between these two extremes, showing short-range, medium-
high specific surface area, variable charge, and unique physical range, or limited long-range order. Short-range order is observ-
behavior impart special properties to soils that contain them. able by techniques that probe the local environment of each atom,
Although often associated with soils formed from volcanic mate- such as nuclear magnetic resonance (NMR) or x-ray photoelec-
rial (Andisols), allophane and imogolite are found within a wide tron spectroscopy. X-ray diffraction peaks are indicative of, at
range of soil orders and derived from a variety of parent materials. least, medium-range order, whereas long-range order is detect-
Ferrihydrite, a poorly crystalline iron oxide that often occurs with able by electron microscopy. Poorly crystalline materials lack
allophane and imogolite, is covered elsewhere in this handbook. medium-range repetition of structural units in at least one of the
A timely review by Parfitt (2009) considered the role of allophane three spatial dimensions; that is, well defined electron or x-ray dif-
and imogolite in biogeochemical processes, Dahlgren et al. (2004) fraction patterns (XRD) are not produced. Allophane and imogo-
reviewed volcanic soils, and Floody et al. (2009) discussed indus- lite practically represent the range from amorphous to crystalline
trial applications of allophane and other natural nanoclays. materials (Fyfe et al., 1987). In the interest of brevity, allophane,
imogolite, and poorly crystalline iron hydrous oxides will be
referred to collectively as short-range ordered (SRO) materials.
23.1  Structure of Poorly In spite of their wide occurrence as intermediates in soil for-
Crystalline Materials mation, allophane and imogolite were, until the second-half of
the Twentieth Century, missed or ignored because of their vir-
23.1.1  Definition of Short-Range
tual absence from XRD. When they were found to be important
Ordered Materials
constituents of soils derived from volcanic ash (Taylor, 1933;
Crystalline materials exhibit long-range order in their atomic Yoshinaga and Aomine, 1962; Abidin et al., 2007), researchers
structure. Structural features repeat over scales of at least microm- turned to a variety of methods more conducive to their identifica-
eters in a single crystal or over several particles in a powder. Such tion, characterization, and quantification. These include selective
minerals display narrow x-ray diffraction peaks and their crystal dissolution by oxalic acid to quantify Si and Al, thermoanalytic
habit can be directly observed at the scale of an optical micro- methods to identify and quantify specific minerals, structural
scope or by the naked eye in the case of large crystals. Amorphous characterization by vibrational spectroscopy (IR and FTIR)
materials, on the other hand, exhibit no order, even in the local (Farmer et al., 1977; Dahlgren, 1994), and electron microscopy

23-1
23-2 Properties and Processes

(Wilson, 1987). Short-range structural information has been A

obtained with solid-state NMR and x-ray absorption spectros-
copy (XAS). Even the diffuse peaks in XRD patterns are useful to
identify and quantify poorly crystalline materials (Cruz and Real, C
1991). More recently, computer modeling has been employed to
test proposed structures against spectroscopic data and to deter-
B
mine which structures give an energy minimum (Guimaraes et
al., 2007; Creton et al., 2008; Zhao et al., 2009). The application of
such methods to determine imogolite and allophane structure is 250 nm
discussed in the following sections.

23.1.2  Structure of Imogolite

Imogolite is a mineral with relatively constant chemical com-
position (SiAl2O5 · 2H2O), only six-fold coordination for Al,
as many as seven x-ray diffraction peaks and two very broad
“bands” (Table 23.1), and a distinctive tubular morphology
100 μm
observable under the electron microscope (Figure 23.1). Thus,
imogolite has the major features of a crystalline mineral, but
some consider it paracrystalline because each tube displays long-
range order primarily in one dimension—along the length of the
tube (Greenland, 1982). Diffraction patterns and electron micro-
graphs, however, show that bundles of imogolite are aligned in
an array with a repeat distance of around 2 nm, consistent with
the diameter of the tubes (Figure 23.1; Cradwick et al., 1972).
Thus, imogolite displays an added dimension of repeating units
similar to layered aluminosilicates with regular stacking.
The Al in imogolite occurs in a gibbsite-like sheet and the
Si is coordinated to three oxygen atoms and one hydroxyl
group. The oxygen atoms are shared with the Al octahedra and FIGURE 23.1  Electron micrographs of synthetic imogolite with selected
the apical hydroxyls point toward the inside of the imogolite area electron diffraction pattern (top left) (Yang et al., 2008), natural imo-
tube (Figure 23.2; Cradwick et al., 1972; Zhao et al., 2009). The golite from pumice (bottom left), and allophane from pumice (center).
separation distances between close-packed tubes are typically (Reproduced from Parfitt, R.L. 2009. Allophane and imogolite: Role in soil
around 2.3 nm for natural and 2.7–3.2 nm for synthetic imogolite biogeochemical processes. Clay Miner. 44:135–155. With the permission
(Mukherjee et  al., 2005) and the repeat distance along the of the Mineralogical Society of Great Britain & Ireland.) The cartoon at
gibbsite sheet (c-axis) is 0.84 nm (Wada and Yoshinaga, 1969). the top right shows the orientation of imogolite nanotube bundles. (From
Bonelli, B., I. Bottero, N. Ballarini, S. Passeri, F. Cavani, and E. Garrone.
TABLE 23.1  Powder X-Ray Diffraction 2009. IR spectroscopic and catalytic characterization of the acidity of
Peaks for Proto-Imogolite Allophane imogolite-based systems. J. Catal. 264:15–30.)
and Imogolite
Unraveling the structure of imogolite relies on spectroscopy
Proto-Imogolite
Allophane Imogolite
and modeling. Infrared spectra give absorption bands indicative
of both the gibbsite-like sheet and the orthosilicate anion. The
d (nm) I d (nm) I Si–O stretching vibration at 960 cm−1 is consistent with unpo-
1.2vba 70 1.6vb 100 lymerized orthosilicate groups and the OH-stretching bands
0.43vb 10 0.79 70 are consistent with Al–OH and Si–OH structures described by
0.34vbb 100 0.56 35 Cradwick et al. (1972). In addition, the band at 348 cm−1 indi-
0.22vbb 50 0.44 10 cates that one hydroxyl of the octahedral Al sheet is replaced
0.19a 10 0.41 10 by the silica oxyanion. This band distinguishes imogolite and
0.17 10 0.37 20 proto-imogolite allophane from other SRO aluminosilicates
0.14b 20 0.33vb 65 (Farmer et al., 1977). Molecular dynamics simulations that
0.31 5 generate XRD patterns and vibrational spectra based on the
0.26 5 Cradwick model compared favorably with the experimental
0.225vb 25 ones (Creton et al., 2008).
a Also present in halloysite-like allophane. Solid-state NMR spectra also support the above model for imo-
b Present in all three allophanes. golite (Goodman et al., 1985; Wilson et al., 1986; He et al., 1995).
Poorly Crystalline Aluminosilicate Clay Minerals 23-3

(a)

(b)

H
out
d Al–O

O
in
dAl–O
Al

dSi–O Si

(c)

FIGURE 23.2  Polyhedral representations (left panel) and atomic structures (right panel) of (a) imogolite sheet and (b) imogolite nanotube with
Nμ = 9. (c) The local map of atomic structure. Si, Al, O, and H atoms and some representative bonds are indicated. (From Zhao, M., Y. Xia, and
L. Mei. 2009. Energetic minimum structures of imogolite nanotubes: A first-principles prediction. J. Phys. Chem. C 113:14834–14837.)

