Sanjay K. Sharma-Heavy Metals in Water - Presence, Removal and Safety-Royal Society of Chemistry (2014) PDF

11:25:17.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP001
Heavy Metals in Water

Presence, Removal and Safety
11:25:17.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP001 View Online
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Heavy Metals In Water

Presence, Removal and Safety
Edited by
Sanjay K. Sharma
Department of Chemistry, JECRC University, Jaipur, India
Email: drsanjay1973@gmail.com
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Print ISBN: 978-1-84973-885-9

PDF eISBN: 978-1-78262-017-4
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A catalogue record for this book is available from the British Library
r The Royal Society of Chemistry 2015
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Preface
Agriculture and industrial developments are not possible without the in-
dispensable element water. All living and non-living things require water for
their existence in one way or another. So, if somebody says that water is the
liquid of life, it is absolutely correct. Nobody can live without water.
The population explosion, increasing urbanization and industrialization
are the major reasons for the depletion of water availability worldwide and
thats why the water crisis has become a global challenge today. Scientists,
policy makers and academicians are continuously trying hard to address this
problem to the best of their knowledge and abilities, but without complete
success.
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Besides the water crisis, the availability of safe water is another associ-
ated challenge. Because of various types of pollutants and impurities present
in water, whatever water is available is not always safe. Unfortunately
drinking such unsafe water is the fate of billions of people around the
world and pure water is always a dream for them.
Dissolved solids, synthetic dyes, agriculture runos, industrial euents
and microorganisms are a few of the things responsible for making water
unsafe. The presence of heavy metals is an add-on to this list, and these are
so dangerous that they may actually lead to death. Metals such as arsenic,
cadmium, chromium, copper, lead, mercury, nickel and zinc are commonly
found at contaminated sites and in aqueous systems. For example, arsenic
poisoning claims thousands of deaths every year in Bangladesh and West
Bengal in India, while lead is very toxic to living organisms, accumulating in
the bones, brain, kidney and muscles, and may be the cause of many serious
disorders such as anaemia, kidney diseases, nervous disorders, sickness and
even death.
The presence of heavy metals in water is due to both natural and an-
thropogenic sources. Natural sources may include parent rocks and metallic
Heavy Metals in Water: Presence, Removal and Safety

Edited by Sanjay K. Sharma
Published by the Royal Society of Chemistry, www.rsc.org
v
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vi Preface
ores and, on the other hand, agriculture (fertilizers, animal manures,

pesticides), metallurgy (mining, smelting, metal finishing), energy pro-
duction (leaded gasoline, battery manufacture, power plants), micro-
electronics, sewage sludge and scrap disposal can be included in the
anthropogenic sources.
Removal of these heavy metals is a big problem for everyone. Examples
of the many techniques being tried to achieve this include biosorption,
bioremediation, phytoremediation, photocatalytic processes, use of func-
tionalized magnetic nanoparticles and use of industrial and agricultural
waste.
This book is a sincere eort to showcase the latest research in the field of
heavy metals removal, written by leading scientists and researchers. At this
point in time I express my gratitude to all contributors who made this vol-
ume possible. I hope that the chapters presented will be a good source of
reference material for scientists in their further research and development.
Also, I hope that this book provides an insightful text on the theme of
heavy metals removal and processes that are being studied, optimized and
developed to sustain both mankind and nature.
I sincerely welcome feedback from all my valuable readers and critics.
Happy reading!
Sanjay K. Sharma
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Jaipur, India
Acknowledgments
This is the opportunity to express my thanks and gratitude to my friends,

colleagues, supporters and well wishers and to let them know that I am so
grateful to have had them, and their valuable cooperation, along with me
during the journey of this bookHeavy Metals in Water: Presence, Removal
and Safety.
First of all I express my special thanks to all the esteemed contributors,
who deserve special mention for providing their writings, without which this
book could not be possible.
I sincerely acknowledge my parents Dr M.P. Sharma and Mrs Parmeshwari
Devi, my wife Dr Pratima Sharma and all other family members for their
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never-ending encouragement, moral support and patience during the course

of this book.
I acknowledge the active interest and useful suggestions from Ackmez
Mudhoo, University of Mauritius, Mauritius. Thanks Ackmez!
I also thank Mr Amit Agarwal and Mr Arpit Agarwal (Vice Chairpersons,
JECRC University, Jaipur) and Professor S.S. Pabla (Vice Chancellor, JECRC
University, Jaipur) for their appreciation and encouragement.
My children Kunal and Kritika always deserve special mention as they are
my best companions, who energize me to work with refreshed mood and
motivation.
Special thanks go to the team at the Royal Society of Chemistry behind this
publication, without whose painstaking eorts this work could not have
been completed in a timely manner. Thanks RSC!
I am also grateful to many others whose name I have not been able to
mention but whose association and support has in no way been any less.
Sanjay K. Sharma
Jaipur, India

vii
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This book is for Pratima, my wife, without whose love, support and
cooperation I could not achieve anything in my life.
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About the Editor
Prof. (Dr) Sanjay K. Sharma is a very well known

author and editor of many books, research journals
and hundreds of articles over the last 20 years.
At present Prof. Sharma is working as Professor &
Head, Department of Chemistry, JECRC University,
Jaipur, India, where he is teaching engineering
chemistry and environmental chemistry to B. Tech
Students, green chemistry, spectroscopy and or-
ganic chemistry to MS students and pursuing his
research interest in the domain area of green
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chemistry.
His research interests are green chemistry, heavy metals removal, bio-
polymers and green corrosion inhibition. Dr Sharma has 15 books on
chemistry from nationalinternational publishers and over 52 research
papers of national and international repute to his credit.
He has also been appointed as Series Editor by Springer, UK, for their
prestigious book series Green Chemistry for Sustainability, where he has
been involved in editing 12 dierent titles by various international con-
tributors so far.
He is a member of the American Chemical Society (USA), Royal Society of
Chemistry (UK) and International Society for Environmental Information
Sciences (ISEIS, Canada) and is also a life member of various international
professional societies including the International Society of Analytical Sci-
entists, Indian Council of Chemists, International Congress of Chemistry
and Environment, Indian Chemical Society, etc.
Dr Sharma is also associated, as an Editorial Board Member or a reviewer,
with more than 15 international journals, including the prestigious Green

xi
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xii About the Editor
Chemistry, Green Chemistry Letters & Reviews, Ultrasonics and Ultrasonics

Sonochemistry, etc.
His recently published books are:
Biosurfactants: Research Trends and Applications (CRC Taylor & Francis,

USA)
Waste Water Reuse and Management (Springer, UK)
Advances in Water Treatment and Pollution Prevention (Springer, UK)
Green Corrosion Chemistry and Engineering (Wiley, Germany)
Handbook of Applied Biopolymer Technology: Synthesis, Degradation and
Applications (Royal Society of Chemistry, UK)
Handbook on Applications of Ultrasound: Sonochemistry and Sustainability
(CRC Taylor & Francis, USA)
Green Chemistry for Environmental Sustainability (CRC Taylor & Francis,
USA)
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Contents
Chapter 1 Contamination of Heavy Metals in Aquatic Media:

Transport, Toxicity and Technologies for Remediation 1
Ravindra K. Gautam, Sanjay K. Sharma, Suresh Mahiya and
Mahesh C. Chattopadhyaya
1.1 Introduction 1
1.2 Sources of Heavy Metals 2
1.3 Environmental and Health Risks 4
1.4 Remediation Technologies 7
1.4.1 Membrane Filtration 7
1.4.2 Phytoremediation 8
1.4.3 Heterogeneous Catalysts and Catalysis 10
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1.4.4 Photocatalysts 10
1.4.5 Electrocoagulation 11
1.4.6 Clays/Layered Double Hydroxides (LDHs) 12
1.4.7 Biomass and Biosorption of Metal Ions 13
1.4.8 Magnetic Nanoparticles as Nanosorbents 15
1.4.9 Removal of Iron and Manganese from Water 15
1.5 Concluding Notes 18
Acknowledgements 18
References 18
Chapter 2 Photocatalytic Processes for the Removal of Toxic

Metal Ions 25
Pankaj Chowdhury, Ali Elkamel and Ajay K. Ray
2.1 Introduction 25
2.2 Advanced Oxidation Processes for Heavy Metal
Removal 27
2.3 Basic Principle of Heterogeneous Photocatalysis 29

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xiv Contents
2.4 Mechanism of Photocatalytic Reactions 29
2.5 Thermodynamics of Photoreduction of Different
Metal Ions 30
2.6 Dependence of Photoreduction Kinetics on Different
Parameters 31
2.6.1 Effect of Initial Metal Ion Concentration 31
2.6.2 Effect of Photocatalyst Mass 32
2.6.3 Effect of ElectronHole Scavenger 33
2.6.4 Effect of Light Intensity 33
2.7 Recent Challenges in the Photocatalytic Process 34
2.7.1 Photoreactor Development 34
2.7.2 Photocatalyst Development 35
2.8 Application of Photocatalysis for the Removal
of Heavy Metals 35
2.8.1 Group 6 Metal (Chromium) 35
2.8.2 Group 10 Metals (Nickel and Platinum) 37
2.8.3 Group 12 Metals (Zinc, Cadmium and Mercury) 37
2.8.4 Group 15 Metalloid (Arsenic) 39
2.9 Conclusions 40
Acknowledgement 40
References 40
Chapter 3 Removal of Dissolved Metals by Bioremediation 44

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Subhajit Majumder, Suresh Gupta and Smita Raghuvanshi
3.1 Heavy Metals in Wastewater 44

3.2 Regulatory Limits of Heavy Metals 45
3.3 Physico-Chemical Treatments of Heavy Metals 46
3.3.1 Ion Exchange 46
3.3.2 Chemical Precipitation 46
3.3.3 Electrochemical Precipitation 47
3.3.4 CoagulationFlocculation 47
3.3.6 Adsorption 48
3.4 Bio-based Separation for Heavy Metal Removal 49
3.5 Applicability of Isolated Strains and their Efficiency 50
3.6 Application of Genetically Modified Microorganisms 52
3.7 Conclusion 52
References 53
Chapter 4 Functionalized Magnetic Nanoparticles for Heavy Metals

Removal from Aqueous Solutions 57
Ravindra Kumar Gautam, Sanjay Kumar Sharma and
Mahesh Chandra Chattopadhyaya
4.1 Introduction 57
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Contents xv
4.2 Sources of Heavy Metals in the Environment 58
4.3 Toxicity to Human Health and on Ecosystems 62
4.4 Magnetic Nanoparticles 64
4.5 Synthesis of Magnetic Nanoparticles 64
4.5.1 Coprecipitation 65
4.5.2 Hydrothermal Syntheses 68
4.5.3 Microemulsions 69
4.5.4 Thermal Decomposition 69
4.6 Magnetic Nanoparticles in Wastewater Treatment 69
4.6.1 Magnetic Nanoparticles as Nanosorbents
for Heavy Metals 70
4.7 Modeling of Adsorption: Kinetic and Isotherm
Models 73
4.7.1 Kinetic Studies for Adsorption of Heavy
Metals 73
4.7.2 Equilibrium Isotherm Modeling 75
4.8 Thermodynamic Analysis 77
4.9 Recovery of Metals and Regeneration of Magnetic
Nanoparticles 78
4.10 Conclusions 78
Acknowledgements 79
References 79
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Chapter 5 Arsenic Contamination: An Overview 86

Maurizio Carotenuto, Giusy Lofrano and Sanjay K. Sharma
5.1 Introduction 86
5.2 Chemical Characteristics 87
5.3 Arsenic Distribution in the Environment 90
5.3.1 Natural Sources 90
5.3.2 Anthropogenic Sources 94
5.3.3 Arsenic in Water, Air and Soil 96
5.3.4 Arsenic in Plants and Biota 98
5.3.5 Arsenic in Foods and Drugs 100
5.3.6 Metabolisms and Toxicity of Arsenic 102
5.3.7 Natural Groundwater Arsenic
Contamination 105
5.4 Arsenic Removal from Water and Wastewater 105
5.4.1 Coagulation and Flocculation (CF) 107
5.4.2 Adsorption 110
5.4.4 Constructed Wetlands 114
5.4.5 Advanced and Integrated Technologies 116
5.5 Concluding Remarks 117
References 118
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xvi Contents
Chapter 6 Removal of Iron and Manganese from WaterChemistry
and Engineering Considerations 122
Keisuke Ikehata, Andrew T. Komor and Yao Jin
6.1 Introduction 122

6.2 Chemistry of Iron and Manganese Oxidation
and Removal 124
6.2.1 Iron and Manganese Generation and
Removal in Natural Waters 124
6.2.2 Chemistry of Iron Oxidation and Removal 125
6.2.3 Chemistry of Manganese Oxidation and
Removal 127
6.3 Engineering Considerations for Iron and Manganese
Oxidation and Removal 129
6.3.1 Source Water Quality Analysis 130
6.3.2 Treatment Process Considerations 133
6.4 Conclusions 138
Acknowledgements 139
References 139
Chapter 7 Heavy Metal Pollution in Water Resources in

ChinaOccurrences and Public Health Implications 141
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Keisuke Ikehata, Yao Jin, Nima Maleky and Aijun Lin

7.2 Heavy Metals in Water: Definitions and Their Health
Effects 142
7.2.1 Brief Discussion on Heavy Metal Definitions 142
7.2.2 Fate of Heavy Metals in Water 143
7.2.3 Toxicological Properties of Heavy Metals with
Major Public Health Relevance 143
7.3 Heavy Metals in Chinese Water
ResourcesBackground 148
7.3.1 Chinas Recent Industrial Developments and
Heavy Metals in Water 148
7.3.2 Current Water Quality Standards and
Recent Trends 148
7.3.3 Current Discharge Standards for Heavy
Metals in Wastewater 152
7.3.4 Sources of Heavy Metals in Chinese
Water Resources 152
7.4 Recent Heavy Metal Pollutions in Chinese
Water Resources 155
7.4.1 Impacts of Mining, Smelting and Other
Industrial Wastewaters 155
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Contents xvii
7.4.2Impacts of Wastewater Irrigation on
Water Resources in China 158
7.4.3 Heavy Metal Pollution in Rivers and Drinking
Water Sources in Beijing 159
7.4.4 Human Health Risk Assessment of Heavy

Metals in Drinking Water Sources in China 159
7.4.5 Heavy Metal Contamination in the
Sediments of Rivers and Lakes 161
7.5 Concluding Remarks 162
Acknowledgements 163
References 163
Chapter 8 Heavy Metals Distribution in Surface Water Samples

of Taihu Lake, China 168
Hou-Qi Liu, Ying Liu, Guang Liu and Xue-Bin Yin

8.2 Methods 169
8.2.1 Sample Collection 169
8.2.2 Sample Processing and Analytical
Procedures 170
8.3 Results 170
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8.3.1 Chromium (Cr) 170

8.3.2 Lead (Pb) 170
8.3.3 Cadmium (Cd) 171
8.3.4 Zinc (Zn) 172
8.3.5 Copper (Cu) 172
8.3.6 Arsenic (As) 173
8.3.7 Cobalt (Co) 173
8.3.8 Nickel (Ni) 174
8.3.9 Tin (Sn) 174
8.3.10 Manganese (Mn) 175
8.4 Discussion and Conclusions 175
References 176
Chapter 9 Use of Nanotechnology against Heavy Metals Present

in Water 177
Ming Zhang, Bin Gao, Jin Jin, Hao Chen, Ying Yao,
June Fang and Anne Elise Creamer

9.2 Nanoclays 178
9.2.1 Nano-Kaolinite 179
9.2.2 Nano-Montmorillonite 179
9.2.3 Nano-layered Double Hydroxides 180
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xviii Contents
9.3 Nanosized Metal Oxides 180
9.3.1 Nanosized Titanium Oxides 181
9.3.2 Nanosized Ferric Oxides 181
9.3.3 Nanosized Aluminium Oxides 183
9.3.4 Other Nanosized Metal Oxides 184

9.4 Nanostructured Carbon Materials 184
9.4.1 Carbon Nanotubes 184
9.4.2 Graphene 185
9.4.3 Other Nanostructured Carbon Materials 187
9.5 Potential Negative Environmental Impact
of Nanotechnology 187
9.6 Conclusions 188
References 188
Chapter 10 Modified and New Adsorbents for Removal of Heavy

Metals from Wastewater 193
M. A. Barakat and Rajeev Kumar

10.2 Heavy Metals in Industrial Wastewater and Toxicity 194
10.3 Treatment Processes for Heavy Metals Removal 196
10.4 Adsorptive Removal of Heavy Metals 198
10.4.1 Adsorption of Heavy Metals on Modified
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Natural Materials 198

10.4.2 Adsorption of Heavy Metals on Industrial
By-products 200
Agriculture and Biological Wastes
(Biosorption) 202
Biopolymers and Hydrogels 205
10.5 Batch Equilibrium Studies 207
10.6 Summary 208
References 208
Chapter 11 Natural Clays/Clay Minerals and Modified Forms for

Heavy Metals Removal 213
Alfin Kurniawan, Suryadi Ismadji, Felycia Edi Soetaredjo
and Aning Ayucitra

11.2 Structural Features of Clays and Clay Minerals as
Heavy Metals Sorbent 218
11.3 Surface Modification Techniques of Clays and Clay
Minerals for Enhanced Heavy Metals Sorption 222
11.3.1 Thermal Activation 225
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Contents xix
11.3.2 Chemical Activation/Conditioning 227
11.3.3 Pillaring, Grafting and Intercalation
Techniques 230
11.4 Isotherms, Kinetics and Thermodynamics
Evaluation of Heavy Metals Sorption onto Clays and

Clay Minerals 237
11.5 Conclusions 242
References 243
Chapter 12 Heavy Metals in Tannery Wastewater and Sludge:

Environmental Concerns and Future Challenges 249
Giusy Lofrano, Maurizio Carotenuto, Ravindra Kumar
Gautam and Mahesh Chandra Chattopadhyaya

12.2 Heavy Metals in Tannery Wastewater and Sludge:
Treatment Options 250
12.2.1 Characteristics 250
12.2.2 Treatment Options: Removal and Recovery 253
12.3 Environmental Concerns 256
12.3.1 Exposure Pathways and Health Effects 256
12.3.2 Phytotoxicity 257
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12.4 Future Challenges 258

References 258
Chapter 13 Fluorides in Different Types of Aquatic Systems and their

Correlation with Metals and Metalloids 261
C. Christophoridis, I. Pasias, E. Mitsika, S. Veloutsou and
K. Fytianos
13.1 HeavyMetals and Fluorides in the Environment 261

13.1.1Natural Sources 262
13.1.2Anthropogenic Sources of Fluorides 263
13.1.3Fluoride Content in Environmental
Samples 265
13.1.4 Health Effects of Fluorides 265
13.2 Relation Between Fluorides and Metals/Metalloids 269
13.2.1 Role of Physico-chemical Parameters
and Ions 269
13.2.2 Fluoride and Arsenic Correlation 272
13.3 Fluoride Removal Techniques 274
13.3.1 Membrane Methods 274
13.3.2 Adsorption Methods 276
References 277
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xx Contents
Chapter 14 Use of Industrial and Agricultural Waste in Removal of
Heavy Metals Present in Water 281
June Fang, Bin Gao, Yining Sun, Ming Zhang and
Sanjay K. Sharma

14.2 Sorption Mechanisms 283
14.2.1 Biomass Sorbents 283
14.2.2 Inorganic Sorbents 283
14.3 Adsorption Models 284
14.4 Modification Methods 284
14.4.1 Physical 285
14.4.2 Chemical 286
14.5 Sorption Studies 286
14.5.1 Differences Between Materials in the
Adsorption Rate of a Metal 287
14.5.2 Effect of pH on Adsorption 291
14.5.3 Raw versus Modified Materials 292
14.5.4 Effect of Temperature on Adsorption 293
References 294
Chapter 15 Biosorption of Metals From the Basics to High Value

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Catalysts Production 296

Teresa Tavares and Cristina Quintelas

15.2 Metals of Environmental Concern 297
15.2.1 Arsenic 297
15.2.2 Cadmium 298
15.2.3 Chromium 299
15.2.4 Copper 299
15.2.5 Mercury 300
15.2.6 Lead 301
15.2.7 Nickel 301
15.2.8 Zinc 302
15.3 Biosorption Mechanisms: Physical
and Biochemical Aspects 303
15.3.1 Assimilation 303
15.3.2 Adsorption 304
15.3.3 Biodegradation 306
15.4 Factors Affecting Biosorption 307
15.4.1 Solution pH 307
15.4.2 Bulk Temperature 308
15.4.3 Contact Time 308
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Contents xxi
15.4.4 Competing Ions Present on Solution 308
15.4.5 Initial Concentration of Metal Ions and of
Biomass 308
15.4.6 Cell Age 309
15.5 New Perspectives 309

References 310
Chapter 16 Chromium in Tannery Wastewater 315

Mariliz Gutterres and Bianca Mella

16.2 Forms of Chromium in Nature 316
16.2.1 Chromium in the Environment 318
16.2.2 Chromium in Water 319
16.3 The Processing of Leather 320
16.3.1 Tanning with Chromium Salts 323
16.4 Unitary Operations in Tannery Effluents Treatment 327
16.4.1 Preliminary Treatment 327
16.4.2 Primary Treatment 329
16.4.3 Secondary Treatment 329
16.4.4 Tertiary or Advanced Treatment 330
16.4.5 Sludge Treatment 330
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16.4.6 Wastewater Reuse 331

16.4.7 Chromium Recovery for Tanning by
Chemical Precipitation 332
16.4.8 Electrocoagulation of Chromium 335
16.4.9 Other Treatment Techniques for
Chromium Recovery 338
References 340
Subject Index 345

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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001
CHAPTER 1
Contamination of Heavy
Metals in Aquatic Media:
Transport, Toxicity and
Technologies for Remediation
RAVINDRA K. GAUTAM,a SANJAY K. SHARMA,*b
SURESH MAHIYAb AND MAHESH C. CHATTOPADHYAYA*a
a
Environmental Chemistry Research Laboratory, Department of
Chemistry, University of Allahabad, Allahabad, 211 002, India; b Green
11:25:29.
Chemistry & Sustainability Research Group, Department of Chemistry,

JECRC University, Jaipur, 303905, India
*Email: drsanjay1973@gmail.com; mcc46@redimail.com
1.1 Introduction
The term heavy metal refers to any metal and metalloid element that has a
relatively high density ranging from 3.5 to 7 g cm 3 and is toxic or poisonous
at low concentrations, and includes mercury (Hg), cadmium (Cd), arsenic
(As), chromium (Cr), thallium (Tl), zinc (Zn), nickel (Ni), copper (Cu) and
lead (Pb). Although heavy metals is a general term defined in the litera-
ture, it is widely documented and frequently applied to the widespread
pollutants of soils and water bodies.1 These metals are found widely in the
earths crust and are non-biodegradable in nature. They enter into the
human body via air, water and food. A small number have an essential role
in the metabolism of humans and animals in very trace amounts but their
higher concentration may cause toxicity and health hazards. The hazardous

1
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2 Chapter 1
nature of heavy metals has been recognized because of their bioaccumula-

tive nature in biotic systems. They can enter into the environment through
mining activities, industrial discharge and from household applications,
into nearby bodies of water.
1.2 Sources of Heavy Metals

Heavy metals dier widely in their chemical properties, and are used ex-
tensively in electronics, machines and the artifacts of everyday life, as well as
in high-tech applications. As a result they are able to enter into the aquatic
and food chains of humans and animals from a variety of anthropogenic
sources as well as from the natural geochemical weathering of soil and
rocks. The main sources of contamination include mining wastes, landfill
leaches, municipal wastewater, urban runo and industrial wastewaters,
particularly from the electroplating, electronic and metal-finishing indus-
tries. With increasing generation of metals from technologies activities, the
problem of waste disposal has become one of paramount importance. Many
aquatic environments face metal concentrations that exceed water quality
criteria designed to protect the environment, animals and humans. The
problems are exacerbated because metals have a tendency to be transported
with sediments, are persistent in the environment and can bioaccumulate in
the food chain. Some of the oldest cases of environmental pollution in the
world are due to heavy metal use, for example, Cu, Hg and Pb mining,
11:25:29.
smelting and utilization by ancient civilizations, such as the Romans and the
Phoenicians.
The heavy metals are among the most common pollutants found in was-
tewater. These metals pose a toxicity threat to human beings and animals
even at low concentration. Lead is extremely toxic and shows toxicity to the
nervous system, kidneys and reproductive system. Exposure to lead causes
irreversible brain damage and encephalopathic symptoms.2 Cadmium is
used widely in electroplating industries, solders, batteries, television sets,
ceramics, photography, insecticides, electronics, metal-finishing industries
and metallurgical activities. It can be introduced into the environment by
metal-ore refining, cadmium containing pigments, alloys and electronic
compounds, cadmium containing phosphate fertilizers, detergents and
refined petroleum products. Rechargeable batteries with nickelcadmium
compounds are also sources of cadmium.35 Cadmium exposure causes
renal dysfunction, bone degeneration, liver and blood damage. It has
been reported that there is sucient evidence for the carcinogenicity of
cadmium.3
Copper, as an essential trace element, is required by biological systems for
the activation of some enzymes during photosynthesis but at higher con-
centrations it shows harmful eects on the human body. High-level exposure
of copper dust causes nose, eyes and mouth irritation and may cause nausea
and diarrhea. Continuous exposure may lead to kidney damage and even
death. Copper is also toxic to a variety of aquatic organisms even at very low
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Contamination of Heavy Metals in Aquatic Media 3
concentrations. Mining, metallurgy and industrial applications are the

major sources of copper exposure in the environment.
Zinc is also an essential element in our diet. Too much zinc, however, can
also be damaging to health. Zinc toxicity in large amounts causes nausea
and vomiting in children. A higher concentration of zinc may cause anemia

and cholesterol problems in human beings. Mining and metallurgical pro-
cessing of zinc ores and its industrial application are the major sources of
zinc in the air, soil and water. It also comes from the burning of coal.
Nickel occurs naturally in soils and volcanic rocks. Nickel and its salts are
used in several industrial applications such as in electroplating, automobile
and aircraft parts, batteries, coins, spark plugs, cosmetics and stainless
steel, and is used extensively in the production of nickelcadmium batteries
on an industrial scale. It enters into the water bodies naturally by weathering
of rocks and soils and through the leaching of the minerals.4 The water
soluble salts of nickel are the major problems of contamination in aquatic
systems.5 Paint formulation and enameling industries discharges nickel
containing euents to the nearby bodies of water.6 Nickel is also found in
cigarettes, as a volatile compound commonly known as nickel carbonyl.7
Arsenic is found naturally in the deposits of earths crust worldwide. The
word arsenic is taken from Zarnikh in Persian literature, which means yellow
orpiment.8 It was first isolated as an element by Albert Magnus in 1250 AD.
Arsenic exists in powdery amorphous and crystalline forms in the ores. In
certain areas the concentration of arsenic may be higher than its normal
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dose and creates severe health hazards to human beings and animals. It
enters the environment through the natural weathering of rocks and an-
thropogenic activities, mining and smelting processes, pesticide use and
coal combustion. The toxicity of arsenic as a result of the contamination of
groundwater bodies and surface waters is of great concern. Arsenic exists as
arsenate, As(V), and arsenite, As(III), in most of the groundwater.912 Ad-
sorption and solution pH commonly controls the mobility of arsenic in the
aqueous environment.1317 Metal oxides of Fe, Al and Mn play a role in the
adsorption of arsenic in aquatic bodies.1820 Arsenic has been found nat-
urally at high concentration in groundwater in countries such as India,
Bangladesh, Taiwan, Brazil and Chile. Its high concentration in drinking
water causes toxic eects on humans and animals.
The toxicity of mercury has been recognized worldwide, such as in
Minamata Bay of Japan. Mentally disturbed and physically deformed babies
were born to mothers who were exposed to toxic mercury due to con-
sumption of contaminated fish. The natural sources of mercury are volcanic
eruption, weathering of rocks and soils, whereas anthropogenic mercury
comes from the extensive use of the metal in industrial applications, its
mining and processing, applications in batteries and mercury vapor lamps.
Methyl mercury is more toxic than any other species of mercury.
Extensive use of chromium compounds in industrial applications has
discharged huge amounts of wastewater containing toxic chromium species
into water bodies. Chromium enters into the environment by natural inputs
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4 Chapter 1
and anthropogenic sources. Volcanic eruptions, geological weathering of

rocks, soils and sediments are the natural sources of chromium, whereas
anthropogenic contributions of chromium come from the burning of fossil
fuels, production of chromates, plastic manufacturing, electroplating of
metals and extensive use in the leather and tannery industries.21 Hexavalent
chromium is more toxic than trivalent chromium.
1.3 Environmental and Health Risks

Cadmium is the most toxic element, even at its low concentration in the food
chain and has been found to cause of itai-itai disease in Japan. Unlike other
heavy metals, cadmium is not essential for biological systems. Hence it has
no benefit to the ecosystem and only harmful eects have been reported. It is
used in the manufacturing of nickelcadmium batteries, plastics and pig-
ments. Phosphate fertilizers and waste dumping are both routes for cad-
mium transference into the environment. Concern regarding the role and
toxicity of cadmium in the environment is on the increase, because it can be
highly toxic to human beings and animals at very low concentrations. Cad-
mium toxicity causes renal dysfunction and lung cancer, and also osteo-
malacia in the human population and animals, in addition to increasing
blood pressure. Smoking of cigarettes is one of the sources of cadmium
poisoning in humans.
Chromium is commonly used in the leather and tanning industries, paper
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and pulp and rubber manufacturing applications. High levels of exposure

cause liver and kidney damage, skin ulceration and also aects the central
nervous system. With plant species it reduces the rate of photosynthesis. It is
also associated with the toxic eects on hematological problems and im-
mune response in freshwater fish. Chromium(VI) causes greater toxicity than
chromium(III) in animal and human health.
Copper has been used by man since prehistoric times. It is used in the
production of utensils, electrical wires, pipes and in the manufacture of
brass and bronze. It has a role as an essential element in human and animal
bodies. However, at a higher dose it shows toxic eects, such as kidney and
stomach damage, vomiting, diarrhea and loss of strength.
Human exposure to lead causes severe toxicity. Higher doses may damage
the fetus and be toxic to the central nervous system. Newborn babies are
more sensitive than the adults. Lead toxicity may harm hemoglobin syn-
thesis, the kidneys and reproductive systems. Exposure to higher doses of
lead may disrupt the function of the central nervous system and gastro-
intestinal tract. Airborne lead may cause the poisoning of agricultural food
by the deposition on fruits, soils and water.7
Mercury is a very toxic element in its organic form and has been the cause
of Minamata disease in Japan. It shows toxicity to the physiology of animals
and human beings. Mercury toxicity has been found to be associated with
physiological stress, abortion and tremors. Methyl mercury is highly toxic
and causes toxic eects on the central nervous system in the human
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population. Mercury can result from volcanic eruptions and degassing. The
exposure to mercury causes toxicity to the brain, blindness, mental retar-
dation and kidney damage.
Nickel plays an essential role in the synthesis of red blood cells; however,
it becomes toxic when taken in higher doses. Trace amounts of nickel do not
damage biological cells, but exposure to a high dose for a longer time may
damage cells, decrease body weight and damage the liver and heart. Nickel
poisoning may cause reduction in cell growth, cancer and nervous system
damage.57
The undesirable presence of iron and manganese in drinking water may
pose a toxicity threat to health. However, iron and manganese are required
by the biological system as they play major roles in the hemoglobin synthesis
and functioning of cells. The presence of these metals in water may cause
staining of cotton clothes and give a rusty taste to drinking water. The major
concerns focus on the dietary intake of iron because a higher dose may pose
acute toxicity to newborn babies and young children. The gastrointestinal
tract rapidly absorbs iron that may pose a toxicity risk to the cells and
cytoplasm. The liver, kidneys and cardiovascular systems are the major
toxicity targets of iron. Neurological disturbances and muscle function
damage are the result of toxic eects of manganese in human bodies.
Heavy metals are highly toxic to the fetus and newborn babies, where
higher levels of exposure exist for human beings, mainly to industrial
workers. Metal ions exposure to newborn babies may damage brain memory,
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disrupt the function of red blood cells, the central nervous system, physio-
logical and behavioral problems. Severe toxicity from these metals may cause
cancers. Exposure of plants to heavy metals may lead to physiological and
morphological changes and damage to cell function and reduce photo-
synthesis rates. Mutagenic changes have also been observed in several plant
species. Metal ion toxicities may lead to chlorosis, bleaching, nutrient de-
ficiencies and increased oxidation stress in plants. Heavy metals obstruct the
growth of microbes.22 Table 1.1 shows the standards for metal concentration
in drinking water and the health eects.
An arsenic presence in groundwater through the weathering of rocks and
sediments and drinking of arsenic contaminated water causes poisoning to
the blood, central nervous system, lung and skin cancer, breathing prob-
lems, vomiting and nausea. Its presence in Third World countries is be-
coming hazardous. The countries that are suering with the problems of
arsenic are India, Bangladesh, Taiwan, China, Brazil, Chile, South Korea,
Thailand and Indonesia. Arsenic is a geogenic problem worldwide but an-
thropogenic sources, such as the processing of metals and manufacture of
pesticides and their byproducts, are contributing equally to the levels of
arsenic in the environment.
Severe toxic eects and poisoning by heavy metal ions worldwide and
strict discharge regulations for wastewater euents to aquatic bodies
requires better treatment techniques. Environmental scientists have de-
veloped several procedures such as coprecipitation, membrane filtration,
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6 Chapter 1
Table 1.1 The standard metal concentration in drinking water and the health
eects.
Metal Eects Drinking water standards
Lead Toxic to humans, aquatic By the Environmental
fauna and livestock Protection Agency

High doses cause maximum concentration:
metabolic poison 0.1 mg L 1
Tiredness, irritability anemia By European Community:
and behavioral changes of 0.5 mg L 1
children Regulation of water quality
Hypertension and (India) 0.1 mg L 1
brain damage
Phytotoxic
Nickel High conc. can cause By the Environmental
DNA damage Protection Agency
Eczema of hands maximum concentration:
High phytotoxicity 0.1 mg L 1
Damaging fauna By European Community:
0.1 mg L 1
Regulation of water quality
(India) 0.1 mg L 1
Chromium Necrosis nephritis and death By the Environmental
in man (10 mg kg 1 of body Protection Agency
weight as hexavalent maximum concentration:
chromium) (hexavalent and trivalent)
Irritation of gastrointestinal total 0.1 mg L 1
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mucosa By European Community:

0.5 mg L 1
(India) 0.1 mg L 1
Copper Causes damage in a variety By the Environmental
of aquatic fauna Protection Agency
Phytotoxic maximum concentration:
Mucosal irritation and 1.0 mg L 1
corrosion By European Community:
Central nervous system 3 mg L 1
irritation followed by Regulation of water quality
depression (India) 0.01 mg L 1
Zinc Phytotoxic By the Environmental
Anemia Protection Agency
Lack of muscular maximum concentration:
coordination 5 mg L 1
Abdominal pain etc. By European Community:
5 mg L 1
(India) 0.1 mg L 1
Cadmium Cause serious damage to By the Environmental
kidneys and bones in humans Protection Agency
Bronchitis, emphysema, maximum concentration:
anemia 0.005 mg L 1
Acute eects in children By European Community:
0.2 mg L 1
(India) 0.001 mg L 1
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Table 1.1 (Continued)
Metal Eects Drinking water standards
Mercury Poisonous By the Environmental
Causes mutagenic eects Protection Agency
Disturbs the cholesterol maximum concentration:

0.002 mg L 1
By European Community:
0.001 mg L 1
(India) 0.004 mg L 1
Arsenic Causes toxicological and World Health Organization
carcinogenic eects guideline of 10 mg L 1
Causes melanosis, keratosis By European Community:
and hyperpigmentation 0.01 mg L 1
in humans Regulation of water quality
Genotoxicity through (India): 0.05 mg L 1
generation of reactive oxygen
species and lipid peroxidation
Immunotoxic
Modulation of co-receptor
expression
ion-exchange resins, photocatalytic reduction and adsorption for treatment

of wastewater euents containing heavy metals.
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1.4 Remediation Technologies

Bioaccumulation of heavy metals in food chains and their toxicity to bio-
logical systems due to increased concentration over time have led to tre-
mendous pressure for their separation and purification. Heavy metals can
enter into water bodies through agricultural runo, industrial euents,
household uses and from commercial applications. We can remove heavy
metals from drinking water very easily with reliable technology. Several
technologies available in the market remove a huge range of metals com-
monly found in drinking water and wastewater euents. There are various
remediation technologies that have been used for the removal of heavy metals
from water/wastewater. These remediation technologies are summarized as:
Precipitation and coagulation

Ion exchange
Membrane filtration
Bioremediation
Heterogeneous photocatalysts
Adsorption
1.4.1 Membrane Filtration

Membranes are complex structures that contain active elements on the
nanometer scale. Modern day reverse osmosis membranes are typically
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8 Chapter 1
homogeneous polymer thin films supported by a porous support structure.

