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Plant Resins
Plant Resins
Chemistry, Evolution,
Ecology, and
Ethnobotany

JEAN H. LANGENHEIM

Timber Press
Portland • Cambridge
 . . . gum, the gum of the mountain spruce.
He showed me lumps of the scented stuff
Like uncut jewels, dull and rough.
—Robert Frost, “The Gum-Gatherer,”
from Mountain Interval, 1920

Page 1, Agathis australis, kauri; page 2, Boswellia, frankincense.

All drawings by Jesse Markman, maps by Gulla Thordarsen and Jesse Markman.

Copyright © 2003 by Jean H. Langenheim

All rights reserved

Published in 2003 by

Timber Press, Inc. Timber Press

The Haseltine Building 2 Station Road
133 S.W. Second Avenue, Suite 450 Swavesey
Portland, Oregon 97204, U.S.A. Cambridge CB4 5QJ, U.K.

Printed in Hong Kong

Library of Congress Cataloging-in-Publication Data

Langenheim, Jean H.
Plant resins : chemistry, evolution, ecology, and ethnobotany / Jean H. Langenheim.
p. cm.
Includes bibliographical references (p. ).
ISBN 0-88192-574-8
1. Gums and resins. 2. Gums and resins—Utilization. I. Title
SB289 .L36 2003
620.l'924—dc21
2002028941
Contents
Preface 13
Acknowledgments 18

PART I
The Production of Resin by Plants 21

Chapter 1 What Plant Resins Are and Are Not 23

Definitions of Resin 23
Terpenoid Resins 26
Terpenoid Synthesis 26
Terpenoid Loss 33
Characteristic Components 34
Phenolic Resins 40
Synthesis and Characteristic Components 41
Substances Confused or Intermixed with Resin 45
Gums 45
Mucilages 47
Oils and Fats 48
Waxes 49
Resin Compounds in Latex 49
Miscellaneous Intermixed Compounds 50

Chapter 2 Resin-Producing Plants 51

Resin-Producing Conifers 52
Classification 52
Pinaceae 54
Araucariaceae 59
Podocarpaceae 62
Cupressaceae 63
5
6 | CONTENTS

Resin-Producing Angiosperms 67
Classification 67
Basal Group 69
Monocots 70
Eudicots 73
Evolutionary Trends in Resin-Producing Plants 98
Taxonomic Distribution of Resin Producers 98
Convergence in Aspects of Resin Production 101
Status of Evolutionary Interpretation 103

Chapter 3 How Plants Secrete and Store Resin 106

Ultrastructural Features of Resin Secretory Structures 107
Sites of Synthesis 107
Export of Resin Components 110
Internal Resin Secretory Structures 112
Canals Versus Pockets or Cysts 112
Conifers 114
Angiosperms 122
Resin in Laticifers 127
Evolution of Internal Secretory Structures 128
External Resin Secretory Structures 130
Glandular Trichomes 130
Epidermal Cells and Bud Trichomes 135

PART II
The Geologic History and Ecology of Resins 141

Chapter 4 Amber: Resins Through Geologic Time 143

How Is Resin Fossilized and When Is It Amber? 144
Distribution of Amber Deposits 147
Sources of Amber 150
Botanical Evidence 150
Chemical Evidence 153
Geologic History of Amber-Producing Plants 156
Amber from Conifers 157
Amber from Angiosperms 172
Amber of Unknown Botanical Source 187
 CONTENTS | 7

The Floras of Amber Forests 189

Baltic Amber Forests 189
Dominican and Mexican Amber Forests 192
Renewed Interest in Amber Research 194

Chapter 5 Ecological Roles of Resins 196

Ecologically Important Properties of Resin 196
Variation in Resin Composition 199
Variation in Resin Quantity 202
Resin Defense of Conifers 203
Ponderosa Pine as a Model System 204
Other Conifer Resin Interactions 210
Ecological Roles in Tropical Angiosperms 219
Copious Resin Production in Tropical Trees 219
Hymenaea and Copaifera as Model Systems 220
Other Angiosperm Resin Interactions 229
Roles of Surface-Coating Resins 237
Shrubs and Herbs in Xeric Communities 237
Subarctic and Boreal Trees 244
Ecosystem Interactions of Resins 247
Resin Use by Bees in the Temperate Zones 248
Pharmaceutical Use of Resin by Coatis 249
Resins as Beetle Pheromones 250
Role of Resin in Ecosystem Nutrient Cycling 251
Herbivore-Induced Terpene Emissions and Tropospheric
Chemistry 252
Future Ecological Research on Resins 253

PART III
The Ethnobotany of Resins 255

Chapter 6 Historical and Cultural Importance of Amber and Resins 257

Amber Trade from the Stone Age to the Classical Age 260
Old Stone Age to the Iron Age 260
Greeks and Romans 267
Baltic Amber from the Middle Ages to the Present 269
Medieval and Renaissance Periods 270
8 | CONTENTS

Seventeenth Through Nineteenth Centuries 273

Twentieth and Twenty-first Centuries 275
Amber in Other Areas 278
Burmese Amber into China 278
Pre-Columbian Amber Trade in Mesoamerica 280
Resin Figurines from Costa Rican Burial Sites 280
Dominican Amber 282
Incense Trade Routes 283
Cannabis and Trade in Its Resin 290
Old World Hashish Cultures 290
Prohibition 295
Resins in Indigenous Cultures 296
Mesoamerica and the Maya 296
Southeast Asia and the Semelai 297
Resins in the Economies of the United States, New Zealand,
and Africa 298
Naval Stores in the United States 298
Kauri Resin in New Zealand 302
Copal in Africa 304

Chapter 7 Oleoresins 306

Naval Stores from Conifers 307
United States 307
Europe 319
Asia 323
Latin America 326
Africa 328
Cedarwood Oil 329
Oily Resins from Tropical Angiosperms 331
Dipterocarps 331
Legumes 334

Chapter 8 Fragrant and Medicinal Balsams 341

The Balsams 342
Conifer Balsams 342
Leguminous Balsams 343
 CONTENTS | 9

Storax and Styrax 347

Elemis 356
Old World Elemis 356
New World Elemis 357
Other Important Balsams 362
Boswellia 363
Commiphora 368
Bursera 373

Chapter 9 Varnish and Lacquer Resins 375

Dammars 375
Confusion in Terminology and Plant Sources 375
Local Use and Export 376
Dammar as a Source of Petroleum 379
Gamboge 381
Sandarac 382
Mastic 385
Varnish 385
Other Uses 388
Acaroid Resin 390
Hard Copals 392
Leguminous Copals 393
Araucarian Copals 399
Lacquers and Specialty Varnishes 406
Anacard Lacquers 406
Barniz de Pasto and Other Rubiaceous Resins 408
Araliaceous Varnishes 410
Amber Varnish 410
Shellac 410

Chapter 10 Miscellaneous Resins 412

Umbelliferous Resins 412
Ammoniacum 412
Asafoetida and Galbanum 413
Silphium 416
10 | CONTENTS

Convolvulaceous Resins 418

Jalap 418
Other Ipomoea Resins 420
Scammony 420
Hashish and Hops Resin 421
Hashish 421
Hops 425
Propolis 427
Allergenic Anacard Resins 429
Poison Ivy, Poison Oak, and Poison Sumac 430
Other Poisonous Anacards 433
Chemistry of the Poisonous Resins 434
Labdanum 435
Desert Shrub Surface Resins 437
Myoporaceae 438
Asteraceae 439
Dragon’s Blood 441
Other Resins 444
Podophylloresin 444
Poplar Bud Resins 445
Guaiac 447
Creosote Bush Resin 447
Gharu Wood 448
Guayule Resin 450
Resins from Latex 452
Conifer Resins 453
Amber in Medicine 455

Chapter 11 Future Use of Resins 457

Traditional Uses 458
Amber Jewelry and Artwork 458
Incense 458
Other Special Uses 459
Medicinal Uses 459
New Therapeutic Uses for Resins 459
Propolis 460
Marijuana 461
 CONTENTS | 11

Industrial Uses 463

Chemical Feedstocks 463
Fuel Sources 465
Tropical Forest Management for Resin Use 466
Extractive and Indigenous Reserves 468
Agroforestry 469
Plantations 471
Enrichment Planting 472
Enhanced Pest Protection of Resin-Producing Trees 473
Archeology and Anthropology of Resins 475

Appendix 1 Resin-Producing Conifers 477

Appendix 2 Resin-Producing Angiosperms 480

Appendix 3 Skeletons of Characteristic Components of Fossil Resins 486

Appendix 4 Age, Location, and Plant Source of Amber Deposits 488

Appendix 5 Common Names, Plant Sources, and Uses of Resins 490

Glossary 494

References 501

Plant Index 569

Subject Index 581

Color plates follow page 432

This page intentionally left blank
Preface

When I was asked by Timber Press to write a new book on resins, including
amber—Howes’s 1949 Vegetable Gums and Resins was the most recent such
effort—the breadth of interdisciplinary coverage seemed too ambitious for an
individual person. There have been so many advances in resin research in the
past half century, including the development of new fields of research such as
chemical ecology, and the exploration of other interesting facets about resins
made possible by new chemical, molecular, and microscopic techniques. With
a little thought, however, I realized that my years of resin research had pre-
pared me to accept the challenge enthusiastically, a challenge that has been
stimulating and rewarding.
My interest in resins began with ambers formed over geologic time and
proceeded rapidly to the evolutionary significance of the ecological roles
resins play in plants. These were natural interests, arising from my training as
an ecologist and paleobotanist. Later, my queries turned to how humans have
used resins throughout history, and my interest in that intensified when I
taught an undergraduate course, Plants and Human Affairs, and coauthored
a textbook on the subject. I became convinced that resins are remarkable
materials indeed, especially in their diversity and the length of time they have
been such versatile substances in the lives of plants and humans. A university
colleague, a philosopher, suggested that resin had created a “cosmos” for me
because of the variety of topics I had been led to investigate: paleobotany,
chemistry, systematics, ecology, anthropology, ethnobotany, art history, etc.
There is no doubt, however, that I could only have delved into such wide-
ranging topics with the collaboration and expertise of many individuals,
which increased the value and enjoyment of the experience. Although most of
the people associated with the development of my research were not directly
involved in my writing Plant Resins, I want to acknowledge their contribu-

13
14 | PREFACE

tions to the learning experiences that enabled me to accept the challenge. It

also is interesting how serendipity played a role in the people I met or the
events that took place, helping me as my research interests ramified.
My research into plant resins began as a member of a paleoecological
expedition to study amber in Chiapas, Mexico, led by entomologists from the
University of California, Berkeley. My role in this expedition was to deter-
mine which trees produced the resin in which a diversity of insects had been
beautifully preserved and the kind of forest in which the trees and insects had
lived. Previously, amber had not been analyzed chemically as a resin but
rather had been described inorganically as a gemstone. My first hint of the
botanical source of the Mexican amber was a chemical one—its use by the
Maya as incense. The burning incense did not smell like burning pine resin,
which had long been thought to be the source of the well-known Baltic amber
and was assumed to be the source of Mexican amber. Thus I collected resins
from all the kinds of resin-producing trees in Chiapas for chemical compari-
son with the amber, ushering me into the world of tropical resins and the for-
ests in which the trees grew.
Fortunately, at this time I became a research fellow at Harvard University
in the laboratory of the geochemist and paleobotanist Elso Barghoorn, who
enthusiastically encouraged my exploration of the chemical criteria for deter-
mining the botanical sources of amber through geologic time. It was neces-
sary to use solid-state analytic techniques, such as infrared spectroscopy,
because the polymerization of amber precluded dissolving it for standard
organic chemical analysis. I subsequently collaborated with spectral chemist
Curt Beck of Vassar College, who I had serendipitously discovered was using
infrared spectroscopy to determine the archeological provenance of Euro-
pean amber. My approach at that time established a new direction in the
study of plant origins of ambers, by including chemosystematic data. Addi-
tionally, my approach had an even larger perspective, of integrating paleo-
ecological data into the understanding of amber-producing plants. These
chemical and paleoecological studies, together with my background as a plant
ecologist, prepared me to be intrigued by the correlation that the greatest
diversity of trees producing copious amounts of resins are tropical angio-
sperms (plants with true flowers). This interest coincided with the rapid
advance of the field of biochemical ecology, and I was swept along with the
tide of its development.
 PREFACE | 15