The 27Al-NMR spectra for various samples of synthetic and natural 23.1.3  Structure of Allophane
imogolite show little or no evidence of tetrahedrally coordinated
Al (Figure 23.3). The 29Si resonance line at −78 ppm of imogolite Allophane refers to a group of SRO aluminosilicate clay minerals
is consistent with Si bound to three Al–O and one OH group and with no long-range order, only two diffuse XRD bands, and vari-
serves to identify imogolite or proto-imogolite allophane in whole able composition, generally ranging from 2:1 to 1:1 Al/Si molar
soils (Wilson et al., 1986). ratio (Harsh et al., 2002). Endmember allophane would be com-
The difference in size between natural and synthetic pletely disordered, but probably does not exist in nature (Fyfe
­imogolite—2.3 vs. 2.7–3.2 nm—can be explained by density et al., 1987). The further structural and chemical characteriza-
functional theory first-principle calculations that show two tion of allophane found in natural environments has led to the
energy minima for the imogolite structure (Figure 23.4). The identification of three major types of allophane. These have been
global minimum occurs with a gibbsite sheet consisting of tentatively named proto-imogolite allophane, halloysite-like (or
9 gibbsite units around the imogolite circumference and a local defect kaolin) allophane, and hydrous feldspathoid allophane.
minimum with 12 gibbsite units (Zhao et al., 2009). These min- Proto-imogolite allophane (Al-rich allophane) has an Al/Si
ima are consistent with the external diameters, circumferences, ratio close to 2, a gibbsite-like sheet of octahedrally coordinated
separation distances, and axial dimensions of imogolite deter- Al, and orthosilicate groups sharing three oxygens with Al.
mined experimentally by XRD and electron diffraction. Thus, proto-imogolite allophane has the same short-range order
23-4 Properties and Processes

29 27
Si NMR Al NMR
–78 –85 –92 –102 –107 55 3

(a) Allophane
* * (KiP, <0.2 μm)

(b) Imogolite
* * (KiG film)

(c) Allophane
* * (PA, <0.2 μm)

(d) Acid-oxalate-treated
* * Allophane (PA, <0.2 μm) –3.5 2.00
Al–O (out) Al–O (in) Si–O
1.670

1.665
1.98
(e) Hot 2% Na2CO3-treated –4.0 1.660
*
Strain energy (kJ mol–1)
* Allophane (KiP, <0.2 μm) 1.96

dAl–O

dSi–O
1.655
1.94
Chemical shift (ppm) –4.5 1.650
1.92 1.645
FIGURE 23.3  29Si and 27Al MAS NMR spectra of (a) Al-rich KiP
–5.0 6 8 10 12 14
allophane (<0.2 μm), (b) imogolite (KiG) film, (c) Si-rich PA allophane
Nµ
(<0.2 μm), (d) acid-oxalate-treated Si-rich PA allophane, and (e) hot 2%
Na 2CO3-treated Al-rich KiP allophane. *, Spinning side band (SSB). –5.5
(From Hiradate, S., and S.-I. Wada. 2005. Weathering process of volcanic
glass to allophane determined by 27Al and 29Si solid-state NMR. Clays
–6.0
Clay Miner. 53:401–408. Figure 3. Reproduced with kind permission of
6 8 10 12 14 16
The Clay Minerals Society, publisher of Clays and Clay Minerals.) Nµ
as imogolite, but does not exhibit the tubular morphology. FIGURE 23.4  Variation of the strain energy of imogolite nanotubes
Instead, it first forms fragments of the imogolite structure, then, (cross section shown above) relative to imogolite sheet as a function of Nμ
depending on solution conditions, forms imogolite or spherical (number of gibbsite units in the circumference). The error bars (<0.003 kJ
allophane particles about 3.5 nm in diameter (Farmer and Russell, mol−1) are smaller than symbols. The bond length evolution of Al–O and
1990). The NMR and FTIR spectra are nearly identical to those for Si–O bonds is plotted in the inset of this figure. (From Zhao, M., Y. Xia,
imogolite (Figure 23.3). The XRD “peaks” are very broad and the and L. Mei. 2009. Energetic minimum structures of imogolite nanotubes:
pattern lacks several lines indicative of imogolite (Table 23.1). A first-principles prediction. J. Phys. Chem. C 113:14834–14837.)
According to one view, allophane with an Al/Si ratio near 1:1
probably has a structure that is closer to kaolinite or halloysite questions about the above models. Specifically, Al-K-XANES
with defects in the tetrahedral sheet. Infrared spectra of Si-rich shows only one octahedral Al site in both imogolite and allo-
allophanes indicate the presence of polymerized silica tetrahe- phane, regardless of Al/Si ratio (Ildefonse et al., 1994). In con-
dra and octahedrally coordinated Al (Parfitt et al., 1980; Farmer trast, gibbsite and 1:1 clay minerals have two octahedral Al sites,
and Russell, 1990; Parfitt, 1990). Both IR and NMR spectra sug- while 2:1 phyllosilicates have one. This implies allophane and
gest that Si-rich allophanes often contain both the halloysite imogolite have a dioctahedral sheet that resembles that of pyro-
and imogolite structural units. The halloysite-like feature in phyllite or mica rather than kaolinite.
the NMR spectrum is characterized by a broad 29Si resonance Another Si-rich allophane with a significant, if not dominant,
around −86 ppm. Varying amounts of the two types of allophane amount of tetrahedrally coordinated Al resembles a hydrous
could account for a large variation in the Al/Si ratios (from 2.5 feldspathoid and contains no imogolite units. The basic struc-
to 1) when found in weathered pumice. Recent solid-state NMR ture appears to be that of a framework silicate with 1:3 Al for
(MacKenzie et al., 1991) and x-ray photoelectron spectroscopy Si substitution. Octahedral Al neutralizes some of the negative
(He et al., 1995) studies of the silica-rich allophane support the charge generated by the substitution and may be associated with
presence of both imogolite-like and defect kaolin-like structures. the inner surfaces of spherical particles. Particles isolated from
Recent Al-K edge x-ray absorption near edge structure a stream deposit in New Zealand are less than 3 nm in diam-
(XANES) analysis of Al-rich allophanes and imogolite, raises eter and form in CO2-charged water that increases in pH as it
Poorly Crystalline Aluminosilicate Clay Minerals 23-5

