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Environmental Chemistry for a Sustainable World

Grégorio Crini · Eric Lichtfouse Editors

Green
Adsorbents
for Pollutant
Removal
Innovative materials
Environmental Chemistry for a Sustainable
World

Series Editors
Eric Lichtfouse, CEREGE, Aix Marseille Univ, CNRS, IRD, INRA, Coll France,
Aix-en-Provence, France
Jan Schwarzbauer, RWTH Aachen University, Aachen, Germany
Didier Robert, CNRS, European Laboratory for Catalysis and Surface Sciences,
Saint-Avold, France
 Other Publications by the Editors

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Organic Contaminants in Riverine and Groundwater Systems

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Grégorio Crini • Eric Lichtfouse
Editors

Green Adsorbents
for Pollutant
Removal
Innovative materials
Editors
Grégorio Crini Eric Lichtfouse
Laboratoire Chrono-environnement, CEREGE, Aix Marseille Univ, CNRS, IRD,
UMR 6249, UFR Sciences et Techniques INRA, Coll France
Université Bourgogne Franche-Comté Aix-en-Provence, France
Besançon, France

ISSN 2213-7114     ISSN 2213-7122 (electronic)

Environmental Chemistry for a Sustainable World
ISBN 978-3-319-92161-7    ISBN 978-3-319-92162-4 (eBook)
https://doi.org/10.1007/978-3-319-92162-4

Library of Congress Control Number: 2018946780

© Springer Nature Switzerland AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
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Preface

A further aspect of water pollution control is the treatment methods by which this control is
to be achieved. The term BATNEEC is now used and means Best Available Technology Not
Entailing Excessive Cost. It is likely that adsorption will find its way into this group of
water treatment technologies. (Gordon McKay 1995)

Over the past three decades, there has been an increasing interest in the phenom-
enon of contaminant sequestration by nonconventional green adsorbents using ori-
ented-adsorption processes. This phenomenon has a high potential for applications in
water and wastewater treatments. Liquid-solid adsorption using green adsorbents can
be simply defined as the removal of contaminants from solutions using products and
by-products of biological, agricultural, and industrial origin. Green adsorbents repre-
sent cheap filter materials often with high affinity, capacity, and selectivity to interact
with contaminants. They are abundant and already available in most places in large
quantities. The list of green adsorbents is extremely extensive, including carbons
from agricultural solid wastes and industrial by-products; agro-food wastes; indus-
trial by-products; natural products, e.g., clays, hemp, flax, and cotton; and biological
materials such as dead biomass, living plants, algae, biopolymers, and fungi.

Cultivation of Lepista nuda, named “blue foot” in French, an edible mushroom, on a composted
substrate. (Copyright: INRA, Jacques GUINBERTEAU 2018)

This book is the second volume of two volumes on Green Adsorbents for Pollutant
Removal published in the series Environmental Chemistry for a Sustainable World.
v
vi Preface

Written by 80 international contributors coming from 23 different countries who are

leading experts in the adsorption field, these two volumes show a typical selection of
green materials used in wastewater treatment, with emphasis on industrial effluents. The
first volume provides an overview of fundamentals and design of adsorption processes.
This second volume focuses on innovative materials. The first chapter by Nadia
Morin-Crini et al. presents hemp-based materials for metal removal. The second chapter
by Leticia B. Escudero et al. describes the biosorption of metals and metalloids on vari-
ous materials. In Chap. 3, Ioannis Anastopoulos et al. present the use of leaves for metal
removal. Then, Anita George Varghese et al. discuss the recent advances in cellulose-
based adsorbents used in environmental purposes in Chap. 4. Ramonna Kosheleva et al.
(Chap. 5), Liliana Giraldo et al. (Chap. 6), and Viraj Gunarathne et al. (Chap. 7) review
activated carbons from food wastes, aerogels and bones, and municipal solid waste
biochar as efficient materials for pollutant removal, respectively. Biosorption of dyes
onto microbial biosorbents is presented by Uttariya Roy et al. in Chap. 8. In Chap. 9,
Shweta Kulshreshtha discusses the use of mushroom biomass to remove pollutants. A
detailed review of green adsorbents for removal of antibiotics, pesticides, and endocrine
disruptors is given by Akeem Adeyemi Oladipo et al. in Chap. 10. In Chap. 11, Prashant
Pandey and Vipin Kumar Saini review the use of pillared interlayered clays as innova-
tive materials for pollutant removal. Finally, in Chap. 12, Dharmendra K. Gupta et al.
discuss the use of green adsorbents for radioactive pollutant removal from natural water.
The audience for this book includes students, environmentalists, engineers, water
scientists, and civil and industrial personnel who wish to specialize in adsorption
technology. Academically, this book will be of use to students in chemical and envi-
ronmental engineering who wish to learn about adsorption and its fundamentals. It
has also been compiled for practicing engineers who wish to know about recent
developments on adsorbent materials in order to promote further research toward
improving and developing newer adsorbents and processes for the efficient removal
of pollutants from industrial effluents. However, the book is not meant to be an
extensive treatise on adsorption and adsorbents. For example, particular aspects on
modeling or biosorption are not considered because the reader can find abundant
information on these topics in the literature. The book will serve two main func-
tions: a readable and useful presentation not only for undergraduate and postgradu-
ate students but also for the water scientists and engineers and a convenient reference
handbook in the form of numerous recent examples and appended information.
The editors extend their thanks to all the authors who contributed to this book for
their efforts in producing timely and high-quality chapters. The creation of this book
would not have been possible without the assistance of several friends deserving
acknowledgment. They have helped by choosing contributors, by reviewing chap-
ters, and in many other ways. Finally, we would like to thank the staff at Springer
Nature for their highly professional editing of the publication.

Besançon Cedex, France Grégorio Crini

Aix-en-Provence Cedex, France Eric Lichtfouse
Contents

1 Hemp-Based Materials for Metal Removal ������������������������������������������    1

Nadia Morin-Crini, Sonia Loiacono, Vincent Placet,
Giangiacomo Torri, Corina Bradu, Mirjana Kostić,
Cesare Cosentino, Gilles Chanet, Bernard Martel, Eric Lichtfouse,
and Grégorio Crini
2 Biosorption of Metals and Metalloids����������������������������������������������������   35
Leticia B. Escudero, Pamela Y. Quintas, Rodolfo G. Wuilloud,
and Guilherme L. Dotto
3 Leaf Biosorbents for the Removal of Heavy Metals�����������������������������   87
Ioannis Anastopoulos, Artis Robalds, Hai Nguyen Tran,
Dimitris Mitrogiannis, Dimitrios A. Giannakoudakis,
Ahmad Hosseini-­Bandegharaei, and Guilherme L. Dotto
4 Cellulose Based Green Adsorbents for Pollutant Removal
from Wastewater�������������������������������������������������������������������������������������� 127
Anitha George Varghese, Sherely Annie Paul, and M. S. Latha
5 Activated Carbon from Food Waste������������������������������������������������������ 159
Ramonna Kosheleva, Athanasios C. Mitropoulos,
and George Z. Kyzas
6 Water Depollution Using Activated Carbons from Aerogels
and Bones�������������������������������������������������������������������������������������������������� 183
Liliana Giraldo, Juan Carlos Moreno-Piraján, Rafael A. Fonseca,
Pablo. Húmpola, and Héctor S. Odetti
7 Municipal Waste Biochar for Energy and Pollution
Remediation���������������������������������������������������������������������������������������������� 227
Viraj Gunarathne, Ahamed Ashiq, Maneesha Prasaad
Ginige, Shashikala Dilrukshi Premarathna, Ajith de
Alwis, Bandunee Athapattu, Anushka Upamali
Rajapaksha, and Meththika Vithanage

vii
viii Contents

8 Dye Removal Using Microbial Biosorbents ������������������������������������������ 253

Uttariya Roy, Suvendu Manna, Shubhalakshmi Sengupta,
Papita Das, Siddhartha Datta, Aniruddha Mukhopadhyay,
and Avijit Bhowal
9 Mushroom Biomass and Spent Mushroom Substrate As Adsorbent
to Remove Pollutants ������������������������������������������������������������������������������ 281
Shweta Kulshreshtha
10 Green Adsorbents for Removal of Antibiotics, Pesticides
and Endocrine Disruptors���������������������������������������������������������������������� 327
Akeem Adeyemi Oladipo, Ayodeji Olugbenga Ifebajo,
and Roozbeh Vaziri
11 Pillared Interlayered Clays for Pollution Remediation������������������������ 353
Prashant Pandey and Vipin Kumar Saini
12 Green Sorbents for Radioactive Pollutants Removal
from Natural Water �������������������������������������������������������������������������������� 377
Dharmendra K. Gupta, Anna Vladimirovna Voronina,
Vladimir Sergeevich Semenishchev, and Soumya Chatterjee

Index������������������������������������������������������������������������������������������������������������������ 397
Contributors

Ioannis Anastopoulos Department of Agrobiotechnology, Agricultural Research

Institute, Nicosia, Cyprus
Ahamed Ashiq Environmental Chemodynamics Project, National Institute of
Fundamental Studies, Kandy, Sri Lanka
Bandunee Athapattu Department of Civil Engineering, The Open University of
Sri Lanka, Nawala, Nugegoda, Sri Lanka
Avijit Bhowal Department of Chemical Engineering, Jadavpur University, Kolkata,
India
Corina Bradu Research Center for Environmental Protection and Waste
Management, University of Bucharest, Bucharest, Romania
Gilles Chanet Eurochanve, Arc-les-Gray, France
Soumya Chatterjee Defence Research Laboratory, Defence Research and
Development Organization (DRDO), Ministry of Defence, Tezpur, Assam, India
Cesare Cosentino Istituto di Chimica e Biochimica G. Ronzoni, Milan, Italy
Grégorio Crini Laboratoire Chrono-Environment, UMR 6249, UFR Sciences et
Techniques, Université Bourgogne Franche-Comté, Besançon, France
Papita Das Department of Chemical Engineering, Jadavpur University, Kolkata,
India
Siddhartha Datta Department of Chemical Engineering, Jadavpur University,
Kolkata, India
Ajith de Alwis Department of Chemical and Process Engineering, University of
Moratuwa, Katubedda, Sri Lanka
Guilherme L. Dotto Chemical Engineering Department, Federal University of
Santa Maria, UFSM, Santa Maria, RS, Brazil

ix
x Contributors

Leticia B. Escudero Laboratory of Analytical Chemistry for Research and

Development (QUIANID), Interdisciplinary Institute of Basic Sciences (ICB),
UNCUYO–CONICET, Faculty of Natural and Exact Sciences, National University
of Cuyo, Mendoza, Argentina
Rafael A. Fonseca Faculty of Sciences, Research Group in Porous Solids and
Calorimetry, University of the Andes, Bogota, Colombia
Dimitrios A. Giannakoudakis Laboratory of General & Inorganic Chemical
Technology, Department of Chemistry, Aristotle University of Thessaloniki,
Thessaloniki, Greece
Maneesha Prasaad Ginige Centre for Environment and Life Sciences, CSIRO
Land and Water Flagship, Floreat, WA, Australia
Liliana Giraldo Faculty of Sciences, National University of Colombia, Bogotá,
Colombia
Viraj Gunarathne Environmental Chemodynamics Project, National Institute of
Fundamental Studies, Kandy, Sri Lanka
Dharmendra K. Gupta Gottfried Wilhelm Leibniz Universität Hannover, Institut
für Radioökologie und Strahlenschutz (IRS), Hannover, Germany
Ahmad Hosseini-Bandegharaei Wastewater Division, Faculty of Health,
Sabzevar University of Medical Sciences, Sabzevar, Iran
Department of Engineering, Kashmar Branch, Islamic Azad University, Kashmar,
Iran
Pablo. Húmpola Faculty of Biochemical and Biological Sciences, National
University of the Littoral, Santa Fe, Argentina
Ayodeji Olugbenga Ifebajo Department of Chemistry, Faculty of Arts & Science,
Eastern Mediterranean University Famagusta, Famagusta, Turkey
Ramonna Kosheleva Hephaestus Advanced Laboratory, Eastern Macedonia and
Thrace Institute of Technology, Kavala, Greece
Mirjana Kostić Faculty of Technology and Metallurgy, University of Belgrade,
Belgrade, Serbia
Shweta Kulshreshtha Amity Institute of Biotechnology, Amity University
Rajasthan, Jaipur, Rajasthan, India
George Z. Kyzas Hephaestus Advanced Laboratory, Eastern Macedonia and
Thrace Institute of Technology, Kavala, Greece
M. S. Latha Department of Chemistry, Sree Narayana College, Chengannur,
Kerala, India
Contributors xi

Eric Lichtfouse CEREGE – Centre européen de recherche et d’enseignement des

géosciences de l’environnement, Université Aix-Marseille, Collège de France,
CNRS, INRA, IRD, Europôle Méditerranéen de l’Arbois, Aix-en-Provence, France
Sonia Loiacono Laboratoire Chrono-Environment, UMR 6249, UFR Sciences et
Techniques, Université Bourgogne Franche-Comté, Besançon, France
Suvendu Manna Department of Chemical Engineering, Jadavpur University,
Kolkata, India
Bernard Martel University of Lille, CNRS, INRA, ENSCL, UMR 8207, UMET –
Unité Matériaux et Transformations, Lille, France
Dimitris Mitrogiannis Department of Natural Resources Management and
Agricultural Engineering, Agricultural University of Athens, Athens, Greece
Athanasios C. Mitropoulos Hephaestus Advanced Laboratory, Eastern Macedonia
and Thrace Institute of Technology, Kavala, Greece
Juan Carlos Moreno-Piraján Faculty of Sciences, Research Group in Porous
Solids and Calorimetry, University of the Andes, Bogota, Colombia
Nadia Morin-Crini Laboratoire Chrono-Environment, UMR 6249, UFR Sciences
et Techniques, Université Bourgogne Franche-Comté, Besançon, France
Aniruddha Mukhopadhyay Department of Environmental Science, University of
Calcutta, Kolkata, India
Héctor S. Odetti Faculty of Biochemical and Biological Sciences, National
University of the Littoral, Santa Fe, Argentina
Akeem Adeyemi Oladipo Faculty of Engineering, Cyprus Science University
Ozankoy-Girne, Girne, Turkey
Prashant Pandey School of Environment and Natural Resources, Doon University,
Dehradun, India
Sherely Annie Paul Department of Chemistry, Bishop Moore College, Mavelikara,
Kerala, India
Vincent Placet FEMTO-ST Institute, CNRS/UFC/ENSMM/UTBM, Department
of Applied Mechanics, Bourgogne Franche-Comté University, Besançon, France
Shashikala Dilrukshi Premarathna Environmental Chemodynamics Project,
National Institute of Fundamental Studies, Kandy, Sri Lanka
Pamela Y. Quintas Laboratory of Analytical Chemistry for Research and
Development (QUIANID), Interdisciplinary Institute of Basic Sciences (ICB),
UNCUYO–CONICET, Faculty of Natural and Exact Sciences, National University
of Cuyo, Mendoza, Argentina
xii Contributors

Anushka Upamali Rajapaksha Faculty of Applied Sciences, Ecosphere

Resilience Research Center, University of Sri Jayewardenepura, Nugegoda, Sri
Lanka
Artis Robalds Department of Environmental Science, University of Latvia, Riga,
Latvia
Uttariya Roy Department of Chemical Engineering, Jadavpur University, Kolkata,
India
Vipin Kumar Saini School of Environment and Natural Resources, Doon
University, Dehradun, India
Vladimir Sergeevich Semenishchev Radiochemistry and Applied Ecology
Department, Ural Federal University, Physical Technology Institute, Ekaterinburg,
Russia
Shubhalakshmi Sengupta Department of Chemical Engineering, Jadavpur
University, Kolkata, India
Giangiacomo Torri Istituto di Chimica e Biochimica G. Ronzoni, Milan, Italy
Hai Nguyen Tran Institute of Research and Development, Duy Tan University, Da
Nang, Vietnam
Anitha George Varghese Department of Chemistry, Mar Thoma College,
Tiruvalla, Kerala, India
Department of Chemistry, Bishop Moore College, Mavelikara, Kerala, India
Roozbeh Vaziri Faculty of Engineering, Cyprus Science University Ozankoy-
Girne, Girne, Turkey
Meththika Vithanage Faculty of Applied Sciences, Ecosphere Resilience
Research Center, University of Sri Jayewardenepura, Nugegoda, Sri Lanka
Anna Vladimirovna Voronina Radiochemistry and Applied Ecology Department,
Ural Federal University, Physical Technology Institute, Ekaterinburg, Russia
Rodolfo G. Wuilloud Laboratory of Analytical Chemistry for Research and
Development (QUIANID), Interdisciplinary Institute of Basic Sciences (ICB),
UNCUYO–CONICET, Faculty of Natural and Exact Sciences, National University
of Cuyo, Mendoza, Argentina
About the Editors

Dr. Grégorio Crini 52, is researcher at the University

of Bourgogne Franche-Comté, UMR Chrono-
environnement, Besançon, France. His current interests
focus on the design of novel polymer networks and the
environmental aspects of polysaccharide chemistry. He
published over 180 papers in international journals and
books, and he is a highly cited researcher. The total cita-
tion of his publications is over 7500 according to ISI
Web of Science, h-index: 32.