Partitioning water and dissolved salts between the membrane and the bulk
solution, and transport of water and salts across the membrane, depend on
the chemical properties of the membrane as well as the physical structures
on nano- to microscales. The nanometer length scale is defined as between

the scale of macroscopic particles suspended in water and dissolved atomic
and molecular species. From a filtration perspective, this intermediate range
contains, for example, colloidal solids, large organic and biological mol-
ecules, polymers and viruses. It also corresponds to the dimensions at which
that we recognize distinct modes of material transport across a membrane.
For a larger dimension of porous membranes, transport is described in
terms of convective flow through pores. On the other hand, transport in a
dense reverse osmosis membrane is typically described in terms of diusive
flow through a homogeneous material.
1.4.2 Phytoremediation
Bioremediation is the technological process whereby biological systems,
plants and animals, including microorganisms, are harnessed to eect the
cleanup of pollutants from environmental matrices.23 During the past few
years, microbe-assisted bioremediations have been widely applied for the
treatment of wastewater contaminated with heavy metals and metalloids.
Here we will address the global problem of heavy metal pollution originating
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from increased industrialization and urbanization and its amelioration by

using plants from various environmental conditions. Conventional tech-
nologies are not cost eective and may produce adverse impacts on aquatic
ecosystems. Microbe-assisted bioremediation and phytoremediation of
heavy metals are cost-eective technologies and metal ion accumulating
plants have been successfully used for the treatment of wastewater.24
Aquatic plants, especially wetland ecosystems, have unique properties to
sequester heavy metals and metalloids.
Wetland ecosystems are much superior in comparison with other con-
ventional methods, for example because of the low cost, frequent growth of
microorganisms, easy handling and low maintenance cost. The rhizospheres
in wetlands provide an enhanced nutrients supply to the microbial eco-
systems of plants, which actively transform and sequester heavy metals
in their biological functions. Constructed wetlands have been actively used
for the treatment of heavy metals from agricultural runo, mine drainage
and municipal wastes. Many aquatic plants such as Phragmites, Lemna,
Eichchornia, Azolla and Typha have been used for the treatment of wastewater
containing heavy metals.
Phytoremediation is a low-cost, low-tech and emerging cleanup technol-
ogy for contaminated soils, groundwater and wastewater.25 Plants are very
sensitive to metals but in phytoremediation wild and genetically modified
plants, including grasses, herbs, forbs and woody species, are mainly used.
The plants take up heavy metals and metalloids through the process of
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phytostabilization, phytoextraction, phytofiltration or rhizoremediation.

However, in contrast to organic compounds the heavy metals and metalloids
cannot be metabolized but accumulate in the plant biomass.26 The biomass
generated by phytoremediation remains very limited in amount and persists,
whereas all the biomass can be utilized in the form of fertilizer, forage,
mulch or for the production of bio-gas.27 Even though it is well known that
metals are toxic to many plants, they have developed some internal mech-
anisms that allow the uptake, tolerance and accumulation of high concen-
trations of metals that would be toxic to other organisms. Many researchers
have reported that aquatic macrophytes viz. Typha, Phragmites, Eichhornia,
Azolla and Lemna are potential wetland plants for removal of heavy metal
and metalloids due to their morphological change.24,28 Being a cost-eective
and easily applicable technique, phytoremediation can be implemented for
their enhancement to metal accumulations and translocations. In general,
two strategies of phytoextraction have been developed, which are: (1) normal
phytoremediation of heavy metals from aquatic bodies through the plants in
their entire growth cycle2931 and (2) chemically induced phytoextraction
techniques to cleanup contaminated water by using metal-tolerant plants to
remove heavy metals and metalloids.32 The eciency of phytoextraction can
be increased by using more biomass producing plant species and with the
application of suitable chelates. Hyperaccumulators or hyperaccumulating
plants are capable of accumulating large amounts of heavy metals and
metalloids, including Ni, As, Zn, Cd and Pb, in their aboveground tissues
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without any toxic symptoms.33

Metals uptake in relation to the external concentration of the toxic heavy
metals may dier due to the dierent genotypes of plants. Those plants that
have low uptake of metals at quite high metal concentrations are called
excluders. These plants have some kind of barrier to avoid uptake of heavy
metals, however, when metal concentrations are at a high level this barrier
losses its function, probably due to the toxic action of the metals. Some
plants have certain detoxification mechanism within their tissue, which
allow the plant to accumulate high amounts of metals.34 Several reports are
available in the literature on the hyperaccumulator plants: Pteris vittata L.
and Thlaspi caerulescens were found to hyperaccumulate As, Minuartia verna
for Pb, Aellanthus biformifolius for Co and Cu, Berkheya coddi for Ni,
Macadamia neurophylla for Mn and Thlaspi caerulescens for Zn.34,35 However,
phytoremediation on a commercial scale is limited because of its low bio-
mass production, limited growth rate and time consumption.35 In order to
compensate for the low metal accumulation, much research has been con-
ducted using synthetic chelators or ligands such as ethylenediaminetet-
raacetic acid (EDTA); S,S-ethylenediaminedisuccinic acid (S,S-EDDS);
nitrilotriacetate (NTA) and naturally occurring low molecular weight organic
acids to enhance the availability of heavy metals and increase phytoextr-
action eciency.36,37
Phytoextraction is a publically appealing green remediation technique.
However, phytoextraction can be eectively applied only for soils and
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10 Chapter 1
wetlands contaminated with specific potentially toxic metals and metalloids.

Many researchers have reported that common crop plants with a high bio-
mass can be triggered to accumulate large amounts of low bioavailability
metals when applied the phytochelates.38,39 In such chemically enhanced
phytoextractions, chelating agents are used almost exclusively as the mo-

bilizing agents.40 However, EDTA was the most ecient chelate to increase
metal uptake by plants of Pb, but the slow degradation of chelating com-
pounds in the root zone limits its application on an industrial scale.41
Nevertheless, more biodegradable chelates, such as NTA, (S,S-EDDS) and
other chelates are also recognized for metals removal. Application of these
chelating agents with plants for the uptake of metal ions is gaining more
popularity and has become an interesting field of research. Several studies
have been carried out using EDTA as a metal chelator for sequestration of
metals.42 The full-scale application for treating wastewater on an industrial
scale should be based on optimization of several parameters such as solu-
bilization of metals, chelates stability, plant roots and the capacity of metal
transport through the shoots of plants.43
1.4.3 Heterogeneous Catalysts and Catalysis

In 1972 Fujishima and Honda discovered the photocatalytic splitting of
water on titanium dioxide (TiO2) electrodes.44,45 Their discovery provided the
foundation stone for photocatalysis. Since this remarkable discovery much
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research has been carried out on the eciency of TiO2 as a photo-

catalyst.4648 During the past few years, the applications of TiO2 for en-
vironmental cleanups have been performed by several laboratories for the
treatment of industrial euents.49,50
During the photocatalysis system, photo-induced reactions take place at
the surface of a catalyst. Depending on where the initial excitation occurs,
photocatalysis can be generally divided into two classes of processes. When
the initial photo-excitation occurs in an adsorbate molecule, which then
interacts with the ground state catalyst substrate, the process is referred to as
a catalyzed photoreaction. When the initial photo-excitation takes place in
the catalyst substrate and the photo-excited catalyst then transfers an elec-
tron or energy into a ground state molecule, the process is referred to as a
sensitized photoreaction. The initial excitation of the system is followed by
subsequent electron transfer and/or energy transfer. It is the subsequent de-
excitation process that leads to chemical reactions in the heterogeneous
photocatalysis process.
1.4.4 Photocatalysts
Reduction of Cr(VI) using semiconductor heterogeneous photocatalysts
has been carried out as an economical and simple method of wastewater
treatment.51,52 Surface-catalyzed Cr(VI) reduction is a very slow reaction and
has been described as a feasible process in the presence of oxide surfaces
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53
such as TiO2. Furthermore, organic donors have a chelation capacity for
the TiO2 surface, which accelerates the reduction of Cr(VI).5457
Testa et al.58 carried out the reduction of Cr(VI) over TiO2 under near-UV
radiation. At pH 2, the addition of oxalate facilitated Cr(VI) reduction. It has
been found that the oxalic acid accelerates the reduction of Cr(VI) over TiO2
particles. Guo et al.59 have synthesized a plasmonic photocatalyst of Ag
AgCl@TiO2 by depositionprecipitation and photoreduction. This photo-
catalyst exhibited ecient photocatalytic activity for the photoreduction of
Cr(VI) ion under irradiation with visible light.
Photocatalytic reduction of Cr(VI) in an aqueous suspension of surface-
fluorinated anatase TiO2 nanosheets with exposed {001} facets has been
performed by He et al.60 The surface fluorination facilitated the adsorption
process by increasing the number of surface OH groups generated. The re-
duction of Cr(VI) occurred because of the oxidative dissolution of H2O on
{001} facets and the Cr(VI) reductions that occurred on {101} facets were
simultaneous reactions.
1.4.5 Electrocoagulation
Electrocoagulation consists of electrodes that act as the anode and cathode,
where oxidation and reduction takes place. Many physicochemical processes
such as oxidation, reduction, coagulation and adsorption govern the elec-
trocoagulation.61,62 Similarly to other treatment techniques, the electro-
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coagulation of heavy metals oers a cost-eective and easy-handling

technique on an industrial scale.63 This technique has been used for the
treatment of dyes, heavy metals, nitrates, fluorides and phenolic compounds
from wastewater.6474 Recently, various workers have investigated electro-
coagulation for the removal of heavy metals from wastewater.7577
Removal of Cr31 from aqueous solution by electrocoagulation using iron
electrodes is a feasible process. Golder et al.78 investigated the removal of
Cr31 from water by electrocoagulation methods. It was found that the co-
agulation and adsorption play very important roles in the removal of Cr31
during electrocoagulation. The removal of Cr31 from aqueous solution was
highest at a higher current density. A multiple electrode was used in the
electrocoagulation system for the removal of Cr31 from aqueous solution
with both bipolar and monopolar configurations.79 This technique can be
used for the treatment of pollutants down to the ppb level, but the high cost
of resin makes the process costly for industrial scale applications.80,81 Gao
et al.82 used a combined electrocoagulation and electroflotation system for
the removal of Cr61 from aqueous solutions. The performance of an elec-
trocoagulation system with aluminium electrodes for removing heavy metal
ions on a laboratory scale was studied systematically by Heidmann and
Calmano.83
Removal of heavy metal ions from wastewater by electrocoagulation with
iron and aluminium electrodes with monopolar configurations was in-
vestigated by Akbal and Camc.84 They explored the influence of electrode
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12 Chapter 1
material, current density, wastewater pH and conductivity on removal per-

formance. The results indicated that an electrocoagulation system with an
FeAl electrode was useful and 100% of the Cu, Cr and Ni were observed
within 20 min with a current density of 10 mA cm 2 and a pH of 3.0. The
performance of electrocoagulation, with an aluminium sacrificial anode, in

the treatment of wastewater containing metal ions has been investigated by
Adhoum et al.85 Cu, Zn and Cr were removed successfully by using this
technique. The method was found to be highly ecient and relatively fast
compared with conventional existing techniques. Direct electrochemical
reduction of Cr61 can be carried out at the cathode.86 The hydroxyl ions
produced at the cathode induce the coprecipitation of Cu, Zn and Cr.8789
1.4.6 Clays/Layered Double Hydroxides (LDHs)

Clays have been widely used for the removal of heavy metals from aqueous
solutions due to their outstanding properties.90,91 Heavy metals can be re-
moved by ion exchange or a complexation reaction at the surface of clays.
During the past few years, surface modifications of natural clays with re-
agents containing metal binding groups have been explored.9193 Several
modification techniques such as intercalation of organic molecules into the
interlayer space and grafting of organic moieties have been applied.94,95
Organic-modified clays based on montmorillonite were prepared by em-
bedding ammonium organic derivatives with dierent chelating function-
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alities for heavy metal removal.96 Montmorillonite intercalated with poly-

hydroxyl Fe(III) complexes was used for the sorption of Cd(II).97 Sodium
dodecyl sulfate modified iron pillared montmorillonite has been success-
fully applied for the removal of aqueous Cu(II) and Co(II).98 Smectite inter-
calated with a non-ionic surfactant shows a good performance for the
removal of heavy metals.99 Through the grafting of inorganic and organic
components, natural clay can be functionalized to obtain a better sorption
capacity.100,101 Heavy metals have been removed through the grafting of
amino or mercapto by reaction with the silanol groups onto the surface of
clays.102,103 Synthesis of layered magnesium organosilicates for the removal
of heavy metals has been carried out with dierent organosiloxanes.104
Sepiolite can be grafted with organic moieties due to its high content of
silanol groups. Liang et al.90 have functionalized the sepiolite by nano-
texturization in aqueous sepiolite gel and surface grafting in toluene with
mercaptopropyltrimethoxysilane. The sorption of Pb(II) and Cd(II) were
studied and it was found that the surface modification can obviously in-
crease the sorption capacities for Pb(II) and Cd(II).
LDH materials appear in nature and can be easily synthesized in the la-
boratory. In nature they are formed from the weathering of basalts or pre-
cipitation in saline solution. All natural LDH minerals have a structure
similar to hydrotalcite, which has the formula [Mg6Al2(OH)16]CO3 4H2O.
LDHs have been prepared using many combinations of divalent to trivalent
cations including Mg, Al, Zn, Ni, Cr, Fe, Cu, Ga and Ca.105118 A number of
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synthetic techniques has been successfully employed in the preparation of

LDHs. There are a number of methods used to synthesize LDHs including
coprecipitation methods, hydrothermal synthesis, urea hydrolysis methods,
solgel methods, ion-exchange methods and rehydration methods.
LDHs have been investigated intensively for anion-exchange properties

due to recent interest in developing the use of anionic clays for environ-
mental remediation. The main characteristic that has been studied is to
clearly characterize the adsorption properties of the materials under vigor-
ous solidliquid interface conditions. The eect of sorbent composition,
surface and bulk adsorption and concentration of adsorption site have been
assessed. The adsorption capacity is significantly aected by the nature of
the counter anion of the LDHs layer. LDHs can be used as precipitating
agents of heavy metal cations for the decontamination of wastewater. Mn21,
Fe21 and Cu21 cations have been removed by synthetic hydrotalcite-like
compounds, with zaccagnaite and hydrotalcite thin films being used for the
remediation of aqueous wastes containing hazardous metal ions.119
1.4.7 Biomass and Biosorption of Metal Ions

During the last few years numerous new processes have been tested suc-
cessfully, many of which have gone into operation and a great number of
papers have been published on biosorption. In this section we will discuss
Biomass based biosorbents and biosorption of heavy metals. Biosorption
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has been defined as the property of certain bio-molecules to sequester

metal ions or other molecules from aqueous solutions.120,121 It diers from
bioaccumulation, where active metabolic transport takes place, as biosorp-
tion involves a passive process in which interaction between sorbent and
sorbate occurs. Biosorption of heavy metals has become a popular and active
field of research in environmental science.122126
Rao et al.127 have studied the removal of Cr(VI) and Ni(II) from aqueous
solution using bagasse based biosorbents. The bagasse was chemically
treated with 0.1 N NaOH followed by 0.1 N CH3COOH. The materials ad-
sorption capacity in order of selectivity for Cr(VI) and Ni(II) was powdered
activated carbon 4 bagasse 4 fly ash and powdered activated carbon 4 fly
ash 4 bagasse, respectively. Values for Langmuir and Freundlich isotherm
constants for sorption of Cr(VI) ions onto powdered activated carbon,
bagasse and fly ash were 0.03, 0.0005 and 0.001, and 0.12, 0.03 and 0.01,
respectively. A lower pH of 6.0 favors the uptake of Cr(VI) and pH 8.0 was
suitable for Ni(II) ions removal. However, an increase in pH values of the
solution reduces the Cr(VI) adsorption because of the abundance of OH
ions, causing hindrance to the diusion of dichromate.128,129 However, the
adsorption capacity was very low and their application for industrial euent
treatment cannot be justified.
Recently, pectin-rich fruit wastes have been investigated as biosorbents
for heavy metal ion removal.130 It has been observed that biosorption of
cadmium by pectin-rich fruit materials and citrus peels were found to be
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14 Chapter 1
most suitable. Equilibrium kinetics were achieved within 3090 min, de-
pending upon particle size. A pseudo-second order model was found to be
more suitable than a first-order model to describe the kinetics. Isotherm
studies show that the data were well fitted to a Langmuir model. It has also
been observed that the metal uptake decreased with decreasing pH, indi-
cating competition of protons for binding to acidic sites. Gurgel and Gil131
have described the preparation of two new chelating materials, MMSCB 3
and 5, derived from succinylated twice-mercerized sugarcane bagasse
(MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two
dierent methods. In the first method, MMSCB 1 was activated with 1,3-
diisopropylcarbodiimide and in the second with acetic anhydride, and later
both were reacted with triethylenetetramine in order to obtain MMSCB 3 and
5. The capacity of MMSCB 3 and 5 to adsorb Cu21, Cd21 and Pb21 from
aqueous single metal ion solutions was evaluated at dierent contact times,
pH and initial metal ion concentrations. Adsorption isotherms were well
fitted by a Langmuir model. Maximum adsorption capacities of MMSCB 3
and 5 for Cu21, Cd21 and Pb21 were found to be 59.5 and 69.4, 86.2 and
106.4, 158.7 and 222.2 mg g 1, respectively.
A few biosorbents have been reported for the adsorption of heavy metals
not only in the form of metallic ions but also organometallic compounds.
Saglam et al.132 have prepared the biosorbents from the biomass of
Phanerochaete chrysosporium, which adsorbed inorganic mercury and alkyl-
mercury species with an anity of CH3HgCl 4 C2H5HgCl 4 Hg21, with
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maximum sorption capacities of 79, 67 and 61 mg g 1, respectively.

The eciency of Parthenium hysterophorous weed for the removal and re-
covery of Cd(II) ions from wastewater has been studied by Ajmal et al.133
These workers reported that the kinetics data for the adsorption process
obeyed the second-order rate equation. The adsorption process was found
to be endothermic and spontaneous in nature. The maximum adsorption
capacity of Cd(II) ions was 99.7% in the pH range 34. The desorption studies
confirm 82% recovery of Cd(II) when 0.1 M HCl solution was used as the
euent. Coconut copra meal, a waste product of the coconut industry, was
used for the removal of cadmium from water.134 The biosorption process
was a spontaneous and exothermic process in nature.
Rao et al.135 tested the biosorption potential of fennel biomass (Foenicu-
lum vulgari) for the removal of Cd(II) from water. It was found that the bio-
sorption of Cd(II) was a chemically controlled process. Removal of Cd(II) was
concentration dependent and increased with an increase in metal ion con-
centration, which showed that the multilayer adsorption takes place at the
surface of the biosorbent and it was best described by a Freundlich isotherm
model and pseudo-second order rate kinetics. El-Said et al.136 utilized rice
husk ash for the removal of Zn(II) and Se(IV) from water. A higher removal
capacity of Zn(II) was found than for Se(IV). The removal capacity increases
with an increase in biosorbent dose from 1 to 10 g L 1.
Recently, Schiewer and Iqbal137 investigated the role of pectin for the
removal of cadmium from water. The carboxyl group plays an important role
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in the surface charge and was responsible for the binding of cadmium onto
the biosorbent surface. Typically, metal binding experiments were carried
out at an optimized pH of 5. A Langmuir isotherm model provided the best
fit. Metal binding kinetics were better described by the first-order model
than by the second-order model.

Removal of mercury from water was carried out using Carica papaya as a
biosorbent.138 Sulfuric acid treated almond husk based activated carbon was
prepared and used for the sorption of Ni(II) ions from water.139 The ad-
sorption capacity was very high and 97.8% Ni(II) ions were removed by an
adsorbent dose of 5 g L 1.
1.4.8 Magnetic Nanoparticles as Nanosorbents

Magnetic nanomaterials are one of the recently highlighted branches of
materials science and technology that have been utilized in the removal of
pollutants from aqueous solutions. Owing to their magnetic properties, high
chemical stability, low toxicity, ease of synthesis and excellent recycling
capability, magnetic nanoparticles have been studied to remove toxic metal
ions from water.
Magnetic nanoparticles are of great interest for researchers from a wide
range of disciplines, including magnetic fluids, catalysis, biomedicine,
drug delivery, magnetic resonance imaging, data storage and environ-
mental remediation.140,141 Although several suitable methods have been
11:25:29.
developed for the synthesis of magnetic nanoparticles for a variety of dif-

ferent compositions, successful application of such magnetic nano-
particles in the areas listed here is particularly dependent on the stability of
the particles under a range of dierent conditions. In the majority of the
envisaged applications, the particles perform best when the size of the
nanoparticles is below a critical value, which is dependent on the source
material but is typically around 1020 nm.142 The design and fabrication of
nanoparticle-based adsorbents has generated great interest in a variety of
scientific communities ranging from chemical, biological and environ-
mental science to engineering. Magnetic nanoparticle-based adsorbents
can be used in the separation and purification of biologically as well
as environmentally relevant target species with high precision and
accuracy.143,144
1.4.9 Removal of Iron and Manganese from Water

The presence of iron and manganese gives an astringent and metallic taste
to drinking water, which causes problems in cooking and in the production
of beverages.145 A simple method of iron and manganese removal consists of
oxidation and ion-exchange resins. The oxidation of iron is dependent on
the solutions pH, and organic matter and carbonate concentration. Oxi-
dation of iron and manganese can be achieved by introducing an oxidizing
agent and it may be done through the application of methods that include
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16 Chapter 1
the addition of oxidants such as chlorine and potassium permanganate.

Activated carbons have also been applied for the removal of iron and man-
ganese from aqueous solutions.146 Klueh and Robinson147 investigated
the sequestration of iron by polyphosphate addition while providing the
necessary disinfection through chlorine addition. They observed that the

presence of calcium in the groundwater inhibited the removal of iron.
The addition of polyphosphate to the groundwater first and the simul-
taneous addition of polyphosphate and chlorine were both fairly successful
at removing the iron.
1.4.9.1 Ion Exchange

Ion-exchange resins provide many advantages and are one of the most
widely techniques used for treatment of wastewater euents.148 Lee and
Nicol149 have used the Diphonix resin to remove ferric iron from a cobalt
sulfate solution with various pH ranges. A lower pH and higher dose of resin
gives a higher removal of iron from solution. Elution of iron was observed
with an increase of Ti(III) in the sulfuric acid eluent. These workers found
that the iron elution enhancement with Ti(III) was due to the combined ef-
fects of a reduction of Fe(III) and competitive adsorption of Ti(III) and Ti(IV)
ions. Lasanta et al.150 studied the equilibrium diagrams for ionic exchange,
which occurs between Fe31 in dierent solutions by a chelating ion ex-
change resin. A mathematical model was used to predict the equilibrium,
11:25:29.
which gave a good fit for the experimental data in various solutions. It had
been observed that solvent type influences the adsorption capacity. Khalil
et al.151 studied the removal of ferric ions by using crosslinked chitosan
resins immobilized with diethylenetriamine and tetraethylenepentamine. It
had been found that the tetraethylenepentamine containing chitosan resin
showed a higher uptake capacity towards Fe(III) compared with diethylene-
triamine containing chitosan resin. Kinetic data showed that the adsorption
process followed the pseudo-second order kinetics. Thermodynamic studies
indicated that the adsorption process was exothermic and spontaneous
in nature.
1.4.9.2 Activated Carbons

Omri and Benzina152 achieved the removal of Mn(II) ions from aqueous so-
lutions by adsorption on activated carbons derived from Ziziphus spina-
christi seeds. The eects of process parameters such as solution pH, initial
metal ion concentration and temperature on the adsorption performance of
activated carbons for Mn(II) ions removal were tested to optimize the system.
Maximum adsorption was obtained at pH 4. Freundlich isotherms followed
the adsorption system and the higher adsorption capacity for a Langmuir
isotherm was 172 mg g 1. Adsorption of iron and manganese ions from
aqueous solution by low-cost adsorbents of palm fruit bunch and maize cobs
was carried out.153 Adsorption of iron ions on palm fruit bunch and maize
View Online
cobs was in the range of 8057%, for initial concentrations ranging between
1 and 10 ppm.
Recently, Mengistie et al.154 performed the adsorption of Mn(II) by
using activated carbons of Militia ferruginea leaves from aqueous solutions
in the batch mode. Adsorption equilibrium was achieved within 2 h. It had

been found that pH 4 was appropriate for Mn(II) removal and 95.8% metal
ions were removed. The adsorption isotherms were best fitted to a Freun-
dlich model, which showed multilayer adsorption at the surface of the
activated carbons. The adsorption kinetics were best fitted to a first-order
kinetic model. Thermodynamic analysis showed that the adsorption pro-
cess was endothermic and spontaneous in nature. Emmanuel and Rao155
studied the adsorption of Mn(II) by activated carbons of Pithacelobium
dulce from aqueous solutions and found a good sorption capacity for metal
ions. The sorption equilibrium was achieved within 50 min. The equi-
librium isotherm was best fitted to a Langmuir isotherm model, which
indicates the adsorption of Mn(II) onto activated carbons was as a
monolayer.
1.4.9.3 Other Treatment Methods

The eect of various organic acids, such as acetic, formic, citric, ascorbic,
succinic, tartaric and oxalic acids, on the removal of iron has been studied by
Ambikadevi and Lalithambika.156 It was found that the oxalic acid gives the
11:25:29.
best results, both at room temperature as well as at high temperatures, be-

cause of its high acid strength, good complexing capacity and reducing
power. The eects of several parameters such as time, temperature and re-
agent concentration were studied for the optimization process. The removal
of iron was found to be B80% by the authors.
Ganesan et al.157 used an electrocoagulation process for removal of Mn(II)
from aqueous solutions using magnesium as the anode and galvanized iron
as the cathode. Several removal parameters such as solution pH, current
density, electrode configuration, inter-electrode distance, eects of coexist-
ing ions and temperature were studied. The results obtained suggested that
the highest removal of 97.2% at a pH of 7.0 was for a current density
0.05 A dm 2 with an energy consumption of 1.151 kWh m 3. Thermodynamic
parameters indicated that the Mn(II) removal was feasible, spontaneous and
endothermic in nature. A Langmuir adsorption isotherm well fitted to the
adsorption system. The kinetic model was best described by a pseudo-second
order rate at the various current densities. Taarel and Rubio158 applied
Chilean zeolite as an adsorbent for removal of Mn(II) ions from aqueous
solutions. The solution pH significantly influenced the adsorption of Mn(II)
removal and the best results were been found at pH 66.8. The removal
kinetics was best fitted with a pseudo-second order model. The equilibrium
isotherm data were best fitted to a Langmuir isotherm model. It was found
that the Chilean zeolite treated with NaCl, NaOH, Na2CO3 and NH4Cl in-
creased its uptake ability in comparison with natural Chilean zeolite.
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18 Chapter 1
1.5 Concluding Notes

The presence of heavy metals and their toxicity to the environment and to
human beings is posing a serious challenge to environmental engineers with
respect to the treatment of wastewater euents prior to discharge into the

nearby water bodies. Several removal techniques have been developed and
applied for the treatment of these wastes to remove the toxic metal ions.
Technologies such as microbe-assisted phytoremediation, ion exchange,
membrane filtration, photocatalytic oxidation and reduction and adsorption
have their own advantages and disadvantages over metal ion sequestrations
from environmental matrices. During recent years the developments in ad-
sorption of heavy metals from aqueous solutions have gained tremendous
popularity among the scientific community as methods to treat industrial
wastewater. Several adsorbents such as clays, LDHs, zeolites, carbon nano-
tubes and their composites, activated carbons, biomass derived biosorbents,
inorganic nanomaterials, inorganic organic hybrid nanocomposites and
magnetic nanomaterials have been synthesized and investigated for their
ability to sequester metal ions from water.
Functionalized magnetic nanoparticles are very promising for appli-
cations in catalysis, biolabelling and bioseparation. In liquid-phase ex-
traction of heavy metals and dyes in particular, such small and magnetically
separable particles may be useful as they combine the advantages of high
dispersion, high reactivity, high stability under acidic conditions and easy
11:25:29.
separation. In this chapter we focused mainly on recent developments in the

synthesis of active adsorbents and nanoparticles. Further, functionalization
and application of magnetic nanoparticles and their nanosorbents for the
separation and purification of hazardous metal ions from the environment
are discussed in detail in a separate chapter in this book.
Acknowledgements
R.K. Gautam thanks the University Grants Commission for the award of a
Junior Research Fellowship (JRF). Suresh Mahiya is grateful to the President,
JECRC University, for the award of Scholarship for his PhD. The authors
equally acknowledge the support and provision of the necessary facilities by
the University of Allahabad, Allahabad, India and JECRC University, Jaipur,
India. The support and encouragement of Prof. V.S. Tripathi from the De-
partment of Chemistry, University of Allahabad, is also appreciated. We also
thank the anonymous editors and reviewers for giving their kind criticisms
and comments, which fuelled the zeal for the manuscript.
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CHAPTER 2
Photocatalytic Processes
for the Removal of Toxic
Metal Ions
PANKAJ CHOWDHURY,*a ALI ELKAMELa AND AJAY K. RAYb
a
University of Waterloo, Department of Chemical Engineering, Waterloo,
ON, Canada; b University of Western Ontario, Department of Chemical
Engineering, London, ON, Canada
*Email: p3chowdh@uwaterloo.ca
11:25:32.
2.1 Introduction
A group of metals and metalloids with high atomic density (46 g cm3) are
referred to as heavy metals. Heavy metals naturally occur in rocks, soils,
sediments and anthropogenic materials.1 Ore minerals such as PbS (galena),
ZnS (sphalerite and wurtzite), CuFeS2 (chalcopyrite), FeCr2O4 (chromite),
etc., are the most common.2 The normal background concentration of these
elements depends on the alliance of metals with waters, soils, sediments and
living organism.1
Metals and metalloids (Fe, Mg, Li, Zn, Cu, Cr, Ni, Co, V, As, Mo, Mn, Se,
etc.) at trace levels play significant roles as microelements in both cells and
tissues of plants and animals. These trace metals serve as enzyme and
protein components and also maintain the ionic balance as well as the
osmotic potential of cells. However, at higher concentration levels the
heavy metals show adverse eects.3 Considering the toxicity and environ-
mental impacts, the term heavy metal generally relates to metals such as