degases (Wells et al., 1977; Childs et al., 1990). Similar particles a low pH solution and will form a stable suspension along with
can be synthesized in neutral to alkaline solutions and IR and imogolite when ultrasonically dispersed. The same pretreatment
NMR spectra are consistent with a hydrous feldspathoid struc- to remove iron oxides and organic material applies. With allo-
ture (Farmer et al., 1979a; Wada and Wada, 1981). No −78 ppm phane, however, separation from imogolite is possible in prin-
resonance is observed in the 29Si NMR spectra, as in imogolite, ciple because it is negatively charged in alkaline solutions where
and the changes in NMR spectra with heating confirm that the imogolite flocculates.
hydrous feldspathoid allophane differs in structure from both After separation, one can discern allophane in electron micro-
proto-imogolite and kaolin defect allophane (MacKenzie et al., graphs, but it is far less distinctive than imogolite (Figure 23.4).
1991; Ildefonse et al., 1994). Ildefonse et al. (1994) used 27Al NMR It generally occurs as an amorphous mass of material coating
and Al-K XANES to characterize Si-rich allophanes from soils other particles. Often the spheroidal morphology is evident in the
and found them to be similar to those found in stream deposits, Al-rich allophane. The spheroids of Al-rich allophane form aggre-
suggesting that Si activity in solution determines their formation. gates that do not disperse easily. Damage from the electron beam
is rapid and care must be taken to obtain good micrographs.
23.2  Identification and Synthesis Like imogolite, allophane is synthesized from millimolar
of Allophane and Imogolite solutions of Al and monomeric Si(OH)4. Allophane can be pre-
cipitated rapidly from solutions at room temperature. Methods,
23.2.1  Imogolite Identification and Synthesis including heated synthesis, have been developed to precipitate
allophane from concentrated solutions—10–100 mM (Ohashi et
Imogolite can be separated from soils and pumice deposits
al., 1998; Montarges-Pelletier et al., 2005). The Al/Si ratio and
after removing material that strongly interacts with its surface.
pH of the matrix solution determine the nature of the products.
Pretreatment usually includes a dithionite–citrate–bicarbonate
Al-rich allophane forms at room temperature from an acidic Al
extraction to remove iron oxides and hydrogen peroxide to
and orthosilicate solution with Al/Si ratio near 2:1. The presence
remove organic matter. Neither significantly dissolves nor alters
of Ca and Mg ions favors allophane formation over imogolite,
imogolite or allophane. Following pretreatment, ultrasonic dis-
whereas Na and K do not (Abidin et al., 2007). Because the acidic
persion of the suspended pumice or soil at low pH (e.g., pH 4
environment keeps Al in octahedral coordination, decreasing
HCl) separates imogolite from phyllosilicate clay minerals. As
the Al/Si ratio while keeping the pH below neutral probably
discussed in Section 23.4.1, imogolite surfaces are positively
favors the defect kaolinite structure. Between pH 6 and 7, the
charged in acid solutions and form stable suspensions, while the
hydrous feldspathoid structure predominates with the propor-
2:1 phyllosilicates flocculate at low pH. Further concentration
tion of tetrahedral Al increasing as the Al/Si ratio decreases
of SRO materials is accomplished by separating the <0.08 μm
(Farmer and Russell, 1990). This structure exists in natural alka-
fraction because average allophane and imogolite particle sizes
line environments, including the Silica Springs deposit in New
are much less than those of the 1:1 phyllosilicates. Of course, no
Zealand (Wells et al., 1977) and many soils (Childs et al., 1990;
purification procedure is ideal; unwanted minerals and some
Ildefonse et al., 1994). Farmer and Russell (1990) reviewed the
alteration of the target material will always be present.
synthesis and occurrence of imogolite and the three types of
While spectroscopic methods elucidate imogolite structure
allophane described here.
and often aid in quantitative methods, electron microscopy is
the most reliable indicator of its presence in soils or successful
synthesis in the laboratory. Both synthetic imogolite and that
isolated from a pumice bed show long, bundled tubes (Figure
23.3  Occurrence of Imogolite and
23.1), whereas, imogolite isolated from a forest soil is somewhat Allophane in Natural Environments
more fragmented (Su and Harsh, 1996).
Allophane and imogolite tend to be associated with volcanic ash
Refluxing an acidic solution with millimolar concentrations
deposits and soils derived from volcanic debris, because the rapid
of aluminum perchlorate and tetraethyl orthosilicate for 5 days
release of Al and Si from materials such as volcanic glass results
at 95°C produces imogolite nearly identical to the natural mate-
in the precipitation of SRO aluminosilicates. The Kitakami pum-
rial isolated from soils or pumice except for the larger diameter
ice beds in Japan have long been a source of relatively pure sepa-
mentioned above (Farmer et al., 1983). The larger diameter may
rates of both allophane and imogolite and are among the most
be due, in part, to the high-temperature synthesis, because imo-
studied of the naturally occurring SRO materials, including the
golite prepared at room temperature has a diameter of about
KiG imogolite in Figure 23.3 (Miyauchi and Aomine, 1966; Wada
23 Å (Wada, 1987). Levard et al. (2009) synthesized imogolite
and Matsubara, 1968; Yoshinaga, 1968; Yoshinaga et  al., 1973).
from decimolar concentrations of Al and Si, perhaps opening
Imogolite was first identified in Ando (dark-colored) soils of
the door to manufacture of large quantities of material.
Japan (Yoshinaga and Aomine, 1962) and allophane was found
to give them many of their unique properties. Since then, SRO
23.2.2  A llophane Identification and Synthesis
aluminosilicates have been identified in soils derived from many
Separation of allophane from natural deposits, including soils, parent materials, including sandstone, gneiss, granite, and basalt
is similar to that of imogolite. Allophane is positively charged in (Harsh et al., 2002). In basalt, ferrihydrite, a poorly crystalline
23-6 Properties and Processes