Eric Lichtfouse 58, is a biogeochemist at the

University of Aix-Marseille, CEREGE, Aix-en-
Provence, France. He got a PhD in organic geochemis-
try at the University of Strasbourg in 1989 for the
discovery of new fossil steroids in sediments and petro-
leum. He has invented the 13C-dating method allowing
to measure the dynamics of soil organic molecules. He
is chief editor of the journal Environmental Chemistry
Letters and former chief editor of the journal Agronomy
for Sustainable Development. He has published the
book Scientific Writing for Impact Factor Journal,
describing the micro-article, a new tool to identify the
novelty of experimental results. He has published 85
research papers, with an h-index of 23, and edited more
than 50 books. He got the Analytical Chemistry Prize of
the French Chemical Society, the Grand University
Prize of Nancy University, and a Journal Citation Award
by the Essential Science Indicators.

xiii
Chapter 1
Hemp-Based Materials for Metal Removal

Nadia Morin-Crini, Sonia Loiacono, Vincent Placet, Giangiacomo Torri,

Corina Bradu, Mirjana Kostić, Cesare Cosentino, Gilles Chanet,
Bernard Martel, Eric Lichtfouse, and Grégorio Crini

Contents
1.1 I ntroduction 3
1.2 H  emp, an Interesting Raw Material 5
1.2.1 Production 5
1.2.2 Types of Hemp-Based Products and Applications 7
1.3 A Novel Application of Hemp-Based Material for Removal of Metals:
A Review of the Literature 11
1.3.1 Biosorption, a Useful Decontamination Process for Contaminant Removal 11
1.3.2 Hemp-Based Materials as Biosorbents 14
1.3.3 Composite Materials 20
1.3.4 Activated Carbons from Hemp 20
1.4 Conclusion 24
References 28

N. Morin-Crini (*) · S. Loiacono · G. Crini

Laboratoire Chrono-Environment, UMR 6249, UFR Sciences et Techniques,
Université Bourgogne Franche-Comté, Besançon, France
e-mail: [email protected]; [email protected];
[email protected]
V. Placet
FEMTO-ST Institute, CNRS/UFC/ENSMM/UTBM, Department of Applied Mechanics,
Bourgogne Franche-Comté University, Besançon, France
e-mail: [email protected]
G. Torri · C. Cosentino
Istituto di Chimica e Biochimica G. Ronzoni, Milan, Italy
e-mail: [email protected]; [email protected]
C. Bradu
Research Center for Environmental Protection and Waste Management,
University of Bucharest, Bucharest, Romania
e-mail: [email protected]
M. Kostić
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia
e-mail: [email protected]

© Springer Nature Switzerland AG 2018 1

G. Crini, E. Lichtfouse (eds.), Green Adsorbents for Pollutant Removal,
Environmental Chemistry for a Sustainable World 19,
https://doi.org/10.1007/978-3-319-92162-4_1
2 N. Morin-Crini et al.

Abstract With the increasing focus on renewable materials and sustainability

issues, the development of non-conventional materials from natural resources and
possessing complexing properties is currently an area of extensive research due to
their potential applications in biosorption processes for pollutant removal. Among
them, the hemp plant, an annual high yielding industrial crop grown for its fibres
and seeds, is one of the most promising material for biosorption of metal ions from
diluted waste streams. In this chapter, an extensive list of hemp-based biosorbent
literature has been compiled and discussed. After a brief description of hemp and its
properties and applications, the chapter gives a general overview of liquid-solid
biosorption processes for metal removal from aqueous solutions onto hemp-based
materials.

Abbreviations

AC activated carbons
CAC commercial activated carbons
DSC differential scanning calorimetry
EDX energy-disperse X-ray spectroscopy
FT-IR Fourier transform infra-red spectrophotometry
MFA microfibrils angle
NMR nuclear magnetic spectroscopy
SEM scanning electron microscopy
SPE solid-phase extraction
TGA thermogravimetric analysis
THC delta-9-tetrahydrocannabinol
XPS X-ray photoelectron spectroscopy
ΔG Gibbs free energy change
ΔH enthalpy change
ΔS entropy change

G. Chanet
Eurochanve, Arc-les-Gray, France
e-mail: [email protected]
B. Martel
University of Lille, CNRS, INRA, ENSCL, UMR 8207, UMET – Unité Matériaux et
Transformations, Lille, France
e-mail: [email protected]
E. Lichtfouse
CEREGE – Centre européen de recherche et d’enseignement des géosciences de
l’environnement, Université Aix-Marseille, Collège de France, CNRS, INRA, IRD, Europôle
Méditerranéen de l’Arbois, Aix-en-Provence, France
e-mail: [email protected]
1 Hemp-Based Materials for Metal Removal 3

1.1 Introduction

Many wastewaters contain significant levels of organic and mineral contaminants

which are toxic or otherwise undesirable because they create, in particular, odor,
bad taste and color. Amongst the numerous techniques of contaminant removal,
liquid-solid adsorption is the procedure of choice as it can be used to efficiently
remove different types of contaminants (Manes 1998; Cooney 1999; Liu and Liptak
2000; Dąbrowski 2001; Yang 2003; Crini and Badot 2008; Sharma and Sanghi
2012). Furthermore, adsorption can produce high quality water while also being a
process that is both technologically simple and economically feasible. So, adsorp-
tion processes from aqueous solutions are important techniques in water purifica-
tion, wastewater decontamination, and many other areas such as recovery and
separation applications.
Carbons are one of the oldest and most widely used adsorbents in industry
(Manes 1998). Indeed, due to their great capacity to adsorb contaminants, commer-
cial activated carbon (CAC) are the most effective adsorbents, and if the adsorption
system is properly designed they give a good-quality output, with concentrations
under the legal limits for discharge waters. This capacity is mainly due to their
structural characteristics and their porous texture which gives them a large surface
area, and their chemical nature which can be easily modified by chemical treatment
in order to improve their properties. The processes that use these usual adsorbents
are often carried out in a batch mode, by adding activated carbon (AC) to a vessel
containing the contaminated solution, or by feeding the solution continuously
through a packed bed of carbon. Adsorption processes using AC are also interesting
because of convenience, easy operation, and their simplicity of design (Manes 1998;
Radovic et al. 2000).
However, although these commercial materials are preferred conventional adsor-
bents for contaminant removal, their widespread industrial use is restricted due to
high cost (Crini 2005; Kyzas and Kostoglou 2014). As such, alternative non-­
conventional adsorbents including products and by-products of biological and agri-
cultural origin, and from forest industries were proposed, studied and employed as
inexpensive and efficient adsorbents – in this case called biosorbents due to their
natural origin and property to bind and concentrate metal ions from aqueous solu-
tions (McKay 1996; Volesky 2004; Blackburn 2004; Crini 2006; Oliveira and
Franca 2008; Crini and Badot 2010; Rezić 2013; Michalak et al. 2013; Vijayaraghavan
and Balasubramanian 2015; Sharma 2015; Muya et al. 2016; Okenicova et al. 2016;
Khalaf 2016; Zhao et al. 2016).
Indeed, the past three decades have shown an explosion in the development of
new materials proposed as biosorbents for metal removal in biosorption-oriented
processes using various contacting systems. These include living organisms (e.g.
algae, bacteria, fungi, and yeasts) and dead biomass (e.g. bark, sawdust, peat, natu-
ral fibres such as cotton and flax, plants, and other organic substances such as bio-
polymers or polysaccharides). Polysaccharides include starch, cellulose, alginate
and chitin and their derived products such as chitosan and cyclodextrins. These
4 N. Morin-Crini et al.

Table 1.1 Examples of biosorbents used in biosorption-oriented processes for metal removal
from water/wastewater with special attention to polysaccharide-based biosorbents (selected
reviews)
Biosorbent Reference(s)
Agricultural wastes Novoselova and Sirotkina (2008); Crini and Badot (2010); Dulman and
(sawdust, bark, peat, Cucu-Man (2010); Fomina and Gadd (2014); Kyzas and Kostoglou
coffee, date pits…) (2014); Westholm et al. (2014); Suba and Rathika (2016); Tapia-Orozco
et al. (2016); Ahmed (2016); De Gisi et al. (2016); Raval et al. (2016);
Anastopoulos et al. (2017a)
Algae (seaweeds) Fomina and Gadd (2014); He and Chen (2014); Kumar et al. (2015);
Dabbagh et al. (2016)
Alginate Nastaj and Przewlocka (2014); Vandenbossche et al. (2015)
Biomass Mudhoo et al. (2012); Gorska et al. (2014)
Cellulose and Hubbe et al. (2011); Mudhoo et al. (2012); Rezić (2013); Vandenbossche
derivatives et al. (2015); Salman et al. (2015); Tran et al. (2015); Ummartyotin and
Pechyen (2016); Kumar et al. (2017)
Chitin, chitosan and Mudhoo et al. (2012); Westholm et al. (2014); Tran et al. (2015);
derivatives Ummartyotin and Pechyen (2016); Zhang et al. (2016); Anastopoulos
et al. (2017b)
Composts Anastopoulos and Kyzas (2015)
Eggshell Ummartyotin and Pechyen (2016)
Extracellular More et al. (2014); Li and Yu (2014)
polymeric substances
Microbial materials Dhankhar and Hooda (2011); Srivastava et al. (2015); Shakya et al.
(fungi, bacteria, (2016); Ayangbenro and Babalola (2017)
yeasts…)
Pectin Vandenbossche et al. (2015); Zhao and Zhou (2016)
Plant materials Fomina and Gadd (2014); Srivastava et al. (2015)
Starch and derivatives Crini and Badot (2010); Morin-Crini and Crini (2013); Vandenbossche
et al. (2015); Sharma (2015); Haroon et al. (2016)

materials are interesting due to the fact that they are abundant in nature, available in
large quantities, inexpensive, and may have potential as biosorbent materials due to
their physicochemical characteristics and particular structure (Volesky 2004;
Blackburn 2004; Crini 2005, 2006). Abundant data can be found in the literature.
Table 1.1 reports some examples of materials used in the biosorption process with
special attention to polysaccharide-based adsorbents.
Actually, numerous works are being conducted on the use of hemp-based materi-
als as biosorbents. Hemp is a fast growing, annual herbaceous (Fig. 1.1) and multi-­
purpose plant. In particular, its bast fibres are natural, cheap, strong, stiff and
lightweight, and have been not only identified as attractive reinforcements for com-
posites (thermoplastic polymers…) and material for wool insulation but also as use-
ful chelating materials.
An analysis of the Web of Science database reveals that 104 publications contain-
ing both the keywords ‘hemp’ and ‘metal’ in the topic category have been published
from 2002 to 2016. Figure 1.2 clearly shows an increase of citations. Each publica-
tion has been cited 15.98 times on the average. Overall this finding shows a growing
research interest. To the best of our literature review, this chapter is the first pub-
1 Hemp-Based Materials for Metal Removal 5

Fig. 1.1 Hemp field (a) and dioecious male plant (b)

Fig. 1.2 Citations of the 104 publications on hemp and metal in the Web of Science Core
Collection, published from 2002 to 2017 (the analysis was performed using the expression ‘hemp
AND metal’ in the topic category, on July 4, 2017)

lished review on the potential use of hemp-based materials in water and wastewater
treatment. After a brief description of hemp and its properties and applications, the
chapter gives a general overview of liquid-solid biosorption processes for metal
removal from aqueous solutions onto hemp-based materials. For this, an extensive
list of hemp-based biosorbent literature has been compiled and discussed.

1.2 Hemp, an Interesting Raw Material

1.2.1 Production

Hemp is one of the oldest domesticated crops known to man. Hemp fibres were used
for textiles and cordages, and the seeds as nutrition for thousands of years. Hemp
originated from Asia and was already cultivated 4500 years ago in China (Ranalli
6 N. Morin-Crini et al.

1999; Bouloc 2013). The first copies of the Bible were made of hemp paper (Ranalli
and Venturi 2004). Hemp bast fibres were the principal natural fibres used for mari-
time ropes and sails for centuries. Oils from hemp seeds were also used for a wide
range of purposes, from cooking to cosmetics. It is estimated that hemp was
imported to Europe by nomads in the sixteenth century (Bouloc 2013). In the mid-
dle of nineteenth century, hemp cultivation decreased with disappearance of the
sailing navy and competition from other natural fibres (cotton, jute…) for textile
applications, and later due to intensive development of synthetic fibres (Milanovic
et al. 2012). In the 1930s, cultivation was forbidden in the vast majority of Western
countries due to the fact that hemp and marijuana come from the same genus and
species plant (Cannabis sativa L.), and this introduced a lot of confusion and social
and political controversies. In the last two decades, the increasing consideration of
natural resources and energy conservation has renewed the interest on hemp as a
“new” low-cost, ecological, biodegradable, sustainable, recyclable, and multi-­
purpose biomaterial (Shahzad 2012; Bouloc 2013; Bono et al. 2015).
Hemp is a dicotyledonous plant from the order of Rosales, from the family of
Cannabaceae, genus Cannabis (Bouloc 2013). Hemp – also called industrial hemp –
refers to the non-psychoactive varieties of Cannabis sativa L. Industrial hemp is often
incorrectly associated with hemp for narcotics due to the fact that the psychoactive
ingredient, delta-9-tetrahydrocannabinol (THC), found in hashish, is present in all
hemp varieties to some extent. European regulations limit THC content to 0.3% in
industrial hemp. In Canada, the THC limit is 1%. Marijuana (called medical cannabis)
contains about 10–30% of THC level (Bouloc 2013; Pacaphol and Aht-­Ong 2017).
Hemp is an annual high yielding industrial crop grown for its fibres and seeds.
This plant is being mainly cultivated in Europe, Canada and China (the largest sup-
plier in the world). France is the top European producer of hemp with an area of
cultivation around 12,000 ha. Other important producing countries are Romania,
Italy, Poland and Hungary (Amaducci 2005; Bouloc 2013; Salentijn et al. 2015).
Since hemp is one of the most efficient plants known for its ability to utilize sunlight
and capture large quantities of CO2 to photosynthesize, with an annual growth up to
5 m in height, production of hemp fiber is experiencing a renaissance again.
Currently, hemp is the subject of a European Union subsidy for non-food agricul-
ture, and a considerable initiative for its further development in Europe is underway
(Ranalli and Venturi 2004; Faruk et al. 2012; Bouloc 2013).
Hemp is considered as an excellent crop for sustainable agriculture. Selection of
a hemp cultivar and the manner of sowing depend on the purpose of the material
produced (fibre or seed). Indeed, there are mainly two groups of Cannabis varieties
being cultivated today: varieties primarily cultivated for their fibre (called industrial
hemp) used for example for construction material, clothing or animal related pur-
poses, and varieties grown for seed from which oil is extracted (breeding, or food);
hemp can also be cultivated as dual-purpose crop that implies that both fibres and
seeds can be processed (Bouloc 2013).
As a biodegradable plant which needs no irrigation or phytosanitary treatments,
hemp is excellent as a crop rotation leader to alternate with crops such as beets or
grains (Amaducci and Gusovious 2010). Furthermore, hemp can also be an e­ xcellent
1 Hemp-Based Materials for Metal Removal 7

predecessor in crop rotation, in particular before winter cereals such as wheat.