To understand tropical resin production, I decided to use the leguminous

tree Hymenaea as a model, partly because I had determined it as the source of
the amber in a number of large New World deposits. The genus has an amphi-
Atlantic distribution, and the history of utilization of leguminous resins
increased my growing interest in ethnobotany. Field investigation of Hymen-
aea led me from Mexico through Central America to South America and
Africa. The formation of the Organization for Tropical Studies (OTS) coin-
cided with my early studies of Hymenaea in Central America, and assistance
from numerous OTS colleagues from various colleges and universities (too
many to name) helped promote the ramifications of my overall investigation
of Hymenaea and my interest in other resin-producing plants.
The center of distribution of Hymenaea is Amazonia and I had the good
fortune to be introduced to the region by the late Richard E. Schultes, long-
time Amazonian ethnobotanical researcher at the Harvard University Botan-
ical Museum. He helped initiate my Amazonian research, which continued
for many years, and importantly, further enhanced my interest in ethnob-
otany. Successful work on Brazilian Amazonian resin-producing plants also
would not have been possible without the strong support and interest of
Paulo Machado and Warwick Kerr, former directors of the Instituto Nacional
de Pesquisas da Amazônia in Manaus; Paulo Cavalcante, Museu Goeldi in
Belém; and others again too numerous to mention. Additionally, I had the
unflagging interest and cooperation of Ghillean Prance, then director of
research at the New York Botanical Garden, and later, director of the Royal
Botanic Gardens, Kew, who was leading the research for Flora Amazônica.
Before I could investigate resin production throughout the geographic
range of Hymenaea, revising the systematics of the genus was necessary since
species had often been described from poor specimens collected during floris-
tic surveys. This is a common situation for many of the plants belonging to
tropical resin-producing families, a problem whose consequences are noted
throughout Plant Resins. The Hymenaea revision, done in collaboration with
a graduate student, Y. T. Lee, was approached as an interface between sys-
tematics and ecology, with amber providing the evolutionary context. During
this revisionary work I interacted closely with tropical legume systematists
such as the late Pat Brenan, Royal Botanic Gardens, Kew, and J. Léonard,
Université de Bruxelles, a specialist on African copal producers. This opened
my thinking on the important relationships of African and New World trees.
16 | PREFACE

My interest in tropical resin-producing plants also expanded to discussion

of taxonomic problems with specialists, including Douglas Daly, New York
Botanical Garden (Burseraceae); T. C. Whitmore, Oxford University (Aga-
this); and Peter Fritsch, California Academy of Sciences (Styracaceae), among
others.
As my resin studies progressed, I had to learn more about the constituents
of present-day rather than fossil resins. Thus I embarked on a determination
of the components of Hymenaea resins with doctoral graduate students Susan
Martin and Allan Cunningham, with assistance from chemists E. Zavarin,
Forest Products Laboratory, University of California, Berkeley; George Ham-
mond, University of California, Santa Cruz; A. C. Oehschlager, Simon Fraser
University; and Duane Zinkel, Forest Products Laboratory, University of Wis-
consin, Madison.
How resin is secreted into storage structures is significant to both plant
defense and human use of resins. So another door to learning opened. In
exploring the anatomy of secretory structures in Hymenaea, I was aided by
the late Ralph Wetmore and I. W. Bailey as well as Margaret McCully, at
Harvard University at the time, all of whom enthusiastically supplied the
needed expertise. Lynn Hoefert, U.S. Department of Agriculture, Salinas,
California, also assisted a graduate student, Gail Fail, with ultrastructural
studies of resin secretion in Hymenaea. I increased my knowledge of resin
secretory structures through contact with other researchers, too, including A.
Fahn, Hebrew University of Jerusalem, and B. Dell and A. J. McComb, Uni-
versity of Western Australia, who studied secretory systems in a variety of
resin-producing plants.
A major interest in the chemical ecology of Hymenaea was followed by
comparison with the related legume, Copaifera. These investigations involved
collaboration with another group of graduate students (Will Stubblebine,
David Lincoln, José Carlos Nascimento, Matthew Ross, Craig Foster, Robert
McGinley, Cynthia Macedo, Eric Feibert, and Susanne Arrhenius) on plant
interactions with insects and fungi. Other avenues to understanding resin
production were opened by graduate students (George Hall, Francisco
Espinosa-García, and Wendy Peer) who worked on the chemical ecology of
redwoods (Sequoia). I also enjoyed numerous stimulating discussions on
defensive mechanisms of other resin-producing plants with colleagues,
including Karen Sturgeon, then at the University of Colorado; Kenneth Raffa,
 PREFACE | 17

University of Wisconsin, Madison; Marc Snyder, Colorado College; John

Bryant, University of Alaska; and numerous others.
Archeological and anthropological studies of resin and amber were car-
ried out in Angola in collaboration with Desmond Clarke, University of Cal-
ifornia, Berkeley. By serving on doctoral dissertation committees at Yale Uni-
versity and the University of Texas, Austin, I learned about the use of resin by
the Semelai in peninsular Malaysia (with Rosemary Gianno) and by the Maya
in Mexico and Central America (with Kirsten Tripplett). Moreover, these
kinds of studies provided opportunities to observe art objects made from
amber, and contacts with museums around the world. And who would not
avail themselves of the opportunities to collect and enjoy amber jewelry!
Thus, from my varied experiences in research on resin and amber, I saw
the need for an up-to-date book because so much disparate information is
scattered throughout the literature. I decided that the book should tell the
whole story of these fascinating plant substances. Despite the importance of
a multidisciplinary approach, and my hope of raising awareness of that, I
divided the book into three parts to make it easier to use by readers with
diverse backgrounds, interests, and goals, who I knew might turn to such a
volume for information. These parts may be read in any order, depending on
the reader’s interest. A glossary is also provided. The three chapters in Part I,
The Production of Resin by Plants, provide biochemical, developmental, and
systematic information. However, this information is repeatedly projected
toward discussion of the value of resins to plants and humans in Parts II and III.
Central to understanding the remainder of the book is my operational defini-
tion of resin, presented in Chapter 1. This definition comes from my struggle
with the confused and vague usage of the term resin that has persisted
through the years. I hope that my definition provides rigor and clarity by dis-
tinguishing resins from other materials with which they are commonly con-
fused (e.g., gums and mucilage) based on three criteria: chemistry, secretory
structures, and ecological roles in the plant. Part I also includes a discussion of
more recent major breakthroughs in the understanding of terpenoid biosyn-
thesis and the ultrastructural evidence for its compartmentation, and how this
new information solves mysteries encountered in ecological studies of resins.
The secretory structures are characterized, and the importance of under-
standing their functions in ecological interactions and human use is discussed.
Furthermore, I introduce the reader to the distribution of resin-producing
18 | PREFACE

plants throughout the plant kingdom and for the first time present evolu-
tionary convergences in different aspects of resin production.
Part II, The Geologic History and Ecology of Resins, includes topics that
have been at the heart of much of my own research. The two chapters have a
phytocentric approach whereas other publications covering these subjects
are more insect-oriented. Questions on when resins first evolved and on
which groups of resin producers have a geologic record are addressed in
Chapter 4. Chapter 5 addresses the question of whether resin production is
primarily a defense against herbivores and pathogens, and presents ecologi-
cal and evolutionary data that support this view.
Part III, The Ethnobotany of Resins, presents in six chapters the substan-
tial roles that different kinds of resins have played in most cultures of the
world throughout human history. In Chapter 11, I consider whether the
importance of resin to humans will become a historical remnant as they are
replaced by petrochemicals and other alternatives, or whether new technol-
ogies as well as policies that preserve plant resources, particularly in the trop-
ics, will enable change in uses of resins and an important future for them.
Plant Resins only provides a progress report on our current knowledge—I
hope this synthesis of the many facets of resins will stimulate future research
on these remarkable plant products.

Acknowledgments
For Plant Resins specifically, I am grateful to friends, colleagues, and organi-
zations who have contributed photographs as well as to those who provided
comments that greatly improved the clarity of the chapters.
Numerous colleagues who shared photographs from their own resin
research include Scott Armbruster, Norwegian University of Science and
Technology; John Lokvam, and John Bryant, University of Alaska, Fairbanks;
Ben LePage, University of Pennsylvania; A. Fahn, Hebrew University of
Jerusalem; Duncan Porter, Virginia Polytechnic University; T. C. Whitmore,
Oxford University; Robert Clarke, International Hemp Association; J. J.
Hoffmann, S. P. McLaughlin, and D. L. Venable, University of Arizona;
Robert Adams, Baylor University; Manuel Lerdau, State University of New
York, Stonybrook; Jason Greenlee, Fire Research Institute, Fairfield, Wash-
ington; Hanna Czeczott, Museum Ziemi, Warsaw, Poland; Adam Messer,
 ACKNOWLEDGMENTS | 19

University of Georgia; David Rhoades, Seattle, Washington; William Gittlin,

Berkeley, California; Douglas Daly, New York Botanical Garden; John
Dransfield, Royal Botanic Gardens, Kew; Rosemary Gianno, Keene State
College, New Hampshire; M. Pennacchio, University of Technology, Western
Australia; Bill Thomson, University of California, Riverside; J. G. Martínez-
Avalas, Universidad Autónoma de Tamaulipas; Rudolf Becking, Humboldt
State University, California; S. P. Lapinjoki, Kuppio University, Finland;
William Crepet, Cornell University; Margaret McCully, Carleton University,
Canada; Kennedy Warne, New Zealand Geographic magazine; Robert
Wheeler, U.S. Forest Service, Fairbanks, Alaska; and Vito Polito, University of
California, Davis. I owe special thanks to David Grimaldi, American Museum
of Natural History, who so generously provided numerous amber photo-
graphs from his research and from his book, Amber, Window to the Past. I also
gratefully acknowledge the following organizations for providing photo-
graphs: Royal Botanic Gardens, Kew; Danish National Museum, Copen-
hagen; and the National Library of New Zealand, Wellington.
I also express my gratitude to those who critically reviewed various drafts
of different chapters: Ken Anderson, Argonne National Laboratory; Eliza-
beth Bell, Santa Clara University; Laurel Fox, University of California, Santa
Cruz; Peter Fritsch, California Academy of Sciences; Jonathan Gershenzon,
Max Planck Institute for Chemical Ecology; Cheryl Gomez, UCSC; David
Grimaldi, American Museum of Natural History; Karen Holl and Ingrid
Parker, UCSC; Campbell Plowden, Penn State University; Kirsten Tripplett,
University of California, Berkeley; and Duane Zinkel, Forest Products Labo-
ratory, Madison, Wisconsin. Again, I extend special thanks to Susan Martin,
U.S. Department of Agriculture Research Laboratory, Ft. Collins, Colorado,
and Marc Los Huertos and Thomas Hofstra , UCSC, for their particular care
and thoughtfulness in reviewing numerous chapters. I also appreciate the
generosity of the time given by classical historian Gary Miles, UCSC, and
anthropologist Rosemary Joyce, UC Berkeley, to discuss details of the Chap-
ter 6 time line.
I greatly appreciate the efforts of Gulla Thordarsen in drafting maps.
Jesse Markman’s contributions are special in that he did all drawings of plants,
most maps, and generally shared in most aspects of the book’s development.
Jesse and I are grateful to Ann Caudle, Science Communications Program,
University of California, Santa Cruz, for her assistance and critical comments
20 | PREFACE

on the plant drawings. The diligent help of the UCSC reference librarians
was invaluable, and the cheerful persistence of the interlibrary loan librarians
was essential in obtaining literature unavailable in our library. I am also grate-
ful for the conscientious efforts of my editor at Timber Press to see that Plant
Resins is as error-free and as understandable to a broad audience as possible.
Finally, the book would not have been possible without Dorothy Hollinger’s
tireless word processing of the numerous drafts.
 PART I

The Production of Resin

by Plants
This page intentionally left blank
CHAPTER 1

What Plant Resins Are and Are Not

The literature on resins, although relatively abundant, is not very pre-

cise as far as exact use of terms is concerned. . . . confusion which, in a
way, reflects the complexity of the world of resins.
—Jost et al. 1989

To understand the many topics covered in Plant Resins, it is necessary to have

a clear idea of what plant resin is and how it differs from other substances
that have been called resins. Different readers doubtless have different con-
cepts of what resin is. Some may be surprised at the number of plants that
produce resin (Chapter 2) and consequently at the breadth and depth of the
influence that resins have had throughout history (Chapter 6). The characteriz-
ation of resins has changed greatly with the development of chemical, molec-
ular, and microscopic technologies to analyze them. Associated with these
technological breakthroughs have been advances in evolutionary and eco-
logical concepts regarding the functions of resins in plants.