iron oxide, often occurs in addition to allophane and imogolite. and proto-imogolite allophane whereas a smaller value indicates
Nevertheless, the largest concentrations of SRO aluminosilicates Si-rich allophane is present. Embryonic halloysite may also par-
occur in deposits of volcanic tephra and soils developed therein. tially dissolve in the oxalate solution (Wada and Kakuto, 1985).
Soils derived from volcanic tephra occur all over the world with Ratios greater than 2:1 may occur when other labile sources of
well studied examples from New Zealand (Taylor, 1933; Wells et al., Al are present, such as hydroxy-Al interlayers in clay minerals.
1977; Parfitt, 1990), Chile (Vicente and Besoain, 1961; Besoain,
1969; Nissen and Kuehne, 1976; Besoain and Gonzalez, 1977; 23.4  Surface Charge Characteristics
Floody et al., 2009), and the Cascade Range of North America
(Ugolini and Dahlgren, 1991). A large deposit of allophane—more
of Short-Range Ordered
than 4000 km2 and 16 m thick—was recently discovered in Ecuador Aluminosilicates and
and may be a source for commercial allophane (Kaufhold et al., Variable-Charge Soils
2009, 2010). McDowell and Hamilton (2009) report that SRO alu-
minosilicates are probably present on Mars and interfere with 23.4.1  Surface Charge Determination
quantification of phyllosilicates on the surface. 23.4.1.1  Operational Definitions
The key factor in the formation of allophane and imogolite in
Two major sources of surface charge on SRO aluminosilicates
soil is sufficient Al and Si in solution. Thus, conditions that lead to
will be considered here, that is, permanent structural charge (σo)
rapid weathering of primary minerals, such as high rainfall and
from isomorphic substitution of Al in Si tetrahedra and variable
low pH, favor their formation. Both imogolite and Al-rich allo-
surface charge due to ion association at surface hydroxyl groups
phane tend to dominate at low pH where Al/Si is high, whereas
(Sposito, 2004). Ion associations with surface hydroxyls include
halloysite and/or Si-rich allophanes form when soluble Si is high
complexed protons (σH), inner-sphere complexes with ions other
(>10−3.45). As a result, low rainfall or xeric-moisture regimes, con-
than H+ (σIS), and outer-sphere complexes (σOS). A charge balance
centrating soluble silica, have been observed to favor halloysite
equation can be written as follows:
formation at the expense of allophane and imogolite (Parfitt
and Wilson, 1985; Singleton et al., 1989; Takahashi et al., 1993).
σ p = σ o + σ H + σ IS + σOS = −σ D (23.1)
Noncrystalline minerals are found in Andisols, Inceptisols,
Entisols, Spodosols, and Ultisols. Generally, allophane and imo-
golite occur in horizons where organic matter is low so that Al where
exists in inorganic complexes. Al-humus complexes, which give σp represents the particle charge or total charge from all
soils many of the same properties attributed to allophanic soils, sources
often dominate organic and A horizons, particularly in forested σD is the diffuse layer charge that consists of the net charge
soils (Dahlgren et al., 2004). Complexation of Al by organic acids from the swarm of hydrated ions around the particle
and humic materials inhibits SRO aluminosilicate formation indi-
cating that free Al3+ or Al-hydroxy complexes may be required. The proton charge on variable-charge surfaces is determined
Short-range ordered materials are generally less stable than by potentiometric titration with H and OH, which adsorb
their crystalline counterparts, particularly kaolinite. Their to surface silanol (≡Si–OH) or aluminol (≡Al–OH) groups.
rapid formation results because the interfacial energy difference Relative proton adsorption is easy to determine from the differ-
between mineral surfaces and an aqueous solution slows nucle- ence between added and remaining protons in solution, but the
ation. Poorly crystalline surfaces have lower surface tensions and absolute proton charge on the surface is not evident because the
nucleate more easily, that is, at a lower saturation index than a initial charge, before titration, is not known. The point of zero
crystalline mineral of similar composition. As a result, allophane net proton charge (PZNPC) is often estimated by the point of
and imogolite are often found as precursors to kaolinite in weath- zero salt effect (PZSE)—the pH at the crossover point of three or
ering soil profiles and may serve as templates for its heterogeneous more titrations at different background salt concentrations. If the
nucleation (Steefel et al., 1990). background salt does not form inner-sphere complexes, only the
Quantification of SRO aluminosilicates in soils is achieved proton charge is determined in the titration. The proton charge is
by selective chemical extraction and solution analysis of Al and more reliably determined by plotting the net adsorbed ion charge
Si (Dahlgren, 1994). Commonly, one extracts the soil first with (σIS + σOS + σD) against proton charge (σH) (Chorover and Sposito,
Na-pyrophosphate, which effectively extracts Al and Fe from 1995). The slope should be −1 and the x- and y-intercepts equal
soil organic complexes, but dissolves little from the inorganic to σo. The PZNPC is then the pH where (σIS + σOS + σD) = −σo.
fraction. Then, an acid ammonium oxalate solution (0.2 M, pH 3) Inner-sphere, outer-sphere, and diffuse layer cations and
selectively dissolves allophane, imogolite, and poorly crystal- anions balance the total negative and positive charge on the sur-
line iron oxides such as ferrihydrite. Subtracting the organically face. Thus, the point of zero net charge (PZNC) can be deter-
complexed from the oxalate-extracted, gives the SRO-associated mined by ion adsorption across a range of pH in an electrolyte,
Al and Fe. Dividing this SRO Al value by the oxalate-extractable such as NaCl, whose ions do not form inner-sphere complexes
Si provides the average SRO Al/Si ratio (Parfitt and Wilson, with the aluminol or silanol groups. Finally, electrophoretic
1985). A ratio near 2:1 suggests a soil dominated by imogolite mobility provides information about the tendency for ions to
Poorly Crystalline Aluminosilicate Clay Minerals 23-7

form outer-sphere complexes with allophane and imogolite. supported by quantum mechanical calculations of charge dis-
Their mobility when suspended in an aqueous solution subjected tribution in imogolite (Guimaraes et al., 2007). The Si-rich allo-
to an electric field depends on the ionic strength of the solution phane, on the other hand, has structural charge arising from Al
and the nature of the surface complexes. The isoelectric point is for Si substitution. However, Su et al. (1992) found in synthetic
the pH where the particles are stationary in the field and is an allophanes of this type that structural charge from tetrahedral
estimate of the PZC—the point where σD = 0. Al was not completely balanced by exchangeable cations. In this
With all Al in imogolite and proto-imogolite allophane in case, it was hypothesized that Al present as hydroxy complexes
octahedral coordination, no structural charge arises from iso- or polymers balanced much of the negative σo.
morphic substitution. Gustafsson (2001), however, proposed The charge characteristics of imogolite and some synthetic
that structural charge could arise from differences in Al–O bond allophanes as determined by these methods are summarized in
valences leading to a weak positive charge on outer tube walls Figure 23.5 and Table 23.2. Because the PZNC and PZSE values
and negative charge in tubular pores. This hypothesis was later of imogolite and Al-rich allophane are all greater than 6, these

2.0 2.5
Imogolite Al/Si 2.01
Allophane Al/Si 1.64
1.6 Na, 0.10 M NaCl Na, 0.01 M NaCl 2.0
Cl, 0.10 M NaCl Cl, 0.01 M NaCl
PZNC(I = 0.10) = 5.8
1.2 |σH| 0.01 M NaCl 1.5 PZNC(I = 0.01) = 6.7
|σH| 0.01 M NaCl
0.8 1.0
H, OH, Na, or Cl adsorbed (mol kg–1)

PZNC = 8.4
0.4 0.5

0.0 0.0

–0.4 –0.5
2 4 6 8 10 12 2 4 6 8 10 12
pH pH

1.5 2.0
Allophane Al/Si 2.02 Allophane Al/Si 1.26
1.5 PZNC(I = 0.10) = 4.1
1.0 |σH| 0.01 M NaCl
PZNC(I = 0.01) = 5.4
1.0 |σH| 0.05 M NaCl
0.5 PZNC = 7.9
0.5
0.0
0.0

–0.5 –0.5
2 4 6 8 10 12 2 4 6 8 10 12
(a) pH pH

3
Electrophoretic mobility (μm s–1/V cm–1)

1 0.01 M LiCl
0.01 M NaCl
0.01 M CsCl
0.01 M Et4NCl
0
3 4 5 6 7 8 9 10 11 12
(b) pH