Hemp is more environmentally friendly than traditional crops. After sowing, culti-
vation is not difficult. The crop requires only rarely the use of plant protection prod-
ucts and hemp requires low fertilization. Easily adaptable to all types of soil and
well-adapted to temperate climates such as in Europe, hemp is appreciated by
organic growers not only for its ease of production but also for its rapid growth
(120–150 days cropping cycle). Fibre hemp may yield up to 25 t above ground dry
matter per ha (20 t stem dry matter per ha) which may contain maximum 12 t/ha of
cellulose, depending on the genetics (e.g. varieties), cultivation practices, climate
and environmental conditions (Bouloc 2013; Ingrao et al. 2015). Hemp also leaves
an excellent quality, weed-free soil at the end of each season. Hemp detoxifies the
soil and prevents soil erosion. Finally, hemp cultivation is a vector of development
for local agricultural resources in emerging countries and an industrial output for
crops in developed countries (Le Troëdec et al. 2011).

1.2.2 Types of Hemp-Based Products and Applications

Hemp is an interesting raw material for its very low-cost, abundancy, renewable char-
acter, particular chemical composition of its fibres including moisture content, macro-
molecular network with numerous hydroxyl groups capable of forming intra- and
intermolecular bonds, and specific physical (low density), mechanical, thermal, acous-
tic and aseptic properties (Păduraru and Tofan 2008; Bouloc 2013; Amaducci et al.
2015). Hemp fibres are also classified as eco-friendly material and good candidates as
a (partial) substitute for synthetic fibres such as glass, carbon or metallic fibres.
Cannabis sativa L. is the source of two types of natural fibres: bast fibres (fibrous
form) and woody core fibres, called hurds or shives (granular form). Its cultivation
also provides seeds for oil production. Hemp stem consists of approximately
20–40% of bast fibres and 60–80% of hurds (Stevulova et al. 2014). The outside of
the stem is covered with bark (called epidermis). Inside the stems are bast fibres and
the woody core. The separation of the bast fibre is carried out through defiberization
or decortication (breaking the woody core of the stems into short pieces and separa-
tion of bast fibre from the hurds) using specialized machineries. The hemp fibres are
situated in the bast of the hemp plant. The byproduct of the hemp stem obtained
after the industrial defiberization process is called chenevotte (constituted from the
xylem tissue of the stem, i.e. the shives).
Technical (multi-cellular) fibres, composed of elementary fiber bundles obtained
by primary processing of stalks are characterized with heterogeneous chemical
composition and fairly complicated structure. The main constituents are cellulose,
hemicellulose and lignin (Table 1.2), while minor components such as pectin and
waxes are regarded as surface impurities (Placet et al. 2014, 2017). As member of
the bast fibre family, hemp contains over 75% of cellulose and less than 10 to 12%
of lignin (compared with 60% and 30% respectively for wood). The bast fibres con-
tain higher amounts of cellulose than the hurds (Table 1.2).
8 N. Morin-Crini et al.

Table 1.2 Chemical Bast

composition of hemp fibres in Component fibres Hurds
wt % (Placet et al. 2017)
Cellulose 57–77% 40–48%
Hemicellulose 9–14% 18–24%
Lignin 5–9% 21–24%

Fig. 1.3 Hemp (Cannabis sativa) stem cross sections – Microscopic observations of fresh trans-
verse sections at two different magnifications after cytochemical staining using the Wiesner
reagent (phloroglucinom-HCl) that gives a purple-red coloration to lignin (X xylem, pf primary
fibres, sf secondary fibres, c collenchyma, e epidermis)

Their structure is complex. Indeed, hemp fibres are very heterogeneous and can
be considered themselves as a composite material comprising three different parts
(Le Troëdec et al. 2011). From the outer to the inner part, fibres consist of a middle
lamella, a primary, a secondary and a tertiary cell wall, build up around an opening,
the lumen. The bast fibres are joined together by the middle lamella, mainly com-
posed of pectin (macromolecules of galacturonic acid) encrusted with lignin that
hold fibres together into a bundle. Next to the middle lamella, the primary cell wall
consists of disorganized arrangements of cellulose fibrils embedded in an organic
matrix of hemicelluloses, lignin and proteins. The secondary cell wall consists of
three layers of cellulose fibrils with different axial orientation that are bound by
hemicelluloses. Each fibre bundle consists of single (elementary) fibres. There are
two types of fibres with approximately the same diameter: (i) the useful primary
fibres (5–55 mm long) and (ii) the short secondary fibres (2 mm long). However, the
cell walls of the bast fibres are 5 to 10 times thicker than those of woody fibres. In
contrast to the high quality of bast fibres, the hurds is the least valuable part of the
plant, chemically close to wood (Stevulova et al. 2014). Figure 1.3 shows micro-
scopic observations of fresh transverse hem stem sections at two different magnifi-
cations showing lignin component.
Above mentioned complex structure and heterogeneous chemical composition
of hemp fibres are the crucial factors that affect their specific characteristics. On
such way, the chemical composition and cell wall microstructure can help to deter-
mine properties and end uses of the fibres. For instance, higher cellulose content and
low cellulose MFA (microfibrils angle) correlate to high strength and stiffness and
1 Hemp-Based Materials for Metal Removal 9

is ideal for polymer reinforcement. From the other hand, polar and hydrophilic
nature of cellulose fibres, mainly as a consequence of their chemical structure, is
limiting factor for the extended use of these fibres in composites (Bismarck et al.
2005). In the same time, this hydrophilic character of the fibres positively affects
their biosorption properties as it will be discussed.
In plant fibres, water can be held in the form of bound water and free water. Free
water can be found as liquid, liquid-vapor mixture or vapor within the fibre lumen.
Bound water interacts with the hydrophilic polymers of the fibre wall. It is absorbed
into the cell wall by hydrogen bonds on the accessible polar hydroxyl groups, gener-
ally termed biosorption sites. The constitutive hydrophilic polymers are classically
classed into three types: (i) cellulose, (ii) hemicelluloses and pectins and (iii) lignins.
Cellulose is made of linear chains of glucose aggregated into microfibrils, includ-
ing highly crystalline parts surrounding by amorphous components (also called
paracrystalline cellulose). Even though cellulose has a high hydroxyl group to car-
bon element (OH/C) ratio, most of them are inaccessible to water molecules, due to
the crystalline organization, and water molecules can gain access only into amor-
phous cellulose. Hemicelluloses and pectins are predominantly amorphous polysac-
charides with high (OH/C) ratio and highly accessible to water molecules. Lignin is
third main type of hydrophilic polymeric constituent. It is an amorphous crosslinked
polymer, composed of phenolic units, that occurs in plant fibres with more or less
amounts, and which has relatively low OH/C ratio when compared to polysaccha-
rides. So the water adsorption capacity in fibre wall is mainly determined by the
amount and accessibility of hydroxyl groups.
The physical and chemical states of water in plant fibres depend on the surround-
ing environment. In ambient air, plant fibres are constantly exchanging moisture
with atmosphere. Water molecules can be found in the form of bound water in the
cell wall and water vapor within the fibre lumen. When fibres are exposed to liquid
water (i.e. submerged in or in direct contact with liquid water), or when freshly cut,
in addition to the bound water that is saturating the cell wall, liquid water can also
fill the lumen by capillary suction. Water absorption in the cell wall is the result of
a combination of complex mass transfer mechanisms as in all the open porous
­materials. It includes water vapor diffusion within the lumen and in the air sur-
rounding the outer surface of the fibre, adsorption on the hydroxyl groups of hydro-
philic polymers and diffusion of bound water in the wall.
When bast tissues or technical fibres are submerged in water, a separation of
fibres is generally observed (see Fig. 1.4) due to the leaching and also to the degra-
dation of the gummy substances (pectins mainly) surrounding the technical and
individual fibres due to the action of enzymes produced by micro-organisms. This
is the mechanism observed during water retting, one of the process employed to
facilitate the separation of the fibres from the stem (Di Candilo et al. 2009).
Its versatility is also another important advantage, being useable in the form of
fibres, felts, powders (byproducts, fragments, shives) and oils, due to the fact that
the entire plant (seeds and plant stem) is recoverable. Indeed, all parts of the hemp
plant can be used for myriad applications (Ranalli 1999; Bouloc 2013; Liberalato
2003; Ranalli and Venturi 2004; Amaducci et al. 2015). Figure 1.5 depicts a
10 N. Morin-Crini et al.

Fig. 1.4 Electron microscopy images of the fibre surface (a) before and (b) after washing by water

Textiles and New Construction Pulp and Paper Industrial

Technical Textiles Products Materials Products
- pulp - coffee filter
- cordage - nonwoven - insulation - packaging - cigarette paper - animal bedding
stalk (bast fibre, hurd)

- bags - biocomposites - fiberboard - printing - wax paper - mulch

- carpeting - geotextiles - biocomposites - special - composite - synthetic plastics
- canvas paper material
- teabags - electrical
Automotive Environment insulation paper
- biocomposites - fiber reinforced - phytoremediation
- fiberglass
- boiler fuel

Energy and Fuel Agro-chemistry Medical

- ethanol - biofuel - bio-pesticides - drugs
- terpenes
seed (oil, nut)

Foods Functional Food Cosmetics and Personal Others Products

- proteins Care - industrial oils - solvents
- salad oil - feed for birds
- flour and fishes - amino acids - body-care - soap - paints - lubricants
- seed cake - beer - nutritional - shampoos - oils - varnish - coating
- beverages supplement - lotions - creams
- perfumes

Fig. 1.5 Examples of multi-purpose hemp applications in domestic and industrial sectors

­ owchart of multi-purpose hemp applications in domestic and industrial sectors.

fl
Hemp fibres and stalks are thus used for numerous applications such as in textiles
(e.g. clothes, sport clothing, jeans, ropes, shoes, bags…) and pulp and paper indus-
tries (e.g. paper products, cardboard, packaging, filters), construction applications,
biocomposites, agrochemistry, mulch and animal bedding. Textiles made from
hemp are easy to produce, durable, versatile and biodegradable. Fibres are also
more resistant to weather and ultraviolet rays than cotton and silk, and can be mixed
with other materials to create clothing hybrids.
Oils are used for applications in cosmetics and body care products (e.g. soaps,
shampoos, lotions, creams, perfumes…), pharmacy (e.g. to reduce acne breakouts
and to improve skin conditions, interesting in dermatitis and eczema treatments),
1 Hemp-Based Materials for Metal Removal 11

food-processing (e.g. health foods, nutraceutical products, protein isolates, bever-

ages, animal food as feed for birds and fishes), agrochemistry, fuel (a by-product of
its cultivation), paint, varnish, detergent, ink and lubricants. In cosmetology,
­hemp-­based oils are interesting as additive due to their high concentration of fatty
acids. In food chemistry, hemp is nutritious thanks to high levels of proteins, essen-
tial amino acids (rich in lanolin and linolenic acids), and other valuable elements
(fibre, iron, potassium, zinc…). In China, hemp is widely used as a component for
food and medicine.
Hemp can also be processed into different forms of felt, with various densities,
used for example in automotive and construction applications (insulation materials)
or as reinforcement in composite materials (plastic composites, biocomposites).
Hemp provides all sorts of good building materials. They are durable, light weight,
affordable to produce, and water-, fire- and rodent-proof. These materials are also
ideal for resisting damage caused by earthquakes, floods or other natural disasters.
Furthermore, the woody core part (shives) and short and entangled fibers obtained
as by-product of hemp processing can be used in lower grade products such as insu-
lation products, fiberboard and erosion control mats, while the fibrous core can be
blended with lime to make strong, lightweight concrete (Ranalli and Venturi 2004;
Shahzad 2012; Keijsers et al. 2013; Kostić et al. 2014).
Other innovative applications such as nanotechnology (e.g. nanomaterials with
similar properties as graphene, supercapacitors and nanosheets), hemp plastic for
3D printing, biocomposites for airplanes, solar panels, bacteria-fighting fabric, bio-
active metabolites such as cannabinoids, terpenoids and flavonoids, bio-pesticides,
in cleaning up air and soil contamination, and biofuel production (with no sulfur
emissions) opens new challenges (Citterio et al. 2003; Rehman et al. 2013). Indeed,
one of the most interesting uses for hemp is in cleaning up soil contamination
through phytoremediation process (Citterio et al. 2003). Hemp could be grown on
soils contaminated with metals or radioactive elements. Hemp plants were shown to
be effective in cleaning the soil around the site of Russia’s Chernobyl nuclear
­disaster (Vandenhove and Van Hees 2003). Recently, they were considered for use
near Fukushima. Hemp is also receiving more and more attention in water and
wastewater treatment.

1.3  Novel Application of Hemp-Based Material

A
for Removal of Metals: A Review of the Literature

1.3.1  iosorption, a Useful Decontamination Process for

B
Contaminant Removal

Liquid/solid adsorption is one of the most frequently used techniques for the decon-
tamination of aqueous media worldwide (Berefield et al. 1982; Volesky 1990;
McKay 1996; Wase and Forster 1997; Cooney 1999; Crini and Badot 2010).
12 N. Morin-Crini et al.

Adsorption is a physical-chemical method of separation in which substances pres-

ent in a liquid become bound to the surface of a solid material (Yang 2003; Volesky
2004). It is a process of partition of the molecule to be eliminated, called the adsor-
bate, between the aqueous solution and the solid, named the adsorbent or biosor-
bent/sorbent, depending on the type of material used.
The technique most frequently used to study adsorption (biosorption/sorption)
phenomena, not only in research laboratories but also in the industrial sector, is the
static approach or batch process. This approach involves mixing a known volume of
water with known concentrations of adsorbate to be processed with a given quantity
of adsorbent, in previously established conditions of stirring rate, stirring duration,
concentration, pH, ionic strength, and temperature. The mixture is stirred for a given
contact time, then separated by a physical step involving centrifugation, sedimenta-
tion or filtration. By determining the concentrations in the supernatant and in the
initial solution it is possible to calculate the efficiency of the solid material, i.e. its
performance in terms of pollutant elimination (Crini and Badot 2010). This effi-
ciency is generally compared to more conventional commercially available adsor-
bent systems, such as activated carbon, alumina or synthetic resins.
Batch methods are the most frequently used since they are simple, quick, and
easy to set up (McKay 1996). In addition, they can be used to study the influence of
a large number of parameters (e.g. pollutant concentration, pH, ionic strength, tem-
perature…) on the efficiency of the biosorbent, while easily obtaining reproducible
results. For instance, by varying the contact time, the quantity of biosorbent or the
concentration of the pollutant(s), it becomes possible to experimentally determine
various isotherms and biosorption/adsorption kinetics and to model the process.
Modeling based on equations with 2 or more unknowns (see in particular the
reviews of McKay and Al Duri (1989) and Ho et al. (2002) and the books of
Berefield et al. (1982), Treybal (1987), Tien (1994), Volesky (1990, 2004) and
McKay (1996)) provide information on adsorption mechanisms and enables inter-
pretation depending on the conditions used in the batch. In industrial applications,
batch techniques are used for example to “neutralize” abnormal peaks in the pollut-
ant load at the entry to the water treatment plant, to recover economically interesting
substances, such as noble metals, or to facilitate the production of denser sludge
(Crini and Badot 2010; Sharma 2015).
Recently, the development of hemp-based materials as biosorbents is an expand-
ing field in the area of pollutant removal. This is an interesting challenge because
the majority of commercial polymers are derived from petroleum-based raw materi-
als using processing chemistry that is not always safe or environmental friendly.
Today, there is growing interest in developing natural low-cost alternatives to syn-
thetic polymers. Hemp could be a promising alternative. Commercial hemp-based
products are usually offered as powders (byproducts), fibres, or felts (Fig. 1.6).
To characterize hemp-based materials, numerous techniques such as Fourier
transform infra-red spectrophotometry (FT-IR), energy-disperse X-ray spectros-
copy (EDX), X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic
spectroscopy (NMR), differential scanning calorimetry (DSC), thermogravimetric
analysis (TGA), contact angle measurement, and scanning electron microscopy
1 Hemp-Based Materials for Metal Removal 13

Fig. 1.6 Pictures of the hemp-based materials used as biosorbents: (a) sawdust, (b) hurds (shives),
(c) fibres and (d) felt

Fig. 1.7 Comparison of the 13C NMR spectra of two felts containing hemp fibres without (in red)
and with (in blue) the presence of an additive (10% of polypropylene)

(SEM) can be used. For example, NMR is a powerful tool for hemp characteriza-
tion. In Fig. 1.7, the solid-state 13C-NMR spectra show the peaks of disordered cel-
lulose in the range 50 and 110 ppm. These broad signals are attributable to the
glucopyranose unit of the cellulose structure of the raw fibres. The spectrum of felt
containing 10% of polypropylene (PP, used as a matrix to reinforce fibres; typical
applications on these composites include automotive interior substrates, furniture
and other consumer products) clearly shows three additional peaks between 20 and
50 ppm due to PP.
14 N. Morin-Crini et al.