25
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26 Chapter 2
cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead
(Pb), zinc (Zn), and metalloids such as arsenic (As).
Heavy metals are released into the environment from several domestic
(automobile exhaust, smelting processes, burning fossil fuels, incineration
of waste, use of sewage sludge) and industrial processes (metal plating, re-
fining ore, mining, fertilizer industry, tanneries, painting, paper industries,
pesticides).1,4,5 The presence of heavy metals in water bodies and soils at
elevated concentrations are not acceptable as they result in health hazards
(Table 2.1).
Heavy metals are toxic to living organisms and show persistence because
of their non-biodegradability. They also impose bioaccumulation problems
Table 2.1 Industrial sources and health eects due to exposure of dierent heavy
metal.4,911
Heavy metals/ MCL
metalloids Use/exposure Health eects (WHO)
Chromium (Cr) i) Electroplating, ii) lather Incidence of 50 ppb
tanning, iii) paint respiratory cancers
industry due to Cr(IV)
Zinc (Zn) i) Mining, Short term illness
ii) manufacturing process named metal fume
fever, restlessness
Cadmium (Cd) i) Electroplating, Nephrotoxic eects, 3 ppb
ii) pigment manufacture, bone damage
iii) plastic production,
11:25:32.
iv) polymerisation
process
Mercury (Hg) i) Pesticides, ii) chlorine- Neurobehavioural 1 ppb
alkali industry, iii) paint disorders, dyslexia,
industry, attention deficit
iv) petrochemical hyperactivity
industry disorder,
intellectual
retardation
Nickel (Ni) i) Electroplating, ii) paint Cancer of lungs and
formulation, iii) mineral nasal sinus,
processing chronic bronchitis,
reduced lung
function
Platinum (Pt) i) Catalytic converter Allergic reaction due
of modern vehicles, to halogenated
ii) mining platinum salt,
platinosis,
respiratory hyper-
sensitive reaction
Arsenic (As) i) Wood preservative, Acute poisoning, 10 ppb
ii) mining, iii) biocides skin cancer, liver
(A major source of arsenic tumours,
in ground water is due to gastrointestinal
mineral dissolution) problem
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Photocatalytic Processes for the Removal of Toxic Metal Ions 27

5
in living tissues. Several past disasters have been reported due to the con-
tamination of heavy metals in aquatic streams. The Minamata tragedy, re-
ported in the mid-1950s, was due to methyl mercury contamination by the
Chisso Corporation into Minamata Bay, Japan.6 Mercury accumulation in
fish gradually poisoned human beings. Post World War II, contamination of
cadmium in the Jintsu river in Japan resulted in Itai-Itai disease.4 Later, in
1998, a Spanish nature reserve was permanently damaged by toxic metal
wastes (Cu, Zn, Cd and Pb) from a mineral-producing plant.7
Heavy metals are in the priority pollutants list of the US Environmental
Protection Agency (EPA).8 The MCL values of dierent heavy metals
are mentioned in Table 2.1. Various technologies are used for the removal/
recovery of toxic metals or metalloids such as ion-exchange, adsorption,
membrane filtration, chemical precipitation, coagulationflocculation and
electrochemical treatment. A comparative review of various technologies
along with their advantages and disadvantages are presented in Table 2.2.
Recently, heterogeneous photocatalysis has been recognized as an emer-
ging technology for heavy metal reduction and recovery. It is a renowned
method where light energy is employed to stimulate the semiconductor
material producing electron-hole pairs, which are eventually involved in the
detoxification of pollutants. The main purpose of this chapter is to elaborate
on the thermodynamics, kinetics and other mechanistic details of the
photocatalytic reduction of metal ions (or metalloids) followed by photo-
reactor and photocatalyst developments. Finally, the application of photo-
catalysis for the removal or recovery of dierent metals/metalloids will be
11:25:32.
discussed in detail.
2.2 Advanced Oxidation Processes for Heavy Metal

Removal
To fulfil the strict environmental regulations, advanced oxidation pro-
cesses (AOPs) have been introduced to eliminate various potential harmful
compounds that cannot be eectively removed by conventional treatment
processes.13 There are a number of AOPs that are used for water treatment,
such as H2O2/UV, O3/UV, O3/H2O2/UV and TiO2/UV.14 AOPs initiate with the
formation of a hydroxyl radical (OH), which has very low selectivity. The
OH radical can drive the oxidation process through to complete min-
eralization of even the least reactive pollutants. These radicals can destroy
biologically refractory pollutants that are characterized by high chemical
stability.15
Heavy metals (or metalloids) removal/recovery basically involves reduction
reactions that produce elemental metals or metal ions at a lower oxidation
state. The only exception is arsenic, which exists in the anionic form and
needs oxidation to be converted to a high oxidation state. Therefore, most of
the AOPs are not useful processes as they cannot undergo a reduction re-
action. However, TiO2/UV has the capability to endure both oxidation and
Published on 16 September 2014 on http://pubs.rsc.org |
28
Table 2.2 Heavy metal removal technologies.12
Treatment method Significant factors Other details Advantages Disadvantages
Ion exchange: using Functional groups (sulfonic For clinoptilolite resin: bath i) High removal eciency, i) Expensive for large
synthetic or natural acid, carboxylic acid and fixed bed operation; ii) fast kinetics, iii) high amounts of wastewater
cation-exchange resin group); pH, initial metal pH range 47; eciency treatment capacity with low conc. of metal
ion concentration, ionic range 55100% ion, ii) regeneration
charge, contact time requirement of resins
11:25:32.
Adsorption: using activated Surface area; electrostatic Physisorption or i) Design flexibility, i) High cost of activated
carbon, carbon nanotube attraction; sorption chemisorption depending ii) generate high quality carbon, ii) performance is
(CNT), low-cost precipitation; surface on the binding treated euents, adsorbent dependent,
adsorbents from functional group of CNTs iii) regeneration is iii) works better at low
industrial or agricultural possible by proper concentration of heavy
waste desorption process metals in wastewater
Membrane filtration: Membrane pressure, RO4NF4UF (membrane i) High eciency, ii) easy i) High cost, ii) complex
ultrafiltration (UF), pore size. For UF: pressure) operation, iii) space saving process, iii) fouling of
reverse osmosis (RO), concentration of metal, membrane, iv) low
nanofiltration (NF), concentration of permeate flux, v) high
electrodialysis surfactant, solution pH, power consumption for
ionic strength RO process
Chemical precipitation: For hydroxide precipitation: Lime, NaOH (hydroxide i) Simple inexpensive, i) Large volume of relatively
hydroxide and sulfide pH 811, use of precipitation); sulfate ii) sulfide precipitation low density sludge, ii) mix
precipitation coagulants (alum, iron reducing bacteria (sulfide is better than hydroxide metal euent is dicult
salt, organic polymers) precipitation) precipitation to remove, iii) sulfide
precipitation may produce
toxic H2S fumes
Coagulationflocculation pH, formation of Common coagulants: i) Better settling, ii) better i) Complete removal not
hydrophilic colloids, FeSO4, FeCl3, sodium sludge dewatering possible, ii) use of several
electrostatic attraction xanthogenate chemicals, iii) sludge
Flocculent: PAC, PFS, PAM generation
Electrochemical treatment: Current density, initial Optimum pH range: 68 i) Rapid and well controlled i) Large capital investment,
Chapter 2
electrocoagulation, metal ion concentration, method, ii) less sludge ii) expensive electricity
electro flocculation, pH generation, iii) 78100% supply
electrodeposition yield
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reduction reactions and is applicable in all the heavy metal and metalloids
removal/recovery processes.
There are numerous photocatalysts such as TiO2, GaP, WO3, ZnO, ZnS, CdS,
etc., that are well known for their photodegradation and complete mineral-
ization capability for water pollutants. Among them, TiO2 is the most active
photocatalyst under photon energy of 300 nmolo390 nm and also shows the
highest stability compared with other photocatalysts of similar class.16
Heterogeneous photocatalytic oxidation/reduction processes became
popular among the AOPs primarily because of the following reasons: (i) the
processes can be carried out under ambient conditions (temperature and
pressure), (ii) the oxidant is strong and less selective, which leads to complete
mineralization, (iii) the processes do not consume any expensive oxidizing
chemicals, (iv) unlike other AOPs it can undergo reduction reactions and (v)
the photocatalysts are less expensive, non-hazardous, stable and reusable.17,18
2.3 Basic Principle of Heterogeneous Photocatalysis

Photocatalysis links two fundamental subjects, photochemistry and cata-
lysis, because of the need for both photons (light) and a catalyst (semi-
conductor) to initiate the chemical reaction. The photons can be provided by
either UV (300388 nm) or visible (388520 nm) light sources, depending on
the semiconductor materials being used. The semiconductor materials are
characterized by a filled valance band (VB) and an empty conduction band
(CB); the VB electron can be activated by a photon with sucient energy
11:25:32.
equal to or greater than the band gap energy (Eg), between the CB and VB.
Upon excitation, the electron moves from the VB to the CB and leaves a
positive charge in the VB, known as a hole (h1). This is commonly known as
charge separation, which is the first step to a photocatalytic reaction
(Figure 2.1). The photogenerated electronhole pairs can subsequently be
involved in several possible reactions: i) recombination of electrons and
holes and dissipation of the input energy as heat, ii) the electron and hole
get trapped in metastable surface states or iii) reaction with electron donors
or electron acceptors adsorbed on the semiconductor surface or within the
surrounding electrical double layer of the charged particles commencing
oxidation/reduction processes.19,20
2.4 Mechanism of Photocatalytic Reactions

A typical photocatalytic process can be described as a four-phase system,
where in addition to the liquid (aqueous, organic solvent), solid (photo-
catalyst) and gaseous phases (oxygen, nitrogen), an electronic phase is in-
volved in terms of a light source. A photocatalytic reaction initiates with the
formation of electron-hole pairs followed by oxidation and/or reduction re-
actions.20 According to Chen and Ray,21 in the presence of an electron
scavenger (oxygen), the oxidation reactions become predominant, whereas
in the presence of a hole scavenger (formic acid, methanol, etc.) one can
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30 Chapter 2
Figure 2.1 Schematic diagram of overall photocatalytic process20 (Copyright 2000

John Wiley & Sons Ltd).
11:25:32.
bypass the oxidation reaction and the reduction reaction becomes the
principle reaction. The photoreduction of metal ions are well addressed by
Chen and Ray,21 where the redox processes are as explained in Scheme 2.1,
where M denotes the metal ion and RH is the organic compound. In the
absence of an organic compound, water is oxidized at a much lower rate
resulting in inferior metal reduction. To undergo a photo-oxidation process
the potential of the valence band needs to be more positive than the oxi-
dation potential of the chemical species. On the other hand, the conduction
band of the semiconductor photocatalyst must be more negative than the
reduction potential of the red-ox pair to endure the photoreduction
process.21
2.5 Thermodynamics of Photoreduction of Dierent

Metal Ions
The feasibility of transformation (oxidation or reduction) of metallic couples
depends on the relative value of the redox potential compared with the level
of the CB and VB of the semiconductor. Figure 2.2 describes the positions of
the VB and CB of TiO2 (anatase) photocatalyst at dierent pH and relates
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Reaction Scheme
Step 1: Initiation
hJ Ebg
TiO2 TiO2 (h+ +e) (2.1)
Step 2: Oxidation of organic compound and water
HO + h+ HO (2.2)
HO + RH R + H2O CO2 + H2O + mineral acids (2.3)
2H2O + 4h+ O2 + 4H+ (2.4)
Step 3: Reduction of metal ion
Mn+ + e M(n1)+ (2.5)

Scheme 2.1 Photoreduction of metal ions.21
11:25:32.
them with the reduction potentials of various metal ions. The position of
both VB and CB are pH dependent, and with unit increments of pH, the
position of the VB and CB move towards a more cathodic potential by 59 mV.
If the redox couple has a potential between EVB and ECB, the transformation
is thermodynamically possible.21 According to the potential versus pH dia-
gram, Au31, Cr61, Hg21, Ag1, Hg221, Fe31, Cu1 and Cu21 show a high
tendency for photoreduction in the pH range 1.07.0. There are a few more
metal ions such as Cr31, Fe21, Zn21, Cd21, Ni21, Pb21 and Mn21 that are not
susceptible to photoreduction in this pH range.21
2.6 Dependence of Photoreduction Kinetics

on Dierent Parameters
There are a few other parameters that aect the photoreduction of metal
ions, such as: i) initial metal ion concentration, ii) photocatalyst mass,
iii) presence of electron or hole scavenger and iv) light intensity.
2.6.1 Eect of Initial Metal Ion Concentration

Photocatalytic reaction kinetics is quite dierent from conventional AOPs,
and usually follows saturation behaviour. The initial rate of photocatalytic
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32 Chapter 2
11:25:32.
Figure 2.2 Position of conduction and valance bands of TiO2 (anatase) and re-
duction potential of dierent metal ions at various pH21 (Copyright 2001
Elsevier).
reaction follows a LangmuirHinshelwood mechanism with respect to initial

metal ion concentration.20
kKC0
r0 (2:6)
1 KC0
According to eqn (2.6), at high concentration (KC c 1), the reaction rate
is maximum and describes a zero-order rate, whereas for diluted solution
(KC{1) the reaction rate is first order.22
2.6.2 Eect of Photocatalyst Mass

The initial reaction rate of a photocatalytic reaction is directly proportional
to the photocatalyst mass. There is an optimum concentration level of the
photocatalyst above which the reaction becomes independent of the pho-
tocatalyst mass. The optimum concentration level largely depends on several
factors, such as light intensity, reactor geometry, photocatalyst particle size
and phase composition. At the optimum level it is assumed that the entire
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photocatalyst surfaces are illuminated with the incident light. Once the
catalyst concentration exceeds the optimum level, a shielding eect of the
particle on the light by the excess particles occurs, although the photo-
catalyst surface area per unit volume of solution increases.20 Chen and Ray23
proposed an equation to demonstrate the eect of photocatalyst mass on

photocatalytic reaction rate:
ri K[1 exp(EbCcatH)] (2.7)
where K is reaction rate constant, Ccat is the catalyst concentration, the light
adsorption coecient of the reaction system is e, b is the exponential term
related to light intensity (its value varies between 0.5 and 1.0) and solution
thickness in the light transmission direction is denoted by H.
2.6.3 Eect of ElectronHole Scavenger

In a photocatalytic reaction, the electrons are involved in the reduction re-
action whereas the holes are involved in the oxidation reaction. The use of an
electron scavenger (usually dissolved oxygen) is necessary in the case of the
oxidation reaction. The photo-oxidation rate of phenol in the presence of
dissolved oxygen is well described by Chen and Ray,23 which also follows the
LangmuirHinshelwood equation:
11:25:32.
kKO2 pO2
kobs (2:8)
1 KO2 pO2
where kobs is the observed kinetic constant for organic compound degrad-
ation, KO2 is the adsorption constant of dissolved oxygen on the TiO2 catalyst
and pO2 is the partial pressure of dissolved oxygen.
On the other hand, the photoreduction process needs a hole scavenger
(usually formic acid or an aliphatic alcohol) in the system along with anoxic
conditions. Generally oxygen is replaced with a periodic or continuous flow
of nitrogen or other inert gases.20
2.6.4 Eect of Light Intensity

With an increase in the light intensity, the photon-flux (number of incident
photons per unit time per unit area) values increase, which improves the
electronhole generation. Thus at very low light intensity, the photocatalytic
reaction follows a first-order rate in light intensity, whereas at high intensity,
the photocatalytic reaction rate is proportional to the square root of the
intensity. According to Herrmann,22 at higher intensity (ca. 25 mW m2) the
rate of electronhole formation exceeds the photocatalytic reaction rate,
which favours the electronhole recombination.
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34 Chapter 2
2.7 Recent Challenges in the Photocatalytic Process

2.7.1 Photoreactor Development
To date the major barrier behind the commercial applications of photo-
catalytic reactors on an industrial scale lies in the eective reactor design.

The scale-up of a chemical reactor is much easier than that of a photo-
catalytic reactor where several additional scale-up diculties need to be
considered, such as flow pattern, catalyst illumination, reaction kinetics,
catalyst contacting, mixing and mass transfer. Transmission of light in a
highly scattering and absorbing medium of a photocatalyst slurry is pretty
challenging and the illumination of the photocatalyst is the necessary con-
dition for the photo-assisted reactions.24,25 There are plenty of interactions
between the light absorption, the transport process and the reaction kin-
etics, making a strong association between the physicochemical phenomena
and this is the basic problem in the development of a proficient photo-
catalytic reactor. The key issue in a photocatalytic reactor is related to light
distribution inside the reactor. So the organization of the light source
reactor assembly influences the reactor design in such a way that in-
dependent consideration is not conceivable.26
The scale-up from a bench-scale to a large-scale operation requires proper
assessment of the irradiation and its distribution inside the photoreactor.
The successful scaling-up of the photoreactor needs a high value for the ab-
sorbed photon flux (number of photons per unit mass of catalyst per unit
time) as well as eective use of the electronhole pair through photo-oxidation
11:25:32.
and photoreduction processes. Moreover, it needs a large photocatalyst sur-

face area inside the reactor to adsorb the target compounds and to absorb the
incident photons. Photo-reactor capacity can be expressed as follows:
QCin X
VR (2:9)
kR
where VR is the photoreactor volume, Q is the volumetric flow rate (m3 s1),
Cin is the inlet concentration of pollutant (mol m3), X is the desired frac-
tional conversion, k is the illuminated catalyst surface area (m2 m3) and R
is the average mass distribution rate (mol m2 s1). Several authors have
proposed dierent designs of photoreactors in recent years, which can be
categorized into four major groups, such as slurry type, immersion type,
external type and distributive type.
Ray25 used the k value to compare the ecacy of dierent photoreactors.
The parameter k denotes the illuminated catalyst mass inside a photoreactor
that can successfully undergo the photocatalysis process. Based upon k
values, scale-up is not possible for slurry and external type annular reactors.
Scale-up would be possible for the immersion type (with novel lamps) and
the distributed type (with hollow tubes) photoreactors with a lesser reactor
volume. In the case of the immersion type photoreactor with a classical
lamp, scale-up is possible at larger reactor volumes.
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2.7.2 Photocatalyst Development

Conventional semiconductor photocatalysts (TiO2, ZnO, etc.) have drawbacks
in visible light activity. These semiconductor materials are active under the
UV range (280390 nm), which is only 4% of the solar radiation. Utilization
of solar radiation for photocatalysis would make the process a green and
sustainable one. The sun is a massive source of energy, from which the earth
receives 1.51018 kWh per year, or approximately 28 000 times the world
consumption for one year. The World Meteorological Organization has
recommended the solar constant value of 1366.7 W m2 outside the at-
mosphere.27 Thus, researchers are willing to utilize the more profuse visible
light (46% of the solar spectrum) for the excitation of semiconductors. Ef-
forts have been made to improve the photocatalytic activity and visible light
response. This includes modification of semiconductor photocatalysts to
expand their photoresponse to the visible region in several ways, such as
doping with a cation/anion, sensitizing with a dye, coupling with another
small band gap semiconductor and implantation of metal ion (Table 2.3).28
2.8 Application of Photocatalysis for the Removal

of Heavy Metals
2.8.1 Group 6 Metal (Chromium)
Chromium shows three oxidation states 2, 3 and 6. In drinking water
11:25:32.
the level of chromium is generally low, but contaminated water can contain
the hazardous chromium(IV). Cr(III) occurs naturally in fruits, vegetables,
grains and meats. It enters into the human body mainly through the food
chain. Cr(VI) is highly toxic in nature so its reduction to Cr(III) is desirable.
Several semiconductor photocatalysts such as TiO2, ZnO, WO3, ZnS, CdS,
SnIn4S8, etc., have been reported for the photoreduction of Cr(VI).3538 Both
thermodynamic and kinetic studies showed that the photocatalytic re-
duction of Cr(VI) under UV irradiation depends greatly on pH.35 Acidic pH
favours the photoreduction process but for better separation of Cr(III) salts,
the photo-reduction is performed at higher pH.35,39 The photoreduction
process is much faster in the presence of hole scavengers such as phenol,
methanol, formic acid, salicylic acid, citric acid, etc.35,38,40,41 Wang et al.35
established the Cr(VI) photoreduction pathway as a direct electron transfer in
the presence of formic acid as a hole scavenger. At pH greater than 6.0, the
TiO2 surface reaches higher negative charges and prevents adsorption for
both Cr(VI) oxyanions and COO. Hence, Cr(VI) reduction through direct
electron transfer will not be favoured at higher pH. However at higher pH the
amount of free COO is more, which may increase the rate of Cr(VI) re-
duction. It has been confirmed that the overall reduction rate of Cr(VI)
declined on increasing the pH, irrespective of the increase of COO in
solution. Unlike other metals, Cr(VI) reduction is not aected by the presence
of oxygen. Results from Lin et al.42 for Cr(VI) reduction at pH 10 contradict
36
Table 2.3 Modification of photocatalyst to expand their visible light activity.
Technique Methodology Example Reference
Cation/anion doping In doped photocatalysts, the dopant forms Cation doping: TiO2 doped with noble 29
an electron donor level in between CB metals, transition metals, post transition
and VB and the band gap is reduced to metals
11:25:32.
make the catalyst visible light active. Anion doping: TiO2 doped with anionic
non-metals (N, S, C, and I).
Valance band controlled Generally the VBs of oxide photocatalysts Bismuth (6s orbital), tin (5s orbital) and 3032
photocatalyst have the 2p orbital of oxygen. On the silver (4d orbital) forms BiVO4, AgNbO3
other hand, few metals contribute to and SnNb2O6.
the formation of the VB of these
photocatalysts above the 2p orbital of
oxygen.
Composite semiconductor In this case a large band gap SnO2, (band gap 3.5 eV) can form a 28
semiconductor is coupled with a small composite with CdS (band gap 2.4 eV).
band gap semiconductor. Electrons from
a conduction band of a small band gap
semiconductor are injected into a large
band gap semiconductor conduction
band.
Dye-sensitization When the sensitization of a large band gap TiO2 becomes visible light active once it 33
semiconductor to the visible region is is sensitized with eosin Y dye.
achieved with a dye at the molecular
level, it is called dye-sensitization.
Defect induced visible light Visible light activity can be achieved by Hydrogenation is an eective route to 34
active photocatalysis heating a semiconductor in an inert impose anamorphous layer on TiO2
gas/vacuum, or incorporation of small (anatase) and thereby extending the
Chapter 2
cations (H1, Li1, etc.) into the lattice. optical absorption to IR region.
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the previous discussion. At pH 10, both Cr(VI) and oxygen compete for the
electron as the thermodynamic driving force for oxygen is much higher
compared with Cr(VI).
2.8.2 Group 10 Metals (Nickel and Platinum)

Group 10 metals show oxidation states of 2 and 4. Nickel is a vital
component of enzymes found in a range of vegetables. Nickel originates
from dierent ores such as millerite, niccolite and nickel glance, along with
sulfur and arsenic. Platinum is found at very low concentrations in air, water
and soil and it has little environmental impact.
Kabra et al.43 reported the solar photocatalytic reduction of Ni(II) ions with
a TiO2 photocatalyst in the presence of citric acid as a hole scavenger. The
Ni21/Ni reduction potential is less negative than the TiO2 CB and thus
photoreduction of Ni(II) is thermodynamically feasible. In the absence of
citric acid, the adsorption over TiO2 was 31.6%, whereas it was reduced to
20.6% in the presence of citric acid. Actually the anionic Ni-citrate formed
was repelled by the negatively charged TiO2 surface. The rate of photo-
reduction of Ni(II) was very low even in the presence of dierent hole scav-
engers such as salicylic acid, EDTA and oxalic acid, as reported by several
authors.4345
Photoreduction of Pt(IV) is studied systematically in the field of photo-
deposition processes. The PtTiO2 photocatalysts have extensive appli-
cations in water treatment as well as in photocatalytic hydrogen generation.
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In a photodeposition method the platinum precursor [Pt(IV)Cl6]2 is reduced

by the photogenerated electron at the valance band of TiO2, and the sacri-
ficial organic reagent acts as hole scavenger.46 [Pt(IV)Cl6]2 is first adsorbed
on the TiO2 surface, then reduced to [Pt(II)Cl4]2 and Pt0 or (Pt0)m (Pt metal
cluster).47 The presence of Pt, Pt(OH)2 and PtO2 on the surface of TiO2 was
confirmed by the authors. In another study, a mixture of Pt(II) and Pt0 states
were identified even after 24 h of photoreduction, which could suggest the
simultaneous agglomeration of Pt atoms and cathode-like reduction during
the particle growth of Pt metal.48
2.8.3 Group 12 Metals (Zinc, Cadmium and Mercury)

Zinc and cadmium show only 2 oxidation states, while mercury shows
both 2 and 1 oxidation states and forms the ions Hg21 and [Hg2]21,
respectively. Mercury also forms several organic compounds containing a
mercurycarbon bond or a mercurynitrogen bond.
Zn(II) can be successfully removed with adsorption over TiO2, but UV
photocatalysis is not worthwhile because of the lower redox potential of
the Zn21/Zn couple (0.76 V) compared with the TiO2 conduction band.
Kajitvichyanukul and Sungkaratana used formate and acetate ions as hole
scavengers to inhibit the electronhole recombination, which thereby con-
siderably enhanced the photoreduction of Zn(II) to metallic zinc.49
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38 Chapter 2
In the case of Cd(II) photoreduction the thermodynamic driving force is

small. The redox potential of the Cd21/Cd couple (0.403 V) is just below
that of the TiO2 conduction band (0.5 V) at pH 7. Nguyen et al. reported
formate ion as the best hole scavenger for Cd(II) reduction under an anoxic
environment. There is also an optimum level of formate ion concentration

(600 ppm carbon) for such a photoreduction.50
Chenthamarakshan et al.51 studied photoreduction of both Zn(II) and
Cd(II) in the presence of formate ion. The photoreduction of Cd(II) was much
faster compared with Zn(II) photoreduction. The reaction rate was first order
at low formate ion concentration (o0.01 M), whereas a zero-order rate was
followed at a higher formation ion concentration. They also mentioned that
formate ion can act as an anchor species on the TiO2 surface and hold two
metal ions. Moreover, upon UV photogeneration of the electronhole, the
formate ion captures the holes from TiO2 and then the electrons are trans-
ferred to the metal ions to undertake the photoreduction process.52
Several studies were performed on the photocatalytic removal of mercury
ion and organic mercury compounds from aqueous solution. The standard
reduction potentials for dierent mercury compounds (HgCl2/Hg0 0.41 V,
Hg2Cl2/Hg0 0.268 V and Hg(OH)2/Hg0 1.034 V) are high enough to
endure the photoreduction process with the TiO2 photocatalyst. Ecient
photoreduction of organic compounds of mercury such as phenylmercury(II)
(C6H5Hg1) and methylmercury(II) (CH3Hg1) are reported under UV
TiO2.5355
The net photocatalytic reduction process can be described as follows:
11:25:32.
Hg21(aq) H2O (hn/TiO2)-Hg0(ads) 2H1 2O2
The photoreduction of mercury ion is much improved in an anoxic atmos-

phere compared with an oxygen atmosphere. Khalil et al.56 reported 45%
improvement of Hg(II) removal in the absence of oxygen in the photocatalytic
system. Both Hg(II) ion and O2 compete for photogenerated electrons in an
air-equilibrated system and results in a low percentage of Hg(II) photo-
reduction. Again a significant TOC drop is observed in the absence of oxy-
gen, which also proves the superior oxidizing property of Hg(II) ion over
oxygen for mineralization.
The photoreduction rate also depends on the amount of Hg(II) adsorbed
onto the photocatalyst surface. In the case of Degussa P25, TiO2 particles are
positively charged at pH below 7.1. Again on increasing the solution pH, the
amount of positive charge decreases, resulting in lesser electrostatic
repulsion between the positively charged TiO2 surface and Hg(II) ion.
Therefore, the degree of adsorption of Hg(II) improved at higher pH values.57
Moreover, the solution pH also influences the potential of the conduction
band electrons and the surface properties of the semiconductor. Wang
et al.57 and Khalil et al.56 performed successful Hg(II) photoreduction at a
moderate acidic pH (4.0) whereas, several other authors5355 found alkaline
pH (1011) to be a better option.
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Another parameter that influences the photoreduction of Hg(II) is the

presence of hole scavengers (sacrificial agent) in the photocatalytic system.
They react irreversibly with the photogenerated holes and moderate the
electronhole recombination probability. In the absence of sacrificial agents
the photogenerated hole would be involved in a kinetically slow reaction

with water.57
2H2O 4h1-O2 4H1
Khalil et al.56 used methanol as a hole scavenger (20 vol%) to enhance the
photoreduction of Hg(II) ions. Wang et al.57 identified formic acid as the
most suitable hole scavenger for photoreduction of Hg(II) ions. Formic acid
is a small molecule that facilitates adsorption on TiO2 followed by oxidation
by positive hole (h ) and produces carbon dioxide and water vapour as
photoproducts. Moreover, formic acid absorbs light with a wavelength lower
than 260 nm to undergo only photocatalytic reactions, no direct photolysis
occurs. According to Wang et al.57 there is a limiting value of formic acid
concentration (5 mM), above which the photoreduction of Hg(II) become
independent of the concentration of the hole scavenger.
2.8.4 Group 15 Metalloid (Arsenic)

Arsenic is a naturally occurring element found in the earths crust. It ranks
20th in abundance comprising about 0.00005% of the earths crust, 14th in
sea water and 12th in human body.58,59 Arsenic exists in several forms, such
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as the oxyanion of trivalent arsenite [As(III)], or pentavalent arsenate [As(V)]

depending on solution pH and redox potential.60 As(III) exists in a non-ionic
form and can bond strongly with the building blocks of protein, resulting in
biological disruptions, and thus it is more toxic than As(V).60 Therefore, pre-
oxidation [As(III) to As(V)] is required for the removal of toxic As(III) species
from aqueous media. Conventional oxidation processes such as H2O2, Cl2,
KMnO4 and granular iron hydroxide are well known. Moreover, the photo-
catalytic oxidation process is an inexpensive process that can also convert
As(III) into As(V).61 Photo-oxidation rate depends on several parameters such
as catalyst loading, light intensity, solution pH, initial concentration of
As(III), dissolved oxygen, presence of Fe(III) salts, presence of humic acids and
Pt loading onto TiO2.62,63 Dutta et al.62 reported a considerable increase in
As(III) oxidation rate with both an increase in catalyst loading (range: 0.002
0.1 g L1) and light intensity (range: 0.8822.5 mW cm2). The oxidation rate
follows a nonlinear rate equation with respect to light intensity (k p Ib) with
a b value of 0.23. They also described As(III) oxidation with a zero-order
kinetic rate. Lee and Choi63 found a positive eect of humic acid and ferric
ion on As(III) oxidation. The eect of humic acid is more prominent at acidic
pH (pH 3) compared with an alkaline one (pH 9). However, Dutta et al.62 did
not find any influence of pH on As(III) oxidation.
Photocatalytic oxidation of As(III) to As(V) can be achieved either via a
superoxide anion (HO2/O2) or via a valance band hole (or HO). Lee and
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40 Chapter 2
63
Choi reported a superoxide anion as a major oxidizing species, which as
supported by Ferguson et al.64 Several other authors61,62,65,66 opposed the
involvement of a superoxide anion and suggested h1/HO as the principle
oxidant for As(III) oxidation. It is very hard to draw a definite conclusion from
these studies as they are based on addition of competitive additives, which

may change the normal oxidation mechanism (Fei et al.67). Fei et al.67 came
up with a photoelectrochemical method without altering the normal oxi-
dation mechanism to clarify the controversy. According to them, both
h1(HO) and superoxide anions play equal roles in As(III) oxidation.
2.9 Conclusions
Heavy metal removal techniques have been discussed extensively in recent
literature. Besides other conventional techniques, a photocatalysis process is
also used for the removal/recovery of heavy metal ions. Various AOPs are
utilized for water/wastewater treatment, which can only undertake oxidative
metal removal and cannot provide reduction of the metal ion. A UV assisted
photocatalysis process is suitable for both oxidation (used for As removal)
and reduction (used for Cr, Zn, Cd, Hg, Ni and Pt removal) reactions for
heavy metal/metalloid removal.
Solution pH is a crucial factor in the reduction of heavy metal ions; this
reduction process is well explained by our research group in previous
studies. There are a few metals, such as Zn21, Cd21, Ni21, etc., whose re-
ductions are not thermodynamically feasible and thus require sacrificial
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agents (formic acid or aliphatic alcohol) to initiate the process. Other factors
such as initial concentration of the metal ion, photocatalyst mass and light
intensity also aect photocatalytic metal reduction.
This chapter has addressed two major challenges in the photocatalysis
process. Photocatalyst development would help us to utilize the abundant
solar radiation. Moreover, photoreactor developments addressing several
key issues have introduced two major reactors, namely immersion type and
distributed type, for final scale-up of wastewater treatment.
Acknowledgement
The first author would like to thank the Natural Science and Engineering
Research Council (NSERC), Canada for financial support.
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11:25:32.
CHAPTER 3
Removal of Dissolved Metals

by Bioremediation
SUBHAJIT MAJUMDER, SURESH GUPTA AND
SMITA RAGHUVANSHI*
Department of Chemical Engineering, Birla Institute of Technology

and Science (BITS), Pilani-333031, Rajasthan, India
*Email: smita@pilani.bits-pilani.ac.in
3.1 Heavy Metals in Wastewater

11:25:36.
Metals are intrinsically persistent in nature1 and play an integral role in the
life processes of living organisms. Heavy metals are elements having atomic
weights between 63 and 200, and a specific gravity of greater than 5.0.2 Some
metals such as Cr, Cu, Ca, Co, Fe, K, Mg, Mn, Na, Ni and Zn are essential up
to a maximum concentration limit and serve as micronutrients. They are
commonly used in redox-processes to stabilize molecules through electro-
static interactions, as components of various enzymes and for regulation of
osmotic pressure.3,4 Many other metals, such as Cd, Pb and Hg have no
biological role and are non-essential and potentially toxic to living organ-
isms, especially microorganisms.4 At high concentration levels, both es-
sential and non-essential metals could change enzyme specificity, imbalance
cellular functions and destroy cell membranes and the structure of DNA.5
Complexes of heavy metal ions such as Cd and Hg are very harmful to cell
vital activity, so the internal concentration and increase of heavy metal ions
should be controlled.6