Definitions of Resin
Resin is sometimes referred to in a general manner, such as sap or exudate,
both of which include numerous substances from plants. Throughout written
history there has been a tendency to characterize resin vaguely as any sticky
plant exudate. In some dictionaries, this definition has been extended to
include substances that are mainly insoluble in water and that ultimately
harden when exposed to air. Nevertheless, the vagueness of even this
amended definition has led to continued confusion with other plant exudates,
including gums, mucilages, oils, waxes, and latex. Some terms such as gum

23
24 | CHAPTER 1 What Plant Resins Are

have often been used synonymously with resin; in fact, one prominent forest
products researcher has referred to the use of these terms as “haphazard”
(Hillis 1987). A better definition of resin, however, has awaited more knowl-
edge about their chemistry, secretory structures, and functions in the plant.
Interest in the chemistry of resins and the secretory structures in which
they are synthesized and stored began in the later 19th century in Germany.
A pioneering book, Die Harze und die Harzebehälter, resins and resin-con-
taining structures, was published by Tschirch and his students in 1906. Recog-
nition that detailed chemical knowledge of plant exudates would be valuable,
perhaps essential, for their commercial utilization led to the voluminous pub-
lications in the 1930s by Tschirch and Stock (1933–36) and others (e.g., Barry
1932). Nonetheless, only with the advent of various kinds of chromatography
and spectroscopy in the 1940s and 1950s was real progress made in identify-
ing the chemical constituents of resins and quantifying their composition. All
the exudates that have been confused with resin in the past can now be distin-
guished from resin in their pure form by chemical composition and by the bio-
synthetic pathways through which they are formed. Information about resin
secretory structures has become available through advances in plant anatomy,
including electron microscopy (Chapter 3), and from ecological studies regard-
ing the survival roles played by resins (Chapter 5). Together, these data provide
criteria for a definition to minimize the confusion surrounding the term resin.
Thus in Plant Resins, plant resin is defined operationally as primarily a
lipid-soluble mixture of volatile and nonvolatile terpenoid and/or phenolic
secondary compounds that are (1) usually secreted in specialized structures
located either internally or on the surface of the plant and (2) of potential
significance in ecological interactions. Note that resins consist primarily of
secondary metabolites or compounds, those that apparently play no role in
the primary or fundamental physiology of the plant. In addition to being pre-
formed and stored in secretory structures, resins sometimes may be induced
at the site of an injury without forming in a specialized secretory structure.
Moreover, resin occurs predominantly in woody seed plants. Amber is fos-
silized resin (Chapter 4).
Although terpenoid resins constitute the majority of copious internally
produced resins that have been used commercially, some important resins are
phenolic. Phenolic resin components occurring on the surfaces of plant
organs have been used, particularly in medicines, and may be useful as a bio-
 DEFINITIONS OF RESIN | 25
mass source of fuel; however, their overall significance is probably greater as
protection for vulnerable plant surfaces. Resin components are derived from
photosynthetically produced carbohydrates that are broken down to pro-
duce simpler compounds (pyruvate products); terpenoid and phenolic com-
pounds are then synthesized via different metabolic pathways (Figure 1-1).

CO 2

Photosynthesis

Primary Carbon Metabolism

Erythro-4-phosphate 3-Phosphoglycerate

Phosphoenolpyruvate Pyruvate
Deoxyxylulose
5-phosphate
Acetyl CoA

Shikimic acid Malonic acid Mevalonic acid Deoxyxylulose

pathway pathway pathway 5-phosphate
pathway

Phenylalanine

Phenylpropanoid
pathway

Terpenes

Phenolic
compounds

Secondary Carbon Metabolism

Figure 1-1. Generalized outline of biosynthesis of terpenes and phenolic secondary compounds
constituting resins, showing interconnection with relevant primary compounds and processes.
26 | CHAPTER 1 What Plant Resins Are

I briefly discuss the biosynthesis of terpenoid and phenolic resins, as well

as some of their characteristic components, as a basis for understanding the
ecological interactions that are important to the plant and to the human use
of its resin. Next, I review the substances that have been confused with resin
or that occur intermixed with it. The distinguishing characteristics may be
difficult to keep clear in some cases because the chemistry, kind of secretory
tissue, and ecological roles of the material in question may be poorly known;
therefore, resin may be ambiguously or dubiously designated in the litera-
ture on plant exudates. There may be a quandary as to whether the material
is really a resin or not, a situation that is unavoidable.
I discuss resins in various categories (e.g., oleoresins, balsams, and copals)
in Part III because these terms have gained prominence through human use of
those resins. Again, there is confusion from varied use of these terms, espe-
cially in regard to the plants producing the resins. A list of common names of
resins, their botanical sources, and major uses is provided in Appendix 5.

Terpenoid Resins
Terpenoid Synthesis
Terpenoids occur in all living organisms but attain their greatest structural
and functional diversity in plants. In fact, terpenoids constitute the largest
and most diverse class of plant compounds. The term terpenoid or terpene is
derived from the German word for turpentine, Terpentin, from which the
first members of this group of chemicals were isolated and their structures
determined (Croteau 1998). Through continual development of chemical
technology, especially gas chromatography–mass spectrometry (GC-MS) and
nuclear magnetic resonance spectroscopy (NMR), the structures of approx-
imately 30,000 terpenoids have been elucidated, but many more doubtless
will be discovered. Although terpenoids exhibit enormous structural diversity
and chemical complexity, they are united by a common biosynthetic origin
that enables them to be grouped in useful categories by linkage of five-carbon
(C5H8) isoprene structural elements. Consideration of these units help in the
visualization of a terpenoid’s biosynthetic assembly, although extensive meta-
bolic rearrangement may complicate the picture. Terpenoids (referred to
interchangeably as terpenes) are sometimes called isoprenoids.
 TERPENOID RESINS | 27

Pathways and Cellular Compartmentation

Two biosynthetic pathways lead to formation of the basic structural unit of
terpenoid synthesis (Figure 1-1). In the well-studied classical mevalonic acid
(MVA) or mevalonate pathway, three molecules of acetyl coenzyme A are
linked, (pyro)phosphorylated, decarboxylated, and dehydrated to yield iso-
pentenyl diphosphate (IPP), traditionally called isopentenyl pyrophosphate.
It has been discovered that IPP can be formed via a different pathway (Lichten-
thaler et al. 1997). Although details of the complete pathway remain to be
elucidated, 3-phosphoglycerate (3-PGA) and two carbon atoms derived from
pyruvate apparently combine to generate a first intermediate, 1-deoxy-d-
xylulose 5-phosphate (DOXP or DXP), then 2-C-methyl-d-erythritol 4-phos-
phate (MEP), which eventually is converted to IPP (Lange et al. 1998, 2000;
Lichtenthaler 1999). This alternate pathway is referred to as the DOXP or
DXP pathway, the MEP pathway, and sometimes as the nonmevalonic or
mevalonate-independent pathway.
IPP and its isomer, dimethylallyl diphosphate (DMAPP), are the actual
five-carbon building blocks for the formation of larger terpenoid molecules
(Figure 1-2). DMAPP serves as a primer to which IPP units can be added in
sequential chain-elongation steps. These reactions, catalyzed by prenyltrans-
ferase enzymes, connect isoprene units to one another. Thus IPP and DMAPP
combine to form a C10 precursor (geranyl diphosphate, GPP) for all 10-carbon
compounds, called monoterpenes. Addition of another molecule of IPP yields
a C15 precursor (farnesyl diphosphate, FPP) for all 15-carbon isoprenoids,
called sesquiterpenes. The structural diversity of sesquiterpenes greatly
exceeds that of monoterpenes because many more types of cyclization can
occur in a precursor with five additional carbon atoms. This diversity is evi-
dent in many resins, and some structures may polymerize, which can result in
the formation of large deposits of fossil resin (Chapter 4). Mono- and sesqui-
terpenes generally are volatile, giving fluidity to the resin as well as acting as
plasticizers for the more viscous components. When only the volatile mono-
and sesquiterpenes occur, they often are called essential oils. This designation,
however, is misleading because these terpenoids are neither essential to plant
metabolism nor are they true oils; essential refers to their essence or fragrance,
and oil to their feel. Essential oils as the only terpenoid fraction occur in a few
trees, for example, those in the Lauraceae (e.g., Laurus, bay trees), but are
found predominantly in herbaceous or shrubby plants, especially those in
28 | CHAPTER 1 What Plant Resins Are

Mediterranean climates (Ross and Sombrero 1991). Occasionally in the resin

literature, the volatile fraction of resin as defined in Plant Resins is referred to
as essential oil and only the nonvolatile fraction is called resin.
Addition of three molecules of IPP to DMAPP gives the C20 precursor
(geranylgeranyl diphosphate, GGPP) of the diterpenes. More than 3000 diter-
pene structures have been defined, usually bearing a variety of oxygen-con-
taining functional groups. Diterpene acids are particularly important in resin.
Doubling (dimerization) of the C15 FPP leads to C30 compounds, the triter-
penes. Triterpenes include a wide variety of structurally diverse substances,
some of which have been so modified that they no longer contain the full
complement of 30 carbon atoms. Numerous skeletal types occur in resin,

Plastid (C20) Diterpenes

GGPP C 20

DOXP 2 IPP
Pathway
(C10 ) Monoterpenes
GPP C 10

IPP

IPP DMAPP (C5 ) Cytosol-ER & Plastid

2 IPP

(C15 ) Sesquiterpenes
FPP C 15
MVA
Pathway 2×

Triterpenes
C 30

Cytosol–Endoplasmic Reticulum

Figure 1-2. Biosynthesis of terpenoids presented according to the compartmentation of the two
pathways. Terpene components of resins are indicated in boxes; volatile components have single
outline and nonvolatile components have double outline. DMAPP, dimethylallyl diphosphate;
DOXP, 1-deoxy-D-xylulose 5-phosphate pathway; FPP, farnesyl diphosphate; GGPP, geranyl-
geranyl diphosphate; GPP, geranyl diphosphate; IPP, isopentenyl diphosphate; MVA, mevalonic
acid or mevalonate pathway.
 TERPENOID RESINS | 29

characterizing some angiosperm families. Di- and triterpenes are nonvolatile

components of resin (Figure 1-2). Resins in most plants generally do not con-
tain both di- and triterpenes in the nonvolatile fraction, however, whereas all
conifers and some angiosperms contain both mono- and sesquiterpenes in
the volatile fraction. Both di- and triterpenes occur in a few genera of the
large tropical rain forest angiosperm family Burseraceae (Chapter 8).
Dimerization of the C20 precursor (GGPP) leads to C40 compounds, the
tetraterpenes, and addition of n C5 isoprene units (n > 8) results in polyter-
penes, well known as rubber and gutta percha. Tetraterpenes and polyter-
penes are not known to be constituents of resin, although resin components
may occur along with polyterpenes in several plants (Chapter 9).
Plant metabolism is extensively compartmentalized at the cellular level.
Compartmentation is significant in regulating terpenoid synthesis because it
allows independent control of different branches of the pathway at different
sites in the cell. Within a compartment, metabolic dynamics depend on the
kinds of enzymes (synthases) present and the permeability of intracellular
membranes to precursors, intermediates, and products.
The two different pathways to IPP appear to be compartmentalized (New-
man and Chappell 1999), with plastids, mitochondria, and cytosol–endoplas-
mic reticulum the compartments in which IPP is converted to various terpen-
oids (Kleinig 1989). Each compartment produces different products. For
resins, the mevalonate pathway operates in the cytosol-ER compartment to
produce sesqui- and triterpenes whereas the alternative DXP pathway operates
in plastids to produce mono- and diterpenes (Figure 1-2). The synthases that
produce terpenes differ for constitutive resin (preformed resin stored in secre-
tory structures) and induced resin (that synthesized at the site of an injury). In
fact, specialized secretory structures for many plant mono-, sesqui-, and diter-
penes, such as those found in resin, are apparently required for synthesis of
constitutive compounds (Gershenzon and Croteau 1990, 1993; Chapter 3).
Therefore, the differentiation of such structures may provide another form of
control over terpenoid production before any events are induced by injury.

Primary Versus Secondary Terpenoids

Although the basic pathways of terpenoid biosynthesis are present in all
plants, relatively few terpenoids are known to play vital roles in plant growth
and development in all plants; these few are considered primary metabolites.
30 | CHAPTER 1 What Plant Resins Are

For example, a sesquiterpene is a precursor to abscisic acid, and a diterpene

is an intermediate in the synthesis of the gibberellic acids; abscisic and gibber-
ellic acids are important plant growth regulators. Steroids are triterpene
derivatives that are essential components of cell membranes. The red, orange,
and yellow carotenoids (tetraterpenes) function as accessory pigments in
photosynthesis and further serve to protect photosynthetic tissues from dele-
terious photooxidative effects. Terpene-derived side chains (e.g., the phytol
side chain of chlorophyll) also help anchor certain molecules in membranes.
The vast majority of the 30,000 known terpenoids are secondary com-
pounds, lacking any apparent role in primary physiological or metabolic
processes in the plant. Thus terpenes are shown as part of secondary carbon
metabolism in Figure 1-1 because most that occur in resin are considered to
be secondary. Additionally, their formation originates from just a few inter-
mediates of primary metabolism, including acetyl coenzyme A, mevalonic
acid, and 3-phosphoglycerate. Many biochemists once thought that these ter-
penoids merely represented ways of disposing of excess acetate, that they
were waste products. With the subsequent rapid development of the field of
chemical ecology, terpenoid secondary compounds have been shown to play
major defensive roles in the survival of the plant and in various interactions
in ecosystems (Chapter 5). Chemists in the 19th and early 20th centuries also
recognized the value of such compounds to humans and began to call them
natural products to distinguish them from chemical compounds synthesized
by humans. The term natural products is commonly used and preferred to the
term secondary chemicals by some chemical ecologists (Romeo et al. 1996).