1.3.2 Hemp-Based Materials as Biosorbents

Hemp-based biosorbents have been proposed for applications in water treatment, in

particular for metal ion removal from aqueous synthetic solutions. Table 1.3 list
some of the researchers whose results are discussed in this chapter and the pollut-
ants they investigated.
The interaction between hemp and metal ions has been intensively investigated
by Păduraru and co-workers using batch and fixed-bed column studies (Tofan and
Păduraru 1999, 2000, 2004; Tofan et al. 2001a, b, 2009, 2010a, b, c, 2013, 2015,
2016a, b; Păduraru and Tofan 2002, 2008). These authors studied the capacity and
mechanism of hemp fibres in removing different metals (i.e. Cd, Co, Cr, Cu, Pb, Ag
and Zn) from aqueous monometallic solutions. Before use raw hemp fibres, wastes
from the textile industry, were purified by boiling for 4 h in a solution containing
soap and soda ash, followed by washing several times with water, and drying in an
oven at 45 °C. Their investigations clearly indicated, for the first time, that hemp
fibres had a high capacity for metals adsorption and were very useful for the treat-
ment of wastewaters. Between 7.5 and 13.5 mg of metal can be eliminated per gram
of fibre, depending on the type of metal. For example, the monolayer adsorption
capacity for Cu(II) Cr(III), Cd(II) and Ag(I) was 9.0735, 4.0006, 2.5909, and
1.2253 mg/g, respectively. In all the experimental conditions tested, the order of
affinity was the same: Cu > Cr > Cd > Ag (Păduraru and Tofan 2002). The results
also reported that hemp waste materials were efficient in removing Co (II), Pb(II)
and Zn(II) from diluted and concentrated aqueous solutions.
In another work, the authors evaluated the thermodynamic feasibility of Pb(II)
biosorption process on hemp by calculating thermodynamic parameters such as
Gibbs free energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS).
Evaluation of these parameters gives an insight into the possible mechanisms of
adsorption. At all studied temperatures (between 277 and 333°K), the ΔG values
were negative, showing the feasibility and spontaneous nature of Pb biosorption on
fibres (Tofan et al. 2010b). ΔG was estimated from the equilibrium adsorption data
under the assumption that the adsorption of a pollutant was reversible and that an
equilibrium condition was established in the batch system. The positive values of
ΔH indicated that Pb biosorption was an endothermic process, favored by tempera-
ture increase. The positive value of ΔS suggested an increased randomness at the
interface of hemp-solution and high affinity of the hemp fibres for Pb ions. Kinetics
were also rapid and could be described by a pseudo-first order model. The Langmuir
model was found to be the most appropriate to describe the adsorption process in all
the case of metals studied.
For Co removal, the authors showed that the biosorption capacity of the fibres
used in column (15.44 mg/g) performed better than that of the batch system
(13.58 mg/g) (Tofan et al. 2013). They explained this result by the fact that the gra-
dient concentration decreased with time in batch experiments while it continuously
increased in the interface of the biosorption zone in the column. The Langmuir
model better described the Co(II) adsorption process on hemp fibres in comparison
 1

Table 1.3 Authors of recent research on pollutant removal by hemp-based materials

Corresponding Experimental
author Country Hemp form Hemp material Pollutant(s) protocol Reference(s)
Crini G. France Fibres, felt, Raw Al, Cd, Co, Cu, Cr, Batch, filtration Loiacono et al. (2017a, b, c); Bugnet et al. (2017a, b)
shives Fe, Mn, Ni, Pb, Zn
Gryglewicz G. Poland Stem Carbonized Atrazine Batch Lupul et al. (2015a, b)
Holub M. Slovakia Shives Raw Cu Batch Balintova et al. (2014)
Kostić MM. Serbia Fibres Raw, modified Cd, Pb, Zn Batch Kostić et al. 2003, 2008, (2010); Pejić et al. 2008,
2009, 2011; Milanovic et al. (2012); Vukčević et al.
Hemp-Based Materials for Metal Removal

(2014a);
Kyzas GZ. Greece Shives Raw Ni Batch Kyzas et al. (2015)
Mintova S. France Fibres Composite Benzene, toluene, Zou et al. (2012)
chlorobenzene
Păduraru C. Romania Fibres Raw, modified, Ag, Cd, Co, Pb, Zn Batch, column Tofan and Păduraru (1999), (2000), (2004); Păduraru
impregnated and Tofan (2002), (2008); Tofan et al. (2001a, b),
(2009), (2010a, b, c), (2013), (2015), (2016a, b)
Rezić I. Croatia Fibres Raw Al, Cr, Cu, Fe, Zn Batch Rezić 2013
Vukčević Serbia Fibres Carbonized Pb, pesticides Batch, solid-phase Vukčević et al. 2012, 2014b, 2015
MM. extraction
Yang R. China Stem Carbonized CO2 Yang et al. (2012)
15
16 N. Morin-Crini et al.

with the Freundlich model. This finding complied with the results of fixed-bed stud-
ies which emphasized that the optimal solution for describing the behavior of the
investigated hemp bed column was provided by the Thomas model.
The authors explained their results by the fact that the main mechanism was
chemisorption of the metal ion via the formation of electrostatic interactions, com-
plexation and ion-exchange. Indeed, strong bonding of metal ions by carboxylic
(present in hemicelluloses, pectin and lignin), phenolic (lignin and extractives), car-
bonyl (lignin) and hydroxyl (polysaccharides) groups were responsible of the
adsorption through chemisorption.
Practical use of hemp has been mainly confined to the unmodified forms using
spiked metal solutions. Although raw hemp fibres were useful for treating contami-
nated solutions, it may be advantageous to chemically modify hemp, e.g. by grafting
reactions on cellulose macromolecules. Indeed, from the polymer chemist’s point of
view, the chemical substitution of cellulose offers enormous challenges. This chem-
ical modification is interesting because, in polysaccharide chemistry, it is well-
known that the grafting of ligands can improve their adsorption properties (Crini
2005; George et al. 2015). Cellulose present an interesting reactivity due to the pres-
ence of numerous hydroxyl groups located on carbons 2,3 and 6 on each glucose
residue of the cellulosic chains. In general, grafting of ligands resulted in fibres with
reduce surface polarity and improved thermal and chelating properties. However,
this chemical treatment can directly alter the surface and bulk chemical composi-
tions of natural fibres. In addition, chemical treatment can also result in removal of
significant amounts of components (cellulose, hemicellulose…), and therefore, it is
important to characterize the modified fibres (Crini 2005; George et al. 2015).
In order to improve the performance of raw hemp fibres, Păduraru’s group pro-
posed a chemical treatment using β-mercaptopropionic acid as chelating agent. This
functionalization permitted to introduce sulphydryl functional groups onto surface
fibres (Tofan and Păduraru 2004). A systematic study on the Ag(I), Cd(II) and Pb(II)
removal onto these raw and modified fibres was realized under similar experimental
batch conditions. For raw and modified hemp, the adsorption capacities were 1.2253
and 10.75 mg/g for Ag(I) and 2.5909 and 14.05 for Cd(II), respectively. This clearly
demonstrated the important role of sulphydryl chelating groups. However, for
Pb(II), the adsorption capacity decreased, but no explanation was given.
Tofan et al. (2015) studied Cr(III) removal from aqueous solutions by adsorption
in a fixed bed column filled with alizarin S impregnated hemp fibres. The break-
through time and saturation time decreased from 110 to 80 min and from 300 to
160 min, respectively, with the increase in the initial concentration from 13.00 mg/L
to 26.14 mg/L. The increase in the initial concentration from 13.00 to 26.14 mg/L
increased the breakthrough adsorption capacity from 4.178 to 6.163 mg/g and
decreased the percentage of Cr(III) removal from 73.57% to 62.64%. The break-
through predictions by Thomas model were found to be very satisfactory. The hemp
impregnated with alizarin S column removed >90% of Cr(III) from three samples of
synthetic wastewaters containing different amounts of other heavy metal ions. All
these findings were significant for the future development of hemp materials for
metal removal from industrial effluents.
1 Hemp-Based Materials for Metal Removal 17

Polysaccharide-based biosorbents present considerable advantage including

their high adsorption capacity and selectivity but also the facility of regeneration.
The regeneration of saturated hemp biosorbent for non-covalent adsorption can be
easily achieved by using an acid solution as the desorbing agent. In a recent work,
batch studies on desorption and multiple adsorption-regeneration cycles for Zn
removal by natural hemp fibres have been carried out by Tofan et al. (2016a). The
best desorption results were performed in acidic medium, where the protons in solu-
tion replaced the Zn ions on the loaded hemp. The efficiency of Zn desorption with
0.1 M hydrochloric acid was higher than that achieved using sulfuric acid of the
same concentration. The amount of Zn desorbed by 0.1 M HCl, 0.1 M H2SO4, and
5% NaCl increased sharply in the first 15–20 min of the process, attaining values
that subsequently stay almost constant (for 0.1 M HCl) or slightly increase (for
0.1 M H2SO4 and 5% NaCl). The adsorptive potential of the tested hemp remained
almost unchanged after three cycles of adsorption-desorption of Zn from solutions.
This showed both the chemical stability of the biosorbents and reproducibility of the
values. The results of this study were also important in order to demonstrate that
regenerated hemp could be used for Zn metal removal from water sources without
the threat of the adsorbent becoming another source of Zn pollution for the environ-
ment. From their numerous results, Păduraru’s research group concluded that hemp
and its derivatives may be a useful and promising biosorbent in water and wastewa-
ter treatment.
Kostić’s group also published a series of papers on the ability of hemp to act as
an effective biosorbent for the removal of metals from aqueous solutions (Pejić
et al. 2009, 2011; Kostić et al. 2010, 2014; Vukčević et al. 2014a). Their results
clearly demonstrated that hemp in fibre form had a high affinity for Cd, Zn and Pb,
in accordance with the results published by Păduraru’s group. In order to obtain
­better adsorption capacities, these authors also proposed to modify fibres by simple
and inexpensive alkaline and oxidative treatments, causing gradual removal of
either hemicelluloses or lignin and altering fibre structure. Observed increase in
adsorption properties was ascribed not only to the decrease of lignin or hemicellu-
loses content, but also to the increased fibre fibrillation, surface peeling and rough-
ness increase, which affects fibre specific surface area. Besides changes in fibre
surface and structure, applied chemical treatments affects the amount and accessi-
bility of functional groups incorporated in the fibre structure. Both chemical treat-
ments used remove the accompanying components from the fibre surfaces, leading
to the liberation of the functional groups, and increasing their amount. Since func-
tional groups act as active sites for adsorption, chemical modification efficiently
improve the adsorption properties of this biosorbent.
Similar materials and results were published by Kyzas’s group for the removal of
Ni from diluted and concentrated solutions (Kyzas et al. 2015). They noted that
adsorption capacities between 160 and 206 mg of Ni per gram of material were
achieved. The differences in the degree of performance were mainly attributed to
the hemp form used (fibres or shives). After chemical modification (by sodium
hydroxide or citric acid), the respective capacities were improved to 237 and
242 mg/g, respectively. A characterization study (FT-IR, XRD, SEM, EDX, crystal-
18 N. Morin-Crini et al.

linity, and cellulose content) demonstrated the surface morphology of the modified
hemp along with some possible biosorption interactions between them and Ni. At
least ten sequential reuse cycles revealed the reuse potential of the modified hemp-­
based materials. The authors concluded that hemp fibres were a promising material
for the removal of Ni from single ion solution mainly through chemical
interactions.
Balintova et al. (2014) studied the removal of Cu onto raw hemp shives and
treated hemp by NaOH. This treatment permitted to remove either hemicelluloses
or lignin. However, no significant differences were obtained. The adsorption capaci-
ties for raw and treated hemp were 3.91 and 4.45 mg/g, respectively (conditions:
dosage = 1 g/100 mL; initial Cu concentration = 50 mg/L, initial pH = 4, and contact
time = 24 h). These performances were compared with those of commercial sor-
bents and similar adsorption capacities were obtained. The authors concluded that
hemp was a useful non-conventional biosorbent for copper removal from acidic
environment.
New hemp fibres derivatives in environmental, pharmaceutical and biomedical
fields to reduce metal pollution and to prevent bacteria growth were proposed by
Cassano et al. (2013). The materials were prepared via esterification of hemp with
2-benzyl-4-chlorophenol (a germicide agent), that was covalently coupled to cellu-
lose backbone of fibres by a heterogeneous process. Carboxylated materials were
also synthetized. FT-IR spectroscopy was used to obtain qualitative information on
hemp fibres after derivatization. The materials were also characterized using dif-
ferential scanning calorimetry. The new materials possessed an excellent in vitro
antibacterial activity in inhibiting Staphylococcus aureus and Pseudomonas aerugi-
nosa growth and also exhibited interesting adsorption capacities toward Cd present
in aqueous solutions. However, the performances for Cd removal were dependent
on pH solution. In addition, their results showed that carboxylated fibres had a
higher chelating capacity than the esters derivatives.
All these studies demonstrated that hemp could be a viable biosorbent for envi-
ronmental applications. However, these previously published works focused on the
removal of only one or two metals at a time using hemp in fibre form. Recently,
Crini’s group proposed the use of a hemp-based material in felt form to treat poly-
metallic aqueous solutions, containing a mixture of six metals, namely Cd, Co, Cu,
Mn, Ni and Zn (Bugnet et al. 2017a, b; Loiacono et al. 2017a, b, c). These six metals
were studied due to their common presence in discharge waters from the metal
industry. Adsorption experiments showed that this non-conventional biosorbent
exhibited interesting adsorption capacities. In 10 min, 1 g of material was able to
remove 7.4 mg of metals (total = 2.14 (Cu) + 1.69 (Cd) + 1.3 (Zn) + 0.93 (Ni) + 0.84
(Co) + 0.5 (Mn)) at a concentration of 25 mg/L for each metal present in 100 mL of
solution. The results were also almost independent of pH between 4 and 6. The fol-
lowing order was obtained: Cu > > Cd > Zn > Ni ~ Co > Mn, while, in single solu-
tion, the order was Cd > Cu > Zn > Co ~ Ni > Mn. Figure 1.8 shows material before
and after batch, indicating the coloring of the felt after metal removal. This was the
1 Hemp-Based Materials for Metal Removal 19

Fig. 1.8 Hemp felt before (left) and after adsorption (right) in a solution containing a mixture of
six metals

first report on the removal of metals from polycontaminated aqueous solutions by

hemp-based material in felt form (Loiacono et al. 2017a).
In another work, in order to ameliorate its adsorption properties towards the
same six cationic metal species, the authors proposed to modify chemically the raw
felt (Loiacono et al. 2017b). The felt was treated with a mixture of maltodextrin
(MALTO), an oligosaccharide obtained from starch hydrolysis, and 1,2,3,4 butane-
tetracarboxylic acid (BTCA) used as cross-linking agent. This chemical treatment
provided ion-exchange properties to the material by introducing carboxylic groups
on hemp fibres. Potentiometric titration data revealed that the quantity of carboxylic
groups was increased from 0 ± 0.09 meq/g for raw hemp to 0.67 ± 0.03 meq/g for
modified hemp. A weight increase of 35% of modified felt confirmed that a cross-­
linking reaction occurred by esterification between BTCA carboxylic groups and
MALTO hydroxyl groups on the one hand, and cellulose hydroxyl group of hemp
fibres on the other hand. The modified material was also characterized using solid
state NMR technique, SEM and EDX. For the total metal load, the adsorption
capacity of modified hemp was determined to be twofold higher than that of non-­
modified felt in all conditions studied. The carboxylic groups present in BTCA were
responsible for metal ion binding through chemisorption mechanism (e.g. complex-
ation, electrostatic interactions, ion-exchange) and their presence in modified mate-
rial positively influenced its performance. Nevertheless, in the multi-component
system studied, strong competition prevails among metallic species for the binding
sites. For modified hemp, the following order was obtained: Cu > Cd > Zn > Mn > Ni
~ Co, while, in single solution, the order was Cd > Cu ~ Zn ~Mn > Ni ~ Co.
Interesting results were also obtained for real effluents containing the same six met-
als (Loiacono et al. 2017a). Crini’s group concluded that raw and modified hemp-­
based materials in felt form can be utilized as an interesting tool for the purification
of metal-containing wastewater because of their outstanding adsorption capacities
and easy of use.
20 N. Morin-Crini et al.