44
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Removal of Dissolved Metals by Bioremediation 45
Environmental pollution due to rapid industrialization is one of the

most significant problems of the last century. The main sources of heavy
metal pollution are mining, milling, plating and surface finishing indus-
tries that discharge a variety of toxic metals such as Cr, Cu, Cd, Ni, Co, Zn
and Pb into the environment. Over the last few decades, the concentration
of these heavy metals in river water and sediments has increased rapidly.
Consequently, concentrations of toxic metals in grains and vegetables
grown in contaminated soils have increased at alarming rates. This poses a
significant threat to humans and the environment because of the toxicity,
non-biodegradability and bioaccumulation.79 These metals have import-
ant roles in dierent biochemical reactions but are poisonous for cells at
high concentrations.6 It is well known that heavy metals can be extremely
toxic as they damage nerves, liver and bones, and also block the functional
groups of vital enzymes.10,11 Some of these metals, such as Cr and Ni, are
listed as possible human carcinogens. The objective of this chapter is to
focus on various biological methods for the treatment of heavy metals and
to give a detailed overview of bioremediation techniques used for toxic
metal detoxification of industrial wastewater. Various physico-chemical
methods used for toxic metal scavenging are also highlighted in this
chapter.
3.2 Regulatory Limits of Heavy Metals

The maximum contamination level (MCL) values for various heavy metals as
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given by the US Environmental Protection Agency (US EPA) are summarized

in Table 3.1. These limits are mandatory for all water supply systems. Nat-
urally occurring water (both surface and groundwater) frequently contains
some of these heavy metals at concentrations 100 or 1000 times more than
the prescribed MCL values. Since these heavy metals are valuable resources
for dierent industrial applications, their removal, recovery and recycling
assume greater significance.
Table 3.1 Selected heavy metals and their

regulatory limits as per US EPA.21
Maximum
contamination
Heavy Metals level (mg L 1)
Arsenic (As) 0.01
Lead (Pb) 0.015
Mercury (Hg) 0.002
Chromium (Cr) 0.01
Cadmium (Cd) 0.005
Zinc (Zn) 5.0
Copper (Cu) 1.3
Manganese (Mn) 0.05
Silver (Ag) 0.05
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46 Chapter 3
3.3 Physico-Chemical Treatments of Heavy Metals

Over the last few decades, several physico-chemical methods have been
widely used for the removal of heavy metals from industrial wastewater, such
as ion exchange, filtration, precipitation, electrochemical treatment, chem-

ical reduction, adsorption, membrane technologies and evaporation re-
covery.1215 Some of these treatment methods are illustrated in the following
sections.
3.3.1 Ion Exchange

Among the various physico-chemical methods developed for heavy metal
removal from wastewater, ion exchange has received much attention in re-
cent years. In this unit process, ions of a given species are displaced from an
insoluble material by ions of a dierent species in solution. The wastewater
containing heavy metals enters one end of the column under pressure and is
passed through the resin bed, which eventually traps the heavy metal ions
and thereby removes them from the wastewater. When the resin capacity
reaches its saturation limit, the column is backwashed to remove trapped
solids and then regenerated. Commonly used matrices for ion exchange are
synthetic organic ion exchange resins. Synthetic Dowex 2-X4 ion-exchange
resin was employed to remove the Cr(VI) from real plating wastewater.16
Research was carried out for the removal of copper ions by using a cation-
exchange resin, Amberlite 200C, in a semifluidized bed.17 Similar experi-
11:25:36.
ments were carried out for the detoxification of cadmium and nickel
contaminated industrial wastewater.18,19 The main disadvantage of ion-
exchange methods lies in its high selectivity and specificity. Secondly,
ion-exchange equipment are very expensive and the metal removal can be
incomplete because of saturation of the bed material.
3.3.2 Chemical Precipitation

Chemical precipitation is used extensively for heavy metal removal from
inorganic euents.20,21 After pH adjustment to the basic conditions, the
dissolved metal ions are precipitated in the form of hydroxide via a chemical
reaction with a precipitating agent such as lime.22 Lime precipitation was
employed for the removal of heavy metals such as cadmium, zinc and
manganese cations with initial metal concentrations of 150, 450 and
1085 mg L 1, respectively, in a batch continuous system.23 However, the
treated euents were unable to meet the stringent limits set by the US
EPA of less than 1 mg L 1. A group of researchers studied the removal
of Ni(II) from a low-strength wastewater with Ni(II) concentration less than
100 mg L 1.24 At pH 7.5 and 10.5, about 71 and 85% of Ni(II) removal were
attained, respectively, with an initial metal concentration of 51.6 mg L 1.
This study reveals the fact that a greater portion of the Ni(II) was precipitated
and removed in the form of insoluble hydroxide compounds with an
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increasing pH. In spite of its wide usage, chemical precipitation requires

large amounts of chemicals to reduce metals to an acceptable level for dis-
charge.25 Other drawbacks include excessive sludge production, increasing
cost of sludge disposal, slow metal precipitation, poor settling and the long-
term environmental impacts of sludge disposal.26
3.3.3 Electrochemical Precipitation

This method is used for removing toxic heavy metals up to parts per million
(ppm) levels. An electrical potential is utilized to maximize the removal
of heavy metals from contaminated wastewater compared with the con-
ventional chemical precipitation method.27 Removal eciency is largely af-
fected by low pH and the presence of other ions. It requires addition of other
chemicals, which eventually leads to the generation of toxic sludge. Direct
disposal of this sludge to the environment creates hazards.
3.3.4 CoagulationFlocculation
Coagulationflocculation can be used to treat wastewater contaminated with
heavy metals. Principally, the coagulation process destabilizes colloidal
particles by adding a coagulant and results in sedimentation.28 Generally,
coagulation is followed by flocculation of the unstable particles into bulky
floccules to increase the particle size.29 Following precipitation with lime,
Charerntanyarak23 used a coagulation process to remove cadmium, zinc and
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manganese ions from synthetic wastewater. At an optimum pH of 11, the

concentrations of Zn(II) and Mn(II) in the treated euent were reduced to
less than 5 mg L 1. In general, coagulationflocculation can treat inorganic
euents with a metal concentration of less than 100 mg L 1. In spite of its
advantages, coagulationflocculation has limitations, such as high oper-
ational costs due to chemical consumption.

Over the last few decades, membrane filtration has received considerable
attention for the treatment of heavy metals in wastewater. Depending on the
size of the particles that can be retained, various types of membrane fil-
tration, such as ultrafiltration, nanofiltration and reverse osmosis, can be
employed for heavy metal removal.27 To explore its potential to remove heavy
metals, Juang and Shiau30 studied the removal of Cu(II) and Zn(II) ions from
synthetic wastewater using chitosan-enhanced membrane filtration. This
study showed that about 100 and 95% rejection can be achieved at pH values
ranging from 8.5 to 9.5 for Cu(II) and Zn(II) ions, respectively, with an initial
Cu(II) concentration of 79 mg L 1 and Zn(II) concentration of 81 mg L 1. The
results indicated that chitosan significantly improved metals removal by
610 times compared with using a membrane alone. Saaj et al.31 employed
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48 Chapter 3
low cost ultrafiltration membrane (UF) membranes for the removal of Cr(III)
and Cd(II) ions from synthetic solution. Their study reveled 86% Cr(III) re-
jection and 93% Cd(II) rejection. Such high rejection rates might be attrib-
uted to the strong interactions between the divalent cations and the positive
charge of the membranes.27 Other researchers have carried out exhaustive

studies for the removal of heavy metals from synthetic and industrial waste-
water using nanofiltration (NF) membranes and reverse osmosis (RO). Ahn
et al.32 carried out investigations for the uptake of Ni(II) ions using electro-
plating wastewater with NTR-7250 membranes. They found that the removal
of Ni(II) was solely dependent on the applied pressure and the initial metal
concentrations. In spite of its benefits, membrane filtration has some major
limitations. A decrease in membrane fouling eventually decreases its per-
formance over time, resulting in a decreased permeate flow rate. This limi-
tation hinders it from wider application in wastewater treatment. Other
major drawbacks are the high energy consumption and the need for ex-
perienced personnel to run the process.33 Selection of the appropriate
membrane largely depends on a number of factors, such as the character-
istics of the wastewater, the nature and concentration of pollutants present
in the wastewater, pH and temperature.
3.3.6 Adsorption
Recently, adsorption has gained much significance as one of the most viable
alternative treatment techniques for wastewater contaminated with heavy
11:25:36.
metals.34 It is a sorption process in which adsorbates are selectively trans-

ferred from the fluid phase to the surface of insoluble, rigid particles (ad-
sorbents) suspended or packed in a column.35 The most widely used
adsorbent for the adsorption of various toxic heavy metal ions is activated
carbon. Hamadi et al. investigated the removal of Cr(VI) from synthetic
wastewater using Granular Activated Carbon (GAC) and found that reduction
in particle size of the adsorbents increases its surface area for adsorption.36
Various studies have been carried out for the detoxification of industrial
wastewater laden with heavy metals such as Cu(II),37 Zn(II)37 and Cd(II).38 In
general, technical applicability and cost-eectiveness are the key factors that
play major roles in the selection of the most suitable adsorbent to treat
wastewater contaminated with heavy metals.
Most of the physico-chemical methods (ion exchange, chemical precipi-
tation, electrochemical precipitation and adsorption) are eective, but the
metal solubility is significantly aected by changes in pH, thus causing
metals to be re-dissolved when the pH of the medium departs from the
optimal range. These conventional processes are sometimes restricted due
to technical or economical constraints and they themselves produce other
waste disposal problems. Moreover, strict environmental regulations restrict
various industries from shifting to the development of environmental
friendly, low-cost and ecient treatment technique for metal-rich
euents.39
View Online
3.4 Bio-based Separation for Heavy Metal Removal

High chemical requirement and ineective metal ion removal are the major
disadvantages associated with conventional techniques. Such methods are
also relatively expensive and sometimes generate secondary wastes that re-
quire subsequent disposal. These disadvantages can further aggravate the
cost of the removal process in the case of contaminated groundwaters and
other industrial wastewaters due to voluminous euents containing low
levels of metal contamination.39 Bio-based separation techniques can be
successfully applied in those areas. Various processes such as transport
through the cell membrane, biosorption to cell walls and entrapment in the
extracellular capsule and oxidation/reduction reactions have been adopted
by nonliving and living microorganisms to remove the heavy metal ions.4044
Microorganisms show a capability of removing heavy metals from aqueous
solutions when the metal ion concentration in the euent ranges from 1 to
20 mg L 1.45 Selectivity in removing the desired heavy metal ions is an added
advantage of bio-based separation techniques. These techniques have been
proved to be some of the most economical and eco-friendly techniques for
the removal of heavy metal ions.
Several studies have been carried out for scavenging heavy metal ions from
wastewater using various biological materials such as algae,46 bacteria,47
fungi48 and yeasts.49 In recent years, researchers have investigated the cap-
acity of these microorganisms for multiple heavy metal ions removal, which
promoted extensive research into bio-based techniques for metal removal.46
11:25:36.
Biosorption studies involving low-cost and dead or living biomass have

shown significant potential for scavenging the heavy metal ions.50 Metal
uptake capacity of various biological materials (fungi, algae and yeasts) has
been evaluated using biosorption isotherm curves by carrying out equilibrium
batch sorption experiments. The eect of various process parameters, such as
contact time, pH, biomass loading, etc., have also been studied extensively.
Recently, it has been reported that live microorganisms possessed higher
heavy metal (nickel) biosorption capacity over dead biomass pretreated with
chemical reagents due to intracellular metal ion uptake.51
Various mechanisms have been proposed for the removal of heavy metals
from wastewater using bacteria, fungi and algae.52 Heavy metal ions can be
entrapped in the cellular structure and subsequently biosorbed onto the
binding sites present in the cellular structure. This method of uptake is
known as biosorption or passive uptake. The heavy metal can also pass
inside the cell across the cell membrane through the cell metabolic cycle.
This mode of metal uptake is known as active uptake. The metal uptake by
both active and passive modes is referred to as bioaccumulation.39 Studies
have been carried out using several types of dead or pretreated microbial
biomass to test their eectiveness towards the removal of heavy metals. Most
of the studies are conducted using synthetic solutions of metals,53 and when
the biosorption potential using real industrial wastewater is tested, the ef-
ficiency turns out to be very low. Often biosorption may not result in eective
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50 Chapter 3
heavy metal remediation. Also, biosorption lacks specificity in metal

binding.54
In recent years, applications of active and growing microbial cells have
been tested in heavy metal removal. Studies revealed the eectiveness and
high specificity of active microbial cells in metal binding due to their ability
for continuous metabolic uptake of metals after physical adsorption, self-
replenishment and the potential for optimization through development of
resistant species and cell surface modification.55,56 Heavy metals that diuse
into the cells during detoxification become attached to intracellular proteins
or chelatins and are then incorporated into vacuoles and other intracellular
sites. These mechanisms of metal detoxification are often irreversible and
ensure that there is less risk of metal release back to the environment.57 Use
of growing cells in bioremoval of heavy metals avoids the need for a separate
biomass production process, e.g., cultivation, harvesting, drying, processing
and storage.39,58 Pumpel et al.58 investigated the procedure of a mixed
consortium of strains that have high metal removal capacities. Mixed species
consortia can better survive under extreme conditions, such as industrial
wastewater of high pH or high metal ion concentrations. Biofilms contain
rich exopolymers, which help in entrapping dispersed solids and biosorp-
tion of dissolved metals. The positive interaction between the species may
also help in the survival of sensitive strains.59 Considering all these char-
acteristics, the applicability of growing cells for the bioremediation of heavy
metals from industrial wastewater appears to be promising.
The non-biodegradable water soluble heavy metal ions are either oxidized
11:25:36.
or reduced by the microorganisms and produce less soluble species. The less
soluble form of these metal ions, which are formed due to biochemical re-
actions, are adsorbed or precipitated on the surface of the adsorbent and the
extra cellular protein of the microorganisms in the biolayer.60 Several studies
on the application of growing microbial cells for metal scavenging have been
reported. The viability of the algal strain isolated from domestic sewage
treatment plants has been tested for Ni(II) remediation.61 A strain of
Pseudomonas spp. was tested for scavenging of Ni, Cd and Co from waste-
water.62 A report revealed that both live as well as dead cells had similar Ni
uptake capacity, although Cd and Co uptake were greater in the live cells. An
acclimated mixed consortium of microbial species developed from activated
sludge has been used to remove Cr(VI) from a synthetic aqueous solution.63 A
study revealed significant removal of Cr(VI) [nearly 84.2% of initial Cr(VI)
concentration]. Table 3.2 presents some microorganism species and con-
sortia of microorganisms used in heavy metal removal.
3.5 Applicability of Isolated Strains and their

Eciency
Recent studies show that the strains isolated from contaminated soils and
activated sludge collected from domestic/industrial sewage water have
View Online

Table 3.2 Microorganisms and mixed consortia having heavy metal removal
capacity.
Microorganisms Toxic heavy metals removed Reference
Bacterial species:
Escherichia coli Hg, Ni 64

Pseudomonas species Cr, As 1
Desulfovibrio species Cu, Zn, Ni, Fe, As 65
Leptothrix species As, Mn, Fe 66
Thiomonas species As, Fe 67
Fungal species:
Aspergillus niger Ni, Cu, Pb, Cr 68
P. Chryogenum Cu, Zn, As, Ni 69
Trametes versicolor Cr, Co 70
Mucor rouxi Cd, Pb, Zn, Ni 71
Algal species:
Brown algae Cu, Cd, Zn, Pb, Cr, Hg 72
Green algae Cu, Hg, Fe, Zn, Pb, Cd 73
Mixed consortium Cr, Cu 35, 63
65
Cu, Zn, Ni, As 74
Cu, Cd, Co, Cr 75
Cd, Cu, Cr, Ni, Pb, Zn 76
Cr, Cu, Pb, Zn
excellent capability for removing heavy metals from wastewater. Roane and
11:25:36.
Pepper investigated the cadmium (Cd) removal capability of dierent strains

of Cd-resistant bacteria.77 Significant reduction of soluble Cd was reported
during growth of plasmid-bearing Bacillus strain H9 and Pseudomonas
strain H1. In a similar study, three strains of bacteria isolated from indus-
trial euents (Enterobacter cloacae and Klebsiella spp.) have shown resist-
ance to high concentrations of Cd, Pb and Cr in the growth media and could
remove approximately 85% Cd during growth.78 Algal strains isolated
from domestic sewage treatment plants have shown much higher uptake
eciency for Ni as compared with the commercial strain.61 Candida spp.
isolated from sewage samples could accumulate significant amounts of Ni
(5771%) and Cu (5268%).79 Larger fractions of metals were accumulated
during the end of exponential growth phase (915 days), indicating that
intracellular accumulation and adaptation of cells enhanced the resistance
and metal ion accumulation.
Various studies have been carried out using fungal and bacterial strains
isolated from sewage to scavenge Cu, Cr, Zn and Pb. Aspergillus niger was
tested for the removal of Cu and Pb from growth media but was less resistant
towards Cr.68 Similar studies have been carried out for ecient Zn uptake by
growing cells of Aspergillus spp. isolated from industrial waste.80 Pseudomonas
aeruginosa could accumulate Cr [0.08 mg mL 1 MRL (minimum risk level)/
uptake eciency] from industrial wastewater.81 The same strains showed 80%
removal eciency of Pb (initial metal concentration 100 mg L 1).82
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52 Chapter 3
Table 3.3 Improvement of heavy metals removal by genetically modified
microorganisms.
Plasmids
Improvement used and
Microorganisms in heavy protein

Reference used metal removal expressed Remarks
1 Pseudomonas Three-fold pTn-MTb1 No study on the eect
putida KT2442 with respect and pCNB1; of other metals on
to bacteria IgaAb-MT removal eciency
for Cd protein was performed
62 Escherichia coli Six-fold with pSUN1 and Pb21, Cd21 do not have
respect to pGMPT3; significant eects on
bacteria for GSM-MT removal eciency;
Ni Mg21, Hg21 have
adverse eect on
removal eciency
76 Pseudomonas 20-fold with Pseudomonas The resistant level
putida KT2441 respect to putida KT-6 observed in the
bacteria for transconjugant was
chromate 10 mmol L 1
chromate while the
control was resistant
only to 0.5 mmol L 1
3.6 Application of Genetically Modified

11:25:36.
Microorganisms
Although using bioremediation is a great idea, quite often the contaminants
are also toxic to the active microbes involved in the bioremediation process.2
This problem can significantly aect the rate of bioremediation. The rate is
reduced with respect to time and after some time the bioremediation
process ceased. A solution to this problem is genetically modified microbes
that are resistant to the extreme conditions of the contaminated site and also
have bioremediation properties. Table 3.3 presents a summary of genetically
modified microorganisms used for the removal of heavy metals.
From the studies discussed here, it is evident that the engineered bacteria
achieve better removal eciency with respect to the natural ones. The im-
provement in removal eciency in all the cases is noticeable.
3.7 Conclusion
Bioremediation using living microbial cells is a feasible alternative to pure
biosorptive removal of metal contaminants from industrial wastewater.
Isolated super-resistant strains from contaminated sites have proved to be
an ecient way to scavenge dierent heavy metals. Genetic engineering may
further enhance the potential of robust environmental strains. Use of mixed
consortia comprising of multiple species has proved advantageous for a
View Online
higher level of metal removal and provided more stability against environ-
mental fluctuations. However, the choice of consortia and carbon/nutrition
source must depend upon the nature of the euents due to the diering
complexing properties of the metals and the nutritional content of the ef-
fluent itself. Thus, there is no universal process to suit all kinds of metal
euents. Moreover, successful reproduction of the processes on a com-
mercial scale, as well as the ability of strains to maintain a constant metal
uptake, need to be tested over time.
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11:25:36.
CHAPTER 4
Functionalized Magnetic
Nanoparticles for Heavy
Metals Removal from Aqueous
Solutions
RAVINDRA KUMAR GAUTAM,*a SANJAY KUMAR SHARMAb
AND MAHESH CHANDRA CHATTOPADHYAYA*a
a
Chemistry, University of Allahabad, Allahabad 211 002, India;
b
Department of Chemistry, Jaipur Engineering College & Research Center,
JECRC, Jaipur, Rajasthan, India
11:25:40.
*Email: ravindragautam1987@gmail.com; mcc46@redimail.com
4.1 Introduction
Heavy metals pollution is a serious threat to aquatic ecosystems because
some of these metals are potentially toxic, even at very low concentrations.
Contamination of heavy metals in the surroundings has done great harm to
human and other organisms due to the high toxicity and carcinogenicity.16
The United States Environmental Protection Agency (USEPA) has classified
heavy metals as priority pollutants. The presence of heavy metals in aqueous
solutions has become a serious challenge for environmental scientists as
they are non-biodegradable and pose toxicity to biological systems. Lead
(Pb), cadmium (Cd), chromium (Cr), nickel (Ni), cobalt (Co), zinc (Zn) and
copper (Cu) are some examples of the toxic metals that exist in wastewater
euents.79 In addition, heavy metals are not biodegradable and tend to

57
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58 Chapter 4
accumulate in living organisms, and they can cause severe problems to both
human health and wildlife. Natural processes and human activities have
polluted and reduced the quality of water resources all over world.
Groundwater and superficial water have been contaminated in various ways,
for example: by mining wastes, by agricultural chemicals, by industrial and

domestic sewage that is sometimes discharged without treatment into
waterways and by natural trace elements (e.g., arsenic).
Since it is important to eliminate or reduce the concentration of heavy
metals in the aquatic ecosystems, various methods and technologies are
commonly applied in the treatment of mining and refining industry eu-
ents before they are discharged into receiving waters. These methods include
precipitation, ion exchange and membrane processes. However, the appli-
cation of some of these methods may be impractical due to economic con-
straints or they could be insucient to meet strict regulatory requirements.
Furthermore, they may generate hazardous products or products that are
dicult to treat.10,11 The traditional coagulation and flocculation processes
use inorganic coagulants, such as aluminium hydroxides in drinking water
treatment. Metal coagulants can be used to partially remove heavy metals
from wastewater,12 but the use of metal coagulants is not 100% eective for
removing metal cations from water at pH 7. The high cost of adsorbents,
such as activated carbon and some ion-exchange resins, used for the treat-
ment of water and wastewater has been conducive to the development of
new more eective and cheaper adsorbents. Bailey et al.13 mentioned that
natural materials that are available in large amounts or industrial waste
11:25:40.
products can also be used as adsorbents.
4.2 Sources of Heavy Metals in the Environment

Various industries that generate heavy metal containing wastewater include
cosmetics, paints and pigments, varnish, metal electroplating, leather pro-
cessing, synthetic fertilizers and mining activities. Wastewater generated
from these industries contains high levels of toxic metal ions. In practice, a
particular industrial activity will generate a specific metal ion, such as the
chromium that is generated in the leather processing industries and elec-
troplating industries generate cadmium and nickel contaminated industrial
euents. Mercury enters the environment through coal combustion. In
general the concentration of heavy metals in industrial euents is much
greater than their prescribed permissible limits in the aqueous solutions, so
there is an urgent need to treat the metal containing euents before they are
discharged into the aquatic bodies. Table 4.1 summarizes the anthropogenic
sources of heavy metals in the environment.
The earths crust contains about 0.00005% of arsenic.14 Arsenic was first
isolated by Albertus Magnus in 1250 AD.15 Weathering and geological re-
actions, microbial activities and volcanic eruptions in nature mobilize the
arsenic. Pesticides and herbicides containing arsenic, mining and various
industrial activities will have toxic eects on biological systems.16
Functionalized Magnetic Nanoparticles for Heavy Metals Removal

Table 4.1 Significant anthropogenic sources of metal ions in the environment and their eect on human beings and animals.
Pollutant Major sources Typical eects References
As Arsenic containing fungicides, pesticides and Exposure of arsenic causes bronchitis and may 1416
11:25:40.
herbicides, metal smelters, byproduct of mining cause cancer at a higher dose. Disrupts the
activities, chemical wastes function of SH group of enzymes in cells and
dissolves the proteins
Cd Cadmium producing industries, electroplating, Exposure to cadmium fumes and vapours damages 26
welding. Byproduct of refining of Pb, Zn and Cu, kidney, causes bronchitis, and intestinal diseases,
fertilizer industry, pesticide manufacture, may lead to cancer, disturbs the function of liver
cadmiumnickel batteries, nuclear fission plants, and brain. Anaemia and hypertension may be
production of TEL used in additives in petrol observed in cadmium poisoning
Cr Metallurgical and chemical industries, processes Toxic to body tissues, can cause irritation, 27
using chromate compounds, cement and asbestos dermatitis, ulceration of skin, perforation of nasal
units septum. Carcinogenic action suspected
Pb Automobile emissions, lead smelters, burning of Absorption through gastrointestinal and 28
coal and oil, lead arsenate pesticides, smoking respiratory tract and deposition in mucous
mining and plumbing membranes, causes liver and kidney damage,
gastrointestinal damage, mental retardation in
children, abnormalities in fertility and pregnancy
Zn Zinc refineries, galvanizing processes, brass Zinc fumes have corrosive eects on skin and can 29
manufacture, metal plating, plumbing cause irritation and damage mucous membranes
Mn Ferromanganese production, organo-manganese Poisoning of central nervous system (CNS), 38
fuel additives, welding rods, incineration of absorption, inhalation, or skin contact may cause
manganese containing substances manganic pneumonia
59
60
Pollutant Major sources Typical eects References
Ni Metallurgical industries using nickel, combustion Respiratory disorders, dermatitis, cancer of lungs 3236
of fuels containing nickel additives, burning of and sinus. Histological alterations in the
coal and oil, electroplating units using nickel epididymis and seminal vesicles; decreases in
salts, incineration of nickel containing substances sperm concentration, motility, abnormalities and
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in fertility. The observed eects include

inflammatory changes in the lungs, atrophy of the
nasal olfactory epithelium, hyperplasia in the
bronchial and mediastinal lymph nodes,
impaired immune function and decreases in body
weight gain, which are probably secondary to the
lung damage
Se Burning of fuels and residual oils, fumes and gases Selenium exposure causes irritation of respiratory 39
from refinery wastes, incineration of paper and tracts, eyes, nose and throat, disturbs the function
other wastes of lungs, liver and kidneys
Hg Mining and refining of mercury, organic mercurials Mercury vapours inhalation causes toxic eects to 1725
used in pesticides, laboratories using mercury protoplasm, methyl mercury compounds are
highly toxic and may damage the central nervous
system and brain
Cu Iron and steel industry, fertilizer industry and Defects in pigmentation, bone formation, 37
burning of wood, discharge of mine tailings, reproduction, myelination of the spinal cord,
disposal of fly ash and disposal of municipal and cardiac function and connective tissue formation,
industrial wastes are the sources of copper in the in addition to defects in growth and
atmosphere hematopoiesis were found to be the
manifestations of copper deficiency
Co Burning of fossil fuels, use of cobalt containing Cobalt disturbs the respiratory system in humans 30
phosphate fertilizers in agriculture, mining of and animals. It decreases the function of
Chapter 4
cobalt ores for metal processing and industrial pulmonary tissues, may cause asthma and lung
applications of cobalt disease. It generates oxidants and free radicals
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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 61
Mercury poses a severe risk of toxicity to the biological world and has been
reported in the Minamata Bay of Japan and San Francisco Bay of the
USA.1725 Extensive use of mercury in the pulp and paper industries, elec-
tronic industries and in the manufacture of plastics and pharmaceuticals
creates a great nuisance from mercury poisoning.

Cadmium is found naturally in rocks and soils. In certain forms and with
high concentrations, cadmium may produce adverse human health and
environmental eects. Cadmium may enter into the environment by natural
as well as human induced sources.26 Some of these natural emission sources
include weathering and erosion of parent rocks, volcanic activity and forest
fires. Anthropogenic sources of cadmium releases include nickelcadmium
loaded batteries, fusible alloys and solders, photographic plates and
photoelectric cells. Because of its unique chemical, mechanical and physical
properties, cadmium is utilized deliberately in a number of important in-
dustrial and consumer applications. These include: nickelcadmium (NiCd)
batteries for both industrial and consumer uses; cadmium corrosion-
resistant coatings on iron, steel, aluminium and titanium; cadmium pig-
ments in plastics, glasses, ceramics, enamels and artists colours; wea-
thering and ultraviolet light stabilizers for poly(vinyl chloride) (PVC); as an
alloying element in soldering, brazing, electrical contacts, high electrical
conductivity and high thermal conductivity alloys; and in electronic com-
pounds such as cadmium telluride and cadmium sulfide employed in solar
cells, detectors, electronic gates, switches, sensors and relays.
Chromium occurs naturally in rocks and soils and exists mainly in three
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forms, which are Cr(0), Cr(III) and Cr(VI). Chromium is discharged into the
environment from natural and anthropogenic sources, with the largest oc-
curring from industrial releases. Chromium is widely used in manufacturing
processes to make various metal alloys such as stainless steel. The anthro-
pogenic sources of chromium are electroplating, leather tanning, textile
production and the manufacture of chromium-based products.27 Burning of
natural gas, oil and coal also releases chromium into the environment.
Lead is a heavy, low melting, bluish-grey metal that occurs naturally in the
earths crust. The major natural ores that contain lead are galena, anglesite
and cerussite. It is usually found combined with two or more other elements
to form lead compounds. Lead is commonly used in pipes, batteries, am-
munition, cable covers and sheets used in shields from radiation. The
largest use for lead is in batteries, which are used in heavy motor vehicles.28
Tetraethyl lead may still be used in gasoline in most of the low-income
countries. It is also still used in a number of developing countries. Anthro-
pogenic activities are the major source of lead in the environment. Lead may
enter the aquatic sources through releases from mining and from industries
that use lead for making various items.
Zinc is mainly found in sulfide deposits. During weathering, zinc is im-
mobilized easily and finds its way into the aquatic systems. Zinc has had
many industrial applications since ancient times, for making bronze and
brass. It is used in galvanizing iron and steel, and zinc sheets are used for
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62 Chapter 4
building purposes. Sulfides and oxides of zinc have been used for making
white paints and ceramics.29
Cobalt occurs naturally in the environment, found in rocks and soils. It is
an essential element for living beings because it is associated with the
synthesis of vitamin B12. Cobalt is used in the manufacture of alloys, per-

manent magnets, paint driers and in industrial catalysts. Soil and sediment
contaminated with industrial pollution may contain high levels of cobalt.30
Chronic exposure to cobalt may cause goitre in human beings.
Nickel occurs naturally in soils and volcanic rocks. Nickel and its salts are
used in several industrial applications, such as in electroplating, automobile
and aircraft parts, batteries, coins, spark plugs, cosmetics and stainless
steel.31 The major anthropogenic sources of nickel in the environment are
metal refining and production of steel. Concentrations of nickel in household
dust can be high and therefore pose an increased risk to young children.
4.3 Toxicity to Human Health and on Ecosystems

Heavy metal exposure causes severe health problems in humans as well as in
animals and creates stress problems in living plants. Small amounts of a few
metals are required by biological systems to activate some enzymes and for
the synthesis of heme, but their higher dose beyond the permissible limits
disrupts the cell functions. Lead is a well known protoplasmic poison and
damages the reproductive system, kidney, causes encephalopathy and dis-
turbs the central nervous system. It obstructs the activation of delta ami-
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nolevulinic acid and thus disrupts its conversion into porphobilinogen,

which is an important step in heme synthesis. Chromium(VI) is toxic and
causes cancer in respiratory systems.40 Cadmium is highly toxic because of
the absence of homeostatic control for this metal in the human body.
Cadmium also acts as an inhibitor of sulfhydryl enzymes in living systems.
Mercury acts as a potent enzyme inhibitor, protein precipitant and corrosive
agents. Mercury toxicity causes neurobehavioural disorders and develop-
mental disabilities in humans. Methyl mercury compounds are some of the
most toxic substances because of their solubility in fat, the lipid fraction of
the membrane and brain tissue. Copper toxicity can lead to weakness,
lethargy and anorexia, as well as damage to the gastrointestinal tract.
Toxicity and health eects of arsenic as a deadly poison have been well
documented.14,41 Long-term exposure to drinking water containing arsenic
causes skin, lung, bladder and kidney cancer as well as pigmentation and
skin problems. This toxic element is known as a protoplasmic and cumulative
poison. Arsenic is found in the groundwater of most countries, such as in
India, China, New Zealand, Mexico, Japan, Bangladesh and the USA. Arsenic
easily crosses the placental membrane and is a well-known teratogen. Arsine
is a byproduct of arsenic, which is extremely poisonous to living organisms.
Mercury toxicity causes changes to genetic material, and alters enzymatic
functions and disturbs the role of the central nervous system.42 Extensive
research has been carried out since its biotransformation and toxic eects
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on biological organisms have been reported. Methyl mercury compounds

pose fatal toxicity to human beings and are some of the deadliest com-
pounds known to biological systems. Cadmium can be taken up by micro-
organisms, phytoplankton and fish directly or through the food chain as a
potentially toxic metal, which can enter the organism via waterborne and
dietary pathways, although regulatory assessments of metal toxicity to
aquatic organisms assume that toxic eects are caused by dissolved metals.
In recent years, concern has been expressed about the possible eects on
aquatic organisms from exposure to cadmium.
The toxicity of a chromium compound depends on the valence state of the
chromium atom and the nature of its ligands. There are several routes to
chromium exposure to humans, which include inhalation, ingestion, dermal
contact and the respiratory tract, etc. The ingestion of Cr(VI) compounds
produces toxic eects, which result in irritation and ulcers of the alimentary
canal and can cause anemia. Cr(III) compounds are much less toxic and do
not appear to cause these problems. Cr(VI) causes lung cancer through the
exposure to chromate dust.4345
The toxic eects of lead can be observed on the central nervous system in
human beings during a long exposure.46,47 Slight increases in blood pressure
in the organisms have also been reported due to the toxic eects of lead.48,49
Exposure to lead also inhibits the synthesis of hemoglobin. Zinc inhalation
in large amounts causes fever and breathing problems in humans. High-
level exposure to zinc may cause depression, vomiting and headaches. Co-
balt is an essential metal for humans and animals as it takes part in the
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synthesis of vitamin B12. However, some serious eects of cobalt are inter-
cellular hypoxia, asthma and pneumonia. Its higher dose may cause the
disease goitre. The cellular bioavailability of nickel (Ni), i.e., the ability of
nickel to enter target cells and to release nickel ions, appears to be a major
determinant of the carcinogenic and toxic eects of nickel compounds.5053
Owing to their detrimental eects on human beings and biodiversity, it
becomes necessary to remediate the heavy metals contained in wastewater
and industrial euents. Several technologies have been developed for the
treatment of metal bearing wastewater; some of these are precipitation, ion
exchange, coagulation, membrane filtration, reduction and activated carbon
adsorption. Many of them have their own advantages and disadvantages
relative to cost eectiveness, maintenance, design and installation and in
the operating systems. Above all, metal ions sequestration by activated car-
bon is still in practice in many countries because of its excellent removal
capacity regarding the heavy metal separation from liquids. However, the
high cost of activated carbons limits their application for real wastewater in
many less-developed countries, which further forces and motivates the de-
velopment of low-cost materials for the separation of metal bearing eu-
ents. Nanomaterials oer great opportunities to treat such types of metal
bearing liquids with high removal capacity. Magnetic nanoparticles are a
type of nanoparticles that can be easily tuned to have the desirable func-
tionalities for better adsorption capacity and can then be recovered by using
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64 Chapter 4
an external high magnetic field. Magnetic nanoparticles oer a green

approach for the treatment of wastewater containing heavy metals, for
management and sustainable development.
4.4 Magnetic Nanoparticles