Enzymology
More than 30 genes have been isolated that encode terpene synthases (often
called cyclases because the reaction products are frequently cyclic), the
enzymes that catalyze formation of the basic skeleton of terpenoids. Sequence
comparison and phylogenetic analyses show that all known terpene synthases
share a common evolutionary origin (Mitchell-Olds et al. 1998, Phillips and
Croteau 1999, Trapp and Croteau 2001). However, Bohlmann et al. (1998b)
have suggested that there are some distinctive differences between gymno-
sperm and angiosperm synthases, indicating a bifurcation in primary metabo-
lism from a common ancestor. They assumed that this bifurcation implies an
independent functional specialization following separation of the gymno-
 TERPENOID RESINS | 31

sperm and angiosperm lineages. This evolutionary comparison of synthases

was made using resin-producing gymnosperms and terpenoid-producing (but
not resin-producing) angiosperms. For example, they found that functional
limonene synthases probably evolved separately in grand fir (Abies grandis)
and mints (Lamiaceae, or Labiatae). Moreover, Savage et al. (1994) found that
synthases producing similar terpenes are immunologically distinct in lodge-
pole pine (Pinus contorta) and grand fir. They hypothesized that there are dif-
ferent ways in which terpene synthase proteins catalyze allylic diphosphates to
cyclic products even between genera in the same family (Pinaceae in this case).
Terpenoid synthases are not very similar to other enzymes except the
mechanistically similar prenyltransferases. Isotopically sensitive branching
experiments and cDNA cloning demonstrate that some of these enzymes have
the unusual ability to synthesize multiple terpene products, which may rep-
resent a way to maximize diversity of compounds using minimal genetic
machinery. Furthermore, the compounds may be produced in fixed ratios,
thus contributing to the regulation of the relative proportions of compounds
in the resin, that is, its composition. These ratios underlie chemical adaptation
in individual trees and chemical diversity in populations (Katoh and Croteau
1998). Limonene synthase is an example of such a synthase, producing mul-
tiple monoterpenes that commonly occur in conifers, for example, (–)-
limonene, myrcene, and α- and β-pinene. Likewise, phellandrene synthase in
Pinus contorta produces α- and β-pinene as well as 3-carene and β-phellan-
drene (Savage et al. 1994) whereas (–)-pinene synthase in Abies grandis pro-
duces (–)-α- and (–)-β-pinene in a fixed ratio, 2:3 (Bohlmann et al. 1998b).
Monoterpenes such as these commonly occur in various conifer and angio-
sperm resins (Figure 1-3).
Expression of cDNAs for several Abies grandis monoterpene synthases
provides evidence that the complex mixture characterizing the resin forms
through a family of both single- and multiproduct enzymes encoded by
closely related genes (Bohlmann et al. 1997). Moreover, constitutive sesqui-
terpenes apparently are produced by even more remarkable synthases (Steele
et al. 1998a). The longer chain length and additional double bond of the far-
nesyl substrate allow greater mechanistic flexibility in the construction of dif-
ferent carbon skeletons. In A. grandis, δ-selinene synthase and γ-humulene
synthase yield 34 and 52 sesquiterpenes, respectively, from farnesyl diphos-
phate. These two constitutive sesquiterpene synthases are among the most
32 | CHAPTER 1 What Plant Resins Are

complex terpenoid synthases. In contrast to constitutive (preformed) sesqui-

terpenes, sesquiterpenes induced by injury, such as α-bisabolene and δ-cadi-
nene, are produced by single-product synthases. Thus there are differences
between synthases of constitutive and induced components of resins as well
as between those of primary and secondary terpenoids. Trapp and Croteau
(2001) have reviewed in detail the status of regulation, molecular genetics of
protein-based genetics, genomic intron and exon organization in conifer resin
biosynthesis, and important future challenges in identifying and isolating
genes in resin pathways.

Monoterpenes

Camphene Limonene β-Myrcene β-Phellandrene α-Pinene β-Pinene

Sesquiterpenes

α-Bisabolene δ-Cadinene β-Caryophyllene

γ-Humulene α-Cedrene γ-Muurolene δ-Selinene

Figure 1-3. Structures of some common mono- and sesquiterpenoids constituting conifer and
angiosperm resins that are used commercially (Chapters 7–10). They include some constituents
produced by multiproduct synthases.
 TERPENOID RESINS | 33

Terpenoid Loss
A balance between the rate of synthesis and rate of loss controls the accumu-
lation of any compound. In the plant’s economy, it is important whether there
is rapid metabolic turnover of secondary compounds, whether some may be
catabolized to primary metabolites late in the life of a plant organ, or whether
some may be released into the environment. A rapid rate of turnover (includ-
ing biosynthetic interconversion, conjugation reactions, and polymerization)
could increase the cost of maintaining a given concentration of defensive com-
pounds and is often thought to be a major component of the cost of plant
chemical defense (Gershenzon 1994a, b). Traditionally, terpenoid secondary
chemicals have been viewed as stable end products of metabolism, although
Burbott and Loomis (1969) demonstrated rapid turnover of monoterpenes
in leaves of detached stem cuttings of peppermint (Mentha). This report was
much cited, especially by ecologists. On the other hand, when Mihaliak et al.
(1991) repeated the experiments using rooted, intact plants, either low rates
or no turnover was detected, suggesting that short-term turnover of mono-
terpenes does not occur normally in mint leaves but is an artifact seen only in
cuttings. In further experiments to test various parameters that could affect
turnover in intact plants, Gershenzon et al. (1993) were unable to detect sig-
nificant turnover in developing leaves of species from a range of taxonomically
distant terpene-accumulating families that synthesize mono-, sesqui-, and
diterpenes and that store the products in various kinds of secretory structures.
In contrast to the lack of evidence for rapid or short-term turnover of
monoterpenes, it is well known that various mono-, sesqui-, di-, and triter-
penes (some of which occur in resin) may be lost from leaves late in their
development. Some monoterpenes in mature leaves of several mint species
are mobilized prior to senescence, when they no longer serve defensive roles
(Gershenzon 1994a, b). These terpenes can be catabolized to water-soluble
glycosides, which apparently are exported to the root and oxidatively
degraded to acetyl coenzyme A (Croteau and Martinkus 1979, Croteau and
Sood 1985, Croteau 1988). Thus, apparently, the fixed carbon of some ter-
penes can be recycled into usable primary metabolites for biosynthesis of new
materials (Figure 1-1). Evidence further suggests that synthesis, storage, and
catabolism of terpenes may be partially controlled by a balance of photosyn-
thesis and use of the photosynthate through growth and differentiation into
various structures and compounds (Loomis and Croteau 1973, Gershenzon
34 | CHAPTER 1 What Plant Resins Are

1994b). Although Gershenzon et al. (2000) found no evidence for monoter-

pene catabolism in peppermint, they suggested that large variances in mono-
terpene incorporation after pulse labeling may have prevented its detection.
Alternatively, they hypothesized that the degradation enzyme in mints may
detoxify monoterpenes that have come into contact with living cells follow-
ing damage to the secretory structures. Although catabolism of terpenes may
have considerable physiological and ecological significance, the data are frag-
mentary and little is known about the process or even if such catabolism
occurs in the complex mixture constituting resin.
Studies of Mentha have shown that the rate of monoterpene biosynthesis,
determined by 14CO2 incorporation, closely correlates with monoterpene
accumulation and appears to be the principal factor controlling the mono-
terpene level of peppermint leaves (Gershenzon et al. 2000). In addition to
lack of detection of catabolic losses through leaf development, volatilization
occurred at a low rate, which on a monthly basis represented less than 1% of
the total pool of stored monoterpenes. Composition of the volatilized mono-
terpenes was sufficiently different from the total plant monoterpene pool that
Gershenzon and coworkers suggested that the volatilized products may arise
from a separate secretory system, as inferred from previous studies using
other plant species (Chapter 3). It is not known if monoterpenes in a resin
respond differently when they are formed in different secretory structures,
especially with the evidence of terpenoid volatilization from conifers and its
role in tropospheric chemistry (Chapter 5).

Characteristic Components
Secondary compounds such as those constituting resin differ from primary
metabolites in having a restricted distribution in the plant kingdom. Usually,
they occur only in particular groups of related plants. Terpenoid resin occurs
in most conifer families but is widely scattered among the major evolutionary
lineages of angiosperms (Chapter 2). Specific terpenoid skeletal types, how-
ever, often characterize taxa such as particular families and genera; thus it has
been assumed that the evolutionary history of various taxa can be significant
to the understanding of the taxonomic distribution of some of these chemicals
(Gershenzon and Mabry 1983).
I introduce a few skeletal structures in this chapter to exemplify compo-
nents of resins in important conifer and angiosperm plant families, discussed
 TERPENOID RESINS | 35

as of value either to the plants themselves or to humans in later chapters.

Conifers only produce internally secreted terpenoid resin whereas angio-
sperms produce both terpenoid and phenolic resins, which may be secreted in-
ternally or on the surface of the plant. This is discussed in detail in Chapter 3.
In addition to the skeletal structure of the compounds, the complexity of
the mixture of compounds constituting a resin is important for ecological
interactions and human use. In general, among the 20–50 or more com-
pounds that constitute a resin, only a few occur in high concentration. The
relative proportions of the compounds in the mixture are called its composi-
tion, which may differ in constitutive and induced resins. Because this mix-
ture involves volatile and nonvolatile fractions, the composition of either
fraction (or just part of it) or both fractions may be analyzed and compared.
The volatile fraction, which has been most intensively studied, usually
consists of mono- and/or sesquiterpene hydrocarbons with some oxygenated
forms and, occasionally, diterpene hydrocarbons. The nonvolatile fraction
of resin is primarily composed of di- or triterpene acids with some alcohols,
aldehydes, and esters in addition to amorphous, neutral substances. The rela-
tive proportion of volatile to nonvolatile compounds, which can vary even
between species of the same genus, determines a resin’s fluidity, viscosity, and
polymerization rate. These in turn influence its ecological properties (Chap-
ter 5) as well as the methods used by humans to collect it (Chapters 7–10).

Conifer Resins
Conifer resins, such as those of the pine family (Pinaceae), are characterized by
a large volatile fraction (20–50%) with monoterpenes predominating over
sesquiterpenes. Both classes most commonly occur as hydrocarbons with a
few oxidized forms, often as trace components. Under natural conditions,
monoterpenes volatilize with varying degrees of rapidity, providing, for exam-
ple, the fragrant aromas in conifer forests during warm weather and those
from indoor Christmas trees. In fact, monoterpene hydrocarbons from these
resins may reach significant proportions in our atmosphere and become trou-
blesome as pollutants. In the soil, monoterpenes from resin may play a role in
the nitrogen cycle in conifer forests by inhibiting nitrification. On the other
hand, some may supply an energy source for forest soil microbes (Shukla et al.
1968), and others washed from conifer forest soils into estuaries may provide
energy for marine microbes (Button 1984). These volatile components of ter-
36 | CHAPTER 1 What Plant Resins Are

penoid resin (both mono- and sesquiterpenes) play a major defensive role
against insects and pathogens in amazingly intricate ways (Chapter 5). In com-
mercial use in the naval stores industry, the volatile mono- and sesquiterpenes
of pine resin produce turpentine, a product used worldwide in solvents and as
a feedstock for the flavor and fragrance industries (Chapter 7). Sesquiterpenes
(e.g., cedrene) are used as cedarwood oil, again particularly in the aroma
industry. Structures of some of the most common volatile mono- and sesqui-
terpenes in various conifer resins are shown in Figure 1-3. Note that the abun-
dant monoterpenes are often the ones produced by multiproduct synthases.