1.3.3 Composite Materials

Zou et al. (2012) proposed a hemp-zeolite composite material obtained by a simple

procedure for the removal of aqueous aromatic organic pollutants (benzene, toluene
and chlorobenzene). This new biosorbent, prepared via in situ crystallization of zeo-
lite L nanocrystals on hemp fibres, exhibited a high removal degree (above 80%).
The order obtained was: chlorobenzene > benzene > toluene. The composite also
presented high flux of 19.9, 19.3 and 20.9 kg/m2 h for chlorobenzene, benzene and
toluene, respectively. The results showed that the removal of the composite was
much higher in respect to only hemp fibres (48%). The better performance of the
composite was explained by an improved absorption ability of the zeolite-hemp
material coupled with higher dynamic separation efficiency. In addition, this new
material possessed high mechanical and chemical stabilities before and after water
purification, demonstrated by XRD and SEM experiments. The authors concluded
that, both materials (zeolite L and hemp) used for preparation of the composite were
environmentally friendly, and made the adsorbents particularly appropriate for
water purification.

1.3.4 Activated Carbons from Hemp

Amongst all the commercial adsorbents materials proposed, activated carbon (AC)
is the most popular adsorbent for the removal of pollutants from the wastewater
(Ramakrishna and Viraraghavan 1997; Derbyshire et al. 2001; Babel and Kurniawan
2003). The world demand of AC is steadily increasing due to its high performance
in many purification and separation processes. The most commonly used raw pre-
cursors are wood, coal, coconut shells and some commercial polymers. However,
the use of carbons based on relatively expensive starting materials is unjustified for
most pollution control applications (Streat et al. 1995). This had led many research-
ers to search for more economic carbon-based adsorbents from non-conventional
resources. Indeed, certain waste products from various industrial by-products
(wastes generated during lactic acid fermentation from garbage, waste carbon slur-
ries…), city wastes (PET bottles, waste tires, waste newspaper…), and agricultural
operations (bagasse, date pits, corn cob…), including lignocellulosic and wood by-­
products (pinewood, sawdust, lignin, sugarcane…), represent potentially economi-
cal alternative material to prepare activated carbon. These waste materials have little
or no economic value and often present a disposal problem. Therefore, there is a
need to valorize these low-cost by-products. So, their conversion into activated car-
bon would add its economic value, help reduce the cost of waste disposal, and most
importantly provide a potentially inexpensive alternative to the existing commercial
activated carbons as reported by Oliveira and Franca (2008).
1 Hemp-Based Materials for Metal Removal 21

Short hemp CARBONIZATION Carbonized ACTIVATION Activated

fibers hemp fibers carbons
- 700°C or 1000°C - 700°C or 900°C
- N2f low: 150 - KOH activating agent
cm3/min - N2 f low: 150 cm3/min
- heating rate: 5°C/min - heating rate: 5°C/min
- heat soak time: 30 min
- washing: water

Fig. 1.9 Scheme of activated carbons production from hemp-based wastes. (Adapted from
Vukčević et al. 2015)

Fig. 1.10 Short hemp fibers before (left) and after (right) carbonization. (Adapted from Vukčević
et al. 2015)

Although hemp has many practical applications, its transformation generates a

high proportion of waste. Development of recycling processes of such biomass
waste is generating great interest, and the production of activated carbon could be an
appropriate solution. There are several reports on the production of activated carbon
from hemp-based materials (Rosas et al. 2009; Vukčević et al. 2012, 2014b, 2015;
Yang et al. 2011, 2012; Sun et al. 2013; Wang et al. 2015; Lupul et al. 2015a, b).
An important work on this topic was done by Vukčević and co-workers (Vukčević
et al. 2012, 2014b, 2015). They proposed activated carbon from waste short hemp
fibres as adsorbent for metal ions and pesticides removal. Activated carbon with
high specific surface area (up to 2192 m2/g) and microporous structure were pre-
pared by carbonization of waste hemp fibres and activation with KOH. Figure 1.9
depicts the synthesis procedure used while Fig. 1.10 shows hemp fibers before and
after carbonization. These non-conventional carbons exhibited high adsorption
properties toward metals such as Pb and 15 pesticides including atrazine, simazine,
22 N. Morin-Crini et al.

malathion and linuron. Their results showed that the adsorption capacities of an
activated carbon depend on the history of its preparation and treatment conditions
such as pyrolysis temperature and activation time. The best efficiency was achieved
with samples with the highest specific surface area and the amount of surface oxy-
gen groups. Many other factors can also affect the adsorption capacity in the same
adsorption conditions such as surface chemistry (heteroatom content), surface
charge and pore structure (Vukčević et al. 2015). In general, specific surface area
and pore size distribution are dominant factors of influence in the case of physical
adsorption of nonpolar organic molecules, while adsorption of inorganic and polar
organic compounds is also influenced by surface chemistry of carbon adsorbent.
The specific adsorption mechanisms by which the adsorption of pollutant takes
place on these non-conventional carbons are still not clear. This is because of the fact
that adsorption onto carbon adsorbent is usually complex process that may occur
through the mechanism of physisorption (e.g. hydrophobic interactions, electro-
static attraction…), and chemisorption (e.g. surface complexation ion-­exchange…).
For example, metal ions adsorption on carbon surface can be considered as physi-
sorption if it occurs through the mechanism of electrostatic attraction between metal
ions and graphene layer’s π electrons. Furthermore, oxygen groups present on the
carbon surface might behave as ion-exchange sites for the retention of metal ions.
From the other hand, surface functional groups can also act as active chemisorption
sites, since oxygen in the surface functional groups possesses a pair of lone electrons
(Lewis base) and therefore may coordinate with electron deficient metal ions (Lewis
acid). In the case of organic molecules, the surface chemistry of the carbon has a
great influence on adsorption, both in the case of electrostatic and non-electrostatic
interactions. Electrostatic interactions, which can be either attractive or repulsive,
strongly depend on the charge densities of both the carbon surface and the adsorbate
molecule, as well as of the ionic strength of the solution. The non-electrostatic inter-
actions, which are always attractive, include van der Waals forces, hydrophobic
interactions and hydrogen bonding. Aromatic compounds can be physisorbed on
carbon materials essentially by dispersion interactions between the π electrons of the
aromatic ring and those of the graphene layers. The presence of aromatic rings, as
well as a branched substituent on the aromatic ring, increased the level of organic
compound adsorption. On the other hand, electron-­acceptor surface groups, present
on the carbon adsorbent surface, can withdraw π electrons from the graphene layers,
decreasing the dispersive interactions and leading to reduced adsorption. On the
base of obtained results, Vukčević and co-workers concluded that application of
hemp wastes as new solid-phase extraction adsorbent was a procedure of choice for
analysis of pesticides in water samples with recoveries comparable or even better
than those obtained with commercial cartridges.
Similar interesting results were published by Lupul et al. (2015a, b). These
authors proposed adsorption of atrazine on hemp stem-based activated carbon with
different surface chemistry using potassium hydroxide as activating agent. The
presence of oxygen and nitrogen functionalities on the carbon surface was found to
be undesirable for atrazine adsorption. The superior adsorbent was obtained by heat
treatment of activated carbon in an inert atmosphere at 700 °C, resulting in a very
1 Hemp-Based Materials for Metal Removal 23

high adsorption capacity due to its enhanced hydrophobicity. Adsorption capacities

were in the range 169–227 mg/g depending on the chemical treatment (Lupul et al.
2015a). The adsorption of atrazine on the studied carbons mainly involves π-π dis-
persive interactions between the atrazine π electron ring and the π electron of gra-
phene layers of carbon. The Langmuir-Freundlich and Langmuir models gave a
better fit for equilibrium isotherms compared with the Freundlich model. Modeling
also showed that the atrazine adsorption process was controlled by an intraparticle
diffusion mechanism into small micropores with a significant contribution from
film diffusion.
Rosas et al. (2009) proposed hemp-based activated carbon fibres by chemical
activation with phosphoric acid at different carbonization temperatures and impreg-
nation rates. Surface properties of the fibres were significantly influenced by the
activation temperature and the impregnation ratio. An increase of either of these
parameters produced a high development of the porous structure of the fibres.
Activated carbon fibres with apparent surface area of 1350 m2/g and mesopore vol-
ume of 1.25 cm3/g were obtained at 550 °C with an impregnation ratio of 3. The
fibres presented a high oxidation resistance due to the presence of phosphorus com-
pounds on the carbon surface. The oxidation resistance results suggested that
C-O-PO3 and mainly C-PO3 and C-P groups act as a physical barrier, blocking the
active carbon sites for the oxidation reaction. The authors concluded that the use of
hemp residues to produce activated carbon was very feasible and presented the
advantage of the potential revalorization of a residual material. Williams and Reed
(2003, 2004), studying the preparation of activated carbon fibres by physical activa-
tion with steam and chemical activation with ZnCl2 of hemp fibres, previously pub-
lished a similar conclusion.
Yang and co-workers (Yang et al. 2011, 2012; Wang et al. 2015) also prepared
activated carbon fibres using hemp bast and a simple method consisting in a
­phosphoric acid activation at different temperatures. These carbons were then used
as sorbents for dye removal. The textural properties of the activated carbon fibres
were found to be strongly dependent on the activation temperature. Activated carbon
fibres exhibited narrow pore size distributions with maxima in the micropore and
small mesopore regions. BET surface area, total pore volume, micropore volume and
mesopore volume increased with the increase of activation temperature up to 450 °C
and then decreased with further heating, and a sample with maximum surface area of
1142 m2/g and total pore volume of 0.67 cm3/g was obtained. Phosphoric acid facili-
tated the conservation of porous structure in the precursor fibres, led to the creation
of tremendous porosity, and resulted in various phosphore-containing functional
structures on the surface and in the bulk phase of the resultant samples. The adsorp-
tion of Acid Blue 9 as guest compound on the sample could be favorably described
by Langmuir isotherm (qmax = 28.75 mg/g), and the adsorption kinetics was found to
be well fitted by the intraparticle diffusion model. Yang et al. (2011) concluded that
hemp bast was a suitable low-cost byproduct for use in the production of activated
carbon for dye removal, thus contributing for the implementation of sustainable
development in both the hemp production and environmental protection.
24 N. Morin-Crini et al.

In another recent work, the same authors presented a new route for high-value-­
added utilization of hemicellulose extracted from hemp stem to prepare well-shaped
carbon spheres (Wang et al. 2015). Activated carbon with high large surface area up
to 2192 m2/g were prepared by an improved low-temperature hydrothermal carbon-
ization method and KOH activation. A pre-carbonization strategy before activation
was also employed to keep activated carbon in perfectly spherical morphology even
at a high KOH/carbon ratio 5/1. The characterization of activated carbon demon-
strated that the surface area, micropore volume, mesopore volume and surface oxy-
gen content all increases with increasing KOH/carbon ratio. Activated carbon
exhibited excellent electrochemical performance due to abundant micropores and
plentiful oxygen functionalities, and showed good adsorption capacities of CO2 and
CH4 at ambient pressure and 0 °C. The authors concluded that activated carbon con-
verted from inexpensive hemp stem could be potential materials for CO2 and CH4
storage (Wang et al. 2015).
Sun et al. (2013) prepared mesoporous activated carbon using hemp stem as pre-
cursors by air-phosphoric acid activation method. The crystallite size of carbon was
small, and its pores was larger. The phosphoric acid solution concentration had a
signification effect on pore structure and adsorption property of activated carbon.
The mesopore activated carbon attained at phosphoric acid solution concentration
of 50% exhibited a maximum BET specific surface area of 1351 m2/g, total pore
volume of 1.21 cm3/g, mesopore pore volume of 0.90 cm3/g and a mesopore fraction
of 74.4%. The resulting carbon had smaller crystal size, developed pore structure,
wider pore size distribution.

1.4 Conclusion

The past decade has seen an intense interest in hemp-based biosorbents for metal
ion removal from aqueous synthetic solutions. Many biosorbents in raw, modified
or carbon forms could be used for this purpose. Outstanding removal capacities for
metals were reported. Table 1.4 presents a summary of some of the highest adsorp-
tion capacities reported (the qmax values are expressed in mg of pollutant per g of
biosorbent). Which material is better? There is no direct answer to this question
because the biosorption capacity depends on the residual concentration of the pol-
lutant in the solution. The uptake by two materials must be then compared only at
the same equilibrium concentration. In addition, the comparison of performance
also depends on several other parameters related to the solution and analytical
method used. Thus, a direct comparison of data obtained using different materials is
not possible since experimental conditions are not systematically the same. However,
the authors believe that hemp can compete with conventional adsorbents for waste-
water treatment. Although interesting works at the stage of laboratory-scale study
has been done, future research needs to look into some of the following: (i) it is
necessary to continue to search for and select the most promising types of
 1

Table 1.4 Adsorption capacities (qmax in mg/g) for various pollutants using hemp-based biosorbents
Biosorbent Contact
Metal Type of biosorbent Technique dosage pH time qmax Reference(s)
Ag(I) Raw fibres Batch 5 1.2253 Tofan and Păduraru (2000); Păduraru
and Tofan (2002)
Ag(I) Sulphydryl fibres Batch 0.25 g/25 mL 5.1 24 h 10.75 Tofan and Păduraru (2004)
Al(III) Raw felt Batch 0.25 g/100 mL 5 1h 6.38 Bugnet et al. (2017b)
Al(III) Carboxylated felt Batch 0.25 g/100 mL 5 1h 10.15 Loiacono et al. (2017b)
Cd(II) Raw fibres 2.5909 Tofan and Păduraru (2000); Păduraru
and Tofan (2002)
Cd(II) Sulphydryl fibres Batch 0.25 g/25 mL 5.75 24 h 14.05 Tofan and Păduraru (2004); Tofan et al.
(2009)
Cd(II) Fibres treated with NaOH Batch 0.5 g/200 mL 5.5 2h 0.078a Pejić et al. (2009)
Cd(II) Fibres treated with NaClO2 Batch 0.5 g/200 mL 5.5 2h 0.039a Pejić et al. (2011)
Hemp-Based Materials for Metal Removal

Cd(II) Raw felt Batch 0.25 g/100 mL 5 1h 27.47 Loiacono et al. (2017a); Bugnet et al.
(2017b)
Cd(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 129.87 Loiacono et al. (2017b)
Co(II) Raw fibres Batch 0.25 g/50 mL 4.5– 6 h 13.58 Tofan et al. (2013)
5
Co(II) Raw fibres Column 4.5– 15.44 Tofan et al. (2013)
5
Co(II) Raw felt Batch 0.25 g/100 mL 5 1h 7.99 Loiacono et al. (2017a); Bugnet et al.
(2017b)
Co(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 37.88 Loiacono et al. (2017b)
Cr(III) Raw fibres Batch 4.006 Tofan and Păduraru (2000); Păduraru
and Tofan (2002)
Cr(III) Fibres impregnated with Alizarine S Batch 8.632 Tofan et al. (2001b)
Cr(III) Fibres impregnated with Alizarine S Column 6.163 Tofan et al. (2015)
(continued)
25
 26

Table 1.4 (continued)

Biosorbent Contact
Metal Type of biosorbent Technique dosage pH time qmax Reference(s)
Cr(III) Raw felt Batch 0.25 g/100 mL 5 1h 6.53 Loiacono et al. (2017a); Bugnet et al.
(2017b)
Cr(III) Carboxylated felt Batch 0.25 g/100 mL 5 1h 15.54 Loiacono et al. (2017b)
Cu(II) Raw fibres Batch 9.0735 Păduraru and Tofan (2002)
Cu(II) Bleached fibres impregnated with Batch 8.0378 Tofan and Păduraru (1999); Tofan et al.
α-benzoinoxime (2001a)
Cu(II) Fibres impregnated with Batch 13.8072 Tofan and Păduraru (1999); Tofan et al.
α-benzoinoxime (2001a)
Cu(II) Shives Batch 1 g/100 mL 4 24 h 3.91 Balintova et al. (2014)
Cu(II) Treated shives with NaOH Batch 1 g/100 mL 4 24 h 4.45 Balintova et al. (2014)
Cu(II) Raw felt Batch 0.25 g/100 mL 5 1h 14.64 Loiacono et al. (2017a); Bugnet et al.
(2017b)
Cu(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 63.32 Loiacono et al. (2017b)
Fe(II) Raw felt Batch 0.25 g/100 mL 5 1h 7.87 Loiacono et al. (2017a)
Fe(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 23.93 Loiacono et al. (2017b)
Mn(II) Raw felt Batch 0.25 g/100 mL 5 1h 4.55 Loiacono et al. (2017a); Bugnet et al.
(2017a, b)
Mn(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 44.25 Loiacono et al. (2017b)
Ni(II) Treated hemp fibres Batch 0.1 g/100 mL 5 24 h 242 Kyzas et al. (2015)
Ni(II) Treated hemp shives Batch 0.1 g/100 mL 5 24 h 237 Kyzas et al. (2015)
Ni(II) Hemp fibres Batch 0.1 g/100 mL 5 24 h 206 Kyzas et al. (2015)
Ni(II) Hemp shives Batch 0.1 g/100 mL 5 24 h 160 Kyzas et al. (2015)
Ni(II) Raw felt Batch 0.25 g/100 mL 5 1h 7.85 Loiacono et al. (2017a); Bugnet et al.
(2017a, b)
N. Morin-Crini et al.
 Biosorbent Contact
Metal Type of biosorbent Technique dosage pH time qmax Reference(s)
1