FIGURE 23.5  Charge properties of synthetic imogolite and allophane determined by (a) potentiometric titration and ion adsorption (From Su, C.M.
et al., Clays Clay Miner., 40, 280, 1992, Figure 1. Reproduced with kind permission of The Clay Minerals Society, publisher of Clays and Clay Minerals.) (b)
electrophoretic mobility (From Harsh, J.B., S.J. Traina, J. Boyle, and Y. Yang. 1992. Adsorption of cations on imogolite and their effect on surface-charge char-
acteristics. Clays Clay Miner. 40:700–706, Figure 4. Reproduced with kind permission of The Clay Minerals Society, publisher of Clays and Clay Minerals.)
23-8 Properties and Processes

TABLE 23.2  PZCs of Synthetic Imogolite by allophane and imogolite in the clay fraction showed the fol-
and Allophanes lowing order of decreasing affinity, which is quite similar to the
PZNC in NaCl selectivity of aluminol groups for divalent metals (Abd-Elfattah
and Wada, 1981):
Material Al/Si 0.10 M 0.01 M PZSE PZC
Imogolite 2.0 8.4 8.4 6.5 >10
Pb > Cu > Zn > Co ≈ Cd > Mg ≈ Ca
Allophane 2.0 7.9 7.9 8.3 10
Allophane 1.6 5.8 6.7 7.7 9
As on Al oxides, Pb, Cu, Zn, and Co appear to form inner-sphere
Allophane 1.2 4.1 5.4 5.9 7.6
surface complexes, whereas Cd, Ca, and Mg are held by elec-
Source: Su, C.M., J.B. Harsh, and P.M. Bertsch. 1992. trostatic forces (Clark and McBride, 1984; Yuan et al., 2002).
Sodium and chloride sorption by imogolite and allo- Alkaline earth and alkali metals, halide anions, NO3, SO4, and
phanes. Clays Clay Miner. 40:280–286. ClO4 will generally exist as outer-sphere complexes or in the dif-
fuse layer of allophane and imogolite. Adsorption of exchange-
materials impart positive charge in acid soils. The Si-rich allo- able cations on allophanic soils appears to be similar to that
phanes may be either positively or negatively charged depending on soils dominated by smectites (Nakahara and Wada, 1994).
on soil pH. The Si-rich allophanes also have a PZSE greater than Highly selective K exchange on Andisols has been reported
the PZNC, another indicator that permanent negative charge (Espino-Mesa and Hernández-Moreno, 1994), but this could
exists in these materials as a result of Al for Si substitution. result from trace amounts of illitic minerals or alunite formation
Imogolite has a PZSE greater than its PZNC, constant adsorp- in addition to reactions with allophane or imogolite. Allophanic
tion of Cl over a large pH range, and an isoelectric point above soils do seem capable of adsorbing large amounts of nitrate
pH 10 (Harsh et al., 1992; Tsuchida et al., 2005), all of which below the root zone, presumably through interaction with SRO
might be due in part to cation distribution inside imogolite tubes aluminosilicates (Maeda et al., 2008). Circumstantial evidence
as well as structural charge distribution from bond valence dif- exists for specific adsorption of Cl on imogolite, as discussed
ferences as discussed above (Gustafsson, 2001). above, but this issue has not been resolved and is not consistent
with electrophoretic measurements (Figure 23.5).
The interaction of allophane and allophanic soils with organic
23.4.2  Interaction with Anions and Cations
matter (discussed in the following section) also affects the sur-
Inner-sphere complexation of anions on allophane and imogo- face charge and sorption properties of the materials. Organic
lite is common. Phosphate, fluoride, citrate, borate, arsenate, and matter can be expected to increase the negative charge on min-
selenite are known to form inner-sphere complexes with SRO erals dominated by aluminol surface groups because of the car-
aluminosilicates. This reaction contributes to σIS and can shift boxylate groups of humic materials. Treatment of allophanic
the points of zero charge (PZCs) of the material. As a result, materials and soils with hydrogen peroxide to remove organic
more negative charge is likely in the presence of these anions, matter increases the PZC (Escudey et al., 1986) and decreases
particularly in acid soils. Caution should be used in interpreting phosphate sorption (Mora and Canales, 1995), respectively.
any strong sorption as surface complexation. Veith and Sposito Conversely, adding iron oxides increases the PZC of allophane,
(1977) and Su and Harsh (1993) showed that phosphate and fluo- rendering the surface more positively charged (Escudey and
ride, respectively, may react with SRO aluminosilicates to form Galindo, 1983). Iron oxides may react selectively with silanol
new solid phases. Boron may substitute into tetrahedral sites in groups, which have an acid PZNPC. The PZNPCs of Fe and Al
coprecipitation with allophane (Su and Suarez, 1997). oxides, on the other hand, are greater than 6.
In soils containing allophane and imogolite, strong interaction
with phosphate can lead to deficiency of this macronutrient in 23.5  Interaction of Allophane
crops. Calcium silicate can be added to such soils to compete for
sorption sites and enhance phosphate availability. The ability of
and Imogolite with Other
SRO materials and allophanic soils to adsorb anions by ligand Soil Constituents
or anion exchange has led to suggestions that they be used to
23.5.1  Organic Matter and Iron Oxides
remove contaminants such as phosphate, selenium, technetium,
glyphosate, chromium, arsenic, and iodine from wastewaters The term “Andisol” comes from the Japanese words ando and sol,
(Wells and Parfitt, 1987; Gu and Schulze, 1991; Babel and Opiso, meaning dark-colored soil. The dark color comes from the fact
2007; Gimsing et al., 2007; Hopp et al., 2008; Opiso et al., 2009; that soils formed from volcanic debris are often high in organic
Ballantine and Tanner, 2010). matter, especially in surface horizons. Noncrystalline materials
Many trace metals and metalloids form surface complexes may play a role in organic matter retention through one or more
with aluminol and silanol groups as evidenced by extensive mechanisms. First, humic substances adsorb strongly to imogo-
studies on silica and aluminum oxides; however, fewer studies lite and allophane (Parfitt et al., 1977; Parfitt, 2009) and sorption
have been performed on SRO aluminosilicates or soils contain- is possibly responsible for inhibiting degradation (Basile-Doelsch
ing them. One study of metal adsorption to a soil dominated et al., 2005; Schneider et al., 2010). Second, reactive Al released
Poorly Crystalline Aluminosilicate Clay Minerals 23-9

from SRO materials complexes with humic and fulvic acids greenhouse gases such as CO2. Dahlgren et al. (2004) stated that
and leads to precipitation and/or inhibition  of  degradation 0.8% of the world’s soils are allophanic and that they contain 5%
(Boudot,  1992; Wada, 1995; Matus et al., 2008). Finally, SRO of the global soil carbon. In his excellent review of the biogeo-
materials may enhance the “humification” of soil organic car- chemistry of allophane and imogolite, Parfitt (2009) points out
bon by facilitating bonding reactions or molecular assemblages that the stabilization of organic matter is partially maintained
(Gonzalez-Perez et al., 2007; Fukushima et al., 2009). In the pres- as forests are converted to pasture, but does not apply to fresh
ence of hydrogen peroxide, allophane associated with Fe may organic matter or plant-derived material. The recalcitrant car-
catalyze the degradation of organic materials, including xenobi- bon originates from microbial byproducts, is stabilized slowly,
otics, by Fenton reactions (Garrido-Ramirez et al., 2010). and persists for thousands of years.
Reaction with organic matter may give soils containing SRO
aluminosilicates an important role in carbon sequestration. If
23.5.2  Water
these materials are instrumental in increasing the residence
time of organic matter in soils, then preserving the soils con- Both a high specific surface area and a high value of the rela-
taining them may be beneficial in order to reduce emission of tive microporosity characterize allophane. The latter probably