Abietane Type Pimarane Type

COOH COOH
Abietic acid Pimaric acid

Labdane Type

COOH COOH
Communic acid Ozoic acid

Clerodane Type Kaurane Type

COOH COOH
Hardwickiic acid Trachylobanic acid
Figure 1-4. Some common diterpene resin acids. Those with
abietane and pimarane structural types characterize conifer
resins whereas those with labdane structural types occur com-
monly in both conifers and angiosperms. The conjugated diene in
communic acid in conifers and ozoic acid in angiosperms enables
polymerization and, hence, formation of amber (Chapter 4).
 TERPENOID RESINS | 37

Nonvolatile terpenes in conifers are primarily diterpene acids. In pines,

these diterpenes constitute what is known commercially as rosin, which has
numerous uses but especially as a source of intermediate chemicals in various
industries (Chapter 7). The nonvolatile fraction increases the viscosity of the
resin, which can enhance the possibility of engulfing herbivores and other
organisms visiting the tree. Such trapped organisms can be beautifully pre-
served in fossilized resin. That is, certain terpenoids polymerize and, hence, are
able to withstand degradation under certain depositional conditions, form-
ing amber (Chapter 4). Extensive accumulations of fossilized resin are signif-
icant components of some coals and even petroleum deposits (Chapter 9).
Diterpenes in conifer resins are characterized by three main skeletal types
(abietane, pimarane, and labdane) that vary quantitatively in different coni-
fer families (Chapter 2). Abietane- and pimarane-type diterpenic acids, for
example, abietic and pimaric acids (Figure 1-4), are most abundant in resins
of Pinaceae, remaining relatively soft and unpolymerized. However, resins
with abietane-type compounds may sometimes become relatively solid with
a hard surface, probably as a result of an abietadiene precursor that is prone
to polymerization. On the other hand, labdane-type acids, such as communic
and agathic acids, may contain conjugated diene compounds that readily
polymerize. Labdane-type compounds are the primary diterpene constituents
in the cedar family (Cupressaceae). All three skeletal types occur in resins of
the araucarian family (Araucariaceae) although large quantities of labdanes
in Agathis result in the production of very hard copals as well as amber
(Chapters 4 and 9). In the Podocarpaceae and Cupressaceae s.l. (Chapter 2),
an oxidation rearrangement leads to the formation of phenolic diterpenes
such as ferruginol and totarol (Thomas 1990).

Angiosperm Resins
Although monoterpenes predominate in the volatile fraction of the resin of
the chemically best known conifers, such as Pinaceae, sesquiterpenes gener-
ally dominate the volatile composition in most, but not all, flowering plants.
For example, the volatile fraction in numerous genera of tropical trees in the
legume family (Fabaceae, or Leguminosae, Chapter 2) consists of sesquiter-
penes that most often occur as hydrocarbons (Figure 1-3). Caryophyllene is
an example of a sesquiterpene that commonly occurs in angiosperm resins.
The volatile fraction of resins from the large tropical family Dipterocarpaceae
38 | CHAPTER 1 What Plant Resins Are

also is composed of sesquiterpenes, similar to those in leguminous resins. In

both families there are genera in which the volatile fraction predominates,
thus producing a more fluid resin that has been used medicinally and for fuel
oil (Chapter 7), whereas in other genera the nonvolatile fraction predomi-
nates, resulting in a more viscous resin used for varnishes (Chapter 9).
On the other hand, the volatile fraction of resins in the large tropical fam-
ily Burseraceae is much more diverse than that of resins of legumes and diptero-
carps. It contains large proportions of both mono- and sesquiterpenes, giving
it the characteristic high degree of fragrance when used for incense (Chapter 8).
Monoterpenes that commonly occur in conifer resins are important in burser-
aceous resins, along with numerous sesquiterpenes with diverse skeletal frame-
works (Figures 1-3 and 1-5). Aregullin et al. (2002) found a sesquiterpene lac-
tone (8-β-hydroxasterolide) in Trattinnickia resin. This is the first report of a
sesquiterpene lactone, so common in the Asteraceae, in Burseraceae.
Diterpenes are the dominant components in the nonvolatile fraction of
leguminous resins. They form the very hard copals used for varnishes (Chap-
ter 9) because of the presence of labdadiene-type acids (or alcohols) such as
ozoic acid (Figure 1-4) or zanzibaric acid, which are enantiomers of commu-
nic acid. These components also can lead to fossilization of the resin in the
legume Hymenaea, as they do in the conifer Agathis (Chapter 4). Leguminous
resins also contain numerous other diterpenoids that do not polymerize, such
as the clerodane-type hardwickiic acid.
In some angiosperm families, triterpenes rather than diterpenes dominate
the nonvolatile composition of the resin. For example, triterpenes primarily
with tetra- or pentacyclic skeletons (Figure 1-5) characterize resins from the
large tropical families Burseraceae, Dipterocarpaceae, and Anacardiaceae.
Resins from Burseraceae typically have tetracyclic euphane / tirucallane, and
pentacyclic lupane, ursane, and oleanane triterpene skeletal types (Khalid
1985). Other structural types have been found in species of the chemically
complex myrrh-producing genus Commiphora (Waterman and Ampoto
1985), however, emphasizing the great structural diversity of triterpenoids in
Burseraceae. They have been much used medicinally (Chapter 8). Although
α- and β-amyrins (Figure 1-5) occur in other plants, they are known to be
components of resins only in the Burseraceae, where they are common. Inter-
estingly, in Bursera, diterpenes occasionally occur along with triterpenes
(Becerra et al. 2001).
 TERPENOID RESINS | 39

Although the nonvolatile fraction of dammar resins from the Dipterocar-

paceae also consists largely of triterpenes, the skeletal types are different from
those of Burseraceae; the nonvolatile fraction of dipterocarps consists pri-
marily of the tetracyclic dammarane series (Figure 1-5). The volatile fraction
is composed of sesquiterpenes; cadinenes in some taxa may polymerize to
form bicadinenes, structurally considered as triterpenoids (Chapter 4). Resins
from certain genera of Anacardiaceae have some triterpene components in
common with those of Dipterocarpaceae, but they are generally more numer-
ous and have not been completely characterized (Mills and White 1994).
The structures of more than 200 terpene compounds elucidated by Ghis-
alberti (1994) from the Australian resin-producing shrub family Myopor-
aceae demonstrate the complexity that can occur in one family of only three
genera. Myoporum, a small genus, is characterized by furanoid sesquiter-

Lupane Type Ursane Type

R R

HO HO
R = CH3 Lupeol R = CH3 α-Amyrin
R = CH2OH Betulin R = COOH Ursolic acid
R = COOH Betulinic acid

Oleanane Type Dammarane Type

HO HO
R = CH3 β-Amyrin Dammaradienol
R = COOH Oleanolic acid
Figure 1-5. Examples of some structural types common in triterpenoid resin compo-
nents in the large tropical families Burseraceae, Dipterocarpaceae, and Anacardiaceae
(Chapters 8–10).
40 | CHAPTER 1 What Plant Resins Are

penes (Figure 1-6); (–)-ngaione is the best known because it is toxic to live-
stock, but freelingyne was the first acetylenic terpene isolated from natural
sources. In contrast, species of the large genus Eremophila (Plate 21) accumu-
late quantities of diterpenes that are all structurally and stereochemically
unique. These diterpenes exhibit configurational differences from those of
conifers and angiosperms (particularly legumes), with labdane, abietane,
pimarane, and kaurane skeletons (Figure 1-4) that arise along the pathway to
the physiologically necessary gibberellins (Figure 1-2). Thus Richmond and
Ghisalberti (1994) suggested the possibility that diterpenes in Eremophila
are synthesized by processes different from those observed in most terrestrial
plants. Among the novel diterpenes, Eremophila generates numerous struc-
tural types (e.g., bisabolane, serrulatane, cedrane, and eremane) that bear
resemblance to sesquiterpenes (Figure 1-6). Eremophila resin is an example of
the amazing diversity of structural types that can occur even within one genus;
other such cases may become evident as more resins are analyzed in detail.

Phenolic Resins
Phenolic compounds, those that include an aromatic ring plus at least one
hydroxyl group (OH), are a dazzlingly diverse group of plant products. They
are equally diverse in function, which includes structural support (lignin),
pigmentation of flowers and other organs, protection from antioxidants and
ultraviolet light, signaling between plants and animals or microbes, and plant

Furanosesquiterpenes Diterpenes
(cedrane skeleton)
H
O
H
O
O
H
(−)-Ngaione

Figure 1-6. Novel sesquiterpenes and diterpenes characterize the

resins of the Australian desert shrub Eremophila (Myoporaceae),
including furanosesquiterpenes and diterpenes with skeletons that
bear a resemblance to sesquiterpenes, sometimes called
isoprenologues of sesquiterpenes.
 PHENOLIC RESINS | 41

defense. Such compounds frequently have several hydroxyl substituents, and

some of the hydroxyl groups are often further substituted to form ethers,
esters, or glycosyl (sugar) derivatives. Flavonoids, compounds with a C15
skeleton consisting of two benzene rings connected by a three-carbon bridge,
are one of the most bioactive phenolic groups. Highly hydroxylated or sugar-
substituted flavonoids are water soluble but many flavonoids are poorly
water soluble or lipophilic, as are some simpler phenolics. Such lipophilic
compounds are constituents of plant phenolic resins. Surprisingly, although
water-soluble phenolic compounds are abundant in conifers, phenolic resin
does not occur (Chapter 2). Internally produced phenolic resins occur only
sporadically in flowering plants. More commonly, lipophilic compounds are
intermixed with terpenoids in angiosperm resins, particularly those covering
the surface of young organs.

Synthesis and Characteristic Components

Several metabolic pathways are involved in the synthesis of the mixture of
components constituting phenolic resin. The shikimic acid pathway is the
source of aromatic amino acids such as phenylalanine (Figures 1-1 and 1-7). A
key step toward the formation of many components of phenolic resin is enzy-
matic conversion of phenylalanine to cinnamic acid, a reaction catalyzed by
the important regulatory enzyme phenylalanine ammonia-lyase (PAL). Cin-
namic acid is a simple C9 phenolic compound called a phenylpropane because
it contains a six-carbon (phenyl) benzene ring and a three-carbon (propyl) side
chain (C6–C3). Phenylpropanoids derived from cinnamic acid are building
blocks for many other phenolic compounds produced by the phenylpropanoid
biosynthetic pathway. For example, benzoic acid derivatives, with a skeleton
of a six-carbon benzene ring with a one-carbon substituent (C6–C1), are
formed from phenylpropanoids by cleavage of a two-carbon fragment from
the side chain. Cinnamic acid, benzoic acid, and its derivative, benzaldehyde
(Figure 1-8), occur in the internally produced phenolic resins of such different
plants as Myroxylon, leguminous trees that yield Peru balsam (Figure 8-2),
and Xanthorrhoea, the Australian grass tree (Plate 12 and Chapter 9).
Eugenol, found in numerous angiosperm resins, is synthesized in some cases
from a phenylpropane derivative. Lignans (e.g., nordihydroguaiaretic acid,
NDGA, Figure 1-8) are relatively common dimeric phenylpropanes that occur
in surface leaf resins in desert shrubs such as Larrea, creosote bush (Plate 14).
42 | CHAPTER 1 What Plant Resins Are

Flavonoid components of phenolic resin are based on a structure of two

benzene rings connected by a C3 bridge (C6–C3–C6), which is synthesized
from components of two distinct pathways. One benzene ring and the C3
bridge arise from the shikimic acid–phenylpropanoid pathway whereas the
other benzene ring is formed from acetate units via the malonic acid pathway
(Figures 1-1 and 1-7). Often, the C3 chain cyclizes with an adjacent hydroxyl

Acetyl CoA
Shikimic acid
pathway

Phenylalanine

Malonic acid
pathway
Phenylpropanoid
pathway

Phenylalanine
ammonia-lyase
(PAL)

Cinnamic acid

Phenylpropanoids Lipophilic Flavonoids

Phenolic Resin Components

Figure 1-7. Generalized biosynthetic outline of phenylpropanoids and

lipophilic flavonoids, two major groups of compounds characterizing
phenolic resins.
 PHENOLIC RESINS | 43

group to form an oxygen-heterocyclic ring, and various classes of flavonoids

are distinguished by the oxidation state of the C3 chain or heterocyclic ring.
Many flavonoids occur as water-soluble glycosides. Those lacking a sugar
substituent, called aglycones, often are lipophilic components of phenolic
resin; these components frequently are members of flavonoid structural sub-
classes called flavones, flavanones, or flavonols. Flavonoid aglycones bearing
fewer than five hydroxyl groups are hardly soluble in water. O-Methylation
or methylenedioxy ring formation are also ways to mask reactivity of phe-
nolic groups, at the same time increasing lipid solubility and volatility (Har-
borne 1980). Significant chemical features of the phenolics constituting resins
are a reduced number of hydroxyl substituents (Figure 1-8) and a variable
number of phenolic groups that are O-methyl substituted (methoxylated).
Such lipophilic flavonoids commonly co-occur with terpenoids, particularly
sesqui- and triterpenes (Wollenweber and Dietz 1981, Wollenweber and Jay
1988). Lipophilic flavonoids are less well studied than water-soluble ones
and are best characterized in bud exudates from northern temperate zone
angiosperm trees such as birches (Betula, Plate 33) and poplars (Populus)
and in leaf resins of arid-zone shrubs such as monkey flower (Mimulus, Plate
22) and yerba santa (Eriodictyon, Figure 2-15). Diplacone and diplacol,
lipophilic flavonoids from Mimulus, are shown in Figure 1-8.
Another way of introducing lipid solubility into phenolic compounds is to
attach a hydrophobic side chain. The allergenic phenolic (catechol) com-
pounds found in resins of Anacardiaceae are of this type (Figure 1-8; Chap-
ters 9 and 10). Alternatively, one or more terpene (prenyl) residues may be
attached to phenolic compounds to form prenylated phenolics (e.g., tetra-
hydrocannabinol, Figure 1-8). Most frequently, the terpenoid substituent is
attached directly to the benzene ring, but it also can be attached to a pheno-
lic group. Paseshnichenko (1995) summarized numerous prenylated pheno-
lics, pointing out that they occur in nearly every phenolic structural class. He
suggested that terpenoid and phenolic metabolism are linked through a con-
trol mechanism that regulates the distribution of precursors such as acetate,
required for biosynthesis of both terpenoids and phenolics. Phenylpropanoid
and flavonoid biosynthetic enzymes appear to form assemblies or complexes
that cluster at the ER (Hrazdina and Wagner 1985, Winkel-Shirley 1999).
Because the ER also appears to be the site of synthesis of most sesqui- and
triterpenes, the opportunity exists for close localization of the synthesis of
44 | CHAPTER 1 What Plant Resins Are

flavonoids and terpenoids and for their subsequent transport to a common

storage site. These findings provide a plausible biochemical explanation for
Wollenweber and Dietz’s (1981) and Wollenweber and Jay’s (1988) observa-
tion that lipophilic flavonoids frequently co-occur with sesqui- or triterpenes,
as well as explaining the existence of so many prenylated phenolics. Much
remains to be learned about the biosynthesis and co-occurrence of phenolics
with terpenoids, and doubtless many mixtures of terpenoids and phenolics in
resins will be reported.