The special and superior properties of nanomaterials have attracted much
attention in the past two decades. In particular, magnetic nanoparticles
(MNPs) with their inherent magnetic properties and high surface-to-volume
ratio have continued to draw considerable interest because of their diverse
potential applications in the biological, environmental and medical diag-
nostic fields. MNPs have been used in drug delivery, magnetic resonance
imaging, separation, biosensors and hyperthermia therapy5456 and en-
vironmental applications. The most commonly used magnetic particles are
magnetite (Fe3O4) and maghemite (g-Fe2O3). Other types of magnetic par-
ticles are pure metal (Fe and Co) and spinel type ferromagnets (MeO Fe2O3,
where M Ni, Co, Mg, Zn or Mn). Owing to their unique size, biocompati-
bility, low toxicity and superparamagnetic properties, magnetic nano-
particles are emerging as promising tools in various fields, such as physics,
medicine, biology and environmental and material sciences.54 Over the past
few years several types of iron oxides have been investigated in the field of
nano-sized magnetic particles, among which magnetite (Fe3O4) is a very
useful candidate since its biocompatibility has been well established.54 In
recent decades, numerous synthetic methods have been developed to syn-
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thesize iron oxide nanoparticles, including coprecipitation,57 solgel syn-

thesis,58 microemulsion synthesis,59 sonochemical reaction,60 hydrothermal
reaction,61 thermal decomposition,62 laser pyrolysis,63 etc. Among all the
reported techniques for the synthesis of MNPs, the coprecipitation method
has gained more popularity through simple tools and bulk productivity. In
comparison with ferromagnetic materials, magnetic nanoparticles exhibit
superparamagnetism, with a smaller size of B2030 nm.64 The smaller size
of magnetic nanoparticles gives an interesting advantage as the entire sur-
face area of the nanoparticles is increased.
4.5 Synthesis of Magnetic Nanoparticles

During the past few years, a large number of the published articles on
nanoparticles have described ecient routes to attaining shape-controlled,
highly stable, low-cost, ecofriendly and narrow size distribution magnetic
nanoparticles. Currently, several popular methods, including coprecipita-
tion, microemulsion, thermal decomposition, sonochemical, microwave
assisted, chemical vapour deposition, combustion synthesis, carbon arc,
laser pyrolysis synthesis, hydrothermal synthesis and solgel synthesis, have
been reported for the synthesis of magnetic nanoparticles.
The synthesis of superparamagnetic nanoparticles is a complex process
because of their colloidal nature. In recent years, synthesis of magnetic
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nanoparticles has gained much popularity within the scientific world. Many
publications have described ecient synthetic routes to the desired shape,
highly stable, functionalized and monodisperse magnetic nanoparticles.
Table 4.2 shows the materials used for coating or encapsulating iron oxide
magnetic nanoparticles and their applications.
4.5.1 Coprecipitation
Coprecipitation is a very simple technique to synthesize iron oxide nano-
particles from an aqueous Fe21Fe31 salt by the simultaneous addition of a
base. The chemical reaction of Fe3O4 formation may be written as:65
Fe21 2Fe31 8OH-Fe3O4 4H2O
According to the thermodynamics of this reaction, complete precipitation
of Fe3O4 should be expected at a pH of between 8 and 14, with a stoichio-
metric ratio of 2 : 1 (Fe31 : Fe21). However, magnetite nanoparticles are not
very stable in an open environment, and are easily oxidized to maghemite.
Fe3O4 2H1-g-Fe2O4 Fe21 H2O
Since oxidation of maghemite is the lesser problem, magnetite nano-
particles can thus be converted into maghemite. Therefore the maghemite
nanoparticles obtained are very stable in harsh environments.66 The main
advantage of the coprecipitation process is that a large amount of nano-
particles can be synthesized in a short time. However, the size distribution of
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nanoparticles is a critical issue.65

Recently, chitosan coated magnetic nanoparticles with a carboxyl con-
taining group has been synthesized for Cu21 removal from liquids.67 The
TEM (transmission electron microscopy) pattern of g-Fe2O3 showed particle
sizes of 110 to 10 nm, while the TEM picture of the chitosan coated magnetic
nanoparticles showed a discrete spherical shape. It was clearly stated that
chitosan coatings significantly altered the morphology of the g-Fe2O3
nanoparticles. It has been shown that the g-Fe2O3 nanoparticles were
coated by the chitosan.
Tai et al.68 fabricated magnetic porous microspheres of Fe3O4@poly-
(methylmethacrylate-co-divinylbenzene) by the simple strategy of a copreci-
pitation reaction. The magnetic microspheres materials, consisting of
polymer-coated iron oxide nanoparticles, were synthesized by the modified
suspension polymerization of methacrylate and divinylbenzene in the
presence of a magnetic fluid. The large surface area and stabilized magnetic
porous polymeric microspheres of Fe3O4@poly(methylmethacrylate-co-
divinylbenzene) were utilized in the adsorptive removal of phenol from
aqueous solution. It has been observed that the distribution of the oleic acid
coated Fe3O4 nanoparticles is comparatively uniform; in addition, the oleic
acid coated magnetite nanoparticles readily aggregate. Recent studies
showed that oleic acid is an excellent candidate for the stabilization of
magnetic Fe3O4 and g-Fe2O3 nanoparticles.68,69
66
Table 4.2 Materials used for coating of magnetic nanoparticles and their applications.
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Size and size

Materials used distribution Applications Advantages References
Silica 10200 nm, narrow Cellular MRI, heavy metal removal Improves biocompatibility, 129, 130
from wastewater, drug delivery, hydrophilicity and chemical stability.
fluorescence Prevents aggregation of particles in
liquid. Provides further
functionalization
Polyethylene glycol (PEG) 2040 nm, narrow MRI contrasting Improves the biocompatibility, blood 131
circulation time and easy to
functionalize
Chitosan 10200 nm, broad Heavy metals separation, drug Natural polysaccharide with 132, 133
delivery hydrophilicity, biocompatibility,
biodegradability, antibacterial
properties and remarkable anity for
many biomacromolecules. Used in
food, biotechnology, biomedicine, food
ingredients, cosmetics, water
treatment
Dextran 1050 nm, narrow Biomedical applications Enhances the blood circulation time, 134, 135
stabilizes the colloidal solution
Polyacrylic acid 820 nm, broad Heavy metals removal, dye removal, Increases the stability and 136, 137
enzyme recovery biocompatibility of the particles and
also helps in bioadhesion
Gum arabic 1367 nm, narrow Heavy metals removal Natural, harmless and environment 138, 139
Chapter 4
friendly polymer, wide applications as
a stabilizer, thickening agent and
hydrocolloid emulsifier, mostly used in
food and pharmaceutical industries
Functionalized Magnetic Nanoparticles for Heavy Metals Removal

Poly(3,4- 11 nm, narrow Heavy metals removal Promising conducting polymer because 140
ethylenedioxythiophene) of its high conductivity, excellent
(PEDOT) environmental stability and simple
acid/base doping/dedoping chemistry
Humic acid 10190 nm, broad Heavy metals removal Enhances the stability of 141
nanodispersions by preventing their
aggregation
Polynisopropylacrylamide 1025 nm, broad Hyperthermia, protein separation, Thermoresponsive polymer, surface 142144
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(PNIPAAm) controlled drug release hydrophilicity or hydrophobicity can be

varied easily
Dimercaptosuccinic acid B6 nm Heavy metals removal Excellent chelating agent for heavy 145
(DMSA) metals
Thiol B111.06 nm Removal of Hg from water Excellent adsorbent for sequestration of 146
Hg from water
KH570 18.8 nm It can be utilized in seals and medical Highly stable because of the of the 147
fields chemical bonding between FeOSi
Chitosanpoly(acrylic acid) 145 nm Removal of Cu21 from aqueous Fe3O4CSPAA composite particles were 148
solutions of high adsorption capacity, reusable
and biodegradable
Citric acid 611 nm Enhanced contrast in oil reservoir Stability of superparamagnetic iron oxide 149
rock formations nanoparticles at dierent pH values
Poly(ethylene glycol) 511 nm Enhanced contrast in oil reservoir Stability of superparamagnetic iron oxide 150
rock formations nanoparticles at dierent pH values
Cyanoguanidine 20 nm Adsorption of Hg(II) ions from Multi-cyanoguanidine modified 150
aqueous solutions magnetic chitosan nano-absorbent has
a unique selectivity for Hg(II) from
mixed metal ions solution
3-Aminopropyltriethoxysilane Adsorption of Cd(II) ions from The aminated-CoFe2O4SiO2 magnetic 151
aqueous solutions microspheres displayed ecient
enrichment of cadmium and easy
separation by an external magnetic
field
67
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68 Chapter 4
70
Hong et al. demonstrated that precipitation of Fe3O4 nanoparticles with
NH4OH instead of NaOH gives a better crystallinity, higher saturation
magnetization and smaller size. Nitrogen, which is passed during the pre-
cipitation, protects the Fe3O4 nanomaterials from oxidation but also reduces
the particle size when compared with methods without oxygen removal.
Magnetic nanoparticles, Fe3O4 or g-Fe2O3, prepared under alkaline con-
ditions of NH4OH, can be suitably stabilized with silica to form well-
dispersed magnetic silica nanospheres. It provides several advantages over
other stabilization materials. The change in the SiO2 : Fe3O4 ratio controls
the particle size distribution.
4.5.2 Hydrothermal Syntheses

Several scientists have reported the hydrothermal synthesis of magnetic
nanoparticles for a wide range of applications.7173 Hydrothermal reactions
are performed in aqueous solutions at high temperature and pressure. The
reaction conditions, such as solvent, temperature and time, usually have
important eects on the products synthesized by hydrothermal methods.
There are mainly two routes for the synthesis of magnetic nanoparticles via
hydrothermal conditions: hydrolysis and oxidation or neutralization of
mixed metal hydroxides. Bulk production of magnetic nanoparticles can be
obtained using this technique.72 Wan et al.73 have successfully synthesized
Fe3O4 nanostructures with dierent morphologies, such as Fe3O4 nano-
particles, nanorods and nanowire bundles via a developed hydrothermal
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route. Fe3O4 nanoparticles with uniform size and relatively better mono-
dispersity were synthesized at room temperature. It was reported that the
synthesized product was mainly composed of uniform Fe3O4 nanoparticles
with an average diameter of about 20 nm. The selected area electron dif-
fraction (SAED) pattern indicated the crystalline nature of the synthesized
materials. As a result, the prepared Fe3O4 nanoparticles showed uniform size
and relatively better monodispersity.
Cao et al.74 reported a new reaction route to obtain rice- and cube-shaped
single-crystalline a-Fe2O3 nanostructures via a reaction between
Fe(NO3) 9H2O and NH3 H2O in ethylene glycol at 200 and 280 1C, re-
spectively. The morphology of the products was studied using TEM and
high-resolution TEM. The single-crystalline nature of synthesized a-Fe2O3
was confirmed by the strong spots of the SAED pattern. On the basis of these
results, the authors have indicated that the reaction temperature plays a key
role in varying the morphology of the synthesized a-Fe2O3. The following
equation shows formation of magnetic nanoparticles:
Fe(NO3)3 3NH3 H2O-Fe(OH)3 3NH4NO3
and a-Fe2O3 particles will form through a two-step phase transformation,
according to the equation:
Fe(OH)3-b-FeOOH-a-Fe2O3
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4.5.3 Microemulsions
Magnetic nanoparticles can be obtained using the microemulsion pro-
cess.7579 In an eort to make ultra-small, coated and uniform size magnetic
nanoparticles, Santra et al. performed water-in-oil microemulsion mediated
sonochemical synthesis of superparamagnetic iron oxide nanoparticles in

nonionic surfactants.80 The magnetic core was coated with a thin layer of
silica for stabilization of magnetic nanoparticles. The synthesized magnetic
nanoparticles have diameters as small as 12 nm, and the thickness of the
silica coating is as thin as 12 nm.
Vestal and Zhang have used normal and reverse micelle microemulsion
methods to synthesize single-phase CoCrFeO4 nanoparticles with a con-
trolled size range of 616 nm.81 Results obtained in this study showed that
microemulsion methods provide a synthetic approach that allows for high-
quality nanoparticles with a narrow size distribution. This method can be
utilized for the synthesis of magnetic nanoparticles of various morphologies.
However, large amounts of solvents are required and the yield is low.
4.5.4 Thermal Decomposition

Magnetic nanoparticles with smaller size and dierent morphologies can be
synthesized through the thermal decomposition of organometallic com-
pounds in high-boiling organic solvents containing stabilizing sur-
factants.66,82 Thermal decomposition methods can be used for the synthesis
of magnetic nanoparticles. A thermal decomposition route appears to be the
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best synthesizing method for controlling shape and size of magnetic nano-
particles. It gives scalable and high production yield. However, success in
precise particles size control of Fe3O4 nanoparticle has only been achieved
through thermal decomposition using large amounts of toxic and expensive
precursors and surfactants in an organic solvent.83
4.6 Magnetic Nanoparticles in Wastewater

Treatment
Magnetic nanoparticles such as Fe3O4 and a-Fe2O3 have been widely in-
vestigated for the treatment of metal- and dye-bearing wastewater.8486 These
nanoparticles have high surface area, high chemical stability and enhanced
magnetic properties, which lead to high removal capacity. Magnetism of the
nanomaterials is a unique property that autonomously assists in water/
wastewater purification by influencing the physical properties of con-
taminants in aqueous solutions. Thus, magnetic separations of pollutants
have been used extensively in wastewater treatment and environmental
cleanup. Magnetic iron oxide nanomaterials are promising candidates for
larger scale wastewater treatment due to their easy functionalization, low
cost, high adsorption capacity, strong physico-chemical stability and easy
separations. Thus, these nanomaterials can be eciently utilized for the
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70 Chapter 4
treatment of wastewater containing hazardous dyes and toxic metal ions. In

the following sections we describe the application of magnetic nanoparticles
for the rapid removal of heavy metals from aqueous environments.
4.6.1 Magnetic Nanoparticles as Nanosorbents for Heavy

Metals
Heavy metal contamination of aqueous environments is an increasing
worldwide problem. Heavy metals are well known to cause serious en-
vironmental and health problems due to their bioaccumulation through the
food chain, and causes serious damage to the nervous and endocrine sys-
tems of human beings. Therefore, the development of selective and ecient
methodologies for detecting and removing heavy metals from aqueous
media is in great demand.
During recent years, the majority of scientific research and large scale field
applications of materials for the treatment of wastewater containing heavy
metals have focused on magnetic nanoparticles, activated carbon, carbon
nanotubes, biosorbents, zero-valent iron and photocatalysts.8793 Among all
these materials, magnetic nanoparticles, possessing the capability to treat
wastewater on an industrial scale and convenient for magnetic separations,
are the most promising materials for heavy metal removal.
Recently, Feng et al. synthesized monodisperse carboxyl functionalized
superparamagnetic iron oxide nanoparticles, Fe3O4(np)-COOH.88 Represen-
tative TEM images of the Fe3O4(np)-COOH nanoparticles deposited from a
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water dispersion and dried under ambient conditions revealed the presence
of clearly defined features with an average size of B817 nm, with a narrow
size distribution. They examined their ability to adsorb Cd21 from aqueous
solutions. The adsorption eciency of the particles for Cd21 was of the order
of 0.170.20 mmol Cd per mg Fe3O4(np)-COOH, which was amongst the
highest reported in the literature. As reported by the authors, the adsorption
eciency of the 8 nm particles was a bit higher than that for the 17 nm
analogues. It had been clearly observed that an increase in the acidity of the
media led to desorption of Cd21.
In order to provide long term high quality water or to enable water re-
cycling, Girginova et al.94 recently synthesized silica coated magnetite par-
ticles for magnetic removal of Hg21 from water. Silica coated magnetite
particles derivatized with dithiocarbamate groups were evaluated as mag-
netic nanodrivers to remove trace levels of Hg21 from aqueous solutions
using a simple external NdFeB magnet. The authors reported that the
uptake eciency for Hg21 was significantly higher for the particles bearing
dithiocarbamate groups at the surface (74%), as compared with the non-
derivatized silica coated magnetite (24%). On the basis of this study, one can
suggest that this eciency of nanomaterials is related to the high stability of
the chelates formed between the dithiocarbamate group and Hg21.
To further facilitate the adsorption anity of guest molecules on nano-
materials, surface modification, including inorganic and organic coating,
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and covalent binding, has often been explored to enable specific metal
complexation. Amino coated materials showed high sorption capacity for
Cu(II), Co(II), Ni(II), Zn(II), Pb(II), Cr(VI) and Cd(II) from aqueous solutions.95
The SiO2 coating provides plenty of surface hydroxyl groups, which oers
ease of succedent functionalization of magnetite nanoparticles. Wang et al.95

have developed an Fe3O4@SiO2 magnetic nanomaterial for the adsorptive
removal of heavy metals. Strong adsorption capacity for Cu(II), Pb(II) and
Cd(II) was achieved.
Very recently, Song et al.96 prepared polyrhodanine-encapsulated mag-
netic nanoparticles via one-step chemical oxidation polymerization and
investigated their potential for adsorptive removal of heavy metal ions
from aqueous solutions. TEM images showed that the polyrhodanine-
encapsulated magnetic nanoparticles were synthesized with an average
diameter of ca. 10 nm. Typically, 5.0 mg of nanocomposite were used for the
removal of Hg(II) ions at a pH value of 4.0 from solutions. The desired so-
lution sample was shaken, and after the desired contact time the nanoma-
terials were removed from the solution using an external magnetic field.
Inductively coupled plasma mass spectrometry analysis was used to detect
the residual Hg(II) ion concentration in the aqueous media. Similarly, the
adsorption capacities of Cd(II), Mn(II) and Cr(III) ions were also determined. It
was found that 94.5% of adsorption occurred for Hg(II).
Hu et al.97 have synthesized various types of magnetic nanoparticles for
the sequestration of Cr(VI). The adsorption of Cr(VI) was investigated in batch
mode in an acidic medium using 5 g L1 of dierent magnetic nano-
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particles. The Cr(VI) removal performances were compared and the ad-
sorption capacities followed the order: MnFe2O44MgFe2O44ZnFe2O44
CuFe2O44NiFe2O44CoFe2O4. The points of zero charge pHpzc for various
magnetic nanoparticles were measured to be around 7.08.0. MnFe2O4
showed a very high BET surface area in comparison with other syn-
thesized ferrite nanoparticles. The equilibrium times for Cr uptake by
MnFe2O4, MgFe2O4, ZnFe2O4, CuFe2O4, NiFe2O4 and CoFe2O4 nanomaterials
were 5, 45, 30, 20, 15 and 60 min, respectively. MnFe2O4 showed a strong
adsorption capacity for Cr(VI) ions. A 0.01 M NaOH solution was used as an
elutant for recovery of the metal ions.
Recently, Fe3O4 and g-Fe2O3 nanocages were synthesized by using
the solgel method.98 Figure 4.1(a) and (b) shows the TEM microimage for
the synthesized materials. FeSO4 and KOH were poured together to gen-
erate Fe(OH)2; subsequently KNO3 was added to the mixture for the for-
mation of magnetite of 50100 nm [Figure 4.1(c)]. The HRTEM images
were obtained near the center region of hollow nanocages for observation
of the morphologies and structures of the iron oxide nanocages
(Figure 4.2).
Cheng et al.99 applied maghemite (g-Fe2O3) nanoparticles for the se-
questration of metals from electroplating liquids. They have synthesized
maghemite nanoparticles of 60 nm by a coprecipitation method. The
magnetization with respect to the applied field was recorded at room
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72 Chapter 4
11:25:40.
Figure 4.1 (a) Fe3O4 nanocages with glutamic acid, (b) Fe3O4 nanocages with
glutamic acid annealed at 500 1C for 2 h in an oxygen atmosphere and
(c) Fe3O4 nanocages without glutamic acid (reproduced with permissions
from Dr. Jiang, ref. 98).
temperature. It had been observed from the hysteresis loop that the material
had a weak magnetic nature with little hysteresis. The weak magnetism was
due to the presence of a-Fe2O3 as detected by XRD (X-ray diraction). This
indicates that the particles consist of g-Fe2O3 and a-Fe2O3. Pb21 ions were
adsorbed onto g-Fe2O3 nanoparticles rapidly, and equilibrium was estab-
lished within 30 min. The nanospheres of g-Fe2O3 favour the binding of Pb21
ions. Increasing NaCl concentrations from 0 to 3.5% had no eect on the
adsorption of Pb21 on g-Fe2O3 nanoparticles. The adsorption isotherms were
better fitted to the Langmuir model than the Freundlich model.
View Online

11:25:40.
Figure 4.2 HRTEM images of the center region of hollow Fe3O4 nanocages (a) and
g-Fe2O3 nanocages (b) (reproduced with permissions from Dr. Jiang,
ref. 98).
4.7 Modeling of Adsorption: Kinetic and Isotherm

Models
The kinetic values of adsorbentadsorbate interactions can be established by
applying several mathematical equations, of which Lagergrens rate equa-
tion has been used widely in the literature.100 Equilibrium isotherm model
equations such as, Langmuir, Freundlich, Temkin and RedlichPeterson are
used to describe experimental adsorption data in batch mode.101104
4.7.1 Kinetic Studies for Adsorption of Heavy Metals

Kinetic studies help to establish the ecacy of adsorption processes for a
given system and assist in the minimization of operating parameters of real
reactors on an industrial scale. Several kinetic models such as pseudo-first
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74 Chapter 4
order, pseudo-second order, the Bhattacharya and Venkobachar model, the

WeberMorris equation and the Elovich model have been applied extensively.
4.7.1.1 Pseudo-First Order Kinetic Model

A pseudo-first order model can be expressed as follows:100

dq
k1 qe q
dt
where q and qe are the amounts of adsorbate adsorbed (mg g1) at time,
t (min) and at equilibrium, respectively, k1 is the rate constant of adsorption
(L min1). Integration of the above equation with the boundary conditions
t 0, q 0, and t t, q q, gives
ln(qe q) ln qe k1t
This equation can be written in the linear form:
q qe[1 exp(k1t)]
Kinetic adsorptions by numerous magnetic nanomaterials have been stud-
ied using the pseudo-first order kinetic model.
4.7.1.2 Pseudo-Second Order Kinetic Model

A pseudo-second order model can be expressed as:105109
11:25:40.
dq
k2 qe q2
dt
Integration of this equation with the boundary conditions t 0, q 0, and
at t t, q q, results in:
1 1
k2 t
qe q qe
This equation can be stated in the linear form as:

t t 1

q qe k2 q2e
where k2 is the equilibrium rate constant (g mg1 min1).
4.7.1.3 WeberMorris Kinetic Model

The WeberMorris kinetic model110 was first applied by Pavasant et al.111
during the study of biosorption. This model can be expressed as:
q KWMOt
where KWM is Weber Morris rate constant.
View Online
During the study of biosorption of Cu(II), Cd(II), Pb(II) and Zn(II) by C.

lentillifera, Pavasant et al.111 observed that the adsorption process was gov-
erned by two mechanisms, i.e., intra-particle diusion and external mass
transfer. The intra-particle diusion rate constants can be determined by
using the following equation:

p dp KWM 2
D
8640 qe
where D and dp are the intra-particle diusion coecient and mean particle
diameter, respectively.
The external mass transfer process was determined by:
dq 0
KL AC Csi
dt
where A specific surface area of adsorbent, KL0 solidsolution mass

transfer coecient, C concentration of sorbate and Csi saturation con-
centration of adsorbate (mg L1).
4.7.2 Equilibrium Isotherm Modeling

Equilibrium modeling of adsorbentadsorbate interactions has been used to
establish the behaviour of experimental data to optimize the operating
parameters of the reaction in wastewater treatment. Table 4.3 shows some
equilibrium models, which have been extensively applied for the removal of
11:25:40.
heavy metals from waste liquids of industrial origin. Langmuir and Freun-
dlich isotherm models are commonly used in the literature.112116 The
BrunauerEmmettTeller (BET) model117 describes the multi-layer ad-
sorption behaviour of the adsorbent and proposes that the Langmuir iso-
therm adsorption takes place single layer by single layer. The equilibrium
isotherm models can predict the information of removal capacity from
aqueous solutions and also provides the knowledge for metal sequestration
behaviour for dierent metal species in complex solutions.
4.7.2.1 Freundlich Isotherm

The Freundlich isotherm model describes the multilayer adsorption be-
havior of metal ions on to adsorbent nanoparticles. This equation has the
following form:112
qe KF Ce1 = n
It can also be expressed in the linearized logarithmic form:118

1
log qe log KF log Ce
n
where Ce and qe are the equilibrium concentration of the metal (mg L1)
and the amount of solute adsorbed at equilibrium conditions (mg g1),
76
Table 4.3 Equilibrium isotherms models with their advantages and disadvantages used for adsorption of heavy metals.
11:25:40.
Isotherm Functional form Linear form Plot Advantages Disadvantages References

Langmuir qm KL Ce Ce 1 1 Ce Finite saturation Monolayer 101
qe Ce vs: Ce
1 KL Ce qe KL qm qm qe limit so valid adsorption
over a wide
range of
concentrations
Freundlich 1=n
qe KF Ce 1 ln qe vs. ln Ce Simple No saturation 102
ln qe ln KF ln Ce
n expression and limit, not
has parameter structured, not
for surface applicable over a
heterogeneity wide range of
concentrations
Temkin RT RT RT qe vs. ln Ce Simple Not applicable over 103
qe lnKT Ce qe ln KT ln Ce
b b b expression a wide range of
concentrations
Redlich KRP Ce KRP Ce KRP Ce Approaches No special 104
qe ln 1 ln aRP b ln Ce ln 1 vs: ln Ce Freundlich
Peterson 1 aRP Ceb qe qe advantages
(RP) at high
concentration
Chapter 4
View Online
respectively. KF and n are the characteristic constants related to the ad-

sorption capacity (L mg1) and adsorption intensity or degree of favour-
ability of adsorption, respectively. A larger value of n implies a stronger
interaction between metal ions and adsorbent nanoparticles.
4.7.2.2 Langmuir Isotherm

The Langmuir isotherm is a well-known model used for describing heavy metal
sorption onto magnetic nanoparticles. This model assumes that adsorption is
as a monolayer, surface sites are identical and only one molecule adsorbs at a
single site.105,119 The Langmuir isotherm equation can be expressed as:120
KL Ce
qe qmax
1 KL Ce
The linear form of this equation is often written as:118

Ce 1 1
Ce
qe qmax KL qmax
where Ce is the saturation concentration of metal (mg L1), qe is the amount

of metal adsorbed at equilibrium conditions (mg g1), qmax is the maximum
monolayer adsorption capacity (mg g1) and KL is the sorption equilibrium
constant (L mg1), which is related to the energy of adsorption. However, the
model sometimes fails to predict the behaviour of adsorption for dierent
operation parameters under dierent conditions.121
11:25:40.
4.7.2.3 Other Two-parameter Isotherms

The Temkin isotherm, FloryHuggins and DubininRaduskevich equations
are two-fitting parameters, and RedlichPaterson and Sips isotherms use
more than two parameters to predict the adsorption behaviour of metal ions
onto nanoparticles.105
Superior performance for adsorption and the magnetic properties of
nanomaterials tend to be a promising approach to dealing with a variety of
environmental pollutants in aqueous media. Advances in magnetic nano-
particles could provide opportunities for developing new-generation ad-
sorbents with high surface area, new functionalities, excellent adsorption
capacity, simple separation and recyclability. Thus magnetic nanoparticles
may be the future as alternatives in the search for super adsorbents and
solutions for metal sequestration from waste liquids because of their ex-
cellent magnetic properties, which help in the rapid removal and recycling
through an external magnet.122
4.8 Thermodynamic Analysis

Gibbs free energy (DG), change in enthalpy (DH) and change in entropy (DS)
can be correlated with the Langmuir isotherm constants in the estimation of
View Online
78 Chapter 4
thermodynamic parameters. The negative values of DG indicate the spon-

taneous nature of sequestration for metal ions onto nanoparticles. The
endothermic or exothermic nature of adsorption can be proved by using the
value of DH.123,124 A positive value of DS depicts the increase in randomness
at the solidsolution interface.125

DG can be associated with the Langmuir isotherm constant by the fol-
lowing equation:126
DG RT ln KL
Enthalpy and entropy changes are also related to the Langmuir equi-
librium constant by the following expression:
DS DH
ln KL
R RT
Thus, a plot of ln KL versus 1/T gives a straight line, depending on the
experimental data. The values of DH and DS can be obtained from the slope
and intercept of this plot.
4.9 Recovery of Metals and Regeneration of Magnetic

Nanoparticles
Desorption is particularly necessary when the synthesis of the material is
costly. Regenerability of loaded magnetic nanoparticles is a key factor for
11:25:40.
improving the economy of an adsorption process. The cost eectiveness of

magnetic nanoparticles to remove heavy metals from aqueous solution de-
pends on its recycling capability after the loading of the metals. Desorption
can be carried out to recycle the spent nanoparticles during metal seques-
tration. A suitable selection of elutant can recycle the magnetic nano-
particles for further adsorption use.127,128 A good elutant must have the
following characteristics: they should be non-destructive to the adsorbent,
cheap, ecofriendly and eective in nature.
4.10 Conclusions
Magnetic nanoparticles oer a tremendous opportunity to treat wastewater
containing toxic metal ions because of their high surface area, high physico-
chemical stability, multi-functionality, ease in coating and the low cost of
synthesis. Several routes for synthesis of magnetic nanoparticles have been
developed and practiced, viz., coprecipitation, microemulsions, hydrothermal
and thermal decomposition for rapid and highly ecient removal of guest
molecules from aqueous solutions. However, the coprecipitation method is
one of the most celebrated synthesis routes for magnetic nanoparticles due to
their low cost, ease of operations, ease in design and high yield.
Magnetic nanoparticles oer a new vista for separation and purification
technology for heavy metals. These multi-functional magnetic nanoparticles
View Online
have been successfully applied for the reduction of toxic metal ions up to the
ppb level in waste treated water. Magnetic nanoparticles loaded with toxic
metal ions in water can be eectively recovered and regenerated with the
help of an external magnetic field. The regenerated nanoadsorbent can be
successfully and eectively applied for recycling and treatment of waste-

water. As discussed in some reports, the extreme acidic or basic conditions
of solutions can corrode the nanoparticles and loss of function groups oc-
curs. Thus, the stability of the nanoparticles in the treatment of heavy metals
strongly depends on the pH of the solution.
Nanotechnology oers lots of advantageous potential for todays society,
but, similar to other techniques, it has also some drawbacks. Increasing use
of nanoproducts and nanoadsorbents will increase the risk of nanopollu-
tants in the environment. Hence, there is an essential need for research to
solve these problems and overcome the challenges that have been discussed
in this chapter. In addition, there is further need for the study of nano-
particles behaviour, fate and eects in the dierent spheres of the ecosystem
on a timely basis. Recent trends and widespread use of nanomaterials in the
environmental area is extremely new and it needs further research before on-
site applications because of the nanotoxicity of the materials.
However, magnetic nanoparticles present tremendous potential for
treating wastewater containing toxic metal ions because of their high surface
area, high physico-chemical stability, multi-functionality, ease of coating
and low cost of synthesis. Overall these nanomaterials can be successfully
and eectively applied for the recycling, treatment and sustainable man-
11:25:40.
agement of water.
Acknowledgements
R. K. Gautam thanks the University Grants Commission, New Delhi, for the
award of a Junior Research Fellowship (JRF). M. C. Chattopadhyaya acknow-
ledges the support and necessary facilities provided by the University of
Allahabad, Allahabad. We are grateful to Prof. V. S. Tripathi, Department of
Chemistry, University of Allahabad, Allahabad, for support and encourage-
ment during the study. We also thank the anonymous reviewers for giving
their kind criticisms and comments, which fuelled the zeal for the manuscript.
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11:25:40.
CHAPTER 5
Arsenic Contamination:
An Overview
MAURIZIO CAROTENUTO,*a GIUSY LOFRANOb AND
SANJAY K. SHARMAc
a
Department of Chemistry and Biology University of Salerno, via Giovanni
Paolo II, 84084 Fisciano (Sa), Italy; b Department of Environment, Waste
Divison, Salerno Province, via Mauri 61, 84129 Salerno, Italy; c Department
of Chemistry, JECRC University, Jaipur-303905, India
*Email: mcarotenuto@unisa.it
11:25:46.
5.1 Introduction
Arsenic is a ubiquitous trace element with a natural presence, not only in the
environment (rocks, soils, natural waters and groundwater) and in living
organisms but also in some foods (such as rice, vegetables, seafood and
milk). In recent decades, following a series of serious accidents in dierent
parts of the world, the study of arsenic has become of increasing interest due
to its high toxicity.
The word arsenic is derived from the Persian word Zarnikh, meaning
yellow orpiment, which was adopted in ancient Greek in the form arsenikon.
Since its discovery in 1250 by Albertus Magnus, arsenic has been at the
centre of many controversies in the history of mankind for its use as a
powerful and discreet deadly poison. Many arsenic compounds, in fact, are
odourless and tasteless with a high solubility in water, which make it an
element at high risk for humans. Ingesting food or drinking water that
contains more than 0.01 mg L1 of inorganic arsenic can be dangerous,
while a content of inorganic arsenic greater than 60 mg L1 is fatal to living