12.5 12.5

Al(OH)3(a)
12.0 12.0

11.5 11.5

11.0 11.0
HAS
B max
log[Al3+] + 3pH

Microcrystalline gibbsite Hydr

10.5 ox
yalum 10.5
Proto-imo inosi
golite licate
HAS HAS
10.0 B min B 10.0

9.5 9.5
Gibbsite
9.0 9.0
Chalcedony

SiO2(a)
8.5 8.5

8.0 8.0
–4.4 –4.2 –4.0 –3.8 –3.6 –3.4 –3.2 –3.0 –2.8
log[H4SiO4]

FIGURE 23.6  Stability relations for proto-imogolite (Lumsdon and Farmer, 1995), Si-rich allophane (HASB), gibbsite, and microcrystalline
gibbsite. (From Dobrzynski, D. 2007. Chemistry of neutral and alkaline waters with low Al3+ activity against hydroxyaluminosilicate HASB solubility.
The evidence from ground and surface waters of the Sudetes Mts. (SW Poland). Aquat. Geochem. 13:197–210.)

(Two-ion parameter log[Al3+] + 3pH versus log[H4SiO4] in waters with log[Al3+] < −10 (size—188 samples). Solubility lines for amorphous Al(OH)3
and SiO2 forms plotted at 7°C, after solubility constant for gibbsite (log K 25 = 8.11), microcrystalline gibbsite (log K 25 = 9.35), and Al(OH)3(a)
(log K 25 = 10.8) calculated using the van’t Hoff equation. Solubility constant log K7 for chalcedony and amorphous SiO2 calculated using the
analytical expression after Nordstrom et al. (1990).

Proto-imogolite solubility line at 7°C plotted for the reaction:

0.5Al 2SiO3(OH)4 (s) + 3H + = Al 3+ + 0.5H 4SiO4 + 1.5H2O

(log K 25 = 7.02, ΔH = −96.8 kJ mol−1) after Lumsdon and Farmer (1995).

HASB solubility line for the reaction:

Al 2Si 2O5 (OH)4 + 6H + = 2Al 3+ + 2H 4SiO4 + H2O (log K 7 = 14.0 ± 0.7)

with uncertainty of solubility plotted.)

23-10 Properties and Processes

results largely from micropores formed from aggregates of parti- Babel, S., and E.M. Opiso. 2007. Removal of Cr from synthetic
cles because the porosity decreases with the shrinkage observed wastewater by sorption into volcanic ash soil. Int. J. Environ.
on drying. As a result, water retention in allophanic soils is very Sci. Technol. 4:99–107.
high at a given water potential compared to soils dominated by Ballantine, D.J., and C.C. Tanner. 2010. Substrate and filter mate-
crystalline clays. This, in part, accounts for the high productiv- rials to enhance phosphorus removal in constructed wet-
ity often seen in forested soils high in SRO materials (Martini lands treating diffuse farm runoff: A review. N.Z. J. Agric.
and Luzuriaga, 1989; Nizeyimana, 1997). Macroporosity is also Res. 53:71–95.
high in most allophanic soils resulting in good infiltration and Basile-Doelsch, I., R. Amundson, W.E.E. Stone, C.A. Masiello,
hydraulic conductivity. The latter parameter has been found J.Y. Bottero, F. Colin, F. Masin, D. Borschneck, and J.D.
to decrease significantly in soils at pH values where allophane Meunier. 2005. Mineralogical control of organic carbon
is known to disperse easily (pH = 3 and 11) (Nakagawa and dynamics in a volcanic ash soil on La Reunion. Eur. J. Soil
Ishiguro, 1994). Sci. 56:689–703.
The aqueous solubility of imogolite and proto-imogolite Besoain, E. 1969. Imogolite [allophane] in volcanic soils in Chile.
allophane shows them to be less stable than kaolinite at soluble Geoderma 2:151–169.
silica activities expected in natural soils (Farmer et al., 1979b; Besoain, M.E., and M.S.P. Gonzalez. 1977. Mineralogy, genesis
Percival, 1991; Su and Harsh, 1994; Gustafsson et al., 1998; and classification of volcanic ash soil derivatives of the cen-
Su and Harsh, 1998; Wada and Kakuto, 1999). However, imogo- tral-south region of Chile. Cienc. Invest. Agrar. 4:109–130.
lite and proto-imogolite allophane are more stable than halloy- Bonelli, B., I. Bottero, N. Ballarini, S. Passeri, F. Cavani, and
site at low Si activity (Su and Harsh, 1994). Thermodynamically, E. Garrone. 2009. IR spectroscopic and catalytic character-
halloysite is stable relative to imogolite at a log Si(OH)4 activity ization of the acidity of imogolite-based systems. J. Catal.
greater than about −3.5. Halloysite is more stable than allophane 264:15–30.
at a lower Si activity, but allophane formation in preference to Boudot, J.P. 1992. Relative efficiency of complexed aluminum,
halloysite is commonly observed in soils at log (H4SiO4) > −3.45 noncrystalline Al hydroxide, allophane and imogolite in
(Singleton et al., 1989). This incongruity may indicate that soil retarding the biodegradation of citric acid. Geoderma
solution analyses performed at a later date may not be relevant 52:29–39.
to the time of mineral formation. Kinetic considerations may Childs, C.W., R.L. Parfitt, and R.H. Newman. 1990. Structural
favor the SRO materials relative to halloysite; this certainly is studies of Silica Springs allophane. Clay Miner.
true relative to kaolinite. The solubility constants determined 25:329–341.
for imogolite and allophane may be incorrect or the solid phases Chorover, J., and G. Sposito. 1995. Surface-charge characteris-
controlling the solubility of Al, such as gibbsite or Al complexed tics of kaolinitic tropical soils. Geochim. Cosmochim. Acta
with organic matter, may not be well understood (Gustafsson 59:875–884.
et  al., 2001). Current solubility data seem to support different Clark, C.J., and McBride, M.B. (1984). Chemisorption of Cu(II)
solubility constants for synthetic and soil imogolite—log Ksyn = and Co(II) on allophane and imogolite. Clays Clay Miner.
6.05 and log Ksoil = 6.60 at 25°C for the reaction: 32:300–310.
Cradwick, P.D.G., V.C. Farmer, J.D. Russell, C.R. Masson, K. Wada,
3+ and N. Yoshinaga. 1972. Imogolite, a hydrated aluminum
0.5(HO)3 Al 2O3SiOH(s) + 3H = Al + 0.5H 4SiO4 + 1.5H2O
+
silicate of tubular structure. Nat. Phys. Sci. 240:187–189.
(23.2) Creton, B., D. Bougeard, K.S. Smirnov, J. Guilment, and O. Poncelet.
2008. Molecular dynamics study of hydrated imogolite. 1.
The solubility of minerals in soils is complicated by nonequilib- Vibrational dynamics of the nanotube. J. Phys. Chem. C
rium conditions, difficulty in speciating soluble ions, particu- 112:10013–10020.
larly Al, and determination of controlling phases (Gustafsson Cruz, M.D.R., and L.M. Real. 1991. Practical determination of
et al., 2001). Nevertheless, the chemistry of soil solutions and allophane and synthetic alumina and iron-oxide gels by
natural waters may often be determined by these rapidly formed, x-ray-diffraction. Clay Miner. 26:377–387.
but persistent, poorly crystalline materials (Dobrzynski, 2007) Dahlgren, R.A. 1994. Quantification of allophane and imogo-
(Figure 23.6). lite, p.  430–451. In J. Amonette and L.W. Zelazny (eds.)
Quantitative methods in soil mineralogy. SSSA, Madison, WI.
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Farmer, V.C., B.F.L. Smith, and J.M. Tait. 1979b. The stability, free Harsh, J.B., S.J. Traina, J. Boyle, and Y. Yang. 1992. Adsorption
energy and the heat of formation of imogolite. Clay Miner. of cations on imogolite and their effect on surface-charge
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Floody, M.C., B.K.G. Theng, P. Reyes, and M.L. Mora. 2009. He, H., T.L. Barr, and J. Klinowski. 1995. ESCA and solid-state
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from Tanzania. Geoderma 138:127–132. R. Jahn, and R. Dohrmann. in press. Quantification of allo-
Gonzalez-Perez, J.A., C.D. Arbelo, F.J. Gonzalez-Vila, A.R. phane clay from Ecuador. Clays Clay Miner. 58:707–716.
Rodriguez, G. Almendros, C.M. Armas, and O. Polvillo. Levard, C., A. Masion, J. Rose, E. Doelsch, D. Borschneck,
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Appl. Pyrol. 80:369–382. perature and ambient pressure: A promising route for inex-
Goodman, B.A., J.D. Russell, B. Montez, E. Oldfield, and pensive nanotubes. J. Am. Chem. Soc. 131:17080–17081.
R.J.  Kirkpatrick. 1985. Structural studies of imogolite and Lumsdon, D.G., and V.C. Farmer. 1995. Solubility characteristics
allophanes by aluminum-27 and silicon-29 nuclear magnetic of proto-imogolite sols—How silicic-acid can de-toxify alu-
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MacKenzie, K.J.D., M.E. Bowden, and R.H. Meinhold. 1991. The Parfitt, R.L. 1990. Allophane in New Zealand—A review. Aust. J.
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 IV
Soil Biology and
Biochemistry:
Soil Biology in Its
Second Golden Age
E.A. Paul
Colorado State University