Phenylpropanoids
O OH H
CH CH COOH C C O

Cinnamic acid Benzoic acid Benzaldehyde

Dimeric Phenylpropanoid Prenylated Phenol

OH
OH

OH
HO
O C5H11
OH
Nordihydroguaiaretic acid (NDGA) Tetrahydrocannabinol (∆1-THC)

Prenylated Flavonoid Phenolic Allergens

HO OH
OH
O OH

OH
OH R R
O
R = C15H23 Pentadecylcatechol
R = C17H23 Heptadecylcatechol
R = H Diplacone
R = OH Diplacol
Figure 1-8. Structures of some of the kinds of phenolic compounds characterizing
phenolic resins.
 SUBSTANCES CONFUSED WITH RESIN | 45

Substances Confused or Intermixed with Resin

Gums
Gums are often confused with resins, and terpenoid resins are frequently
called gums commercially. In fact, only relatively recently have importers and
exporters distinguished gum from resin in the naval stores industry (Chapter
7). Gum has not only been confused with resin but with latex-containing
polyterpenes, for example, rubber (gum boots) and chicle (chewing gum).
Clouding the issue further, a general definition of gum as “any plant sub-
stance that is both sticky and elastic as well as any glue used to bond sur-
faces” can be found in some dictionaries. Such definitions are not based on
properties that clearly distinguish the various sticky exudates such as gum,
resin, and latex (Table 1-1). Chemically, true gums are complex chains of
hydrophilic polysaccharides (complex sugars) derived from monosaccharide
(simple sugar) moieties such as galactose, arabinose, and rhamnose, and
hence, are neither terpenoid nor phenolic in origin. Whistler (1993) described
in detail the very complex structure of exudate gums.

Table 1-1
Characteristics of resins, gums, mucilages, oils, waxes, and latex. Secretory tissues
are discussed in detail in Chapter 3

PRIMARY COMPONENTS SOLUBILITY SECRETORY TISSUE

Resins Terpenoids; phenolic Lipid soluble Canals, pockets,

compounds cavities, trichomes,
epidermal cells
Gums Polysaccharides Water soluble Cavities
Mucilages Polysaccharides Water soluble Idioblasts, epidermal
cells, trichomes,
ducts, cavities
Oils (fats) Fatty acids and glycerol Lipid soluble None
Waxes Fatty acids esterified Lipid soluble Unspecialized
with long-chain alcohols epidermal cells
Latex Complex mixture, Lipid soluble Laticifers
may include
terpenoids, phenolic
compounds, proteins,
carbohydrates, etc.
46 | CHAPTER 1 What Plant Resins Are

Gum is also formed differently from resin. Gummosis, as formation of gum

is called, results primarily from metamorphosis of celluloses and hemicellu-
loses in the plant cell wall into unorganized amorphous substances. Starch
also may be a source of gum formation. Gums usually are thought to be
caused traumatically, induced by microbial infection as well as by insect
attack and mechanical injury (Fahn 1979). Therefore, Whistler (1993) con-
sidered gum an induced natural defense mechanism. However, some long-
time gum researchers do not agree that trauma is essential to the formation of
gum (D. M. W. Anderson, pers. comm.).
Fahn (1979) showed that the process of gummosis begins after the for-
mation of special groups of undifferentiated parenchyma cells, instead of nor-
mal wood elements, in some plant families. The rose family (Rosaceae),
including fruit trees such as cherry, peach, and plum, is a good example. Dis-
integration of cell walls (Figure 1-9) leads to formation of a cavity, which fills
with the polysaccharides that constitute gum. Vessels that carry water in the
wood also may be filled with gum, formed only from the lamella of the sec-
ondary cell wall; gum is also formed in bark tissue, however, as in Acacia
species that produce gum arabic. When this exuded gum material hardens, it
can produce masses that resemble resin. Where the gum touches the bark, it

surface wax
cuticle proper
cuticular layer
middle lamella
primary cell wall
secondary cell wall
plasma membrane

epidermal cell

Figure 1-9. Schematic drawing of wax on a leaf surface, showing the epidermal cells, their
plasma membranes, primary and secondary walls (with middle lamella above), covered by a
cuticular layer (formed by cutin, wax, and cell wall carbohydrates), the cuticle proper, consisting
of cutin embedded in wax, and a top coating of surface wax. Resin exuded from specialized
epidermal cells and glands can burst through the cuticle onto the leaf surface and become
intermixed with wax (Chapter 3).
 SUBSTANCES CONFUSED WITH RESIN | 47

may absorb tannins and become yellow. Confusion of gum with resin seems
to occur particularly in exudations from leguminous trees such as Acacia and
mesquite (Prosopis); these gums are yellow, similar to the color of some
resins, even amber.
Kino, which forms in the wood of plants such as Eucalyptus, is a type of
gum that contains polyphenols. Kino veins develop in the zone of traumatic
parenchyma cells produced by the cambium following injury. Groups of cells
accumulate large quantities of red phenolic compounds; then these cells break
down to form ducts into which the phenolics are released (Fahn 1979, Hillis
1987). The term kino is adapted from a West African word for gum from a
leguminous tree, African rosewood (Pterocarpus), which was used medici-
nally in Europe (Burkill 1966).
Some plants produce both gum and resin. Cell walls surrounding the
lumen of resin secretory structures in plants such as Commiphora and mango
(Mangifera) slough off during duct development, thus incorporating carbo-
hydrate material into their resin (Bhatt 1987). Halpine (1995) reported traces
of amino acids in resins of artists’ materials. She indicated that the hydroxy-
proline found in some resins may result from breakdown of cell walls because
the main cell wall protein, extensin, contains as much as 25% 4-hydroxy-
proline. Sometimes when resin is induced by injury, gummosis occurs as cavi-
ties are created during breakdown of the cells in which terpenoid resin is syn-
thesized. Again, in this manner, cell wall carbohydrates and, possibly, amino
acids can become incorporated into the resin (Chapter 3). These resins are fre-
quently referred to as gum resins because they may be slightly hydrophilic
before they harden or swell somewhat when first put into solvent. A number
of resins from both conifers and angiosperms belong to this category, such as
those from spruce (Picea) and Araucaria among conifers and from the trop-
ical leguminous Hymenaea and burseraceous Commiphora among angio-
sperms (Chapter 2).

Mucilages
The term mucilage is sometimes used colloquially to describe an aqueous
solution of gum because of certain similarities between the two substances.
However, mucilage and gum are clearly distinguishable by several criteria
(Table 1-1). Plant mucilages are water-soluble complex acidic or neutral poly-
saccharide polymers of high molecular weight; as with gums, some compo-
48 | CHAPTER 1 What Plant Resins Are

nents are closely related to cell wall compounds (e.g., galactose, arabinose,
xylose, rhamnose, and galacturonic acid). In fact, their occurrence involves
only a few enzymatic changes from these compounds. Differing from gum ,
however, mucilage occurs in various structures such as single secretory cells,
canals and cavities, epidermal cells, and trichomes. This variability is reflected
in the diversity of function and wide distribution of mucilages. For example,
they serve multiple roles in higher plants, such as reserve food sources, water
retention in succulents, lubrication for growing tips, regulation of germina-
tion in seeds, and seed dispersal.
Mucilage can become mixed with resin in surface coatings. In some
plants, such as alders (Alnus, Betulaceae), the buds and developing leaves or
their stipules, which envelop the shoot apex and leaf primordia, may bear
glandular trichomes that secrete sticky substances containing either mucilage
or resin, or both (Chapter 3). In Populus (Salicaceae), palisade-like epidermal
cells under the cuticle may secrete both resin and mucilage. Mucilage also
occurs commonly with phenolic leaf resin in leaves of the sticky monkey
flower (Mimulus, Scrophulariaceae). Apparently, the relative proportion of
mucilage to flavonoids varies between Mimulus species, which grow as herbs
in moist habitats and as shrubs in dry areas.

Oils and Fats

Many components of resin are referred to as oils. For example, mono- and
sesquiterpenes are called essential oils, cupressaceous resins with large quan-
tities of sesquiterpenes are called cedarwood oil, and some leguminous resins
are known as copaiba oil (Chapter 7). Oils and fats (and waxes), however, are
distinguished chemically from terpenes in being alcoholic esters of fatty acids.
Oils and fats are formed by synthesis of fatty acids from carbohydrates, fol-
lowed by the combination of these fatty acids through enzymatic action with
glycerol to form esters (triglycerides). Fatty acids are long hydrocarbon chains
that carry a terminal carboxyl group, giving them the characteristics of a
weak acid. Glycerol forms a link with the carboxyl groups, serving as a car-
rier for fatty acids.
Plant fats differ only slightly from oils in having fatty acid constituents
that are more or less solid rather than liquid at ordinary temperatures. Fatty
acids do occur in some conifer resins. For example, fatty acids (predomi-
nantly C18 oleic and linoleic) are co-isolated with rosin as by-products from
 SUBSTANCES CONFUSED WITH RESIN | 49

pine resins in the kraft pulping process (Chapter 7). They also occur in abun-
dance in the resin of glandular trichomes on the leaves of some Australian
shrubs (Chapter 3). The utility of oils and fats to the plant is a bit obscure,
although those in the seed constitute an abundant reservoir of stored energy
for early growth of the seedling.

Waxes
Waxes are not macromolecules but, rather, complex lipid-soluble mixtures
whose common components are alcoholic esters of fatty acids and straight-
chain alkanes, for example, CH3(CH2)24CH2OH and CH3(CH2)27CH3. Long-
chain ketones and aldehydes, and free fatty acids, also occur in waxes. Wax
occurs in almost all vascular plants as an important constituent of the cuticle,
which acts as a protective coating on the epidermis of leaves, stems, and
fruits, reducing desiccation or abrasion, or resisting pest attack (Figure 1-9).
Cuticular waxes are synthesized by epidermal cells; they leave these cells as
droplets, passing through pores in the cell wall into the cuticle. Wax, as the
top coating of the cuticle, often crystallizes into an intricate pattern of
platelets or rods, giving the surface a whitish bloom.
Other compounds may occur in waxes; hence, wax may differ chemically
in different organs and with age, season, and local conditions. Components
of resin such as various triterpenoids, for example, become intermingled in
cuticular wax (Wollenweber et al. 1998). In fact, they can become a major
constituent in some leaf waxes; for example, oleanolic acid forms 70% of
grape (Vitis) leaf wax. Even in glaucous species of the succulent genus Dud-
leya, β-amyrin in one species, taxarone in another, constitute about 40% of
the cuticular wax (Manheim and Mulroy 1978). In addition, resin produced
in epidermal glands may burst through secretory structures to mix with wax
on the leaf surface (Chapter 3).