86
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Arsenic Contamination: An Overview 87
organisms. Gastrointestinal disturbances, vomiting and coma until death are

the usual symptoms of acute poisoning occurring in approximately 30 min
after ingestion. Much more insidious is the chronic poisoning leading to
anaemia, leukopenia, skin cancer and other internal cancers. The wide-
spread use of arsenic as a poison resulted because the symptoms of arsenic

poisoning can be associated with other diseases and its common availability
and low cost. It was frequently used as poison until the advent of the Marsh
test (1836), a sensitive chemical test for its identification. For this reason,
arsenic has been called the Poison of Kings and the King of Poisons. Its use
has in fact been known and reported for a long time. Although the earliest
documented case of arsenic poisoning is associated with the killing of
Britannicus by the hand of his stepbrother Nero to make certain of the
government of the Roman Empire in 55 AD, the most debated historical fact
that features arsenic concerns the death of the French Emperor Napoleon
Bonaparte, in exile on St. Helena after his defeat at the battle of Waterloo.
From the autopsy, his death on May 5, 1821 was attributed to stomach
cancer by Dr Franois Antommarchi, but in 1964 a series of tests carried out
on the Emperors hairs, collected immediately after his death and preserved
in a museum, showed that the arsenic content was 40 times higher than the
normal level, confirming the suspicions that his killing was the result of
chronic poisoning.13
In addition to humans, arsenic may also have toxic eects on plants or
eects of accumulation can occur within them, thus entering the food chain
of animals and humans in this way. For rice plants, some studies have es-
11:25:46.
tablished a threshold of toxicity average of 40 mg of inorganic arsenic per kg

soil. Higher concentrations induce inhibitory eects on the growth of the
plantations.
In recent years, due to its high toxicity, distribution and mobility,
arsenic has received significant attention. The purpose of this chapter is to
provide a clear and comprehensive description of the situation for arsenic
contamination in the world. Through an examination of the available lit-
erature, the screening and selection of existing data, some site-specific
issues will be discussed, in anticipation that this will be useful for
expanding our knowledge on the global problems related to arsenic
contaminations.
5.2 Chemical Characteristics

Arsenic is a metalloid belonging to Group VA of the Periodic Table of the
elements. The atomic mass number of its isotopes varies between 68 and 80,
but isotope 75 is the most stable. The elementary form of arsenic is a solid
that occurs in three allotropic forms: yellow (alpha), black (beta) and grey
(gamma). The grey form, rhombohedral, is the most stable at room tem-
perature. The chemical and physical properties of arsenic are shown in
Table 5.1.
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88 Chapter 5
Table 5.1 Chemical and physical properties of the most stable form of arsenic at
room temperature (reprinted from Mudhoo et al.11 with kind permission
of Taylor and Francis).
Property Value/description
Atomic number 33
Atomic mass average (g mol1) 74.921 59
Atomic radius () 1.33
Ground state electronic configuration 1s22s22p63s23p64s23d104p3
Atomic volume (cm3 mol1) 13.1
Covalent radius () 1.21
Ionic radius () 0.58
Aspects Silvergrey brittle non-metal flakes
Crystal structure Rhombohedral
Oxidation state 3, 0, 3, 5
Electrochemical equivalents (g amp1 h1) 0.931 77
Electron work function (eV) 3.75
Electronegativity (Pauling units):
Pauling 2.18
AllrodRochow 2.2
Sanderson 2.82
MullikenJae 2.26 (20% s orbital)
Allen 2.211
Heat of fusion (kJ mol1) 369.9
Ionization potential First: 9.81
Second: 18.633
Third: 28.351
Valence electron potential 74
Ionization energy (kJ mol1) First: 947
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Second: 1798
Third: 2735
Boiling point (1C) 603
Melting point (1C) 808
Critical temperature (1C) 1400
Heat of vaporization (kJ mol1) 34.76
Coecient of linear expansion (K1) 0.000 004 7
Electrical conductivity (cm1) 34 500
Electrical resistivity at 20 1C (nO m) 333
Thermal conductivity (Wm1 K1) 50.2
Density a 27 1C (g cm3) 5.72
Enthalpy of atomization at 25 1C (kJ mol1) 301.3
Vapour pressure (mmHg) at 372 1C 1
Enthalpy of fusion (kJ mol1) 24.44
Molar volume (cm3 mol1) 13.08
Optical refractive index 1.001 552
Specific heat (J g1 K1) 0.33
Estimated crystal abundance (mg kg1) 1.8
Estimated oceanic abundance (mg L1) 3.5
Bulk modulus (GPa) 22
Mohs hardness 3.5
Brinell hardness (MPa) 1440
OSHA time weighted average (TWA) 0.5
Permissible exposure limit (mg m3)
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Being a very reactive element, arsenic is never found in nature in a pure

state (As), but combined with many metal elements such as lead, mercury,
gold and iron to form alloys and with non-metallic elements such as oxygen,
fluorine, chlorine, sulfur, carbon and hydrogen to form oxides, hydrides,
sulfides, arsenates and arsenites.

Among the heavy metalloids, As is unique in having a great mobility at pH
values typically found in groundwater (pH 6.58.5) and under both oxidizing
and reducing conditions. Arsenic occurs in four oxidation states (3, 0, 3,
5) and is found in nature in both inorganic and organic forms. Elementary
As is not soluble in water or in non-oxidizing acids, while the arsenic com-
pounds, which are generally non-volatile with the exception of the gaseous
arsine (AsH3) or arsenious trioxide (As2O3), may readily dissolve. In waters
and under oxidizing conditions, the thermodynamically more stable As form
is the pentavalent As(V) forming the arsenate (AsO43), whilst under reducing
conditions the As mostly exists in the tetravalent form As(III)7 with the for-
mation of arsenite (AsO33). Organic As, rarely quantitatively important, is
produced through the activity of some bacteria (such as Escherichia coli,
Flavobacterium sp., Methanobacterium sp.) and fungi (such as Aspergilus
glaucus, Candida humicola), which may induce some biomethylation phe-
nomena (addition to the arsenic of CH3)810 leading to the formation of
monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and tri-
methylarsenic oxide (TMAO) mostly in surface waters that are highly im-
pacted by industrial pollution. Some of these organic arsenic compounds
are, at room temperature, in gaseous or liquid form with low boiling
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temperatures.
In contrast to many toxic trace metals (e.g., Pb21, Cu21, Ni21, Cd21, Co21,
Zn21) that precipitate as oxide, hydroxide, carbonate or phosphate, or more
likely because it strongly adsorbs to hydrous metal oxides, clay or organic
matter near the typical pH of most groundwater, arsenate tends to persist in
solution at relatively high concentrations (tens of mg L1) even at high pH
values. For this reason and together with its relative mobility over a wide
range of redox conditions, arsenic compounds are the most common trace
contaminants in groundwater and the most problematic issues in the en-
vironment. At moderate or high redox potentials arsenic can be stabilized as
H3AsO4, H2AsO4, HAsO42 and AsO43. However, under most reducing
(acid and mildly alkaline) conditions and lower redox potential, the As(III)
species (H3AsO3) is predominant. The species As0 and As3 are rare in
aquatic environments (Figure 5.1).7,12
Arsenic is the main component in over 200 minerals (60% are arsenates,
20% are sulfates and salts of sulfur and the remaining 20% are arsenites,
oxides, silicates and elemental arsenic) but only some of these are found in
considerable amounts, such as realgar (AsS), orpiment (As2S3) and arseno-
pyrite (FeAsS).13 In Table 5.2 the major arsenic minerals occurring in nature
and their distribution are reported.
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90 Chapter 5
Figure 5.1 The EhpH diagram for arsenic at 25 1C and 101.3 kPa (reprinted from
Wang et al.6 with permission of Elsevier).
11:25:46.
5.3 Arsenic Distribution in the Environment

Arsenic occurs naturally throughout the environment through the action of
concomitant natural processes (such as dissolution of arsenic minerals or
volcanic activity) and/or by anthropogenic activities (such as uncontrolled
mining and metallurgical industrial discharges, application of arsenic-based
pesticides and fertilizers, dissolution of wood preservatives, fossil fuel
combustion and municipal waste and waste treatment). Many of the en-
vironmental problems are related to its rapid mobilization caused mainly by
weathering of rock, biological activity and volcanic activity. Arsenic, like
other naturally occurring minerals, tends to cycle in the environment
(Figure 5.2) ensuring that humans are always and unavoidably exposed to
As.1 Figure 5.2 shows the flow paths of arsenic in the environment with the
estimated fluxes among the various reservoirs.
5.3.1 Natural Sources

Arsenic is the 20th most abundant element in the earths crust at a concentration
that varies depending on the type of rock in dierent geographical regions.
The average value in igneous rocks is 1.5 mg kg1 but this value increases
(E5 mg kg1) when the silica content increases (volcanic glasses). In sedi-
mentary rocks, the concentration is slightly higher (510 mg kg1), while in
Arsenic Contamination: An Overview

Table 5.2 Major arsenic minerals occurring in nature and their locations.
Mineral Composition Occurrence Location
Arsenic As In hydrothermal veins and deposits Germany, France, Czech Republic,
containing other arsenic minerals Romania, USA, Peru, Borneo, Japan,
(CoAg sulfide veins) Peoples Republic of China
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Proustite Ag3AsS3 A late-forming mineral in hydrothermal Germany, Romania, Czech Republic,

deposits, in the oxidized and enriched France, Italy, USA, Canada, Chile, Mexico
zone, associated with other Ag minerals
and sulfides
Rammelsbergite NiAs2 In hydrothermal veins formed at medium Germany, Austria, Poland. France,
temperatures with other NiCo minerals England, Scotland, Bulgaria, Sweden,
Morocco, USA, Canada, South Korea,
Norway
Saorite (Co, Fe)As2 In hydrothermal veins of moderate USA, Canada, Germany, Sweden, Spain,
temperature and pressure Italy, Australia, Norway
Seligmannite PbCuAsS3 In hydrothermal veins Argentina, Austria, Bolivia, Canada,
Peoples Republic of China, Croatia,
Czech Republic, Finland, France,
Germany, Greece, Hungary, Ireland,
Italy, Namibia, Norway, Peru, Republic of
Macedonia, Switzerland, Ukraine, USA
Smaltite CoAs2 Canada, Norway, Germany, Morocco Italy,
Czech Republic
Niccolite NiAs A minor component of NiCu ores in high- Germany, Austria, Czech Republic, France,
temperature hydrothermal veins USA, Bolivia, Morocco, Iran, Vietnam
Realgar AsS Most commonly as a low-temperature Germany, Switzerland, Romania, Czech
hydrothermal vein mineral associated Republic, Macedonia, Russia, Japan,
with AsSb minerals; also as volcanic Peoples Republic of China, USA
sublimations and in hot-spring deposits;
in carbonate and clay sedimentary rocks
91
92
Mineral Composition Occurrence Location
Orpiment As2S3 In low-temperature hydrothermal veins, USA, Slovakia, Bosnia-Herzegovina,
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hot springs and fumaroles; also Macedonia, Iran, Turkey, Russia,

commonly as an alteration product of Georgia, Peoples Republic of China,
arsenic minerals, especially realgar Peru
Cobaltite CoAsS In high-temperature hydrothermal Sweden, Germany, England, Canada,
deposits, as disseminations, and as veins Australia, Morocco
in contact metamorphosed rocks
Arsenopyrite FeAsS Of hydrothermal origin, typically one of Germany, Portugal, Sweden, Greece,
the earliest minerals to form. Found in England, USA, Mexico, Canada, Japan,
pegmatites, high-temperature gold- Brazil, Republic of South Africa,
quartz and tin veins, and in contact Australia, France, Russia
metamorphic sulfide deposits; less
commonly of low-temperature
hydrothermal origin. Also in gneisses,
schists and other metamorphic rocks
Tennantite (Cu, Fe)12As4S13 In hydrothermal veins and contact England, Ireland, Germany, Poland,
metamorphic deposits Switzerland, Kazakhstan, USA, Mexico,
Peru, Chile, China, Namibia, Sweden,
Japan, France, Russia
Enargite Cu3AsS4 In hydrothermal vein deposits formed at Peru, Argentina, Philippine Islands,
medium temperatures. Also as a late- Taiwan, Japan, USA, Austria, Serbia,
stage mineral in low-temperature Italy, Namibia, Chile, Mexico, Spain,
deposits Russia
Arsenolite As2O3 An oxidation product of other arsenic- Germany, Czech Republic, France,
Chapter 5
bearing sulfides in hydrothermal veins; England, Greece, Italy, USA, Canada
may be formed in mine fires or in
burning coal seams
Arsenic Contamination: An Overview

Claudetite As2O3 A secondary oxidation product derived Portugal, Spain, France, Czech Republic,
from realgar, arsenopyrite, or other Germany, Namibia, USA
arsenic-bearing minerals. Also produced
as a sublimate during mine fires
Scorodite FeAsO4 2H2O A secondary mineral formed by oxidation Germany, Czech Republic, Austria,
of As-bearing sulfides England, Algeria, Namibia, Brazil,
Mexico, USA, Japan, Australia
Annabergite (Ni, Co)3(AsO4)2 8H2O An uncommon secondary mineral, formed Germany, Slovakia, Austria, Spain,
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by the alteration of CoNi-bearing England, Scotland, Greece, Morocco,

arsenides and sulfides, in the oxidized Iran, Bolivia, Mexico, USA, Canada,
zone of hydrothermal mineral deposits Australia, Japan
Hoernesite Mg3(AsO4)2 8H2O A secondary mineral
Haermatolite (Mn,Mg)4Al(AsO4)(OH)8
Conichalcite CaCu(AsO4)(OH) An uncommon secondary mineral in the Spain, England, USA, Mexico, Chile,
oxidized zone of copper deposits, Namibia
typically an alteration product of
enargite
Adamite Zn2(OH)(AsO4) A secondary mineral in the oxidized zone Chile, Mexico, USA, France, Germany,
of zinc- and arsenic-bearing England, Greece, Namibia, Australia
hydrothermal mineral deposits
Domeykite Cu3As Of hydrothermal origin Chile, Bolivia, Mexico, USA, Canada,
Sweden, France, Germany, England,
Iran, Norway, Czech Republic
Loellingite FeAs2 In mesothermal deposits associated with Austria, Poland, Germany, Spain, Norway,
other sulfides and with calcite gangue; USA, Canada, Australia Norway,
also in pegmatites Germany, Czech Republic
Pharmacosiderite Fe3(AsO4)2(OH)3 5H2O An oxidation product of arsenic-bearing England, France, Germany, Slovakia, USA,
sulfides Australia
93
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94 Chapter 5
Figure 5.2 A simplified diagram of the arsenic cycle.
metamorphic rocks it is comparable to that of the concentration of igneous

and sedimentary rocks from which it derives (approximately 5 mg kg1 or
less). The sands and sandstones (sandy rocks cemented with clay and quartz)
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tend to have lower values, reflecting the absence of arsenic in their dominant
minerals, such as quartz and feldspar with a mean value of the toxic element
of about 4 mg kg1. Argillaceous deposits have values of As concentrations
higher than the sandstones (typically about 13 mg kg1) reflecting the
greater proportion of the content of sulfates, oxides, organic matter and clay.
Marine argillaceous deposits have higher concentrations of As (up to 15 mg kg1)
than non-marine deposits reflecting the grain-size distributions and the
higher S concentrations. Arsenic concentrations in coal and bituminous
deposits are very high (100200 mg kg1) while in carbonate rocks they are
low (about 3 mg kg1) reflecting the constituent minerals. High contents of
arsenic, up to 2900 and 400 mg kg1, were found in rocks rich in pyrite and
iron oxides and phosphates, respectively.
With respect to the sediments, the arsenic content varies between 3 and
10 mg kg1 and the baseline world soil concentration is about 7 mg kg1. An
increase in the arsenic content of the sediments and soils is observed in
mining areas where As is found in close association with transition metals
such as Cd, Pb, Ag, Au, Sb, P, W and Mo.12
5.3.2 Anthropogenic Sources

Although to a lesser extent, human activities have contributed to increasing
the content of arsenic in soil and water.12 The main anthropogenic activities
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responsible for the accumulation of arsenic in the environment, resulting in

the contamination of soils, sediments, water courses (rivers and lakes),
groundwater and the atmosphere, are the extraction and fusion of metals,
the combustion of fossils fuels, the preservation of wood, the production
and application of pesticides, disposal and incineration of municipal and

industrial waste.
Li and Thornton,2 studying arsenic contamination in the soil of some
mining areas of England (Derbyshire, Cornwall and Somerset), found that in
the first 15 cm the As values were very high (16925 mg kg1).
Large quantities of fly and heavy ash containing arsenic are produced by
industries related to metal smelting and refining of base metals and fuels, as
well as thermal and power generating stations where coal, oil, fossil fuels
and waste are combusted during energy production. It was observed in
particular that the content of arsenic (of which more than 90% appears to be
arsenate) is present in the more dangerous ash particles (mostly in diam-
eters of o2 mm), because having a typical atmospheric residence time of
approximately 9 days, they are transported by wind a great distance from the
place of production and subsequently fall-out, contaminating a broad area.
During this period arsenic particulate matter may be inhaled, deposited in
the respiratory tract and absorbed into the blood.
For many years in the past (up to 5060 years), arsenic-based products
(such as lead arsenate (PbAsO4), calcium arsenate (CaAsO4), magnesium
arsenate (MgAsO4), arsenate (ZnAsO4) and arsenite (ZnAsO3) of zinc, etc.)
were used indiscriminately as pesticides (insecticides and fungicides) in vast
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agricultural areas, both in open fields and greenhouses, especially in those

with intense floricultural situations, producing a high accumulation of this
element. Studies conducted by Australian researchers have shown that in
many soils of southern Australia and Tasmania, devoted to the cultivation of
orchids, the arsenic concentrations exceed 2500 mg kg1.
Although many products containing arsenic have been banned in the last
decades (pesticides, herbicides), some of these are still used today, for ex-
ample, to preserve the wood from attack by pests. In the period 19841988,
in Canada the annual sales of arsenic as chromate copper arsenate (CCA),
containing 18.5% CuO, 34% As2O5 and 47.5% CrO3 (w/w),3 varied between
about 650 and 1300 tons. Exposure to sunlight and other weathering activ-
ities increases the rate of leaching of preservative from the trees that are
treated, increasing the level of As pollutant found in the surrounding soil
where such compounds will persist over the years.12
Another cause of contamination of soils is the presence of arsenic as an
impurity in commercial fertilizers. Repeated fertilizations lead to the long-
term accumulation of As in the soil. In particular, the phosphate fertilizers
may sometimes contain high amounts of arsenic in the form of an impurity.
Experimental tests on the use of pesticides containing arsenic in
Australian livestock have also shown the ability of this element to accumu-
late in animal tissues and to remain at relatively high concentration levels
even after the slaughter of cattle, threating human health.
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96 Chapter 5
5.3.3 Arsenic in Water, Air and Soil

Local geology, hydrogeology and geochemical characteristics of the aquifer,
as well as climate changes and human activities, are the greatest contribu-
tors to the occurrence of arsenic in natural water. Several studies have shown
that about 19% of the soluble forms of soil related arsenic reaches surface
water and groundwater via run-o and leaching.14 The major arsenic content
in unpolluted natural water has been attributed to several natural geo-
chemical processes. An arsenic concentration typically ranging from 0.001 to
0.010 mg L1, rising to 0.1005.000 mg L1, has been detected in waters
which are in contact with ores or tailings, waters near former mining or
smelting sites.15 High levels of arsenic can also occur naturally in geo-
thermal springs such as in New Zealand,13 up to 8.5 mg L1, in Japan16 with
a value between 1.8 and 6.4 mg L1 and at Yellowstone National Park (WY,
USA), where As concentrations often exceed 1.00 mg L1. However, not all
geothermal springs are contaminated with As. The concentrations in
groundwater depend on the arsenic content of the bedrock and the high
tendency in aquifers for the physical and geochemical conditions to be
favourable for As mobilization and accumulation. Unusually high values
have been reported in carbonate spring waters in New Zealand, Romania,
the Russian Federation and the United States (0.41.3 mg L1), artesian wells
in Taiwan, China (up to 1.8 mg L1) and groundwater in Cordoba, Argentina
(up to 3.4 mg L1). Seawater ordinarily contains 0.0010.008 mg L1 of
arsenic.13
The maximum permissible As concentration in drinking water is
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0.050 mg L1, while the recommended value by the EPA and WHO13 is
0.010 mg L1. Drinking water is the significant contributor to oral intake in
regions where the As concentrations in well-water or in mine drainage areas
are very high. More commonly, drinking-water sources generally contain
arsenic at concentrations of less than 0.010 mg L1.
Higher concentrations of arsenic have been found in the porewater ex-
tracted from unconsolidated sediments than in the overlying surface water.
Measures of dierent inorganic arsenic species (arsenate, arsenite and total
arsenic) concentrations in the porewaters collected from 18 piezometers
installed in a thick till and clay-rich aquitard sequence located in southern
Saskatchewan (Canada), are in the ranges of from 0.00031 to 0.097, 0.00071
to 0.021 and 0.0032 to 0.098 mg L1, respectively. Arsenic concentrations up
to 100 mg L1 have been found in porewater extracted from sediments af-
fected by mining contamination (tailings, mineral-rich deposit) in the
province of Ontario. High concentrations of As(III) (40.3 mg L1) were de-
tected in sediment porewater in an area contaminated from historic gold
mine operations (Moira watershed, Ontario), while As concentrations in the
surface water of the Moira River and Moira Lake are up to 0.075 and
0.05 mg L1, respectively, with the 98% as As(V)4 possibly being the result of
the reducing conditions below the sedimentwater interface, which pro-
motes the reduction of As(V) to As(III).14 It is known that As(III) and As(V) are
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usually the main soluble species in waters with relative proportions of As(V)
and As(III) varying according to sources, pH and redox conditions, and mi-
crobial activities. Aggett and OBrien5 found stratification of arsenic con-
centrations in some lake waters due to varying redox conditions that can be
explained by the depleted oxygen levels at the bottom of lake waters as a

result of biological activities and the re-suspension of sediment porewaters
near the sedimentwater interface.
The principal fate of arsenic in waters is related to adsorption onto min-
eral surfaces and in particular onto Fe oxides or Mn oxides under neutral or
mildly acidic conditions. This tendency has become the basis for removing
arsenic from contaminated waters. Competition between arsenic and other
sorbates (i.e., PO43, SO42, MoO42) on clay and oxide minerals has also
been demonstrated. It was reported that As(V) adsorption was slightly less at
equal concentrations of PO43, but it was greatly reduced when PO43 was
present at ten times its concentration. Also, MoO42 inhibited As(V) ad-
sorption but only at a pH value of less than 4.6
Bicarbonate ion is eective in arsenic leaching from sediment samples.
A linear correlation between arsenic quantity extracted and the concen-
tration of NaHCO3 has been reported. In several areas around the world a
positive and significant correlation between arsenic and NOM (natural or-
ganic matter) has been demonstrated. Arsenic release from soil and sedi-
ments into a water column through competition for available adsorption
sites may be enhanced by the presence of NOM, forming aqueous complexes
and/or changing the redox chemistry of the site surface and arsenic species.
11:25:46.
It could also inhibit arsenic release by serving as a binding agent and/or by

forming insoluble complexes. Arsenic biochemistry may also be significantly
influenced by NOM in the aquifers.6
Concentrations of organoarsenic compounds are generally low. A study
made on waters of the Moira Lake, Ontario6 have demonstrated that organic
arsenic concentrations range from only 0.000 01 to 0.0015 mg L1 while As(III)
was between 0.007 and 0.075 mg L1, and As(V) was 0.019 to 0.058 mg L1.
Atmospheric As is usually present in particulate form as inorganic arsenic
(principally as As2O3 powder9) from both natural sources, such as soil ero-
sion by the wind, volcanic activity, volatilization of the element from the soil,
aerosols of seawater or forest fires, and anthropogenic pollution such as the
burning of fossil fuels, automobile exhaust and tobacco smoke, and returns
to the earths surface through wet and dry deposition. It has been estimated
that volcanoes, microbial activity and the burning of fossil fuels release
3000, 20 000 and 80 000 metric tons per year of atmospheric As, respectively.
Nriagu and Pacyna7 estimated that anthropogenic sources of the toxic
element in the atmosphere (about 18.8 tons per year) represent approxi-
mately 70% of the global flow of As pollution.
Typical levels of As in ambient air in the United States range from o1 to
3 ng m3 in remote areas, whereas 20 to 30 ng m3 have been detected in
urban areas without substantial industrial emissions. Mean levels for the
European regions are between 0.2 and 1.5 ng m3 in rural areas, 0.5 and
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98 Chapter 5
3 3
3 ng m in urban areas and not more than 50 ng m in industrial areas.13
In Prague, airborne arsenic concentrations reported in the past were found
to average 450 ng m3 in winter and 70 ng m3 in summer. The concen-
trations of As in the waters of rain and snow in rural areas are invariably low
and typically less than 0.03 g L1, but in areas aected by the foundry
business and volcanic emissions they are generally higher. Indeed, Andreae
et al.8 found a concentration of As of about 0.005 mg L1 in the rain of these
areas. Unless significantly contaminated by industrial sources, atmospheric
precipitations contribute little to the enrichment of As in surface water
bodies and groundwater.12
In air, arsenic species are present absorbed on particulate matter, with the
organic species being of negligible importance except in areas of arsenic
pesticide application, or they may escape through soil and water surfaces
due to microbial activity. However, the dominant species are variable de-
pending on the emission sources. Arsenate is usually the predominant in-
organic species while arsenite is likely to be dominant near smelters and
roasters, coal burning and volcanic sources.9 Arsine (AsH3) may be derived
from landfills and peats.9
Arsenic can also be found in tobacco smoke, especially if the tobacco
plants have been treated with lead arsenate insecticide. It is estimated
that the arsenic content of mainstream cigarette smoke is in the range of
40120 ng per cigarette. If consumption is 20 cigarettes per day, the daily
intake from this source would amount to 0.82.4 mg.
Occupational exposure to arsenic occurs primarily among workers in the
11:25:46.
copper smelting industry, at power plants burning arsenic-rich coal and

from using or producing pesticides containing arsenic. Inhalation exposure
to arsenic can also take place during the production of gallium arsenide in
the microelectronics industry, demolition of oil-fired boilers and metal ore
mining.10
5.3.4 Arsenic in Plants and Biota

All living organisms have the ability to extract arsenic from the environment
and each one, from Escherichia coli to man, has developed detoxification
pathways. It is found to be cumulative in living tissue, because once ingested
it can be excreted very slowly. Arsenic bioavailability, uptake and phyto-
toxicity to living organisms are influenced by factors such as arsenic con-
centration and its species, living organism species, environmental properties
and concentrations of competing ions (e.g., phosphate and sulfate).
Commonly observed arsenic concentrations in plants range from 0.2 to
14.0 mg kg1 (dry weight) depending exclusively on the concentration of
arsenic in the soil and at least 1367% of the total arsenic in vascular plants
was inorganic forms. However, these low concentrations do not mean that
animals will be poisoned by consuming contaminated plants, because plant
injury occurs before toxic concentrations can appear.11 More elevated
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1
concentrations (3.61220 mg kg dry weight) have been reported in plants
grown near a mining activity area in Canada.6 Values ranging from 4 to
263 mg kg1 (dry weight) in Myriophyllum exalbescens, a common pond weed
in the lakes in the vicinity of the base metal smelter at Flin Flon, Manitoba,
have been reported.6 In contaminated lakes, arsenic concentrations were

found in the range of from 150 to 3700 mg kg1 in macrophytes.14
Arsenic distribution among the dierent parts of a plant is highly variable.
Seeds and fruits have a lower As concentration than leaves, stems or roots,
with the skin having higher concentrations than the inner flesh. The edible
portions of vegetables seldom accumulate a very high quantity of As, because
most plants will be killed or severely stunted long before the concentration
in their tissues reaches values that pose a health risk (Ontario Ministry of the
Environment). The arsenic content found in plants will also depend on soil
conditions. It is recognized that with equivalent soil As concentrations,
plants grown on sands or sandy loam soil usually have higher total As
contents than those grown on heavier-textured soils. Plants generally absorb
the least amount of soil As at neutral soil pH while a reduction of plant
uptake has been found on increasing soil organic matter by adding compost,
manures or other organic soil amendments. A lime addition tends to im-
mobilize As12 whereas adding phosphate compounds to high-As soils in-
creases plant uptake. This phenomenon could be explained because of the
chemical similarity between P and As.
Arsenic is also cumulative in animal tissue, but with a wide range of
concentrations due to the variance in arsenic ingested in dierent areas.
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Brooks et al.16 measured the arsenic contents of aquatic organisms in a

stream in a gold-mining district in Nova Scotia. It ranged from 0.002 to
0.059 mg kg1 (dry weight) for mayfly larvae, 0.002 to 0.18 mg kg1 (dry
weight) for caddisfly larvae and 0.63 to 3.2 mg kg1 (wet weight) for the
banded killifish (minnow). Among marine animals, arsenic is found to be
cumulative to levels of from 0.005 to 0.3 mg kg1 in coelenterates, some
molluscs and crustaceans, but in some shellfish the concentration could
be over 0.100 mg g1. The average arsenic content in freshwater fish is
0.000 54 mg g1 on the basis of total wet weight, but some values reach as
high as 0.0770 mg g1 in the liver oil of freshwater bass. In the coastal area of
British Columbia, an average arsenic concentration of 1.4 mg kg1 was found
in the ooligan grease, a marine food fat rich with vitamin A and omega-3 fatty
acids.17 Ebsuda et al.18 examined the total arsenic concentration in ringed
seals from Pangnirtung. Arsenic concentrations ranged from 0.07 to
0.15 mg kg1 (dry weight) in the hair to 0.77 to 1.51 mg kg1 (wet weight) in
the blubber. The arsenic concentrations in the oyster tissue and the fucus
were about 4.0 and 41.0 mg kg1, respectively. The predominant organic ar-
senic compounds that are found in marine mammals are arsenobetaine
(470%) and arsenocholine, which are very resistant to chemical degradation.
The predominant arsenic species (470%) in marine mammals was
arsenobetaine, an organoarsenic species. Notable high accumulation of
arsenic in the blubber was measured, accounting for about 90% of the total
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100 Chapter 5
arsenic. In Meager Creek hot springs, British Columbia (Canada), the

highest arsenic concentrations were found in microbial mats, algae and
moss, ranging from 56 to 350 mg kg1 (dry weight).
In mammals, analyses have revealed that most body tissues contain less
than 0.00030.147 mg g1 (dry weight), with the exception of hair, nails and
teeth and other keratin-rich tissues where inorganic arsenic has a special
anity. The normal amount of arsenic in human hair is about 0.000 08
0.000 25 mg g1 while a concentration of 0.0010 mg g1 is an indication of
poisoning. Nail clippings from a patient with acute arsenic poisoning con-
tained arsenic at 0.00200.130 mg g1, whereas the normal arsenic con-
centration in nail ranged between 0.000 09 and 0.000 59 mg g1. The arsenic
content of urine can normally vary from 0.005 to 0.040 mg per day (total).
Acute and sub-acute poisoning will produce an excess of 0.100 mg per day.
Great daily variation of arsenic exists and depends on the amount of arsenic
in various foodstus. In general, it is found that organic arsenicals are more
rapidly excreted than inorganic forms, where As(V) compounds are cleared
faster than those of As(III).11
Gamberg and Braune15 reported that arsenic residues in the kidney
of male Yukon wolves were 0.51 (o18 months) and 0.21 mg kg1 (dry
weight) (1936 months). Values were slighter higher for females, 0.57 and
0.25 mg kg1, respectively. Arsenic residues in the liver of male wolves were
0.31 (o18 months) and 0.21 mg kg1 (dry weight) (1936 months), whereas
the values were 0.17 and 0.14 mg kg1 for female wolves.
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5.3.5 Arsenic in Foods and Drugs

The presence of As in soil, water, air, plants and all living organisms means
that finding arsenic in foods is unavoidable. In many foods the concen-
tration is very low, normally less than 0.25 mg kg1 (see Figure 5.3) with the
Figure 5.3 Arsenic content of common foods (data from Jones20).