Ni(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 40.98 Loiacono et al. (2017b)
Pb(II) Fibres treated with NaOH Batch 0.5 g/200 mL 5.5 2h 0.078a Pejić et al. (2009)
Pb(II) Fibres treated with NaClO2 Batch 0.5 g/200 mL 5.5 2h 0.037a Pejić et al. (2011)
Pb(II) Raw fibres Batch 0.25 g/50 mL 5 24 h 25.05 Tofan et al. (2010b, c)
Pb(II) Sulphydryl fibres Batch 0.25 g/25 mL 3.03 24 h 23 Tofan and Păduraru (2004)
Pb(II) Carbonized fibres SPE 0.2 g/50 mL 2h 15.89– Vukčević et al. (2014b)
24.18
Zn(II) Fibres treated with NaOH Batch 0.5 g/200 mL 5.5 2h 0.078a Pejić et al. (2009)
Zn(II) Fibres treated with NaClO2 Batch 0.5 g/200 mL 5.5 2h 0.038a Pejić et al. (2011)
Zn(II) Raw fibres Batch 0.25 g/50 mL 5 24 h 21.047 Păduraru and Tofan (2008)
Zn(II) Raw fibres Batch 0.5 g/200 mL 5.5 2h 8.3 Vukčević et al. (2014a)
Zn(II) Raw felt Batch 0.25 g/100 mL 5 1h 10.59 Loiacono et al. (2017a); Bugnet et al.
(2017b)
Hemp-Based Materials for Metal Removal

Zn(II) Carboxylated felt Batch 0.25 g/100 mL 5 1h 68.5 Loiacono et al. (2017b)
CO2 Carbonized fibres 5.62a Wang et al. (2015)
Atrazine Carbonized fibres treated N2 Batch 50 mg/100 mL 1h 263 Lupul et al. (2015a)
Atrazine Carbonized fibres Batch 50 mg/100 mL 1h 227 Lupul et al. (2015a)
Atrazine Carbonized fibres treated HNO3 Batch 50 mg/100 mL 1h 179 Lupul et al. (2015a)
Atrazine Carbonized fibres treated NH3 Batch 50 mg/100 mL 1h 169 Lupul et al. (2015a)
Atrazine Carbonized fibres Batch 0.2 g/50 mL 3h 14.5–15.5 Vukčević et al. (2015)
Nicosulfuron Carbonized fibres Batch 0.2 g/50 mL 3h 11.6–19.5 Vukčević et al. (2015)
Dimethoate Carbonized fibres Batch 0.2 g/50 mL 3h 11.8–14.7 Vukčević et al. (2015)
a
in μmol/g
27
28 N. Morin-Crini et al.

hemp-­based material; (ii) the experimental conditions should be chosen to simulate

real wastewater containing metals; (iii) much work is necessary to demonstrate the
possibilities on an industrial scale using real wastewaters and discharge waters.

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Chapter 2
Biosorption of Metals and Metalloids

Leticia B. Escudero, Pamela Y. Quintas, Rodolfo G. Wuilloud,

and Guilherme L. Dotto

Contents
2.1 Introduction 37
2.1.1 Metals and Metalloids in the Environment 37
2.1.2 Biosorption 39
2.2 Biosorption for Green Chemistry Development 41
2.3 Mechanisms Involved in Metal and Metalloids Biosorption 44
2.3.1 Chemical Binding 44
2.3.1.1 Complexation 45
2.3.1.2 Coordination 45
2.3.1.3 Chelation 45
2.3.2 Ion Exchange 46
2.3.3 Physisorption 46
2.3.4 Micro–Precipitation 46
2.3.5 Oxide–Reduction 47
2.4 Biosorption Equilibrium, Thermodynamic, and Kinetics 47
2.4.1 Conventional Equilibrium Models 48
2.4.2 Statistical Physics Models 51
2.4.3 Thermodynamic Parameters 51
2.4.4 Reaction Kinetic Models 52
2.4.5 Diffusional Mass Transfer Models 54

Abstract Industrial activities such as mining operations, refining of ores and com-
bustion of fuel oils play a relevant role in environmental pollution since their wastes
contain high concentrations of toxic metals that can add significant contamination
to natural water and other water sources if no decontamination is previously applied.
As toxic metals and metalloids, including arsenic, cadmium, lead, mercury, thal-

L. B. Escudero (*) · P. Y. Quintas · R. G. Wuilloud

Laboratory of Analytical Chemistry for Research and Development (QUIANID),
Interdisciplinary Institute of Basic Sciences (ICB), UNCUYO–CONICET, Faculty of Natural
and Exact Sciences, National University of Cuyo, Mendoza, Argentina
e-mail: [email protected]
G. L. Dotto
Chemical Engineering Department, Federal University of Santa Maria, UFSM,
Santa Maria, RS, Brazil

© Springer Nature Switzerland AG 2018 35

G. Crini, E. Lichtfouse (eds.), Green Adsorbents for Pollutant Removal,
Environmental Chemistry for a Sustainable World 19,
https://doi.org/10.1007/978-3-319-92162-4_2
36 L. B. Escudero et al.

2.5  iosorbents Used for Heavy Metal Removal

B 55
2.5.1 Bacteria 55
2.5.2 Fungi 60
2.5.2.1 Molds 61
2.5.2.2 Mushrooms 61
2.5.2.3 Yeast 62
2.5.3 Algae 63
2.5.4 Plant–Derivatives and Agricultural Wastes 65
2.5.5 Chitin–Chitosan Based Materials 68
2.6 Bio–Nano–Hybrids Materials 70
2.7 Conclusions, Trends, and Perspectives 75
References 76

lium, vanadium, among others, are not biodegradable and tend to accumulate in
living organisms, it is necessary to treat the contaminated industrial wastewaters
prior to their discharge into the water bodies. There are different remediation tech-
niques that have been developed to solve elemental pollution, but biosorption has
arisen as a promising clean–up and low–cost biotechnology. Biosorption is one of
the pillars of bioremediation and is governed by a variety of mechanisms, including
chemical binding, ion exchange, physisorption, precipitation, and oxide-reduction.
This involves operations (e.g. biosorbent reuse, immobilization, direct analysis of
sample without destruction) that can be designed to minimize or avoid the use or
generation of hazardous substances that have a negative impact on the environment
and biota, thus following the concepts of “green chemistry” and promoting the envi-
ronmental care. Furthermore, it has to be specially considered that the design of a
biosorption process and the quality of a biosorbent are normally evaluated from the
equilibrium, thermodynamic, and kinetic viewpoints. Therefore, a successful bio-
sorption process can be only developed based on multidisciplinary knowledge that
includes physical chemistry, biochemistry and technology, among other fields.
In this chapter, we explain in detail all the aforementioned aspects. State of the
art applications of biosorbents for metals and metalloids removal are carefully
revised based on a complete analysis of the literature. Thus, it is evidenced in this
chapter that the main points to consider regarding biosorption are the type of bioma-
terial (e.g. bacteria, fungi, algae, plant–derivatives and agricultural wastes, chitin–
chitosan based materials) and the presence of a broad set of functional groups on
their surface that are effective for the removal of different toxic metals and metal-
loids. In fact, removal percentages as high as 70–100% can be found in most works
reported in the literature, which is demonstrating the excellent performance obtained
with biosorbents. Also, biosorbents have evolved with the help of nanotechnology
to modern bio–nano–hybrids materials having superlative sorption properties due to
their high surface area coming from the nano–materials structures and multifunc-
Exploring the Variety of Random
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anxious scrutiny; but imagining it to be the effect of curiosity, it did
not excite in him any remark. Ardent, at this rencontre, seemed to
be in a state of surprise and wonder that kept him speechless. He
gazed upon the prepossessing features of the fair stranger as
earnestly as if he had no other faculty than that of seeing. The kind
and anxious look that met his own—the arms that clasped his neck
so firmly, and the gentle voice that murmured his name, convinced
him of a fact of which he was almost incredulous. It was Optima.
“By what fortunate chance did you escape the death I felt assured
that you had met with?” inquired Ardent, after, at Oriel’s request, he
had for the purpose of privacy retired to a chamber in one of the
neighbouring habitations.
“When I found the boat sinking, I clung to it,” replied his
companion; “and when it again rose to the surface I floated on it.
The blow which it had received from the ship had propelled it a
considerable distance, and the force of the waves carried it still
farther. The plunge I had received, for some minutes took my breath
away; and, although I held on with all my strength to the boat, the
heavy waves continually breaking upon me, and the alarming
position in which I found myself placed, made me quite incapable of
uttering a sound. As soon as I was able to comprehend the extent of
my danger, the thought that I was separated from you, and the fear
that you had perished in the sea, made my heart sink within me. I
clung instinctively to the floating vessel; but I had no desire to live. I
had seen enough of that dreadful conflagration to fill me with terror;
and I had not recovered from the feelings it occasioned, when I was
left alone, friendless, and about to be engulphed in the waters. All
around me was so dark that I could see nothing; but the saltwater,
as it dashed over me, scarcely allowed me to open my eyes if I could
have seen, and my strength was being rapidly exhausted. I soon
sunk into a state of stupor. How long this lasted I do not know; but
on recovery, I found myself in a cabin, receiving every attention that
my wants required; and, on inquiry, I found that I had been picked
up by the crew of a ship, which, attracted by the glare of the
burning vessel, had sent out a boat, in hopes of affording assistance
to the survivors.”
“I was saved in a similar manner,” remarked Ardent.
“When they had taken me into the boat they did not proceed any
farther,” continued Optima, “as they observed that another vessel
had sent out a boat’s crew upon the same errand, and having no
spare time at their command, they left the other boat to pick up the
survivors, and returned with me to the ship. I discovered also that
the vessel to which I had been conveyed had left Sydney with
emigrants for the very colony to which we were proceeding. I told
my story to my preservers, and many who heard it were kind and
compassionate. An offer was made me by the wife of a settler to
remain with her in the capacity of domestic servant, which offer I
accepted without hesitation. One thing was a great consolation to
me, and that was the conviction that you had been saved. I knew
that you were a strong swimmer, and as I had been told that a party
had been sent from the ship to rescue the crew of the boat they had
run down, I concluded that you were in safety.”
“You were right, dear Optima!” said the captain’s clerk; “I was
taken on board that ship, and have since held in it a responsible
situation.”
“Believing you to have been rescued, I continued to live, with the
hope that I should meet you again,” continued Optima. “I arrived at
the colony. The persons whose protection I had accepted, settled at
Sydney, where the husband commenced business as a builder, in
which he succeeded beyond his expectations. I was very well
treated, and labour being exceedingly valuable in the colony, my
exertions were rather profitable to me. At that time I entertained the
idea that as all our property was consumed in the fire, you must be
very much in want of a variety of comforts to which you had been
used; and as the expectation of my meeting you again was never
absent from me, I laboured diligently, and saved all my earnings as a
provision for our future support.”
Ardent could only look his gratitude, and rapturously kiss the hand
he held in his own.
 “It was such a pleasure to me, dear Ardent,” resumed his
companion, “to count my gains as fast as they accumulated, and I
kept saying to myself ‘a little more and there will be enough to begin
the world again with;’ and I thought how happy I should be able to
make you, and I kept hoping we should soon meet—and every day
passed by in imagining what we should do, and in enjoying a
happiness of my own creating. Every time I heard that a ship was in
the bay, I came down to the beach in hopes of finding you among
the passengers. I scrutinised every one that left the vessel so closely
that I offended some and surprised others; but although I met with
repeated disappointments, I never left off expecting your arrival. By
this time I had saved about two hundred dollars, and whether it
became known, or whether the scarcity of females brought me into
such consideration, I do not know; but scarcely a day passed
without my receiving an offer of marriage.”
“An offer of marriage!” exclaimed Ardent in surprise.
“Yes, dear Ardent,” replied Optima. “The men seemed frantic after
me. I was not safe any where. If I went to pay a bill, it was sure to
conclude on the part of the tradesman with an offer of his hand and
heart. If I entered the market, no sooner had I made a purchase
than I received a proposal. I was besieged in all hours and at all
places,—I may almost say that I received a new suitor at the corner
of every street. It was in vain I told them I was married, and showed
them my wedding ring. They saw that I had no husband with me,
and they were desirous of supplying his place; and men even of a
superior rank continually plagued me with their proposals. It is
scarcely necessary to say that I gave them all a negative answer;
but these were things that they did not appear to understand, for
the more frequently I refused, the more frequently they again
proposed. At last I was obliged to state how I was situated to the
lady with whom I was staying, and she spoke to her husband; and
he took measures that put an end to the persecution. And now, dear
Ardent, that my anticipations are realised, we will be so very happy
—won’t we?”
 It is easier to imagine what was the answer than to describe it. It
is sufficient to say that Oriel Porphyry made a considerable addition
to the two hundred dollars which the devoted Optima had saved,
that enabled the young couple to take a promising farm up the
country, with every prospect of enjoying a life of continued
happiness.
“It is very strange,” remarked the young merchant to Zabra on his
return to the ship, “it is very strange that I have had no
communication from my father. I expected one at Athenia, but I
received no intelligence. I expected one at Constantinople—there I
met with the same result; and I then made sure of meeting with one
at New Sydney, but was there equally unsuccessful. It makes me
very uneasy.”
“Possibly he may have nothing of importance to write about,”
replied Zabra. “Things at Columbia may remain in the same state as
at his last despatch.”
“I doubt it. I doubt that the emperor will remain satisfied with his
prerogatives curtailed to the extent to which they have lately been
reduced,” said Oriel Porphyry. “There is no sincerity in these men.
They will break any compact when it suits their convenience. They
have no notion of either honour or honesty: and the emperor is a
weak, vain, foolish man, proud, tyrannical, and deceitful. Such a
man must be ever scheming to regain his former power; and if he
think it be practicable he will not be particular as to the means he
will employ for that purpose. I am much afraid my father has fallen a
sacrifice to his patriotism.”
“It cannot be,” observed his companion. “They would not dare
harm him.”
“Dare!” echoed his patron. “What evil will not bad men dare? And
did not that proud upstart Philadelphia load his honourable limbs
with chains and thrust him into a loathsome dungeon to die the
lingering death of starvation? He dared do that, and I doubt much
whether a worse villainy could have been perpetrated. I hope to live
to see the time when I shall have an opportunity of bringing him to
an account for these and other atrocities. If my good sword be true,
and my arm has lost none of its power, I’ll not leave his worthless
body till I have relieved it of his equally worthless soul.”
“What!” exclaimed Zabra, with considerable excitement, “would
you be thus revengeful to the father of Eureka? You too, who a short
time since seemed ready to forgive him all his errors on account of
his relationship to her. What has changed you? Why would you
follow the bad examples of bad men? That he is not what he should
be is too true; but that is no reason why you should become his
executioner. Do you think that Eureka could regard you with
affection when you came to her stained with her father’s blood? I
am surprised that you should have given utterance to such a
sentiment.”
“I knew not till lately the atrocities he had committed, and the
savage disposition he possessed,” replied the young merchant; “and
I can see no more harm in killing such a monster than there is in
destroying a mad beast.”
“How different then your feelings must be to those of your father,”
observed the other. “He knew what was due to humanity, and
practised it, and he was the person best entitled to call for
vengeance, but he was satisfied with justice. Professing the regard
you do towards Eureka, nothing could surprise me more than to
hear you proclaim so inhuman a wish.”
“It is impossible for me to help feeling exasperated against him,”
said Oriel. “Imagine for a moment yourself in my situation. Let your
father be as mine is, the kindest and noblest of his species; know
that he who never did harm to any living creature, but sought to
create happiness throughout the world—was fettered and reviled,
and left lingering in filth and darkness for three days, enduring all
the pangs of famine; and if you have a heart within your breast, and
a soul that hates the cowardly vices of despotism, you will feel as I
do, and long for an opportunity to punish your father’s persecutor, in
a manner worthy of his crimes. I know that your relationship to the
offender must stand in the way of your seeing the justice of the
punishment I would inflict: but I am no hypocrite Zabra. I cannot
disguise my detestation of such a monster; and although next to
Eureka and my father I honour you, even your opposition would not
make me change a sentiment so natural and appropriate.”
“Leave Philadelphia to his own feelings, which sooner or later will
be sufficient punishment,” responded Zabra. “Touch him not if you
value the love of Eureka. She I know has little cause to feel much
affection for him, but bad as he is she never can be brought to look
upon his destroyer with any feeling save that of repugnance.”
“If that be the case I hope he will keep out of my way,” rejoined
the young merchant; “for I think I could endure anything rather than
her dislike; but the absence of intelligence from my father has
certainly made me suspicious. I am almost determined to return to
Columbia without proceeding to England.”
“I do not think such a course advisable, Oriel,” observed Zabra.
“There may be a thousand things that prevent your father’s
correspondence, or he may have written, and the despatches may
have been lost. If this be the case, and there is a great probability
that it is, he would be very much vexed at your returning without
having accomplished your voyage.”
“Well, I will proceed, but I will only make a brief stay among the
antiquities of England, and then steer direct for Columbia,” replied
Oriel Porphyry: “I have very strong doubts about things being
exactly right there. The accounts I have heard are of a contrary
tendency; but if the storm is to be, it will come unexpected. If any
attempt be made by the government to restore the old order of
things, I hope they will have the goodness to wait till my return
before they commence their proceedings. There is a powerful
regiment of horse, composed of the young citizens of Columbus, of
which I have the command; I believe that they are devoted to my
will; and even with these, although they are not above a thousand
strong, I would make such a stand as would soon bring around me
all the brave spirits in the country: I only wish for an opportunity to
try the experiment.”
“Will you never dismiss these delusive visions,” said his young
friend, anxiously. “I thought that you were at last becoming
reconciled to a more useful and amiable way of life.”
 “You have been deceived, Zabra,” observed Oriel; “I have been
more quiet, but not less ambitious. This passion for glory has
become a part of my nature; it is with me at all times. I think of it
and dream of it. It is the anticipation of finding the opportunity for
greatness that makes me able to endure the tedious inactivity of my
present mode of existence. I shall never be satisfied till I acquire the
power for which I yearn.”
“What an unhappy nature yours must be then,” replied Zabra.
“You have every hope of happiness within your reach; yet because it
does not come clothed in the gorgeous draperies in which you wish
it to appear, you seem desirous of dismissing it, as of not sufficient
value to be enjoyed. I had hoped that you had become wiser; I had
hoped, too, that you had been more solicitous for the happiness of
Eureka. I am afraid all my labour has been thrown away, and that I
shall have to return to her with the intelligence that your ambitious
hopes have stifled every feeling of affection.”
“There you wrong me,” exclaimed the young merchant, “you
wrong me exceedingly. My aspirations for greatness are never
separate from my hopes of Eureka; because the first are merely the
result of the latter. It is useless attempting to check the impulses
which urge me on. I must be what I am; and while my state of
being, and the purposes which it creates and would see fulfilled,
cannot in any way dishonour Eureka, nothing will convince me that
they are to be condemned. From my own knowledge of her
character, I cannot imagine that she would regard my efforts for
advancement with the feeling which you have stated she possesses.
Her own greatness of soul must bring her to look with
commendation on another, who evinces a desire to obtain a similar
greatness: this ambition is a passion so entirely of her own creating,
that she cannot, with any justice, be displeased with its exhibition.”
“How little you seem to know of the nature of her whose love you
possess,” replied Zabra, in a low, tremulous voice; “no doubt, she
would feel gratified at any circumstance which would exalt you in the
estimation of your countrymen. The honour you might receive would
be her glory as much as yours, and the fame you might obtain
would find none more desirous of its security than herself. But it was
not for these things that she loved you. Ambition formed no part of
the qualities that called into existence her admiration—which, having
acquired its full growth, cannot be made more perfect by the
greatness you covet; and that admiration must continue as long as
the qualities that called it into operation exist. But knowing your
desire to acquire renown, and knowing the nature of that feeling is
to swallow up all the more amiable aspirations, and being aware that
the only way to its acquirement is through a thousand terrible
dangers, she cannot help the conviction, that she would rather
possess your affection as you were, than live in continual fear, to
witness your superiority, as you may be.”
“Let us say no more about it,” said Oriel. “It is very evident that
neither can convince the other. I may be positive that I am going
right, and you may be positive that I am going wrong; but it is time
spent to no purpose, if we cannot be brought to change our
opinions.”
“Remember, I am only doing my duty,” replied the youth. “I warn
you, because the path you desire to take is surrounded by dangers.
If you are determined on going on, I say, go on and prosper; but if
you go on, and fail, the bitter disappointment you will experience will
not only render yourself miserable, but must make equally unhappy
her whose felicity you appear so desirous of creating. If you must go
on, Oriel, I say again—go on, and prosper.”
 CHAP. III.