Paolo Nannipieri
University of Florence

24 Microbiota  Raffaella Balestrini, Valeria Bianciotto, Paola Bonfante, Michael Schloter, Sharath Srinivasiah,
R. Greg Thorn, Kurt E. Williamson, and K. Eric Wommack. ......................................................................................................... 24-1
Viruses in Soil Ecosystems  •  Acknowledgments  •  References  •  Structure and Function of Prokaryotes
in Soil  •  References  •  Soil Fungi  •  References  •  Mycorrhizae  •  Acknowledgments  •  References
25 Soil Fauna  Michael Bonkowski, M.A. Callaham, Jr., Marianne Clarholm, David C. Coleman, D.A. Crossley, Jr.,
Bryan Griffiths, Paul F. Hendrix, Robert McSorley, Mark G. St. John, and P.C.J. van Vliet. .......................................................... 25-1
Protozoa  •  References  •  Nematodes  •  References  •  Microarthropods  •  References  •  Macroarthropods  • 
References  •  Enchytraeidae—Oligochaeta  •  References  •  Earthworms  •  References
26 Microbially Mediated Processes  Susumu Asakawa, Else K. Bünemann, Emmanuel Frossard, E.G. Gregorich,
Jan Jansa, H.H. Janzen, Michael A. Kertesz, Makoto Kimura, Loretta Landi, David Long, Terence L. Marsh,
Paolo Nannipieri, Astrid Oberson, Giancarlo Renella, and Thomas Voice..................................................................................... 26-1
Phosphorus and Sulfur in Soil  •  References  •  Bacterial Transformations of Metals in Soil  •  References  •  Microbially
Mediated Processes: Decomposition  •  References  •  Anaerobic Microbially Mediated Processes  •  References  •  Soil
Enzymes  •  References
27 Nitrogen Transformations  Richa Anand, Jean-Claude Germon, Peter M. Groffman, Jeanette M. Norton,
Laurent Philippot, James I. Prosser, and Joshua P. Schimel. ............................................................................................................27-1
Biological Nitrogen Fixation  •  References  •  Nitrogen Mineralization–Immobilization
Turnover  •  References  •  Nitrification  •  References  •  Denitrification  •  References  •  Nitrogen
in the Environment  •  References
28 Molecular Techniques  Judith Ascher, Maria Teresa Ceccherini, Yin Chen, Guo-Chun Ding, Holger Heuer, Jiri Jirout,
Deepak Kumaresan, J. Colin Murrell, Giacomo Pietramellara, and Kornelia Smalla.................................................................... 28-1
Cultivation-Independent Detection of Genes Present in Soil Bacteria  •  References  •  Expression of Genes
in Soil  •  Acknowledgment  •  References  •  Stable-Isotope Probing and Its Application in Soil Microbiology  •  References