Resin Compounds in Latex

Latex typically is a thick, creamy white, milky (as the Latin root lac indicates)
emulsion. Sometimes, it may be a thin, clear, yellow or orange, aqueous sus-
pension. In either case, latex comprises a complex of substances such as ter-
penoids—mono-, sesqui-, di-, tri-, and polyterpenes (rubber)—proteins, acids,
carbohydrates, tannins, alkaloids, and minerals (Table 1-1; Fahn 1979).
Often, resin is listed as a component of latex in members of some families
Other documents randomly have
different content
thought but to enjoy the meal he was preparing. When the meat
was cooked he ate greedily, then disappearing for a few seconds,
returned with more. This he disposed of in the same way.
For perhaps half an hour he continued to sit near the fire, but
rising in a regretful manner, at last, he covered the embers with
ashes, then disappeared and returned no more.
Until far into the night Ree and his four companions remained
watching, then cautiously withdrew. The moonlight filtered through
the leafless branches of the trees and the air was very frosty. For
warmth and rest Kingdom led the party to the hollow whitewood.
Here a conference was held and the decision reached to return to
the camp in the gully just before daybreak.
Whether the others slept Ree did not know. They all were
wrapped in their blankets and very quiet. But he knew that he did
not sleep, nor could he had he tried. The loss of John, the burned
cabin, the whole sorrowful end of all the bright hopes of a few
weeks before kept his thoughts too unhappily occupied, and he was
glad of the darkness that it concealed his grief and pain.
Sometime before dawn Sergeant Quayle stretched himself and
sat up. Kingdom did likewise and the others were also soon astir.
With the same care as before, they moved upon the haunted ravine,
and chose their places, each a little distance from the others, but all
where they could hurry down the steep hillside at a moment’s
notice.
The sun was just rising as the tenant of the lonely camp came
suddenly into the light, stretching himself and yawning.
The click of the Sergeant’s rifle as he cocked it was the signal,
and it sounded loud enough. Silently, swiftly and almost noiselessly
the five men descended the bluff, and, almost before the murderer’s
yawn permitted his mouth to close, it was open again, but this time
in extraordinary astonishment. He was surrounded by stern, strange
faces.
 CHAPTER XXIII—ONE MYSTERY
CLEARED AWAY

It was daylight when with parting war-whoops the Indians left the
scene of the terrible fire they had kindled, dragging John Jerome by
the thongs which bound him. But they took with them flames which
threatened even greater danger to the Paleface boy—the fires of
excitement, hate and merciless cruelty which the night’s barbarities
had kindled in their brains. John realized this full well. Though the
savages had been rough and brutal in their treatment of him before,
now they were still more so. No indignity, no suffering was too great
to be inflicted upon him.
Little wonder is it that on his own account poor John wished for
but two things—the slightest opportunity to escape, or the end of it
all quickly. Only the thoughts of Return, and how his friend would be
searching for him everywhere, as soon as news reached his ears,
buoyed up the wretched lad’s drooping spirits and gave him strength
to endure the cruelties heaped on his defenseless head.
Tired out after their night’s carousal, most of the savages lay
down to rest upon their arrival at the village, and John was allowed
also to sink into a troubled sleep, though watched constantly. It was
about noon when he fully awoke, to find that something out of the
ordinary was taking place. By degrees he discovered what it was,
learned that Captain Pipe had returned and that explanations were
being made concerning the burning of the cabin.
Lone-Elk took upon himself the whole responsibility for the
offense. The Little Paleface was a witch, he declared, and his
brother, the White Fox, was a spy upon the Indians, and on the
pretext of befriending Fishing Bird, had gone to Wayne’s camp to
carry word of the movements of the Delawares.
The Seneca would have put the loyalty of Fishing Bird himself to
the Delawares in question had he dared to do so, but he gained his
point without it; gained all he sought—praise for his own loyalty to
the cause of the Indians as a whole; no censure for the pillage and
destruction of the white boys’ cabin, and last and greatest of all, the
assurance that the captive, Little Paleface, would be put to death.
Let him be burned at the stake, Lone-Elk argued. Some of the
younger Delawares had never seen a prisoner suffer by fire. It would
warm their blood and teach them how to punish their enemies.
“By fire, then, let the witch be killed,” Captain Pipe had ordered,
and the terrible sentence reached John Jerome in his guarded hut a
little later.
Four warriors came. They roughly stripped him of all clothing
excepting his fringed buckskin trousers, and painted his face and
body black. Thus he was left for the time, as the hour of his torture
was to be the following morning. But he was told to prepare for
death and formed bluntly that with the rising of another sun he
would bid farewell to earth forever.
In vain did John ask to see Captain Pipe. The chief would not go
near him. He asked for Gentle Maiden, knowing that she would
intercede for him if she could. No word was taken to her. He asked
for Neohaw. The old medicine-man came. He heard the lad’s appeal,
and shook his head.
“Neohaw can do nothing,” he declared. “Lone-Elk is in favor with
all the Delawares and with their great chief, Hopocon. No one can
help the Little Paleface. Neohaw believes not that the Paleface
brother killed Big Buffalo. Yet all the Delawares have harkened to the
tale of the Seneca and the white boy must die. Let him then go
bravely to the fire. Let him sing boldly to the last the death songs
that his fathers taught him.”
John thanked the aged Indian for his sympathy and said no
more. He did feel better, somehow, to know that there was one
friend left in the village, where so many times he had been received
with greatest favor in days gone by, and resolved that if die he must,
it would be bravely.
Something very like tears, however, dimmed his eyes as he
thought of his unhappy end. He held them back with an effort and,
lest they come again, and be taken as evidence of fear or cowardice,
he prayed for strength to meet the awful fate he must suffer like a
man. He breathed a prayer for comfort for Ree Kingdom and for the
dear ones in far-away Connecticut, when the news of his death
should reach them.
It was night now. The Indians made the most of it. Their war
cries, as once again they engaged in the terrible dance, led, as
always, by the bloodthirsty Seneca, were frightful. But to John
Jerome a peace which passeth understanding had come, and with
thoughts of all the happy days his young life, so soon to close, had
known, and in his heart a trusting faith that One who died for others
would be with him to the end, he fell at last into soothing, restful
slumber.
At dawn John awoke. The village was quiet. The two savages
who stood guard over him seemed to be the only ones not still
asleep, save for a trio of squaws rekindling the fires before their
wigwams. The air was chill and raw, but crows were cawing lustily,
and a bluejay screeched his harsh song near by. Soon the sun rose,
pale but clear. It was a pleasant morning to be alive, a most gloomy
one to die.
Patiently the prisoner of the Delawares awaited the
executioners. They soon would come, he thought, and nerved
himself to meet them without a tremor. His lip quivered the least bit
and a lump came in his throat, but outwardly he was so calm that
the Indians watching him marveled at his courage, and told one
another in whispers that witches were more than human.
The morning went quickly by. Expecting each minute to see
Lone-Elk and others coming for him, time seemed to John to go both
slow and fast; slow, that no one came; fast, because each minute
was so precious. Hope had not wholly left him, either. It might be,
even now, he thought, that Neohaw or Gentle Maiden, or maybe
Long-Hair or Little Wolf, had successfully interceded in his behalf.
At last two Indians came to relieve those who guarded the
prisoner. The Delawares were stirring about in numbers now. John
asked the new guards for food and it was brought to him. Then
Neohaw came. In a kindly way he told the boy that the time of the
burning had been changed and the torture fire would not be lighted
until night. Against Lone-Elk’s wishes, Captain Pipe had decided on
this, as he had no wish to participate in the terrible festivities. He
planned to go away near evening and leave everything to the
Seneca.
All day the more cruel of the Delawares exhibited their
impatience. All day squaws were busy adding to the collection of
wood about the burning-post, set firmly in the ground at the edge of
the collection of huts and wigwams that comprised the town.
Between the logs of his prison John could plainly see all that went
on.
It was late in the afternoon. Night’s shades were deepening.
The sun had nearly sunk from view and a soft, golden light rested
for a time on the bosom of the little lake.
With a glad cry an Indian came leaping into the village. Fishing
Bird it was, and his joy at being safe at home once more was great.
In a moment, however, his happiness vanished. In a trice he
discovered the burning-post and the fagots piled near it. He guessed
its meaning instantly, and his fears were immediately confirmed as
he made inquiry.
Captain Pipe was just leaving the village but stayed a few
seconds to give Fishing Bird greeting. He listened gravely to the
younger Indian’s plea that the Little Paleface be spared. He shook
his head. Then Fishing Bird told of the rapid ride Return Kingdom
had made through the woods to save a Delaware’s life, and called
Long-Hair and Little Wolf to tell of the part they had had in that
undertaking.
“A council shall be held. The Delawares will give the one
accused of witchcraft a fair trial,” said the chief at last. “If then it is
found that, as a witch, the Little Paleface killed a warrior of the
Delawares, he must suffer the penalty. Fishing Bird can ask nothing
more.”
Very soberly the friendly Indian approached the place of the
white boy’s confinement and told him that for the present his life
was spared.
John’s happiness in seeing the loyal fellow once again, and in
having another friend at hand, was inexpressible. Soon he had
learned all that the Delaware could tell him concerning Ree and what
the latter had been doing.
“One thing, then, Fishing Bird, you must do for me,” he said.
“Let Ree Kingdom know that I am to have a trial. Get Captain Pipe
to let you bring him and his friends here.”
“Fishing Bird will bring them. Tell nobody,” the Indian whispered,
and withdrew.
Before the coming of another day the Indian friend of the boy
pioneers had left the village. He had found that the time of the
council the Delawares would hold to place Little Paleface on trial
would be the following afternoon. The torture fire would be lighted
in the evening, if the boy was found guilty, as was very certain to be
the case. It was with great news to tell and many conflicting
thoughts in mind, therefore, that he sped through the woods to
meet Return Kingdom at the spot agreed upon.
Thus while Fishing Bird hastened to the meeting place from one
point, Ree was making his way toward the same ledge of rocks from
another. Without the least difficulty the lone occupant of the
mysterious camp had been captured and taken away. While Jim
Small and another of the woodsmen watched the camp from the
bushes to surprise and make prisoners of any confederates of the
fellow, should such put in an appearance, Sergeant Quayle and the
fourth of his squad held the murderer in close quarters at the hollow
whitewood. Search of the camp would not be made, it was agreed,
until Kingdom’s return with Fishing Bird.
Ree and the Delaware reached the place of meeting at about
the same time. As the redskin came up, Kingdom searched his face
anxiously for some clue to the tidings he brought. It was vain to do
so. Indian-like, he could conceal his thoughts completely and he
wanted the pleasure of telling what he had accomplished before its
substance was surmised.
He soon did tell, however, all that had happened and very
soberly, indeed, did Ree receive the news. How glad he was that
Fishing Bird had reached the village so opportunely need not be told.
The great question was what could be done to rescue John Jerome?
“We’ll ask the Sergeant what he thinks about it,” said Kingdom
as the Delaware told more fully of the desperate situation their
friend was in. “Come, we must hurry. There’ll be not a minute to
lose.”
Another surprise awaited Ree when the old poplar was reached.
“Whist! The dirty British pig has tould iverything!” whispered
Sergeant Quayle, meeting Kingdom and the Indian at the edge of
the thicket. “A foine thing it is, too, so it is!” And with these words
the disgusted Irishman led the way forward.
Within the hollow tree there lay a great bulk of a fellow
groveling on the leaf-strewn earth, bewailing his fate, pleading for
mercy, and altogether making of himself a most miserable,
loathsome spectacle.
 “Oh, if I’d knowed it would come to this!” he blubbered. “Don’t
let them punish me! Oh, kind gentlemen, save me! Let me go away
and sin no more! Won’t some one speak a kind word to me?”
The abject fear of the craven, now that his crime had found him
out, would have been pitiable had his whole manner not been so
utterly contemptible.
Giving little heed to the guilty wretch, however, Ree at once
apprised the Sergeant of the news Fishing Bird had brought and the
latter was immediately sent to summon Jim Small and his
companions for a conference.
While he was gone Sergeant Quayle told, with many expletives
and many invectives against the British, the confession the murderer
had made. The fellow’s name, it developed, was Lobb. He had been
connected in an unofficial way with the British garrison at Detroit
and had served a number of times as a go-between for the English
officers in certain of their more or less secret dealings with the
Indians. In consequence of these services he was chosen to
accompany two men sent to encourage hostilities among the
savages to the south of Lake Erie and as near the border of the
American settlements as they should deem it prudent to go.
The party traveled by canoe, Lobb had said, and coasting along
the southern shore of Lake Erie, readied and ascended the
Cuyahoga river. In the course of this trip they fell in with Lone-Elk,
roaming the woods alone, as his frequent custom was. The Seneca
was not unknown to the men, for he had visited Detroit and offered
his services to the British when forced to flee from his home among
his own people.
 For various reasons, but principally because they feared some
news of their presence would reach Fort Pitt or Gen. Wayne, the
men concluded to do all their business with the Indians of the
locality through Lone-Elk. He would distribute their bounty, the
powder and the bullets they brought, also gold for those who cared
for it.
Not long had the men been in the vicinity when they decided to
visit the salt springs of which they had heard a great deal. To
conceal their identity they concluded, also, that they would make
some salt while there, pretending that such was the sole purpose of
their presence.
It was at the springs that Lobb’s cupidity got the better of his
natural cowardice and what little decency he possessed. With a view
to obtaining the gold in the party’s possession, and thinking then to
escape to the east in disguise, he concealed himself and shot both
his comrades just as they were preparing to leave the springs. To
convey the impression that Indians had done the awful deed he
scalped both men. Then, filled with fear lest the bodies be found
before he could get away, he had dragged them into the woods and
covered them with brush.
“Well, why did he hang around here? What did he say about the
lead mine?” asked Ree, as the Sergeant finished.
“Sure, it’s all the farther he wint with his black yarn, fer with ‘ye
dirty cur, ye!’ I give him a push an’ a shove an’ he landed where he’s
still layin’, hard an’ fast ferninst the ground there.”
Lobb was questioned further by Kingdom immediately. The boy
believed he saw in the loathsome creature’s story reason to believe
that the Delawares had been grievously deceived by the Seneca.
 Whining and groaning, the self-confessed murderer continued
his story. He had been afraid to go on east from the springs, he said,
and made all haste back to the Cuyahoga, where he and his
companions had established headquarters in a small cave, originally
pointed out to them by Lone-Elk.
From here he dared move in no direction. He was afraid to
return to Detroit—afraid to go east, west, north or south. Knowing of
the presence of the two boy pioneers, a few miles away, his fears
were greatly increased lest they discover him and guess his guilty
secret. Day after day, then, he had lived in the hole in the hillside,
coming out only at night to prepare food, or when forced to go in
search of fresh meat.
Imploring mercy and begging for freedom, the fellow concluded
his statement.
“You’ve told everything, have you!” Kingdom asked with as little
harshness as his feelings would permit.
“Aye, master, aye—everything,” Lobb whined.
“So it was you, then, who supplied Lone-Elk with lead and
bullets, and his story of a lead mine was a story and nothing more?”
the boy demanded.
“I guess so. I don’t know anything about a lead mine, master.
Truly I don’t know anything about it. I do remember though, come
to think, that Lone-Elk said once that I was his lead mine and I must
look out that the Palefaces didn’t find it out.”
“You hear that, Sergeant?” exclaimed Ree, with some
excitement. “Now let us see whether that sneaking Seneca will
continue to rule the Delawares!”
 CHAPTER XXIV—WHO KILLED BIG
BUFFALO