OLD ENGLAND.

“We are approaching the British Islands, are we not?” inquired Oriel
Porphyry.
“Yes, Sir, the land lies right ahead,” replied the captain.
“There are several of these islands, I believe,” added the young
merchant.
“There are a great number on ’em o’ different sorts and sizes,”
said Hearty; “but them as is most visited are England and Ireland.”
“What is the meaning of the prefix to the word land in each of
these names?” asked Oriel of the professor.
“England or Ingle-land means the land of the fire side,” replied
Fortyfolios. “Ingle is an old British word meaning the fire at which
the inhabitants of a house warmed themselves or cooked their food.
The natives have been from the earliest times, famous for their love
of the comforts of this fire, which was usually made of coal dug out
of the earth, that made a cheerful blaze in a room, and their
attachment to their ingles procured the island the name of Ingle-
land, which, in course of time was abbreviated into the name of
England.”
“I doubt that very much, don’t you see,” here observed Dr.
Tourniquet; “for in my opinion, England has a totally different
derivation. The aborigines of the island were principally fishermen,
and very appropriately had given to them the name of angle-ers,
which means people who fish. Each separate kingdom was called a
kingdom of the Angles, from the natives using an angle, and the
whole island was called Angle-land, or the land of the angle, which
for shortness was soon afterwards called England.”
 “’Tis nothing of the kind, Dr. Tourniquet,” rejoined the professor
warmly. “I wonder you should have started such an absurd idea.”
“It is quite as reasonable as yours at any rate, don’t you see,”
remarked the doctor.
“It has no such pretension,” said the other in a decided manner. “I
can prove that the fire or ingle was a national characteristic of the
people.”
“And I can prove that fishing or angle-ing was a national
characteristic of the people,” added his antagonist.
“Pooh!” exclaimed one, contemptuously.
“Pish!” cried the other.
“Ingle-land,”—resumed the professor.
“Angle-land,”—said the doctor, interrupting him.
“Now, Dr. Tourniquet, I beg I may not be interrupted by your
ridiculous blunders,” observed Fortyfolios with considerable asperity,
and a look of dignity peculiar to himself.
“The blunder is on your side, don’t you see,” replied the surgeon,
with a chuckle of satisfaction exceedingly annoying to his
companion.
“Never mind if it be Ingle-land or Angle-land,” exclaimed Oriel
Porphyry. “All we know for certain is, that it is now called England.
But how do you account for the adoption of the other name?”
“Of the derivation of that word there can be no doubt—it explains
itself,” said Fortyfolios. “Ireland means the land of ire. The natives
from time immemorial have been known to be excessively irascible.
They would quarrel upon the slightest cause, and fight from no
cause at all. They would fight when they were hungry, upon which
occasion, as was very natural, they fought for a belly-full. They
would fight for liquor; they would fight for fun; they would fight for
love; they would fight to get drunk, and then fight to get sober. The
happiest men among them were those who were most frequently
beaten, and such persons were known to be the best friends as
were continually trying to knock out each other’s brains. These men
consequently got the appropriate name of Ire-ishmen, and the island
was called Ire-land.”
 “There you’re wrong again, don’t you see,” observed Tourniquet.
“The name Ire-land was derived from Higher-land, to express that
the country was more elevated in the estimation of the natives than
any other part of the globe. They entertained the most preposterous
ideas about the importance of their island. They stated that when
the rest of the world was sunk in barbarism, their Higher-land was
the seat of intelligence, and virtue, and superior bravery. They
asserted that their soldiers were the only soldiers that ever existed,
and that their agricultural labourers were ‘the finest pisantry in the
world.’ But there was certainly something very singular about them;
and even their brick-layers’ labourers were odd men. The island was
also called by the natives The Emerald Island, I believe because it
sometimes produced Irish diamonds. The Green Isle was another of
its names—and this was derived from the greenness of the people.
The men went by the name of ‘the boys’ long after the age at which
other boys became men; and even the oldest of the old men among
them, when he breathed his last, was said to die in a green old age.”
“It is extraordinary to me, Dr. Tourniquet, that you will give
utterance to such fallacies,” remarked the professor. “The facts are
exactly as I have stated them.”
“The facts are exactly as I have stated them,” said the other with
marked emphasis.
“Was there not a very celebrated character styled St. Patrick, who
flourished at one time among the Irish?” inquired the young
merchant.
“Certainly there was,” replied Fortyfolios. “Patrick, Pater Rick—or
Rick being the abbreviation of Richard—Father Richard, was a poor
monk——”
“That I deny!” eagerly exclaimed the doctor. “For, as it is stated in
a very ancient poem I have met with,
‘St. Patrick was a gintleman
And born of dacent paple.’”

“That is no authority,” resumed Fortyfolios. “I affirm that he was a

poor monk and——”
 “I maintain that he was a gentleman,” replied the other.
“I insist that you do not interrupt me, Dr. Tourniquet,” exclaimed
the professor angrily. “He was an exceedingly pious and virtuous
man, and by his example and precepts did a great deal of good
among his countrymen.”
“Yes,” said the surgeon, gravely, “I have met with an authority that
says
‘He gave the frogs and toads a twist,
And banished all the varmint.’

Now the usual reading of this couplet is that he drove the frogs and
toads out of the country; but if we look to the meaning of the word
twist, we shall find that it means an appetite: a man with a twist
means a man with a certain facility in swallowing anything eatable
that comes before him; and as we know that frogs at one time were
considered a great delicacy by the ancients, it is not unreasonable to
imagine that St. Patrick was a great epicure, and swallowed all the
frogs and toads in the island.”
“Preposterous!” exclaimed Fortyfolios; “he was a saint whose
prayers had the efficacy of ridding the country of every venomous
thing it contained. But there is a remarkable legend connected with
his history, which I will relate to you as I found it in a very ancient
poem preserved in the Columbian Museum. It appears that he was
one fast day on a visit at a house, and he desired dinner might be
brought to him; but the family having already dined there was no
fish, the usual food for fast days, for his meal; in fact there was
nothing eatable in the larder but a leg of mutton. With great regret
the people of the house acquainted him with the real state of the
case: but the good saint, with a benevolent smile, as the poet
describes, merely said,
‘Send my compliments down to the leg
And bid it come hither a salmon.’”

“And what was the result?” inquired Oriel.

 “To use the simple and expressive words of the poem,” replied the
professor, with his usual gravity,
“‘And the leg most politely complied.’”