IV-1
IV-2 Soil Biology and Biochemistry: Soil Biology in Its Second Golden Age

S
OIL BIOLOGY, THE STUDY OF soil organisms and their nitrogen (Bardgett et al., 2005). Because of the close interaction
processes, discusses the most abundant living organ- of the living cells with external enzymes and the soil mineral
ism on earth. The early characterization of visible fungi, matrix, soil has been often described as a self-controlled liv-
such as that in the Theatrum Fungorium, published in 1675 ing entity with many similar characteristics over many parts of
and Leeuwenhoek’s microscopic investigation of bacteria dur- the world (McGill, 2007). The factors controlling biochemical
ing the same century, represented the initial creation of this reactions and those affecting population and soil organic mat-
field from an observational viewpoint. The study of organisms ter turnover are similar. Thus, while individual soils show the
and soil processes started with Darwin’s explanation of the interaction of these factors with their environment (Morris and
role of earthworms in soil formation. The studies in the mid- Blackwood, 2007), many advances will be made by studying the
nineteenth century of nitrogen transformations by Warington, unifying principles (Fierer et al., 2009) that control soil biology
Lawes, and Gilbert (Paul, 2007) represented the beginnings of on a global basis.
scientific soil process studies. However, the true recognition of Soil biochemistry, a second component of soil biology, refers
this field occurred during the period of 1890–1910 when organ- to both the physiology and chemistry within the living cells
isms carrying out the processes necessary for decomposition that catalyze life’s functions, as well as the activity of external
and nitrogen and sulfur cycles were described by Beijerinck and enzymes. Important biological molecules (i.e., nucleic acids and
Winogradsky (Waksman, 1932). That period has been named proteins, including extracellular enzymes) can be adsorbed by
the “golden age” of soil microbiology (Waksman, 1932). The surface-reactive particles (i.e., clays), thus becoming protected
advent of tracers in the mid-twentieth century allowed the mea- against the degradation reactions of proteases and nucleases
surement of the dynamics of the processes in situ. Molecular without losing their activity. The capacity of the immobilized
techniques that were adapted to soils came about 100 years after enzyme to catalyze the target reactions, and the availability of
the first golden age with the initial paper of Torsvik (1980). Great the extracellular adsorbed DNA to be taken up by competent
advances in molecular techniques, for both the study of biologi- bacterial cells to be incorporated into the bacterial genome, is
cal nuclear materials and for modern studies of organic matter strongly affected by the soil matrix consisting of silts, clays, and
structure, have occurred during the last 20 years. The soil biol- sesquioxides (Stotzky, 1986; Nielsen et al., 2006; Pietramellara et
ogy chapters in this book describe these advances in the clas- al., 2009). This section of the handbook contains chapters on soil
sification of the soil organisms and the measurement of their biota, the status and origin of soil enzymes, and the meaning of
processes. The progress and advancement of our knowledge has current enzyme assays. Organisms that inhabit soil carry out the
been so profound that we can depict this section as the “second nutrient transformations that make life possible (Coleman and
golden age” of soil biology. Crossley, 1996). As decomposers of the products of photosyn-
The soil bacteria and archaea, ranging in size from 0.2 to a thesis and thus plant growth, the soil biota complete the carbon
few microns in diameter, have populations between 109 and cycle. The current global change problems result from a dis-
1010 organisms per gram of soil. The smallest soil biota include turbance of a very old steady state between photosynthesis and
the submicroscopic viruses and prions that require living cells decomposition. Decomposition proceeds at a slightly smaller
for reproduction. They exist in soil in numbers equivalent to rate than photosynthesis (Stevenson, 1994) resulting in a buildup
the bacteria. The larger, filamentous fungi often have a simi- of the soil organic matter, which is so essential to sustainable
lar biomass to that of the bacteria, but in examples such as the agriculture, ecosystem functioning, and carbon sequestration in
Armillaria, associated with multiple tree roots they can exist as global change. Soil at 15–20 × 1015 g C has twice as much C as the
a single organism with an area of several hectares (Thorn and atmosphere. The recent utilization of photosynthesized C stored
Lynch, 2007). The recently discovered archaea, with their spe- in coal and oil deposits over millions of years, the cultivation of
cial cell structures, in addition to the predatory protozoa, com- soils, and the disturbance of ecosystems, such as occurs in fires,
prise the remainder of the soil microorganisms that carry out is upsetting this steady state and has caused our current climate
the majority of nutrient transformations in soil. The archaea change problems by returning, rather than fixing, more CO2
and bacteria are characterized by a lack of a nucleus and other into the atmosphere (Ojima, 1992). For a long time, it has been
structures, such as mitochondria, yet these are the only organ- hypothesized that recalcitrance of organic substrates in soil was
isms that contain the complex enzyme systems for N2 fixation, the main driver of soil organic matter survival in the long term.
nitrification, methane oxidation, and reduction, and the inor- Clear analytical evidence now shows that inherently recalcitrant
ganic sulfur and metal transformations (Killham and Prosser, plant compounds such as n-alkanes and lignins turn over faster
2007). Although these are the earth’s oldest living inhabitants, than bulk soil organic carbon (Marschner et al., 2008).
their small size and lack of morphological diversity had made Nitrogen is as important to life and soil organic matter forma-
their study difficult until the advent of the soil molecular stud- tion as is carbon. In addition, many of the same organisms that
ies (Torsvik, 1980). While less in number and biomass, the soil decompose carbon also mineralize nitrogen.
animals, or fauna, play significant roles in soil mixing, or bioen- Nitrogen also undergoes numerous inorganic reactions,
gineering, and the consumption of microorganisms (Coleman such as nitrification–denitrification and N2 fixation, which are
and Crossley, 1996; Lavelle et al., 2004). The total soil biota com- primarily carried out by bacteria and archaea that complete
prise 2%–5% of the soil organic carbon content and 4%–8% of its the complex nitrogen cycle and make plant growth possible
Soil Biology and Biochemistry: Soil Biology in Its Second Golden Age IV-3

(Norton, 2008). Where N is present in excess quantities, these analysis of their numbers and classification. Molecular methods
reactions can also cause water pollution and the release of green- for the study of archaea, bacteria, and fungi have richly contrib-
house gases that are much more potent than carbon dioxide. uted to our new knowledge of the vast array of organisms in soil.
The great diversity of soil biota, in addition to the importance At least 90% of the bacteria and archaea active in soil are yet to
of their metabolism, their large numbers, and the possible sig- be identified, and the fungi and nematodes are being reclassified.
nificance of still-to-be-identified soil organisms, increase the Process probes have revolutionized our understanding of the
value of the study of soil biology from a pure science–natural functioning of the important mycorrhizal organisms and their
history standpoint. This diversity also contributes to ecological associations with plants. The development of new techniques,
stability (Wall, 2004). Due to the wide variety in both number such as those for the rapid throughput of molecular information
and type of decomposing organisms, the loss of one or two spe- in pyrosequencing and the combination of tracers and molecu-
cies may not affect this process. However, specialized processes, lar techniques as used in stable-isotope probing indicates that
such as nitrification carried out by a few specialized bacteria, more advances are forthcoming. Soil biology can only progress
can be affected and would only be more sensitive to disturbance. based from an integrated knowledge of all organisms involved
The vast competitiveness and number of organisms assure the and an increased understanding of the methods of analysis,
breakdown of most organics, whether natural or man-made, and their strengths, and limitations (Andren et al., 2008). In spite of
also serve in self-cleansing the soil of potential disease-carrying the diversity in both soil processes and soil organisms, there is
organisms. Even so, soil is not infallible. Overloading with man- now also a recognition of the great unity in the biotic and abiotic
made chemicals and toxic organisms can lead to a breakdown of controls that affect both the organisms and their processes. This
this self-cleansing characteristic. section has brought together both the recent knowledge and the
The field of soil biology has both greatly benefited from and fundamental unifying principles in a readable format with good
contributed to present breakthroughs in molecular biology. reference to both classical and modern literature. It should com-
These techniques are now available to a wide range of ecologists, prise both an excellent introduction to the soil biota, as well as a
microbiologists, and soil scientists, and al