Even before Kingdom finished questioning the murderer, Fishing Bird

had come up bringing the two woodsmen from the gully. All three
were quickly informed of Lobb’s confession and of the discovery of
John Jerome and the great danger surrounding him. The entire party
looked to Ree for a suggestion.
“We’ve got to act and act quickly,” the lad said in a low tone. “If
Fishing Bird will be our escort, I propose that we go to the Delaware
town as fast as we can go. If Captain Pipe can be made to
understand that Lone-Elk has deceived the Delawares in one way,
we can, with Fishing Bird’s help, and Lobb’s confession, bring him to
his senses about this witchcraft business.”
“Lone-Elk’s a bad ’un. He killed a Seneca and had to leave
home,” put in Lobb, who had listened attentively.
“Huh!” snorted Sergeant Quayle. “Cain killed Abel an’ had to
leave home; but he didn’t go bush-whackin’ two men from behind!”
“And what about Mr. Lobb, anyhow! We can’t leave him, once
we’ve had the pleasure of his company?” put in Jim Small, with
sarcasm.
“Take him along,” said another of the woodsmen.
 “Yes, that is what I had in mind,” Ree answered. “He can tell
Pipe what he has told us. But we must be moving, men! It’s a long
tramp and time’s flying!”
Without loss of time the party got under way. No one
questioned the wisdom of Kingdom’s plan, although, if the truth
were known, two of the men at least, looked for a lively scrimmage
as a result of the undertaking. But they did not falter. Indeed, it is a
question if they did not rather relish the prospect of a brush with the
Delawares. Lobb was completely disarmed but he was not bound.
“I give ye my word, master, I’ll not try get-tin’ away,” he said.
“Whist! Give me yer chances in the hereafter; one’s as good as
’tother,” retorted the Sergeant contemptuously, and then informed
the murderer further that the slightest attempt on his part would
result in his being shot first and asked as to the meaning of it
afterward.
The fellow made some very humble answer but he grew
decidedly thoughtful and rather sullen as the marchers hurried
rapidly through the woods. There was a gleam of satisfaction in his
eyes, too, when the party passed the clearing and saw only a heap
of ashes and the chimney where the boys’ cabin had stood. He was
thinking. He was planning to betray his captors and with Lone-Elk’s
help to turn the tables upon them. How well he succeeded will soon
be told, for now comes a part of this history which all participants
therein remembered throughout their lives, and which left its
impress upon the people of Captain Pipe’s town long after the village
itself had ceased to be.
The day was bright and clear. Though not warm, neither was it
very cold, and the south wind which sighed in the leafless branches
of the trees and gently rippled the waters of the little lake seemed
soft as velvet. The Delawares were in fine spirits. With savage
rapture they looked forward to the terrible celebration the night
would bring.
From the lower towns on the Muskingum Captain Pipe had
brought encouraging news of Indian successes along the border and
almost without exception his warriors were enthusiastic for the final
conflict with Wayne’s “Legion,” which, they believed, would not be
long in coming. They felt perfect confidence as to the outcome. They
had seen his raw recruits. They did not know then that “Mad
Anthony” had no intention of marching upon them until his troops
were trained. This and much else they learned in time and to their
sorrow.
But there was another reason for a feeling of happiness in the
Delaware town, and particularly was Lone-Elk, the Seneca, in a good
humor. This very day there had arrived the two warriors whom
Captain Pipe had sent with an offering of white wampum to the
friends of him Lone-Elk had slain. Not as compensation, not as
damages for the injury done, had the gift of wampum pure and
white been sent, but as a plea for forgiveness; as a symbol of the
slayer’s penitence and sorrow.
It was somewhat unusual for an offering of peace to be
accepted so long after the crime had been committed, and it was
known, too, that Lone-Elk’s offense had been particularly cruel. So
was there very good reason for the Seneca to shake hands with his
Delaware friends and receive their congratulations.
Captain Pipe thought the outcast seemed less truly sorry for his
crime than he should have been. He little liked the haughty manner
in which the one so lately restored to a place of honor and respect in
his own tribe and nation bore himself. Perhaps he thought, also, that
the Seneca was less appreciative of the service rendered him than
he should have been. Nevertheless he gave the bold warrior his
hand and told him that, though he was now free to return to his own
people, he would have a place of honor among the Delawares as
long as he chose to remain with them.
John Jerome heard by degrees of what had happened. He
wondered if the Seneca would not now be less bitter toward him,
and more fair and honorable. But he was grievously disappointed.
Lone-Elk showed himself more hostile, if possible, than before; more
keen to carry out his plot to avenge the pretended killing of Big
Buffalo by witchcraft; more intense in his hatred.
As he learned just how matters stood, John’s only hope for
escape lay in Return Kingdom and the men of whom Fishing Bird
had told him. He knew they would attempt to rescue him, but seeing
how greatly they were out-numbered, fear of the outcome worried
him more and more. It was bad enough for him to suffer, he
declared within himself, again and again, without dragging Ree and
others to the same fate.
The hour of the council to inquire into the guilt of the prisoner
arrived. The Indians assembled and once again John found himself
in the long, low bark house where always in the past he had met the
Delawares as friends. Captain Pipe and every buck and warrior of
the village was in attendance; but more conspicuous than any of
them, more proud and more erect, was Lone-Elk, the Seneca. In his
hands he held the hatchet brought by him from the cornfield of the
young Palefaces, the hatchet with which, he said, Big Buffalo had
been slain. It was the evidence that-would substantiate his story of
the witch’s work.
Captain Pipe stated the purpose of the council briefly and
quietly. Then he informed the prisoner that the Delawares would
hear what he had to say, but urged him to confess his sin and not,
on the eve of death, be guilty of a lie.
With face and body blackened, his hands bound to a stick
behind him, the accused boy arose. He tried to be bold and fearless,
but, though he looked the Indians squarely in the eyes, he could not
speak as he wished to do. His voice did not falter, but the words
seemed somehow to refuse to come.
The charge against him was false, he said, and time would
prove it. Never except in fair fight had he harmed any Indian. He
would leave it to Captain Pipe to judge if he had not always
conducted himself as a friend of the Delawares. He reminded them
how, only the past winter, he had brought their women and children
food while the able men were away for the fighting that had taken
place. With a suppressed sigh as he saw how little impression he
had made on the hostile faces round him, John sat down.
In an instant Lone-Elk was on his feet. With head thrown back
and flashing eyes he repeated the story of the cloud which drifted
over the lake—repeated again the whole miserable tale he had told
so many times before. Then he exhibited the hatchet taken from the
shock of corn on which a crow of most strange appearance had the
same day been seen.
 THEY ASKED HIM TO GO WITH
THEM.

“Lone-Elk well knows who put the tomahawk where he got it,
Captain Pipe,” the prisoner found courage to say. But for doing so
the warriors beside him smartly rapped his head with their knuckles,
and the Seneca gave him a look of hate so fierce, so vindictive it
startled him.
“The white brother’s time for speech is over,” the chief made
answer coldly, and Lone-Elk now resuming his seat, he said: “The
Delawares will hear any who wish to speak further.”
 A travel-stained figure glided swiftly from the door to Captain
Pipe’s side and spoke to him in quick, low tones that few could hear.
It was Fishing Bird.
“There are Palefaces who wait with a white flag, Palefaces who
wish to be heard,” the chief announced, in the Delaware tongue.
“Fishing Bird may bring them here.”
Lone-Elk, with glaring eyes, rose hastily and would have
remonstrated but with a kindly, yet imperious wave of his hand
Captain Pipe motioned to him to sit down, and he obeyed.
In another minute Return Kingdom, followed by five other white
men, stepped into the Council House.
“Captain Pipe,” said Kingdom at once, “we have put down our
guns and come here without arms to say a few words to the
Delawares which they may be surprised to hear. The Delawares are
in council and it is a proper time to speak to them. We ask nothing
more than that you let us be heard.”
“The Delawares will listen to White Fox,” the chief answered.
“While the council lasts we shall be as friends. When it is over the
Paleface brothers may go their way.”
“We thank Captain Pipe and all the Delawares,” Kingdom
answered in clear, loud, friendly tones. “We have come to you with
important news. We are received as your friends and we shall be
such while in your village. The news we bring will not be pleasant to
all of you. For the Delawares have been deceived. There is one here
who has led Captain Pipe and many of his people to believe he knew
of a secret mine from which he could supply them with much lead
and with bullets.”
 Kingdom paused for an instant, and as he did so Lone-Elk for
the first time caught sight of Lobb standing between two of the
woodsmen. The look he darted toward the fellow was venomous.
There is no doubt but what he thought the Englishman had revealed
his secret, then led the white men thither to betray him.
But after the one quick, black look the Seneca seemed quite
indifferent to the presence of any of the white men. He concealed
his thoughts completely and the Delawares who cast questioning
glances toward him were amazed at his composure. Not so with
Captain Pipe, however. He had seen on Lone-Elk’s brow the awful
scowl which came and went so quickly, and to him it spoke volumes.
The pause in Kingdom’s speech was very short, and few of the
Delawares noticed for a time the effect his words had produced
upon their chief. It was not until later that they saw on his face the
fixed expression of stony coldness dreaded by all of them.
“There is one among you who has sought to advance himself
and his own ambitions by taking advantage of the other Indians,”
Kingdom went on. “Three white men were sent from Detroit with
lead, bullets, powder and gold for the Delawares and other warriors
hereabouts. To one Indian only were the lead and bullets and
powder given. True, he gave them to the Delawares, but he led
them to believe that from a secret mine did he obtain the supplies
he brought them. So did he gain power and influence with Captain
Pipe’s people.
“Now, hear me further. Two of the three men sent by the British
to carry stores from Detroit for the Delawares and others have been
murdered. The third man killed them. He has confessed his crime
and told the whole story of why the Indians did not all share equally
in the goods brought for them. This man is here!”
Putting all the emphasis he could muster into his closing
sentences, Kingdom signalled his friends as he concluded, and Lobb,
trembling and ashy pale, was pushed into the foreground.
“You have heard what I have told the Delawares,” Kingdom
quietly said. “Do you know if it is true?”
The boy’s voice was calm and low, but in the death-like silence
of the Council House every word was plainly heard by all, and with
intensest interest the savages awaited the answer.
“Yes; it’s true,” muttered Lobb with a look half of terror, half of
appeal and apology toward the Seneca.
“Now point to the one who received the gifts intended for all the
Indians, not for him alone,” Kingdom commanded.
The murderer looked anxiously about him. He trembled so he
could hardly stand, but made no other move.
“Point!” thundered Kingdom. “You know him well!”
“There!” came with a groan from the frightened fellow’s lips,
and his outstretched finger indicated Lone-Elk.
On the Seneca’s face there was an expression so threatening
that even Kingdom was alarmed. But he continued his talk boldly.
“He who has deceived the Delawares in one way will deceive
them in another. Will they listen when his voice is raised against one
who has always been their friend? Will the Delawares allow him to
shield himself from suspicion by telling them Big Buffalo was killed
by witchcraft? Will they do this? Are the Delawares men? Have they
not honor and fairness?”
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