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1
exception of seafood (2.416.7 mg kg ) and in certain crustaceans (more
than 100 mg kg1), where the dierent As forms range between 5.7 and 17%
inorganic arsenic, 1.1 and 3.6% monomethylarsonate (MMA), 6.6 and 27%
dimethylarsinate (DMA) and 47.9 and 75.2% arsenobetaine. The higher
concentrations are thought to occur because marine creatures ultimately

feed on plankton. As seen previously, the higher species of As in seafood are
arsenobetaine or arsenocholine, which are some of the forms of As deriva-
tives that are not acutely toxic because of their low biological reactivity and
their rapid excretion in urine.
Wine made from grapes sprayed with arsenic pesticides may contain ap-
preciable levels of arsenic (up to 0.5 mg L1) in the trivalent inorganic form.
Arsenic concentrations in vegetables grown in Bangladesh and on sale in
the United Kingdom have shown a mean level of 0.0545 ppm. Although
Bangladesh-grown vegetables were 2- to 3-fold higher in As content than UK-
grown vegetables, the concentrations found were far lower than the 1 ppm
regulatory limit established for the United Kingdom.19
The intake of arsenic in Japan (0.1260.273 mg per day), where the diet has
a large seafood component, is higher than that in Europe (o0.045 mg per day)
and the United States (o0.060 mg per day).
The medicinal virtues of arsenic have been acclaimed for nearly 2500
years. In Austria, peasants consumed a large quantity of arsenic for softness
and cleanliness of the skin, to give the plumpness to the figure, beauty and
freshness to the complexion and also to improve breathing problems.11
In 1909, the first synthetic chemotherapeutic agent (Salvarsan, salvation
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by arsenic) was released by the Nobel Prize winning German pharmacologist

Paul Ehrlich and was the first eective treatment of syphilis. Other re-
searchers have developed As compounds for the treatments of a variety of
diseases.21 In 2000, the US Food and Drug Administration approved the use
of arsenic trioxide for treatment of relapsed or refractory acute promyelocytic
leukemia. It should also be noted that even after As compounds were phased
out of use in human medicine, some were later reintroduced as feed
additives.
In 1998 the use of arsenic feed additives was prohibited in Europe, how-
ever, the same arsenic additives are presently approved for use in United
States poultry feeds, along with their permitted usage levels and indications
for use (Figure 5.4). The addition of 50 ppm roxarsone (28.5% As) would add
14.25 ppm As to feeds exposing the birds, over the duration of their lives, to
considerably more As than the tolerance limit established by the OSHA
(0.5 ppm). However, most As passes through the bird unchanged and re-
mains in the litter.
Arsenic compounds with lead, calcium and cooper were used as insecti-
cides, herbicides, defoliants, fungicides for many years, but their insolubility
in water meant they would have been washed o by a good rain, making
them ineective.20
Inorganic As compounds are also used in common industrial processes
(Table 5.3) to remove impurities (particularly Fe) to produce clear glass, to
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102 Chapter 5
Figure 5.4 Feed additives containing As approved for use in US poultry feed.
Indication for use: arsanilic acid growth promotion and feed eciency,
improved pigmentation; nitrosone prevention of blackhead; roxarsone
increased rate of weight gain, improved feed eciency, and improved
pigmentation, suppressing Salmonella and other enteric organisms that
can cause food safety hazards for consumers (data from Jones20).
make rounder lead shot, to harden and increase the durability of plates and
posts in lead acid batteries, to produce colour in fireworks, to act as an alloy
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in the bronzing process, to act as an alloy with gadolinium in integrated

circuits and in laser materials to convert electricity directly into coherent
light.22
5.3.6 Metabolisms and Toxicity of Arsenic

The intake of dierent forms of inorganic and organic As species is related to
respiratory routes for dust and fumes, and oral routes for arsenic in water,
beverages, soil and food, while there is little evidence of dermal absorption.
The study of the kinetics and metabolism of these compounds in animals
and humans is a complex matter because each form of As has dierent
physico-chemical properties and bioavailability. The absorption rates are
generally low (o10%); however, for certain forms of arsenic higher rates may
be observed.10 Studies on percutaneous absorption of H3AsO4 from water
and soil in rhesus monkeys ranges from 6 to 2%, while in human cadavers it
ranges from approximately 1 to 2% over a 24 h period.11 Both inorganic
As(III) and As(V) are found to cross the placenta of laboratory animals and
similar conclusions are found in cord blood and maternal blood (9 mg L1)
of maternalinfant pairs exposed to drinking water containing high arsenic
concentrations (200 mg L1).11 The bioavailability of ingested inorganic
arsenic depends on: (1) the matrix in which it is found (food, water,
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Table 5.3 Common inorganic As compounds and their industrial uses.
Compounds Chemical formula Uses
Arsenic acid H3AsO4 0 5H2O Manufacture of arsenates, glass
making, defoliant, desiccant for
cotton, wood treating process

Arsenic disulfide As2S2 Shot manufacture (leather
industries), pest control,
pyrotechnics, depilatory agent,
paint pigment, shot manufacture,
taxidermy
Arsenic AsF5 Doping agent in electroconductive
pentafluoride polymers
Arsenic pentasulfide As2S5 Paint pigments, light filters, other
arsenic compounds
Arsenic pentaoxide As2O5 Arsenates, insecticide, dyeing and
printing, weed killer, coloured
glass, metal adhesives
Arsenic thioarsenate As(AsS4) Scavenger for certain oxidation
catalysts and thermal protectant
for metal-bonded adhesives and
coating resins
Arsenic tribromide AsBr3 Analytical chemistry and medicine
Arsenic trichloride AsCl3 Intermediate for organic arsenicals,
ceramics
Arsenic trifluoride AsF3 Fluorinating reagent, catalyst, ion
implantation source, dopant
Arsenic trioxide As2O3 Pigments, ceramic enamels,
decolorizing agent in glass,
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insecticide, rodenticide, herbicide,

preparation of other As
compounds
Arsenic trisulfide As2S3 Pigments, reducing agent,
pyrotechnics, glass used for
infrared lenses, semiconductors,
hide tanning
Arsenic hydride AsH3 Organic synthesis, doping agent for
solid state electronic compounds
Monomethylarsonic (CH3)AsO(OH)2 Pesticide industry
acid (MMA)
Dimethylarsinic acid (CH3)2AsO(OH) Pesticide industry
(DMA)
beverages or soil), (2) the solubility of the arsenical compound itself and
(3) the presence of other food constituents and nutrients in the gastro-
intestinal tract. The fate of ingested arsenic in humans depends on two
processes: the oxidation and reduction reactions between inorganic As(V)
and As(III) in the plasma and the consecutive methylation reactions in the
liver. Arsenate is rapidly reduced to arsenite, which is subsequently partly
methylated. The same studies have hypothesized that the main site
of methylation is the liver, suggesting that methylation may begin to be
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104 Chapter 5
1 11,23
limiting at doses of about 0.0030.015 mg As kg per day. DMA is the
main metabolite in humans. Under normal conditions, i.e., without exces-
sive ingestion of inorganic As, the urinary excretion consists of about 20%
inorganic As, 20% MMA and 60% DMA.24 Arsenobetaine is absorbed and is
excreted unchanged.11,23 Studies with radioactively labelled arsenate (74As)

in humans have shown that 38% of the dose is excreted in the urine within
48 hours and 58% of the total within 5 days.25
The arsenic can accumulate in keratin-containing tissues, skin, hair and
nails (used as indicators of past arsenic exposure) and can be excreted in
human milk, although the levels are low.26 In human blood, the As is quickly
cleared, so analyses on these types of media are used only as indicators of
very recent and/or relatively high level exposure in poisoning cases or in
cases of chronic, stable exposure. Also, measures of the total arsenic
(As MMA DMA) in urine are used as biomarkers of recent arsenic ex-
posure, even though this approach has become uncommon because of
certain organoarsenicals (for example, the non-toxic arsenobetaine) present
in substantial amounts in certain foodstus are excreted unchanged in
urine.27 Since consumption of seafood (e.g., marine fishes, crustaceans, bi-
valves, seaweeds) by humans produces an increase in the total urinary ar-
senic excretion,24 As assessment using this type of analysis will result in an
overestimation of exposure.
Arsenic toxicity depends not only on chemical forms and oxidation states
but also on other factors such as physical state (gas, solution or powder
particle size), rate of absorption into cells, rate of elimination, nature
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of chemical substituents in the toxic compound, and, of course, the pre-

existing state of the patient. It decreases in the order: arsines
(AsH3)4As(III)4(MMAO(III))4DMA(III)GS4DMA(V)4MMA(V)4[org As(III)]/
As(V)/arsonium compounds/As.11 The toxicity of an element is related to the
inactivation of enzyme systems, which serve as biological catalysts. The As(V)
does not react directly with the active sites of the enzymes,11 but first reduces
to As(III) before exerting its toxic eect. As(III) interferes with enzymes by
bonding to HS and OH groups, especially when there are two adjacent HS
groups in the enzyme. The inhibitory action is based on inactivation of
pyruvate dehydrogenase by complexation with As(III), whereby the generation
of adenosine-5-triphosphate (ATP) is prevented. As a result, the amount of
pyruvate in the blood increases, energy production is reduced and finally the
cell is slowly damaged.
Chronic exposure to inorganic arsenic may give rise to several health
eects, including eects on the gastrointestinal tract, respiratory tract, skin,
liver, cardiovascular system, hematopoietic system, nervous system, etc. The
earliest reports date back to the latter part of the 19th century when the
onset of skin eects (including pigmentation changes, hyperkeratosis and
skin cancers) were linked to the consumption of arsenic in medicines and
drinking water.10
The chemical similarity between phosphate compounds and arsenate
compounds allows As to substitute in vital compounds or reactions. Mead28
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observed that As does not directly interact with DNA. The eects occur
through indirect alteration of gene expression via disruption of DNA
methylation, inhibition of DNA repair, oxidative stress or altered modulation
of signal transduction pathways. Thus, toxicity of arsenate compounds
(particularly at low doses) is apparently dependent on exposure to other toxic

cofactors such as exposure to tobacco smoke, malnutrition, ultraviolet light
exposure, Se deficiency, reduced animal protein intake, marginal Ca status
and folate deficiency.
5.3.7 Natural Groundwater Arsenic Contamination

Arsenic polluted waters have been mainly reported in India and Bangladesh,
but its occurrence is actually a worldwide concern.6 Background concen-
trations of As in groundwater are less than 10 mg L1 in most countries and
sometimes substantially lower. However, values quoted in the literature
(under natural conditions) show a very large range from o0.5 to 5000 mg L1.
High concentrations of arsenic are found in groundwater in a variety of
conditions including both oxidizing (under high pH) and reducing
aquifers and in areas aected by geothermal, mining and industrial activity.
Most high arsenic groundwater provinces are the result of natural occur-
rences. Table 5.4 reports episodes of arsenic contamination around
the world.
5.4 Arsenic Removal from Water and Wastewater

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The excessive levels of arsenic in the environment, in particular in the

groundwater, has led to the development of arsenic removal processes all
over the world. There are numerous review papers on arsenic removal
technologies, some of which were recently published by Jiang,29 Bissen and
Frimmel,30 Mudhoo et al.,31 Jain and Ali32 and Mondal et al.33 Existing ar-
senic removal technologies that have been reported in the literature (over
2000) can be lumped into the following main processes: coagulation and
flocculation,34 adsorption and ion exchange,35 membrane,36 biological
treatments,37 advanced oxidation3840 and constructed wetlands.41 Many of
the arsenic treatment technologies are eective at removing arsenic in the
pentavalent state. A pH adjustment is required to convert As(III) into As(V).30
Figure 5.5 gives a summary of the optimal pH ranges for several arsenic
treatment technologies.
Adsorption and coagulation processes are particularly sensitive to pH and
they function most eectively at the lower end of the natural pH range. The
use of activated alumina (AA) at a natural pH may be a cost-eective option
for many small water systems. In addition to aecting arsenic treatability,
pH can also have a significant eect on disinfection, coagulation and
chemical solubility/precipitation within a distribution system. Most of the
established technologies for arsenic removal make use of several of these
processes, either at the same time or in sequence. Some of these methods
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106 Chapter 5
Table 5.4 Episodes of arsenic contamination around the world.
Concentration
Country Source Population (mg L1)
Asia: South west coast of Well water 140 000 0.01.82
Taiwan (19611985)
West Bengal-India Groundwater 86 000
Sri Lanka Well water
China (1980s) Groundwater 2 000 000 0.202.00
Northern India Well and 0.050.545
springs
Bangladesh Groundwater 25 000 000
Fukuoka Prefecture, Well water 40.01
Japan
Vietnam Groundwater 0.0013.05
America: Mexico (19631983) Drinking water 200 000 0.0080.624
Antofagasta, Chile Drinking 130 000 0.8
incident (19591970) supplied
water
Monte Quemada of Drinking water 10 000 40.1
Cordoba, Argentina
1955
San Antonio de los Drinking water 5000 0.470.77
Cobres, Argentina supply
Pampa Province of Groundwater 0.10.316
Cordoba
Millard Country, Utah, Drinking well 0.180.21
USA water
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Lane Country, Western Well water 0.051.7

Oregon, USA (1962
1963)
Lessen Country, Well water 0.051.4
California, USA
Rocky Mountain, Well water 0.100.41
Ontario, Canada
Halifax County, Nova o3
Scotia, Canada
Fairbanks, Alaska USA Well water 40.05
Fallon, Nevada, USA Drinking water 40.1
New Hampshire, USA Drinking water 0.00030.180
Europe: Hungary (19411983) Well water 0.064.00 mg
Spain Well water
Oceania: New Zealand 1961 Thermal water o8.5
are quite simple, but the disadvantage associated with them is the pro-
duction of large amounts of toxic sludge, which needs further treatment
before disposal into the environment. In the following paragraphs an at-
tempt has been made to review and update the recent advances made in the
technological developments in arsenic removal technologies and to explore
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Figure 5.5 Optimal pH ranges for arsenic treatment technologies (reprinted from
Jain and Singh42 with kind permission of Elsevier).
the potential of those advances to address the problem of arsenic con-

tamination. Each of these methods will be described briefly, together with
the related works in order to discuss treatment cost, operational complexity
and disposal of arsenic bearing treatment residual, which should be con-
sidered before selection of the appropriate arsenic removal/treatment
method.43
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5.4.1 Coagulation and Flocculation (CF)

5.4.1.1 Process Description
Historically the coagulation and flocculation (CF) process is among the
most common method used for arsenic removal. In this process, fine par-
ticles in the water first aggregate into coagulates, because of the addition of
coagulants that produce the destabilization of colloids by neutralizing the
forces that keep them apart (coagulation). Later, the addition of polymers
(flocculation) leads to the formation of bridges between flocs that bind the
particles into large agglomerates or clumps, which are separated from water
through filtration.43
5.4.1.2 Mechanisms of Removal

To date three main removal mechanisms of arsenic during CF have been
suggested:
adsorption involving the formation of surface complexes between sol-

uble arsenic and active sites of formed hydroxides;
coprecipitation with incorporation of soluble arsenic species into a
growing hydroxide phase by inclusion, occlusion or adsorption;
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108 Chapter 5
precipitation and formation of insoluble compounds (such as

FeAsO4).44
However, there is still insucient data and more experiments are required
for a better knowledge of these mechanisms.
5.4.1.3 Factors Aecting Eciency

Coagulants. The coagulation process is traditionally performed by adding
ferric ions, however aluminium, titanium and zirconium coagulants have
also been attempted, but were less ecient than iron ones.44 Besides iron
and aluminium compounds, manganese, calcium and magnesium com-
pounds have also been found to be eective coagulants for eliminating ar-
senic from water in a neutral medium.29,45 Several studies have reported
that arsenic removal from drinking water by coagulation with FeCl3 is
more eective than other coagulants such as Fe2(SO4)3, FeSO4 and
Al2(SO4)3.4649 Moreover, FeCl3 is also preferable with respect to its main
competitor, Al2(SO4)3, because of the suspected harmful eect of the latter
in causing Alzheimers disease.50 The arsenic removal is also dependent
on the pore size of the membrane filter disks used for the coagulation
process,46 since coagulates smaller than the pore size can pass through
the filter and remain in the water. As is known in filtration, the larger the
filter pores, the lower the capital and operation costs and the higher the
separation eciency. Therefore, there is a great significance in enlarging
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arsenic-borne coagulates in order to improve the coagulationfiltration

process for arsenic removal. Coagulations are usually enhanced by ad-
justing the pH and electrolyte concentration to reduce the absolute values of
the zeta potentials of particles and by optimizing the coagulation kinetics.
Furthermore, it can also be performed by adding appropriate coarse
particles, in which fine particles in suspensions coat coarse particles in the
form of multilayers. In this regard Song et al.45 carried out an enhanced
coagulation process with ferric ions and coarse calcite (3874 mm).
The enhanced coagulation followed by conventional filtration (with
filter paper as the filter medium) achieved a very high arsenic removal
(over 99%) from high-arsenic water (5 mg L1 arsenic concentration), pro-
ducing cleaned water with a residual arsenic concentration of 13 mg L1.
Table 5.5 reports the advantages and drawbacks of alternative inorganic
coagulants.
Natural organic matter and other interfering substances. Owing to the

poor capacity of As(III) to create bonds with Fe(III) salts, when CF is car-
ried out with iron salts, an oxidation step is required to better remove
As(III).18 However, in the presence of NOM, most oxidative reagents cannot
be used because of the formation of toxic oxidation by-products. Therefore
these matrix conditions need to be adapted for the drinking water treat-
ment step.44 Pallier et al.44 evaluated the influence of organic matter on
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Table 5.5 Advantages and drawbacks of alternative inorganic coagulants.
Coagulants Advantages Drawbacks
Al2SO4 18H2O Easy to handle and apply Adds dissolved solids
Most commonly used (salts) to wastewater
Produces less sludge Eective over a limited

than lime pH range
Most eective between
pH 6.5 and 7.5
Na2Al2O4 Eective in hard waters Often used with alum
Small dosage High cost
usually needed Ineective in soft waters
Polyaluminium Floc formed is more Not commonly used
chlorides (PACl) dense and faster setting Little full scale data
than alum compared with other
aluminium derivatives
Fe2(SO4)3 Eective between pH 4 Adds dissolved solids
and 6 and 8.89.2 (salts) to wastewater
Usually need to add
alkalinity
FeCl3 6H2O Eective between pH Adds dissolved solids
4 and 11 (salts) to wastewater
Consumed twice as much
alkalinity as alum
Fe2SO4 7H2O Not as pH sensitive Adds dissolved solids
as lime (salts) to wastewater
Usually need to add
alkalinity
Ca(OH)2 Commonly used Very pH dependent
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Very eective Large amounts of sludge

May not add salts to Overdose can result poor
wastewater euent quality
arsenic removal by the CF processes on both a model water with a low

mineral content and a natural water sample. According to their studies:
(1) As(III) removal depends on coagulant dose and on the number of sites
available on hydroxide surfaces rather than on coagulation pH; (2) As(V)
removal depends on the zeta potential of the colloidal suspension and is
more influenced than As(III) by coagulation pH and the presence of or-
ganic matter; and (3) organic matter removal follows As(V) removal. Silicate,
phosphate and sulfate interfere with arsenic removal.51 Indeed, phosphate
and arsenate strongly compete for the surface sites of the sorbents and this
competitiveness is influenced by the nature of the sorbents, the pH, the ini-
tial [AsO43] : [PO34] molar ratio and the residence time. However, Fe, Mn
and Ti oxides are more eective in sorbing AsO43 than PO34.
pH. Since the removal of arsenic is pH-dependent, several studies have

focused on optimizing the coagulation pH range. The eect of Al speci-
ation on arsenate As(V) removal during the coagulation process was re-
cently investigated by Hu et al. from the viewpoint of Al hydrolysis species
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110 Chapter 5
52
transformation. The results showed that As(V) removal eciency was
positively correlated with the content of (Al13) Al(III) species during the co-
agulation process. Weak acidic conditions (pH 57) were found to be
the optimal pH range to remove As(V) because (Al13) Al(III) species, espe-
cially for AlCl3, are largely formed in situ from the transformation of
monomeric Al species. Through regulating Al speciation, pH adjustment
could improve As(V) removal and AlCl3 could benefit most from this.
The authors confirmed that adsorption on hydroxide flocs that formed
was the most active mechanism for As(V) removal by Al-based coagulants.
Among the dierent pH conditioners that were tried to provide a
favourable pH for arsenic removal, it was reported that KHCO3 and
NaHCO3 are the most ecient pH conditioners for simultaneous removal
of As(III) and Fe(II).53
5.4.1.4 Drawbacks and Advantages

Although CF processes are easy to operate, several disadvantages are as-
sociated with this technology, which can be highlighted as follow:
production of by-products
release of taste and odour compounds due to chlorination
toxic sludge disposal
post-treatment is required.
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5.4.2 Adsorption
Adsorption is a mass transfer process that involves the accumulation of
substances at the interface of two phases, such as a liquidliquid, gasliquid,
gassolid or liquidsolid interface. Adsorption phenomena are operative in
most natural physical, biological and chemical systems. The substance being
adsorbed is the adsorbate and the adsorbing material is termed the ad-
sorbent. The properties of adsorbates and adsorbents are quite specific and
depend upon their constituents. The constituents of adsorbents are mainly
responsible for the removal of any particular pollutants from wastewater.
Adsorption operations employing solids such as activated carbon, metal
hydrides and synthetic resins are used widely in industrial applications for
purification of waters and wastewaters.

van der Waals forces and electrostatic forces between adsorbate molecules
and the atoms which compose the adsorbent surface are the main processes
of the physical adsorption (physisorption).43 When the attraction forces
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between adsorbed molecules and the solid surface are due to chemical
bonding, the adsorption process is called chemisorption.

The factors aecting the adsorption process are: (1) surface area, (2) nature
and initial concentration of adsorbate, (3) solution pH, (4) temperature,
(5) interfering substances and (6) nature and dose of adsorbent. Adsorbents
are characterized first by the surface properties, such as surface area and
polarity.43 Development of ecient adsorbents is thus vital to the successful
application of adsorption in water and wastewater remediation.54 As a
consequence, in recent years a variety of adsorbents have been developed to
improve the performance of the processes.
Conventional adsorbents. With regard to the remediation of wastewater

from the arsenic load, the literature may be considered to be replete with
studies on the development of Fe-modified adsorbents.54,55 Dodbiba
et al.55 compared the environmental performance, in the context of life-
cycle assessment (LCA), of two dierent types of adsorbents, FeCl3-based
and poly-Fe-based, in terms of the adsorption density and the rate of ad-
sorption. A waste product (polyferric sulfate) of the manufacturing process
of titanium dioxide has been used as the main material in the synthesis of
the poly-Fe-based adsorbent. Although the maximum adsorption density
of the FeCl3-based adsorbent was slightly higher when compared with the
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one for the poly-Fe-based adsorbent, the results of LCA indicated that the
environmental burden generated by the poly-Fe-based adsorbent was three
times smaller than the burden generated by the other option. A variety of
Fe-doped carbon based adsorbents have been synthesized for the removal
of arsenic. Fe has a large and selective anity towards arsenic because of
the formation of strong surface complexes, and activated carbon provides a
large surface area for impregnation. The eects of adsorbent dose, its par-
ticle size and initial arsenic concentration on the removal of arsenic from
simulated groundwater by Fe31 impregnated granular activated carbon
(GAC-Fe) were evaluated by Mondal et al.56 Under the experimental con-
ditions, the optimum adsorbent doses for GAC-Fe and GAC were found to
be 8 and 24 g L1, respectively with an agitation time of 15 h. The particle
size of the adsorbents (both GAC and GAC-Fe) has been shown to have a
negligible eect on the removal of arsenic.
Novel adsorbents. More recently, bi-metal (Fe and Al) doped micro- and
nanoparticle based materials have been developed as ecient adsorbents
for arsenic removal.54,57,58 Figure 5.6 contains a flow diagram for the syn-
thesis of the bi-metal (Al and Fe) doped micro- and nano-sized adsorbents.
For instance Kumar et al.54 synthesized Al- and Fe-doped activated micro-
(B0.8 mm) and nano-(B100 nm) sized porous adsorbents that were
shown to possess significant loadings of As(V) (B40 mg/g) ions, which
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112 Chapter 5
11:25:46.
Figure 5.6 Flow diagram for the synthesis of the bi-metal (Al and Fe) doped micro-
and nano-sized adsorbents (modified by Kumar et al.54).
were larger than or comparable to the literature data. A novel nano-

structured FeCu binary oxide was synthesized by Zhang et al.58 The FeCu
binary oxide with a Cu : Fe molar ratio of 1 : 2 had excellent performance
in removing both As(V) and As(III) from water, and the maximal adsorption
capacities for As(V) and As(III) were 82.7 and 122.3 mg g1 at pH 7.0, re-
spectively. The coexisting sulfate and carbonate had no significant eect
on arsenic removal. However, the presence of phosphate obviously in-
hibited the arsenic removal, especially at high concentrations. Moreover,
the FeCu binary oxide could be readily regenerated using NaOH solution
and then used repeatedly, showing it to be a promising adsorbent for both
As(V) and As(III) removal because of its excellent performance, facile and
low-cost synthesis process and easy regeneration.58
Unconventional adsorbents. In order to reduce treatment costs and the

environmental impact of treatment processes, waste materials have also
been used as alternative and promising low-cost adsorbents. It has been
widely recognized that the reuse of a waste material as low-cost adsorbent
to remove As from wastewater could not only decrease the cost of waste-
water treatment, but also reduce the amounts of these solid wastes.59
View Online
Fly ash, originating from coal-fired power stations, was proven to be eec-
tive for the removal of arsenate As(V) from water.60 Li et al.61 optimized an
iron oxide containing fly ash for As removal by heating and washing the
material with acid/alkali solutions, and they found that the adsorption cap-
acity of As(V) onto the modified fly ash was significantly improved com-
pared with that of the un-modified one. Aluminium industry wastered
mudwas also eective for the removal of both As(III) and As(V).62 Ferrous
based red mud sludge (FRS), which combines the ironarsenic coprecipita-
tion and the high arsenic adsorption features, at a dosage of 0.2 or 0.3 g
L1, can be used eectively to remove arsenic from aqueous solutions at
initial concentrations of 0.2 or 0.3 mg L1 according to Li et al.61

The main disadvantages of adsorption processes are:
cost of adsorbents
need of their regeneration
special waste production.

Membrane separation is addressed as a pressure driven process, commonly
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divided into four overlapping categories of increasing selectivity: micro-

filtration (MF), ultrafiltration (UF), nanofiltration (NF) and hyperfiltration or
reverse osmosis (RO). MF can be used to remove bacteria and suspended
solids with pore sizes greater than 0.1 micron. UF will remove colloids, vir-
uses and certain proteins with a pore size of 0.00030.1 microns. NF relies on
physical rejection based on molecular size and charge. Pore sizes are in the
range of from 0.001 to 0.003 microns. RO has a pore size of about 0.0005
microns and can be used for desalination.
High pressures are required to cause water to pass across the membrane
from a concentrated to a dilute solution. In general, the driving pressure
increases as selectivity increases. Clearly it is desirable to achieve the re-
quired degree of separation (rejection) at the maximum specific flux
(membrane flux/driving pressure). Membrane filtration processes allow ar-
senic concentrations in water of from 48 to 12 mg L1 to be achieved.30 The
influence of operating parameters on the arsenic removal by nanofiltration
was recently investigated by Figoli et al.63

Separation is accomplished by MF membranes and UF membranes via
mechanical sieving, while capillary flow or solution diusion is responsible
for separation in NF membranes and RO membranes.
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114 Chapter 5

Several parameters, such as feed concentration, pH, pressure and tempera-
ture on the As rejection and permeate flux, influence the operating con-
ditions. The removal of As(III), using RO membranes turned out to be
strongly aected by the solution pH in the studies of Kang et al.64 and the
removal of arsenate was higher than that of arsenite over the pH range in-
vestigated (310). The arsenite removal increased sharply as the pH in-
creased from 7 to 10 because most of the arsenite exists in the monovalent
anion form at pH 10, while most of the arsenite exists in a neutral molecule
at a pH below 7. The removal of As(V) from synthetic water has been studied
by Figoli et al.63 on a laboratory scale by using two commercial nanofiltration
(NF) spiral-wound membrane modules (N30FN90F). Higher As removal for
both membranes has been reported with an increase in pH and a decrease in
operating temperature and As feed concentration, whereas higher transmem-
brane pressure (TMP) values slightly reduced the removal that was achievable
with the N30F membrane. The permeate flux increased with temperature and
pressure and reached its maximum value at a pH of around 8. Among the
parameters aecting the As rejection, feed concentration plays a key role in the
production of a permeate stream, respecting the limits imposed by WHO.63
Though solar-driven membrane distillation could be an ideal technolo-
gical solution to the groundwater arsenic contamination problem, relatively
little attention has been given to this technique and to membrane distillation,
despite being known since the late 1960s. A solar-driven flat-sheet cross flow
membrane module fitted with a hydrophobic polyvinylidene fluoride (PVDF)
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microfiltration membrane has been tested by Manna et al.65 Exploiting low

grade solar energy with the help a locally made simple solar panel for raising
feed water temperature, they obtained almost 100% arsenic-free water from
contaminated groundwater. Furthermore, the module permitted easy clean-
ing and long hours of operation without any flux decline.

Membrane processes could be a promising technology for As removal from
water. The use of these techniques in environmental protection involves a
number of advantages in terms of no addition of chemical substances, an
easy way to increase the capacity (modular system), separation in the con-
tinuous mode, the possibility to easily join membrane processes with other
unit processes (hybrid processes) and the separation can be carried out
under mild environmental conditions.
5.4.4 Constructed Wetlands

5.4.4.1 Processes Description
In addiction to being costly and creating problems of sludge generation and
disposal, the conventional engineered treatment technologies often become
View Online
sources of As-rich euents. Besides, they are typically located in remote

isolated areas (such as mining sites), thus precluding the transportation of
the euents to large centralized treatment facilities. As such, to prevent As
pollution of watercourses, it is essential to find onsite, decentralized treat-
ment systems that are robust and have low maintenance requirements and
operating costs. Constructed wetlands (CWs) are cost-eective natural sys-
tems successfully used for removing various pollutants including arsenic.41
CWs reproduce the wetland ecosystem by means of engineered systems.
From the technical point of view, constructed wetlands consist of low deep
basins, with long Hydraulic Retention Times (HRTs), filled up with sand,
gravel and earth on a protective coating of a waterproof sheath and planted
with macrophytes. Constructed wetlands are usually classified according to
the dierent types of macrophytes and hydraulic regime in the surface and
subsurface flow plants.