“You see those white cliffs just beginning to show ’emselves,” said
the captain, pointing to the distant coast.
“I see them plainly,” replied the young merchant.
“That’s the coast of England, Sir,” added Hearty. Oriel Porphyry
gazed on the classic shores that were rising before him with a deep
and peculiar interest. He had read so much, and he had heard so
much of the glory of the country he was approaching, and of the
greatness of her people, that the first sight of land awakened in him
the most agreeable associations. He thought of the splendour of her
achievements—he thought of the magnificence of her power—he
thought of her illustrious men—he thought of her noble efforts in the
advance of intelligence—and the white cliff upon which he was
gazing appeared to him to be the most interesting portion of the
world.
“The appearance of the shore from the sea at one time conferred
on England the name of Albion,” said the professor. “From Alba white
—from which word many other names were derived, particularly
album—a white book in great request at one time among the
females of the island, to teach them the art of spoiling paper for the
benefit of the stationers—and albumen, the white of an egg, a sort
of food in great request with the chicken-hearted. Some of the
natives of Albion carried their attachment to the name so far that
they lived in a place which they designated the Albany, and had a
favourite place of resort which they called ‘Whites.’ There was also a
certain building situated in White Cross Street, to which they
proceeded, to show their nationality, by getting white-washed. The
females were remarkable for a partiality to white bread, white wine,
and white linen, and the males evinced an equal fondness for white
bait, white waistcoats, and white hands, and to such an extent did
this favouritism for a particular colour extend, that there was a
neighbouring island, called the Isle of White, to which the
inhabitants of Albion made occasional journeys, for the pleasure of
destroying white ducks, or white muslin: and it was usual for every
generation to be christened in white, to be married in white, and to
be buried in white.”
“What are these vessels approaching us in this threatening
manner,” inquired Oriel Porphyry, as he noticed several old crazy-
looking boats filled with men who were coming towards them with
their crews, howling, screeching, and yelling with all the strength of
their lungs.
“I do not think they mean us any good,” replied the captain: then
turning to some of the sailors standing scrutinising the appearance
of a strange fleet, evidently bearing down upon them, he exclaimed,
“Get the long gun ready, and give these fools a taste of grape if they
attempt to attack us.”
“Ay, ay! Sir,” replied one of the men; and every disposition was
made to repel any assault that might be attempted.
As they approached nearer, it was observed that these vessels
were a vast number of large open boats, some with sails, but most
without, and they were so crammed with men, that many of them
were in danger of sinking every minute. Their crews were clothed in
ragged vestments of every colour and description, and they were
armed with old swords, pistols, guns, pitchforks, and bludgeons, and
these they displayed as they advanced, shouting all the time in wild
savage tones perfectly deafening. A larger boat was in advance of
the others, and in a conspicuous situation in this vessel stood up a
tall fierce-looking man with his head bound round with a hay-band,
and a tattered blanket dropping from his shoulders. He brandished a
rusty sword as he approached, and gave orders to those who
followed, which appeared to meet with implicit obedience. When he
came within gun-shot of the Albatross, he turned round to his
followers and addressed them.
“Boys,” said he, pointing to the ship, “yonder’s the furreners. It’s
meself as ’ill take their big baste iv a ship if ye’ll be all to the fore.
Divle a care ye may take ov their darty guns that their pointing at
yese—its made ov wood they are, and sorrow a harm they can do,
bad luck to ’em. Keep your powther dry, boys, and look to your
flints, and iv we don’t kill and murther and throttle every mother’s
son ov ’em, I’m not King Teddy O’Riley.”
“Sheer off there, you ragamuffins,” shouted the captain through a
speaking trumpet. “Sheer off, or I’ll sink ev’ry soul of ye within gun-
range.”
“Down wid the darty furreners!” screamed King Teddy O’Riley; a
shower of balls whistled past the captain, and on came the over-
loaded boats, with their crews yelling in the most frantic manner.
There appeared to be at least five or six hundred of them, and it
was judged expedient to put an immediate stop to their progress.
The long gun was discharged, which sunk the foremost boat, and
killed the greater portion of its crew. The rest hesitated when they
beheld their monarch swept into the sea; and a well-directed fire of
musketry made them glad enough to commence a retreat as fast as
they could, screaming in hideous chorus as long as they could be
heard.
“Take a boat and see if you can save any of those rascals
sprawling in the water,” exclaimed the captain to the midshipman
Loop.
“Yes, Sir,” was the reply; and the boat having been lowered, a
party proceeded to pick up the wounded and drowning. They
succeeded in saving several, among whom was their illustrious
leader, King Teddy O’Riley, who was brought upon deck, looking very
much deprived of his dignity, his coronet of hay-bands wet and dirty,
and his blanket of state shrunk out of all shape. He created
considerable surprise among his captors, and not without sufficient
cause, for nothing could exceed the eccentricity of his appearance.
His hair was thick and long, and of a dark-red colour. Large, bushy
whiskers of the same tint surrounded his cheeks. His nose was
remarkably red, and his face seamed with the marks of the small-
pox. Below his cloak was a long coat, which did not appear the more
royal for being out at the elbows, and for having lost half its skirt.
His lower garments hung upon him like a bag, and they had the legs
rolled back up to the knees. A pair of old boots, exceedingly down at
heel, out of which the toes of his majesty were seen to peep in spite
of the straw with which they were lined, completed his costume.
“And who the deuce are you?” demanded the captain, after he
had sufficiently scrutinised the appearance of his prisoner.
“Faix and isn’t it King Teddy O’Riley I am?” replied the man.
“And what part o’ the world are you king of, I should like to
know?” asked Hearty in considerable surprise.
“Faix and ain’t I king ov Blatherumskite?” said the other.
“And where, in the name o’ all that’s wonderful, is
Blatherumskite?” inquired the captain.
“And is it yourself that doesn’t know where Blatherumskite is?”
exclaimed his majesty in seeming wonder. “Well the ignorance o’
some people is amazin! Not know Blatherumskite! Be the holy japers
that bates Bannagher, and Bannagher bate the divle. And
Blatherumskite sich a jewel ov a place! Why Blatherumskite’s the
finest kingdom and has the finest paple under the sun. It’s full ov
commodities ov all sorts. It dales in turpentine, brickdust, soft soap,
and other swate mates—tracle, and train oil, pepper and salt, and
other hardware,—pigs, buttermilk, paraties, and other kumbustibles.
Not know Blatherumskite indade! Be this and be that, you’re as
ignorant as a born brute.”
“And what induced you to fire at me, Mr. King Teddy O’Riley?”
demanded the captain.
“Faix and wasn’t it only just to kill ye we fired at ye?” replied the
king, with the utmost simplicity.
“It was, was it?” exclaimed Hearty; “and for what reason did you
attack the ship?”
“Wid no other rason in life than to take it,” responded his majesty.
“I was jist a lading the boys to make a decint on England, wid the
hope ov being able to pick up a few thrifles, when we seed your
ship. ‘The top ov the morning to ye,’ says I, ‘and if I don’t be afther
ransacking ye intirely small blame to me there’ll be.’ And then we
pulled away at the divle’s own rate, and a mighty dale ov divarsion
the boys had about what they’d do wid the big ship when they’d got
her, when widout wid your lave or by your lave, I was regularly kilt,
smashed, and smothered into the wather. And here I am.”
“Well, King Teddy O’Riley, we must be under the necessity of
hanging you,” observed the captain.
“Hang me!” shouted the man, in perfect amazement. “Hang a
king!—hang King Teddy O’Riley? Hang the King ov Blatherumskite?
Why its rank trason? Ye’ll not be afther thinkin ov doin sich a
rebellious action. I shall feel obliged to ye if ye wont mintion it.”
“And what would you have done with us if you had succeeded in
your ridiculous idea of taking the ship?” inquired Hearty.
“Faix and wouldn’t we have kilt every sowl of yese, and taken the
rest prisoners?” replied his majesty.
“Then we cannot do better than follow your example,” observed
the captain; then turning to some of his men, who appeared to
enjoy the scene with particular satisfaction, he exclaimed, “Get a
rope ready at the fore-yard arm that we may hang this fellow!” The
sailors with great alacrity made the necessary preparations.
“Be all the holy saints betwixt this and no where, ye’ll not be
afther taking away the life ov a poor king!” exclaimed his majesty of
Blatherumskite, with the greatest earnestness and alarm. “What’ll I
do now? Sure and I’m in a bad way! Sure and I’ll be done for
intirely! And is it to be hanged I am?” continued he, looking woefully
at the rope that was dangling ready for immediate use. “Is King
Teddy O’Riley to be kilt afther sich a villainous fashion? Oh what a
disgrace for Blatherumskite! What a dishonour to a king. Oh what ’ill
I do—what ’ill I do?”
“Is the rope ready?” inquired Hearty.
“All right, Sir,” said the boatswain.
“Then hoist him up,” replied the captain. The men proceeded to
fulfil the command of their officer.
“Oh it’s in a pretty way I am!” exclaimed the unfortunate monarch,
with tears in his eyes. “Be the holy japers, wouldn’t I change places
wid any body as would like to be hanged in my place. It’s yourself,
Murphy O’Blarney, that’s the good subject,” said the king, addressing
one of his companions with particular and impressive emphasis.
“Sure, and ye’ve got more pathriotism than to let the King ov
Blatherumskite be hanged, when it’s your own loyal neck as would
fit the rope so azy.” Murphy O’Blarney did not seem to hear. “Bad
luck to the likes ov yese for a thraitor,” murmured his majesty. Then,
turning to another of his subjects, he said, “Larry Brogues, it’s great
confidence I place in ye—ye’re a jewel ov a man intirely; and if ye ’ill
jist be afther doing me the thrifling favour ov being hanged in my
place, the best pig I have shall be your’s.” Larry appeared as if he
had lost all relish for pork. “I always said ye were a base ribbel!”
muttered the angry monarch, turning from him to address a third.
“Mick Killarney, a sinsible boy you’ve showed yerself afore to-day,
and little’s the praise I take to meself for not having rewarded ye
according to your desarts; but if ye’ll show your superior
desarnment, by letting the little bit ov a rope be placed round your
neck instead ov mine, it’s meself that ’ill make a man ov ye when I
get back to Blatherumskite.” Mick Killarney turned the only eye he
had in his head, to another part of the ship. “There’s more brains in
the tail of a dead pig, than ’ill ever come out ov yer thick skull, ye
villain!” exclaimed King Teddy O’Riley in a thundering rage: then he
looked very pathetic, wiped his eyes with a corner of his blanket,
and began to chant, in the most miserable tones, the following
words:—
“Who’ll bile the paraties and pale ’em and ate ’em!
Who’ll drink all the butthermilk I used to swallow!
Who’ll hand round the whiskey, and take his own share too
Wid mighty convanience.
“Oh Teddy O’Riley your reign’s put a stop to,
Small blame to your sowl! you’re a king now no longer,
You’re smashed all to smothers, and dished up and done for
In a way most amazin.
“Not brave Alexander, or Nebuchadnezzar,
Who went out to grass wid the rest ov the cattle,
Not Moses, or Boney, nor yet Cleopatra,
Were treated so vilely.
“Its meself that is up to me eyes in amazement
To see you desaved and surrounded by villains,
 Who are wantin to place your poor neck in a halter
Bad luck to their mothers!
“Is it rope you’re desirin? the divle a ha’porth.
Is it hanged that you would be? not me then by Japers,
Oh! there’s sinse and there’s rason in your own way ov thinkin,
You’re cliver intirely.
“But sorrow a hope have ye got to indulge in,
For there hangs the rope like a murtherin blaguard,
Wid a knot at one end, and a noose at the other.
Oh what ’ill I do now?”
Oriel Porphyry, who had laughed exceedingly at the whole scene,
now stepped forward, and, by his interference, saved his majesty’s
life.
“I always thought that Ireland formed a portion of the British
dominions,” observed the young merchant.
“So it did,” replied Fortyfolios, “and enjoyed an unexampled state
of prosperity; but the people were always dissatisfied and
unreasonable; and were ever accusing the government of the
country by which they were ruled of creating that social
disorganisation which was the effect of their own evil habits—and
which had existed, as may be proved by a reference to their own
annals, as far back as it was possible to refer—and, upon the first
opportunity, they threw off their allegiance to the British empire, and
became, as they had previously been, a separate kingdom. As might
have been expected, internal strife now appeared. As had formerly
been the case, the country was cut up into a party of petty
monarchies, that were continually at war with each other. These
having gradually become smaller and more numerous, there is now
a king to every potato-garden, of which class of monarchs his
majesty of Blatherumskite is an example; and when these fellows
are not striving to exterminate each other, they make piratical
excursions to the neighbouring coast, and there create all the
mischief in their power, by robbing, plundering, killing, and burning.”
“We are entering the Nore, now Sir,” remarked the captain.
 “The derivation of the word is exceedingly puzzling,” remarked the
professor, “and I have met with no explanation that has satisfied me.
Some antiquarians trace it to Noah, but they bring forward nothing
which can be relied on in proof of this idea. I must say it is my
opinion that Noah was never in this part of the world. Others ascribe
it to the frequent use of the words ‘Know her,’—as parties of
pleasure used frequently to start in steam-boats from the metropolis
to this place, and then return; and intimacies between the young
males and the young females who had never met previously, used to
spring up during this excursion, and the former used to reply when
they were asked if they knew an individual of the other sex, ‘Know
her? we met going towards the sea,’ and the words at last became
so common that it gave name to the place.”
“You’re wrong again, don’t you see!” exclaimed the doctor. “But I’ll
tell you how the place came by the name. In very ancient times a
company of individuals created a joint-stock association to work a
copper mine of great value which they said had been discovered on
the neighbouring coast, and the people, deluded by the great
anticipations held out by the schemers, invested large sums in the
affair. The shaft was sunk and the mine worked, and the anxious
citizens were every day coming down in crowds to learn the progress
of the mine, but they invariably met with one answer to all their
queries, which was ‘No Ore;’ and this lasted till the bubble burst.
Since then the place was called ‘No Ore,’ which ultimately dwindled
into ‘Nore.’”
“Preposterous!” cried Fortyfolios. “I wonder you can repeat such a
ridiculous conception.”
“I’m positive that my ‘No ore’ is as good as your ‘Noah’ or ‘Know
her,’ don’t you see,” replied the doctor, good humouredly.
“Nothing of the kind, Dr. Tourniquet,” said the other very gravely.
“My derivations are founded on well ascertained facts.”
“And my derivation is founded on better ascertained facts,” added
the surgeon.
“The coast here seems quite deserted,” observed Oriel Porphyry. “I
do not see a habitation—nor a human creature—nor any species of
vessel—nor any sign of life whatever.”
“Possibly the natives have deserted this part of the coast from its
liability to be visited by the Irish pirates,” replied the professor. “But
what a change there must have been in the appearance of this
neighbourhood a few centuries back! Then vessels of every size and
nation might have been seen sailing in almost countless numbers
down the river to the Port of London, which was the mart of the
world. Merchant ships and ships of war, colliers, fishing-vessels,
passage-boats and pleasure-yachts were passing and re-passing
each other at all hours of the day. Then these masses of ruins which
you are passing on each side of the river, were filled with busy
inhabitants engaged in the various labours of traffic. Here ships were
built, fitted out, victualled, and stored, and when manned with a
gallant crew, set sail to visit every quarter of the globe, to dispose of
their cargoes and to bring home the produce of other countries.
There was a battery to prevent the passage of the enemy’s ships in
time of war. A little further on we come to a fashionable watering
place, in which the tired citizens forgot the toils of business in the
pursuit of pleasure. Towns and villages existed on either side; some
of considerable importance, with a numerous population engaged in
every species of manufacture and of laborious employment.”
“The country possesses a most desolate appearance,” remarked
Zabra.
“The natural effect of the cause which produced it,” responded the
professor. “Here all the horrors of war have been exhibited on the
most comprehensive scale, and what warfare left untouched time
has since destroyed. Nothing meets the eye but blackened buildings
and tottering walls. The country is a wilderness—the town a desert.
A little time since all was busy—all was fertile; and every nook and
corner resounded with the stir of the artisan at his craft, and the
mirth of the idler at his pleasure.”
“What part of the island was this called?” inquired Oriel.
“These are the shores of Kent, so called from the ancient word
Kenned, known or famous,” replied Fortyfolios. “It was called the
garden of England, and, if the accounts which describe it are to be
depended on, well did it deserve the title. It was one continued field
of fruit, and flowers, and grain. Forests of magnificent timber
afforded materials for the carpenter and the ship-builder—
plantations of hops gave employment to the cultivators, the
merchants, and the brewers of malt liquors; and orchards of cherries
were in constant demand from one end of the island to the other.
Now the timber has either been cut down, or died of natural decay—
the hop gardens have given place to crops of luxuriant weeds—and
the sweet and luscious fruits have become wild and sour.”
“Here is an extensive collection of ruins on the left—and it seems
once to have been an important place,” observed the young
merchant.
“It was so,” said the professor. “There were the public dockyards,
the arsenal, a college for the education of youth to the profession of
war, manufactures on the most extensive scale of materials
employed in fitting out ships for the war or merchant service, and
conveniences for traffic or accumulation of all sorts of naval and
military stores. There were foundries for cannon—manufactories of
cordage, shot, nails, and ship biscuit—magazines for the safe deposit
of gunpowder—yards for ship-building, and warehouses for apparel:
now you see nothing but the bare walls rising up from the mass of
ruins of which they are a portion. In solitude the wild dog howls
where all was human life and industry; and with the boldness of long
indulgence, the bats congregate in the chambers of the merchants.”
“Here are the remains of a more stately structure than any we
have hitherto passed—was it a palace?” inquired Oriel Porphyry.
“It was nothing more than a hospital for poor sailors, such as had
been maimed in the service of their country,” replied Fortyfolios.
“Indeed!” exclaimed the young merchant, with considerable
surprise.
“Nothing else, I assure you,” added his tutor.
“The government were remarkably attentive to the wants of their
seamen then—they must have valued their services very high to
have lodged them in so sumptuous a building as this appears to
have been,” observed Oriel.
 “Their dwelling was at one time far more magnificent than the
palace of the King of England,” continued the professor. “There was
no edifice erected for such a purpose to equal it in the whole world.
There the wounded sailor passed the rest of his life enjoying every
comfort he required. He had the range of a magnificent mansion,
and an extensive and beautiful park. Proper officers watched over
his health, his diet was strengthening and plentiful, and under the
care of good and pious men his moral wants were equally well
attended to. In another part of the river there used to be a building
of similar extent that had been erected for poor and wounded
soldiers, and they were provided for in a manner equally generous
and considerate.”
“These people were distinguished for their charities, I believe,”
remarked the young merchant.
“They were,” replied Fortyfolios. “They had numberless hospitals in
which the poor, afflicted with disease, or hurt by accidents, were
promptly cared for, and skilfully treated. The ablest physicians, the
most experienced surgeons, and the most skilful nurses waited upon
them; and all that the necessities of their cases demanded was
immediately rendered. They had asylums for females who had
strayed from the path of virtue, where they were taught industrious
and moral habits, and then restored to society capable of taking a
place with its most useful and honourable members. They had
houses of instruction to reclaim young thieves, in which they
received an excellent education, were taught some useful trade, and
then re-entered the community capable of passing through the busy
scenes of life with credit to themselves and others. They had——.”
“They had hospitals and asylums for every vice that disgraces
humanity, don’t you see,” said the doctor, interrupting the speaker
with more bitterness than was usual with him. “The vilest of the vile
were sheltered and preached to, and made comfortable and happy;
but while vice received every possible attention in fine buildings,
with numerous servants, virtue might crawl through the public
streets and starve; and while the rogue was carefully instructed in all
things that were excellent to save his wretched life and soul, the
honest man, struggling with adversity and sickness, was left to die
and be damned. There was no asylum for the virtuous woman; but
the vilest prostitute had always a ready home. Integrity and
intelligence had to fight with famine alone and unnoticed; but
ignorance and dishonesty, profligacy and crime, were sought after
and generously provided for. In fact, under this miserable state of
things there existed a bonus upon vice. If the vile were only vile
enough, they were the objects of universal benevolence: but to be
poor without being vile—oh! it was considered something so
contemptible, that the charitable could not be brought to pay it the
slightest regard.”
For a wonder Fortyfolios made no reply.
“This place is also of considerable importance to the scientific
inquirer,” continued the professor; “for here was a famous
observatory, in which the most illustrious astronomers carried on
their investigations into the motions of the heavenly bodies, and the
laws which govern them. Many interesting discoveries were here
made. From here were calculated the distances of various parts of
the world. The neighbourhood was also distinguished by being a
place of favorite resort of the inhabitants of the metropolis; and
even members of the government used to indulge themselves
occasionally with a trip to this once delightful place, for the purpose
of enjoying a delicacy in the shape of a very small fish, a thousand
of which would scarcely make a sufficient meal.”
“Here are many heaps of stones and fragments of brickwork. I
should suppose that they are the remains of a town of some kind,”
observed the young merchant.
“They cover a space sufficiently extensive to make it probable,”
replied Fortyfolios; “but they ought to be considered as a distant
suburb of the metropolis. They were chiefly inhabited by persons
engaged in the production or sale of naval stores, and boat-builders,
fishermen, and sailors employed in managing the craft upon the
river. In some places there are wharves for merchandise, in others
for coals; here was a factory for the produce of canvass, there an
establishment of engineers who sent steam vessels to every sea that
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