Wastewater treatment is achieved through an integrated combination of
biological, physical and chemical interactions among plants, substrata and
soil. Despite the fact that sorption, precipitation and coprecipitation are the
principal processes responsible for the removal of arsenic in constructed
wetlands, bacteria can mediate these processes and play a significant role
under favourable environmental conditions.
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To date more studies have been conducted on surface flow wetlands than
on subsurface flow wetlands, where the contaminated waters pass through
packed media, instead of flowing above it, thus allowing more extensive
contact between the contaminants and media. Subsurface flow wetlands
could oer greater and more reliable treatment performance than surface
flow wetlands. Vertical flow wetland columns, using a range of filter media
(gravel, cocopeat, zeolite and limestone) were investigated by Lizama
et al.66 They provide an eective onsite treatment for acidic arsenic laden
wastewaters with a pH value of 2.0 0.1 under an average hydraulic
loading of 0.073 m3 m2 d1. On average, limestone wetland columns gave
the highest removal percentage for arsenic (99%) followed by zeolite col-
umns (92%) and gravel columns (43%). In contrast, wetland columns
with cocopeat media only showed a modest capacity for arsenic removal
(9%). Overall, the results indicated that the most eective mechanism
of As removal in vertical flow wetlands is coprecipitation with iron,
which can be enhanced by using alkaline wetland media to increase the
pH of the wastewater. Combinations of media appear worthy of examin-
ation in order to optimize the ecacy and sustainability of heavy metal
removal.
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116 Chapter 5

Subsurface flow wetlands may need regular maintenance or even re-
construction when the media bed become saturated with metals. Despite the
potential advantages of subsurface flow wetlands, the lack of information
about their performance hinders their ready adoption.66
5.4.5 Advanced and Integrated Technologies

5.4.5.1 Electrocoagulation
Electrocoagulation (EC) is a simple, ecient and promising method. As
shown in Figure 5.7, where a conceptual sketch of the electrocoagulation
mechanism is reported, the anodic reaction involves the dissolution of the
metal, and the cathodic reaction involves the formation of hydrogen gas and
hydroxide ions. In this process, the coagulating ions are produced in situ
involving three successive stages: (1) formation of coagulants by electrolytic
oxidation of the sacrificial electrode, such as iron or aluminium, (2) de-
stabilization of the contaminants, particulate suspension and breaking
of emulsions and (3) aggregation of the destabilized phases to form flocs.
Fe/Al is dissolved from the anode generating the corresponding metal ions,
which almost immediately hydrolyse to polymeric iron or aluminium
11:25:46.
Figure 5.7 Conceptual pattern of the electrocoagulation mechanism. M and X are

the electrodes (dierent or same materials) and n is the charge of the
metallic ions produced. The arrows indicate the migration of electrolysis
gases towards the top of the solution (reprinted from Gomes et al.38 with
kind permission of Elsevier).
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38
oxyhydroxides, excellent coagulating agents. The arsenic removal from
aqueous solutions by electrocoagulation (EC) using mild steel electrodes and
dierent electrolytes such as NaCl, NaNO3 and Na2SO4 has been recently
studied by Lakshmipathiraj et al.39 It has been well established that the
electrolyte pH is an important parameter and has a significant influence on

the electrocoagulation eciency.67 Almost 95% of the total arsenic was re-
moved within 5 min from its initial concentration of 10 mg L1; 98% of
arsenic removal was achieved in the presence of NaCl whereas it was around
75% in the presence of Na2SO4 and NaNO3.
Furthermore, it was observed that a certain amount of As(III) was converted
into As(V) during EC. One of the main advantages of the EC process is that
the treatment is carried out without adding any chemical coagulant or
flocculent, thus reducing the amount of sludge that must be disposed of.38
5.4.5.2 Photochemical and Photocatalytic Oxidation

Photochemical and photocatalytic oxidation of As(III) has also been investi-
gated in several studies, as reported by Mondal et al.56 According to
Dutta et al.68 TiO2 photo-catalysed oxidation was able to remove As to below
10 mg L1 (initial concentration 40200 mM).
5.4.5.3 Combined Processes

Wang et al. investigated a novel combined process, consisting of pre-oxi-
11:25:46.
dation, coprecipitation, adsorption and coagulation for treatment of high

arsenic content industrial wastewater.34 KMnO4 was used to initially oxidize
As(III) to As(V), meanwhile the total arsenic concentration was reduced by
about 9%. Then lime and ferrous coprecipitation decreased the arsenic
concentration dramatically (from 423 to 6.8 mg L1). Subsequent ferric and
manganese binary oxide (FMBO) adsorption and a polyaluminium chloride
(PACl) coagulation process, as a final treatment, removed over 99.88% of the
residual arsenic.
Experimental investigations to separate arsenic from contaminated
groundwater using three dierent types of nanofiltration membranes in a
flat sheet cross flow membrane module with a pre-oxidation step for con-
version of As(III) into the As(V) form, were carried out by Sen et al.69 KMnO4
was used as an oxidizing agent in the pre-oxidation step. Arsenic removal
increased from 5063% to 97100% for all the three types of membranes
over a transmembrane pressure range of 512 kgf cm2 on pre-oxidation of
trivalent arsenic. Increasing pH from 3 to 10, As rejection increased by 23%
for the NF-1, 33% for the NF-2 and 26% for the NF-20 membranes.
5.5 Concluding Remarks

Coagulation with iron and aluminium salts in the presence of polyelec-
trolytes followed by a filtration, adsorption onto dierent types of solids
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118 Chapter 5
(activated alumina, activated carbon, activated bauxite and clay minerals),

ion-exchange and membrane technologies are among the most reported
procedures for arsenic removal. However, none of them have been reported
in the technology literature. This can be explained because they present
important drawbacks, such as the diculties in meeting the standards of

quality required by the environmental agencies and the cost or the lack of
robustness.70 In addition, they perform better for the removal of As(V) than
for the removal of As(III), with oxidizing As(III) to As(V) using dierent types of
oxidants usually being recommended. Moreover, the dosing of these
reagents tends to bring down the water quality because of the residues and
by-products formed. Existing processes must thus be optimized and new
processes developed to remove arsenic eciently and to comply with new
drinking water standards.
Taking into account its toxicity to the public health and various com-
ponents of the planetary ecosystem, it is necessary to minimize the arsenic
levels in the environment through the development of new and eective
arsenic removal technologies.
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11:25:46.
CHAPTER 6
Removal of Iron and

Manganese from Water
Chemistry and Engineering
Considerations
KEISUKE IKEHATA,* ANDREW T. KOMOR AND YAO JIN
Pacific Advanced Civil Engineering (PACE), Inc., 17520 Newhope Street,

Suite 200, Fountain Valley, CA 92708, USA
*Email: kikehata@pacewater.com
11:25:49.
6.1 Introduction
As two of the earths most common transition metals, iron (Fe) and man-
ganese (Mn) often occur together naturally in the aquatic environment as
several dierent forms of dissolved ions. Although these two elements have
widespread uses, including metallurgical applications, such as in iron, steel
and other alloys, manganese dioxide (MnO2) in dry cell batteries and an
octane-enhancing agent (methylcyclopentadienyl manganese tricarbonyl) in
unleaded petrol, the sources of iron and manganese in the aquatic en-
vironment are mostly of natural origins, such as weathering of rocks and
sediments that are composed of iron and manganese minerals, as well as
microbial oxidation and reduction.1,2 In addition, various iron salts, such as
ferric chloride (FeCl3) and ferric sulfate [Fe2(SO4)3], are often used as co-
agulants in water treatment, whereas several manganese products, such as
potassium permanganate (KMnO4) and MnO2, are also used as oxidants in
water treatment. Based on a broad classification, both iron and manganese

122
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Removal of Iron and Manganese from Water 123
are considered heavy metals because of their high specific gravities, which
are 7.86 and 7.217.44, respectively.3,4
Under reducing conditions found in many groundwater aquifers, as much
as several milligrams per litre of dissolved iron and manganese may occur
naturally. Dissolved manganese levels can reach almost 10 mg L1 in acidic

groundwater.5 Seasonal occurrences of high dissolved iron and manganese
are also very common in deep lakes and reservoirs where the water column is
thermally stratified during the warm months and an anoxic hypolimnion
develops at the bottom of the lakes and reservoirs.6,7
Although iron and manganese are essential elements to humans and are
relatively non-toxic, ions of these elements in water often cause mild to se-
vere aesthetic problems, such as discoloured water, precipitation, scaling,
staining and metallic water taste (Figure 6.1). Metallic taste and staining in
laundry and toilet staining occur at iron and manganese concentrations
above 0.3 and 0.05 mg L1, respectively.3,4 The United States Environmental
Protection Agency (US EPA) has set the secondary drinking water maximum
contaminant levels (MCL) of 0.3 and 0.05 mg L1 for iron and manganese,
respectively, mostly because of these aesthetic and physical eects.8
Inadequate intake or overexposure of iron and manganese may cause
adverse health eects, although health-based guidelines for these elements
in drinking water are not considered to be necessary. According to the
World Health Organization (WHO)3,4 evidence has been reported for a
number of epidemiological chronic manganese poisonings in humans due
to the consumption of drinking water heavily contaminated with manganese
11:25:49.
Figure 6.1 Concrete walkways and stones stained by iron and manganese through
landscaping irrigation water.
View Online
124 Chapter 6
1
(410 mg L ), while those due to iron exposure is rare. Informal guideline
values of 2 and 0.4 mg L1 have been derived by the WHO for iron and
manganese, respectively, in drinking water based on the results of dietary
surveys, while no formal health-based guideline values have been proposed
to date.9 Iron is not considered mutagenic or carcinogenic in the forms

typically found in the aquatic environment and drinking water. The evidence
for manganese mutagenicity and carcinogenicity via oral exposure routes is
not strong enough to be considered relevant to normal human exposure
from drinking water consumption.4
Because of their ubiquitous presence in conventional drinking water
sources, removal of iron and manganese is one of the most common water
treatment practices. A two-step process with chemical oxidation followed by
filtration is often employed for the removal of dissolved iron and manganese
from water. The oxidants commonly used include oxygen in air, chlorine,
permanganate and ozone. Sand, anthracite, greensand and other synthetic
manganese dioxide media are commonly used as granular filter media to re-
move oxidized iron and manganese. Ion-exchange softening may also be used,
but only on smaller scales. Other treatment methods that may be used for iron
and manganese removal include water reverse osmosis and nanofiltration.
This chapter describes the chemical process mechanisms behind the iron
and manganese removal from water with an emphasis on practical impli-
cations of oxidation kinetics and engineering considerations in the oxidative
treatment of these elements.
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6.2 Chemistry of Iron and Manganese Oxidation and

Removal
6.2.1 Iron and Manganese Generation and Removal
in Natural Waters
As with many other transition metals, iron and manganese have dierent
solubilities depending on the oxidation state and pH, as well as the presence
of other anionic species. Reduced iron [ferrous, Fe(II)] and manganese
[manganous, Mn(II)] ions are highly soluble in water, especially at low pH
and low oxidationreduction potentials (ORP). Groundwater and hypo-
limnion of stratified lakes and reservoirs often become anoxic/anaerobic
because of the absence of dissolved oxygen (DO), which results in dis-
solution of reduced iron and manganese ions into the water. This dis-
solution may be mediated by various iron- and manganese-reducing bacteria
in the presence of organic carbon.10 Some facultative anaerobes such as
Shewanella putrefaciens are able to use oxidized iron and manganese as the
terminal electron acceptors under anoxic conditions. Hydrogen sulfide
(H2S), ammonia (NH3) and other reduced water constituents often occur
simultaneously under the anoxic/anaerobic conditions7 as shown in
Figure 6.2. Manganese reduction may be facilitated indirectly by sulfide
View Online

Figure 6.2 Generation of reduced manganese and sulfide in the anoxic hypolimnion
of a thermally stratified reservoir (unpublished data by the authors).
oxidation that reduces Mn(IV) to Mn(II), which can be mediated by sulfate

reducers such as Desulfovibrio species.10
In the aerobic environment, reduced iron and manganese may return to
their oxidized forms (e.g., MnO2, Fe31) slowly through abiotic or biotic
mechanisms, and precipitate out of the water as MnO2 and Fe(III) oxides and
hydroxides.6 While MnO2 can be present as black coloured particles, water
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containing ferric compounds exerts a reddish brown rust colour. Owing to

its higher oxidation potential (E0 1.229 V), manganese tends to stay re-
duced [Mn(II)] longer than iron (E0 0.769 V) in water.
Natural oxidation and precipitation of iron and manganese is often a
primary cause of turbidity and colour in a drinking water supply when an-
oxic groundwater and hypolimnetic water is pumped from a well or a res-
ervoir without treatment.4 This particulate manganese and iron may cause
staining in laundry, sinks, toilets and bath tubs, and result in dark coloured
deposits in plumbing fixtures and other household, commercial and in-
dustrial appliances, such as dishwashers, water heaters and water softeners.
Thus, an engineered treatment process for iron and manganese removal is
often required or recommended.
6.2.2 Chemistry of Iron Oxidation and Removal

In the presence of DO at pH greater than 6, ferrous iron can be slowly oxi-
dized to mixed iron(II)(III) hydroxide and magnetite, and then eventually to
ferric iron (Fe31), which precipitates as ferric hydroxide:11
Fe21 14O2 2OH-Fe(OH)3(s) (6.1)
Scheme 6.1 Fe(II) oxidation by molecular oxygen.
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126 Chapter 6
This equation indicates that the oxidation of Fe(II) to Fe(III) with aeration
requires hydroxide ion and may be accelerated at high pH. Theoretically,
1 mg of oxygen will oxidize 7 mg of iron. At neutral pH, complete oxidation of
Fe(II) may take 2040 min by aeration. Some reduced iron is complexed with
natural organic matter (NOM) and becomes very stable towards oxidation by
dissolved oxygen. Therefore, aeration is sometimes impractical for iron oxi-
dation. Alternative oxidants, such as free chlorine (gaseous chlorine or so-
dium hypochlorite), chlorine dioxide, potassium permanganate and ozone,
may be used to accelerate the reduced iron oxidation.1214 For example, the
oxidation of Fe(II) by chlorine and potassium permanganate can be shown as:
2Fe21 Cl2 6H2O-2Fe(OH)3(s) 2Cl 6H1 (6.2)
Scheme 6.2 Fe(II) oxidation by free chlorine.
3Fe21 KMnO4 7H2O-3Fe(OH)3(s) MnO2 K1 5H1 (6.3)

Scheme 6.3 Fe(II) oxidation by potassium permanganate.
Solution of oxidized Fe(III) ions has the characteristic orange colour of

rust. At neutral to slightly basic pH (6.59), Fe(III) ions slowly undergo the
following series of reactions:15
Fe31 H2O FeOH21 H1 log K25 1C 2.2 (6.4)
21 1 1
FeOH H2O Fe(OH)2 H log K25 1C 3.5 (6.5)
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Fe(OH)21 H2O Fe(OH)3 H1 log K25 1C 6 (6.6)

Fe(OH)3 H2O Fe(OH)4 H1 log K25 1C 10 (6.7)
Fe(OH)3am Fe31 3OH log K25 1C 38.7 (6.8)
a-FeO(OH) H2O Fe31 3OH log K25 1C 41.7 (6.9)
Schemes 6.4 to 6.9 Fe(III) hydroxylation and precipitation.
When Fe(II) is oxidized to Fe(III), precipitation of amorphous Fe(OH)3am

occurs immediately. Over time, less soluble iron(III) oxide-hydroxide
[a-FeO(OH), goethite] forms.15 The theoretical solubility of Fe(OH)3 is from
108 to 109 mol L1 (0.560.06 mg L1) between pH 7 and 10.16 These solid
iron precipitates can be removed by filtration. Non-reactive (i.e., sand and
anthracite) and reactive (i.e., greensand and MnO2 media) filter media may
be used for the removal of iron precipitates.
Reactive filter media are more ecient than non-reactive filters in re-
moving reduced iron because the solid MnO2 on the greensand and MnO2
media can act as a solid-state oxidant:
2Fe21 2MnO2(s) 5H2O-2Fe(OH)3(s) Mn2O3(s) 4H1 (6.10)
Scheme 6.10 Fe(II) oxidation by solid manganese dioxide.
View Online
Manganese dioxide can be regenerated by the oxidation of manganese(III)

oxide (Mn2O3) by chlorine or ozone. In fact, pre-chlorination at a dose of
0.52 mg L1 is recommended to continuously regenerate the reactive media
during the operation. Periodical filter backwash is also required to break up
the media and remove precipitated iron.

Reduced iron can be oxidized by chlorine dioxide and ozone to Fe(III) and
Fe(OH)3 precipitate can be formed and removed in a similar manner to the
oxidation by chlorine.12,1720 For example, the oxidation of Fe(II) by chlorine
dioxide (ClO2) can be expressed as follows:
Fe21 ClO2 3H2O-Fe(OH)3(s) ClO2 3H1 (6.11)
Scheme 6.11 Fe(II) oxidation by chlorine dioxide.
Ozone and chlorine dioxide are stronger oxidants than the others and may
be able to destroy and oxidize complexed iron and manganese compounds.
It should be noted that chloramines such as monochloramine and
dichloramine are very weak oxidants and are not generally usable for iron
and manganese oxidation.18 The rate constant for iron oxidation by ozone is
8.2 105 M1 s1 at ambient temperature.21
6.2.3 Chemistry of Manganese Oxidation and Removal

Because of the involvement of various manganese species, manganese oxi-
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dation is less straightforward as compared with iron oxidation. In a sim-

plified scheme, reduced manganese is oxidized to MnO2, which is practically
insoluble in water and can be removed by filtration. Oxidation of Mn(II) by
aeration is as follows:
2Mn21 O2 4OH-2MnO2(s) 2H2O (6.12)
Scheme 6.12 Mn(II) oxidation by molecular oxygen.
The oxidation of manganous ion is much slower (440 min at pH 9.5) than
that of ferrous ion and requires more hydroxide.22 The water pH must be
raised to about 9.5 for this to be practical. Thus, manganese removal by
aeration alone is not generally practiced in water treatment and a stronger
oxidant such as chlorine and potassium permanganate is required to achieve
eective Mn(II) ion oxidation:12,23,24
Mn21 Cl2 2H2O-MnO2(s) 2Cl 4H1 (6.13)
Scheme 6.13 Mn(II) oxidation by free chlorine.
3Mn21 2KMnO4 2H2O-5MnO2(s) 2K1 4H1 (6.14)
Scheme 6.14 Mn(II) oxidation by potassium permanganate.

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128 Chapter 6
Actually, the direct oxidation of Mn(II) by chlorine is slow with a very small
apparent rate constant of k 6.4 104 M2 s1 at pH 8 and 22 1C.24
However, adsorption of Mn(II) onto the surface of MnO2, which is a product
of initial Mn(II) oxidation, is very fast (apparent k 4 106 M2 s1).
Mn21 MnO2(s)-(MnMnO2)21(s) (6.15)
Scheme 6.15 Mn(II) adsorption by solid manganese dioxide.
This autocatalytic mechanism makes use of the manganese dioxide

media, such as greensand and synthetic MnO2 granular media, a very at-
tractive and ecient process for Mn(II) removal.23,25 Inert filter media, such
as silica sand and anthracite, may be coated with MnO2 by intentional
manganese seeding or unintentional build-up over time and may be used as
reactive media,26 although the oxidative/adsorptive capacity is much lower
than commercial MnO2 media (Figure 6.3). Oxidative regeneration using
chlorine or other oxidants will oxidize MnMnO2 into two molecules of MnO2:
(MnMnO2)21(s) HOCl H2O-2MnO2(s) Cl 3H1 (6.16)
Scheme 6.16 Manganese dioxide regeneration by free chlorine.
In this way, soluble Mn(II) in source water becomes part of the solid filter
media and the media increase in their size. In reality, the solid MnO2 may be
better represented as MnOx (where x is between 1.64 and 1.99)6 because of
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the co-existence of Mn(II), Mn(III) and Mn(IV).
Figure 6.3 Manganese on filter media using the HACH 1-(2-pyridylazo)-2-naphthol

(PAN) method.30 From the left: blank, fresh anthracite media, used
anthracite media, backwashed used anthracite media and commercial
MnO2 media.
View Online
Oxidation of manganese by ozone is more complex and somewhat

equivocal as ozone is very reactive and a much stronger oxidant and can
oxidize manganese to higher oxidation states. The oxidation of Mn(II) by
ozone occurs mainly through the molecular ozone pathway with a rate
constant of 1.5 103 M1 s1.21 According to Jacobsen et al.,27 the Mn(II)
oxidation mechanism by ozone is the formation of manganyl ion (MnO21),
followed by the formation of Mn(III) ions, which disproportionate into Mn(II)
and Mn(IV).
Mn21 O3-MnO21 O2 (6.17)
MnO21 Mn21 2H1-2Mn(III) H2O (6.18)
2Mn(III)2Mn21 Mn(IV) (6.19)
Mn(IV)-MnO2 (6.20)
Schemes 6.17 to 6.20 Mn(II) oxidation by ozone.
When ozone is provided in excess, manganese can be oxidized to

Mn(VII), which is permanganate (MnO4). Since MnO4 is very soluble in
water, manganese breakthrough and discharge may occur where ozone
is used as an oxidant17 and the treated water exerts a pink colour. This
MnO4 can be slowly reduced to MnO2 by dissolved organics in the water
and may cause discoloration and staining issues. This manganese break-
11:25:49.
through can be alleviated by biological filters, greensand or MnO2 media

filtration.
6.3 Engineering Considerations for Iron and

Manganese Oxidation and Removal
Depending on the local circumstances and regulations, iron and
manganese removal is often desired when the source water contains
elevated levels of these metals. Both the US EPA and the WHO currently
recommend the non-health based limits of 0.3 and 0.05 mg L1 for iron and
manganese in drinking water, respectively.8,9 The selection of the treatment
process for iron and/or manganese removal may depend on the following
factors:
Source water quality

J concentrations of target constituents (iron and manganese)
J presence of other constituents of public health and aesthetic
concerns
J presence of other reduced constituents
Source water quantity

J demand and availability of water resources
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130 Chapter 6
Other considerations
J oxidation by-products
J waste generation and disposal
J treatment costs and benefits

J availability of supplies and consumables
The basic components for an iron and manganese removal system include
pre-oxidation and media filters. Table 6.1 presents the characteristics of
common oxidants used for iron and manganese removal. Although the use
of air is not generally recommended due to its low oxidizing power and slow
reactions,22 mechanical aeration, such as cascade aerators, followed by sand
filtration may be employed as a low-cost treatment alternative for low-
manganese, high-iron source waters in developing countries, as both iron
and manganese pose minimal threats to public health at levels commonly
found in drinking waters.
Various filtration media may be used, including silica sand, anthracite,
greensand and synthetic MnO2 media, to capture Fe(III) and Mn(IV) precipi-
tates, depending on water flow rates and water quality. Practical implications
of the chemical oxidants and filtration media and their characteristics are
discussed in the following subsections.
6.3.1 Source Water Quality Analysis

As with any other water treatment process selections, it is important to
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characterize the source water in terms of the levels of constituents of

interests. Total iron and manganese concentrations can be measured by
using relatively inexpensive colorimetric assays, such as the 1,10-phenan-
throline method and the 1-(2-pyridylazo)-2-naphthol (PAN) method, re-
spectively.2831 Although the determination of total iron and manganese is
normally sucient to design a treatment system, speciation of reduced and
oxidized iron/manganese may be recommended using appropriate meth-
odologies because only reduced species would consume oxidant during the
oxidative treatment. Alternatively, dissolved and particulate iron/manganese
may be determined by filtering samples through a 0.45 mm membrane filter.
It can be assumed that at around neutral pH (68) the majority of the iron
and manganese particulates are in the oxidized form because of their limited
solubilities. In addition, measurement of ORP immediately after sample
collection would also provide a clue as to whether the water is oxidizing or
reducing. Negative ORP implies that the water is reducing and the majority
of the total iron and manganese is likely to be in the reduced form.
In addition to iron and manganese, the source water should be tested for
other co-existing constituents. This is particularly important because other
reduced substances, such as hydrogen sulfide, ammonia and NOM, often
occur simultaneously with iron and manganese in anoxic source water
(Figure 6.2). These reduced substances may compete with iron and man-
ganese for the oxidant (Table 6.2). Therefore, it is advisable to measure the
Removal of Iron and Manganese from Water

Table 6.1 Oxidants commonly used for iron and manganese removal.
Kinetics and rate
Oxidant constants Chemical Sludge
Oxidant Chemicals demands20,25 (M1 s1)19,21,23 cost generation25 Additional benefit Disadvantages Notes
Oxygen Air or purified O2 0.14 mg O2/ Holding time for Minimal 1.9 kg/kg None Very slow Slow Fe
mg Fe(II), Fe(II) is 1 h, Fe(II) oxidation oxidation and
11:25:49.
0.29 mg O2/ impractical for 1.58 kg/kg removal, Mn

mg Mn(II) Mn(II) removal Mn(II) removal
impractical
Free chlorine Gaseous chlorine 0.64 mg Fe(II): 1.7104 Low 1.9 kg/kg Disinfection Halogenated Excellent Fe
(Cl2), sodium Cl2/mg Fe(II), (pH 4) (purchase) Fe(II) DBPs removal, slow
hypochlorite 1.29 mg Mn(II): 6.4104 1.58 kg/kg formation, Mn removal,
(NaOCl), calcium Cl2/mg (pH 8), 4106 Mn(II) chloramines rapid removal
hypochlorite Mn(II) (with MnO2) formation with with solid
[Ca(OCl)2] ammonia MnO2 filter
media
Permanganate Potassium 0.94 mg See Knocke et al.12 Medium 2.43 kg/kg Taste and odour Extra sludge Classic oxidant
permanganate KMnO4/mg for a kinetics study (purchase) Fe(II) control generation, for Fe and Mn
(KMnO4) Fe(II), 1.92 2.64 kg/kg poor removal
mg KMnO4/ Mn(II) disinfection
mg Mn(II)
Chlorine Chlorine dioxide 1.21 mg ClO2/ Fe(II): 3.0103 High (on-site 1.9 kg/kg Good Chlorate and More common
dioxide (ClO2) mg Fe(II), (pH 23) generation) Fe(II) disinfection, chlorite in Europe, less
2.46 mg Mn(II): 5104 (pH 8) 1.58 kg/kg organics formation, common in
ClO2/mg Mn(II) oxidation, taste higher costs North America
Mn(II) and odour
control
Ozone Ozone (O3) 0.43 mg O3/ Fe(II): 8.2105 High (on-site 1.9 kg/kg Excellent Bromate Common in
mg Fe(II), generation) Fe(II) disinfection, formation, surface water
3
0.88 mg O3/ Mn(II): 1.510 1.58 kg/kg organics high capital treatment, Fe
mg Mn(II) Mn(II) oxidation, taste cost, high and Mn
and odour maintenance removal is
control cost, Mn usually a
over-oxidation secondary goal
131
132
Table 6.2 Major interfering constituents.
11:25:49.
Constituent Sources Oxidant demand22,25 Oxidation kinetics19,21,23 Notes

Hydrogen sulfide Sulfate reducing 0.24 mg O2 per mg 108109 M1 s1 with Cl2, Most common co-occurring
bacteria H2S, 2.1 mg Cl2 per 104109 M1 s1 with O3 constituent, odorous
mg H2S, 1.44 mg
O3 per mg H2S
Ammonia Decomposition of 7.6 mg Cl2 per mg 104106 M1 s1 with Cl2, Chlorine reacts very rapidly
biomass, microbial NH3-N, practically 20 M1 s1 with O3, o106 with ammonia to form
reduction no ozone demand M1 s1 with ClO2 chloramines, chloramines
cannot oxidize Fe/Mn, ozone
and chlorine dioxide react
slowly, may be biologically
oxidized
Natural organic Microbial growth, Varies Vary (generally slower than Fe NOM reacts slower than Fe
matter (NOM) degradation of and Mn oxidation) and Mn, may form
biomass, soil complexes with Fe and Mn
organic matter
Pathogenic Faecal Varies (depends on Not applicable Separate disinfectant or
microorganisms contamination Ct requirement) multipoint injection of
chemical may be required
Chapter 6
View Online
levels of other constituents to determine the total oxidant requirement. In

particular, hydrogen sulfide may occur at as much as 10 mg L1 in
groundwater and anoxic hypolimnetic water7,32 and is generally more re-
active towards oxidants than iron and manganese. Thus, special attention
must be paid when the source water to be treated contains elevated levels of
sulfide and manganese because of the slower reactions of manganese oxi-
dation (k 6.4 104 and 1.5 103 M1 s1 with chlorine and ozone,
respectively).21,23
Ammonia also reacts with chlorine very rapidly (k 3.1 106 M1 s1)33 to
form various chloramines (combined chlorine), including monochloramine
and dichloramine. These chloramines are much weaker oxidants than free
chlorine. One milligram of ammoniacal nitrogen may consume up to 7.6 mg
of free chlorine. It is known that the resultant chloramines cannot oxidize
reduced iron and manganese.18 Although no literature can be found
that explored the impact of ammonia and chloramines formation during
iron and manganese removal in the presence of solid MnO2 media, it is
speculated that chloramines have a limited ability to regenerate spent
(i.e., fully reduced) solid media. Use of other oxidants, such as ozone, chlorine
dioxide and permanganate, may be considered if elevated chlorine demand
and incomplete iron and manganese removal due to the presence of ammonia
is becoming an issue. Ozone reacts with ammonia at a much slower rate
(k 20 M1 s1) than with iron and manganese.21 In addition, it is desirable to
use ozone and chlorine dioxide when the majority of iron and manganese
are present as tight complexes with NOM and other chelating agents.
11:25:49.
Besides the removal of reduced chemical substances, including iron and

manganese, it is often required to account for the oxidant requirement in
terms of Ct values (i.e., the product of disinfectant concentration and contact
time) for the inactivation of pathogenic microorganisms when the use of
common disinfectants such as chlorine and ozone is considered. In some
cases, a combination of oxidation and disinfection treatment is used to
achieve dierent treatment objectives.
6.3.2 Treatment Process Considerations

6.3.2.1 Groundwater Treatment
In general, groundwater contains smaller amounts and less variety of
problematic constituents compared with surface water sources. In this case,
pre-oxidation followed by reactive media filtration is often selected for iron
and manganese removal. Historically, a combination of potassium per-
manganate (KMnO4) injection and greensand filtration has been used in
small-scale groundwater treatment systems because of its well-known per-
formance. However, the use of potassium permanganate generates extra
sludge and provides little additional benefits (Table 6.1). The application of
high-capacity, synthetic MnO2 media is increasingly common in medium-
size municipal groundwater filtration plants in the United States. Sodium
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134 Chapter 6
hypochlorite (NaOCl) is often used as a source of free chlorine because of its

low cost, lower hazard and wide availability. The advantage of the use of
chlorine (including NaOCl) is that it provides an eective chlorine residual
that is required for the distribution system. Care must be taken when
treating high-NOM water since there may be a high risk of the production of
halogenated disinfection by-products (DBPs), such as trihalomethanes
(THMs) and haloacetic acids (HAAs). Possible remediation methods for the
DBPs formation may include NOM removal by granular activated carbon
(GAC) adsorption or the use of chloramination as a secondary disinfection.
The use of ozone solely for iron and manganese removal from groundwater
is rare,17 although it may be used in conjunction with other treatment goals,
such as colour removal and primary disinfection.
As described in the previous section, raw water must be analysed for
various water constituents and parameters because co-occurrence of other
reduced constituents, including hydrogen sulfide and ammonia, are very
common. Pre-oxidant dosage must be adjusted accordingly, or the oxidative
capacity may be exhausted and incomplete removal of iron and manganese
may occur. Some of the constituents and parameters require on-site meas-
urements, including hydrogen sulfide, pH, DO and ORP. Performance of
bench- and pilot-scale treatment trials is highly recommended as the data
from these smaller scale experiments can be very useful to determine and
optimize the operational parameters, such as oxidant dosage, media re-
quirements and hydraulic loading rate, as well as to identify any unforeseen
issues, such as DBPs formation.
11:25:49.
Figures 6.4 and 6.5 present a simplified process scheme for a basic
groundwater filtration system for iron and manganese removal and an ex-
ample of such filtration system installations. When properly designed,
constructed and operated, this type of system can continuously achieve less
than 0.05 mg L1 of total iron and manganese, respectively, in finished water
(Figure 6.6). The high-capacity, synthetic MnO2 media could remove iron
Figure 6.4 Simple schematic for a groundwater filtration system for iron and
manganese removal.
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Figure 6.5 A 2200 m3 d1 filtration system for iron and manganese removal.
11:25:49.
Figure 6.6 Iron and manganese removal from groundwater using pre-chlorination
with NaOCl and MnO2 media filtration (unpublished data by the
authors).
and manganese even when pre-chlorine injection was accidentally ceased

and was not provided for more than ten days, if the media had been properly
regenerated prior to the chlorine injection shut-down. Periodical back-
washing is required to break up and remove Fe(OH)3 and excess MnO2 that
have been adsorbed onto the media. The backwash water needs to be dis-
posed of properly according to local regulations.
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136 Chapter 6
6.3.2.2 Surface Water Treatment

In surface water treatment, there are usually multiple treatment goals be-
sides iron and manganese removal, such as primary disinfection, taste and
odour, NOM and turbidity removal. A treatment train composed of several
unit processes is often employed and iron and manganese removal occurs at
several locations. Figure 6.7 shows a simplified process scheme for a typical
surface water treatment system.
In this scheme, iron and manganese removal may occur at several lo-
cations, including pre-oxidation, coagulationflocculationsedimentation,
intermediate ozonation and filtration. Various pre-oxidants may be used,
including gaseous chlorine, NaOCl, ozone, chlorine dioxide and KMnO4,
depending on the cost, availability and other treatment goals and site-
specific considerations (Table 6.1). After the pre-oxidation, oxidized and
precipitated iron and manganese [Fe(OH)3 and MnO2] can be removed by
coagulation, flocculation and sedimentation, although this process is usu-
ally not optimized for iron and manganese removal. In the United States,
intermediate ozonation is often used as a primary disinfection for Crypto-
sporidium and Giardia for taste and odour control.17 Additional iron and
manganese oxidation occurs during the intermediate ozonation. However,
there is a major risk of manganese over-oxidation to permanganate when the
ozone dose has to be increased in order to respond to seasonal water quality
events, such as taste and odour and spring runo. Therefore, the filtration
after ozonation is very important for residual manganese discharge control.
Inert filter media such as silica sand and anthracite may be used if the in-
11:25:49.
fluent manganese level is relatively small (o0.1 mg L1) as media particles

will be coated by solid MnO2 deposit over time that can act as an adsorbent
for soluble over-oxidized or reduced manganese (Figure 6.3). However, the
use of reactive filter media such as greensand or biologically active carbon
(BAC) filters may be recommended if frequent dissolved manganese break-
through has been recognized.17,34 The combined ozonationBAC filtration is
Figure 6.7 Simplified schematics for a surface water treatment system.

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35
commonly used in Japan for taste and odour control. At the end of the
treatment train, a secondary disinfection with free chlorine (NaOCl) or
chloramines (free chlorine ammonia; NH2Cl) is usually provided. No iron
and manganese oxidation is intended or expected at this stage because
additional oxidation and discharge of coloured precipitate formation into

the distribution system is not desirable.
Figure 6.8 shows a field example of manganese removal within a series of
unit processes during an event of a seasonal dissolved and particulate
manganese spike at a full-scale drinking water treatment plant. Pre-
chlorination using NaOCl, coagulation, flocculation, sedimentation using
alum and polymer, intermediate ozonation, anthracite monomedia filtration
and post-chlorination using NaOCl (Figure 6.7) are employed in this water
treatment plant. It can be seen that a majority of manganese removal oc-
curred at the anthracite monomedia filters and that some dissolved man-
ganese (determined by filtering the samples though 0.45 mm pore-size
membrane filters) was converted into particulate manganese by pre-chlorine
and intermediate ozone and removed by sedimentation and filtration.
During the treatment, brown-coloured particulate manganese was observed
in filter backwash water as shown in Figure 6.9.
As with the groundwater treatment systems, data from raw and treated
water quality analysis and bench- and pilot-scale experiments are very useful
and important for designing a new system, as well as for monitoring the
performance of existing systems and achieving optimal water treatment. As
shown in Figure 6.8, testing both dissolved and particulate manganese (and
11:25:49.
iron) at dierent locations is very useful in assessing the performance of the

processes for each unit within the treatment train.
Figure 6.8 Removal of particulate and dissolved manganese within a surface water
treatment system (unpublished data by the authors).
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138 Chapter 6
Figure 6.9 Manganese dioxide in filter backwash water.
When inert filter media are used, caution must be paid when replacing old
filter media with fresh media or performing chemical cleaning of the filter
media. These maintenance activities may cause incomplete manganese re-
moval and manganese breakthrough.26
11:25:49.
6.4 Conclusions
Iron and manganese are essential elements to humans and relatively non-
toxic heavy metals commonly found in drinking water sources such as
groundwater and surface water. They typically exist as dissolved ions in their
reduced forms, Fe(II) and Mn(II), in the water. The sources of iron and
manganese in the aquatic environment are mostly of natural origins, such as
weathering rocks and sediments that are composed of iron and manganese
minerals, as well as microbial oxidation and reduction. Although these
metals pose little public health risks, ions of these elements in water often
cause mild to severe aesthetic problems such as discoloured water, pre-
cipitation, scaling, staining and metallic water tastes.
Removal of dissolved Fe(II) and Mn(II) can be achieved by pre-oxidation
using air (oxygen), chlorine, chlorine dioxide, potassium permanganate and
ozone, followed by media filtration. Both inert and reactive filtration media
may be used. Source water quality is an important factor for designing and
operating iron and manganese removal systems. If properly designed, con-
structed and operated, the oxidative pre-treatment followed by a media fil-
tration process described in this chapter can consistently produce treated
water containing iron and manganese well below their current non-health
based limits of 0.3 and 0.05 mg L1, respectively. However, several reduced
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water constituents, including hydrogen sulfide, ammonia and NOM, are

often present in source waters containing reduced iron and manganese
species. These reduced constituents compete with Fe(II) and Mn(II) for oxi-
dants and may lead to incomplete removal.
While a simple combination of pre-chlorination and high-capacity MnO2

media filtration is often sucient for removing iron and manganese from
relatively clean groundwater, additional treatment processes are typically
employed in surface water treatment where multiple treatment goals, such
as removal of particulate matter and NOM, taste and odour control and
primary disinfection, tend to exist and iron and manganese removal are
often a secondary or tertiary goal.
Acknowledgements
The authors would like to thank their co-workers, namely Mr James A.
Matthews, Ms Janet A. Fordunski, Mr Jacob D. Peterson, Mr Brian W. Reid,
Mr Nathan A. Kramer and Mr Nima Maleky at Pacific Advanced Civil En-
gineering, Inc., for providing technical assistance, valuable insight and in-
spiration for preparing this book chapter.
References
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2. B. Thamdrup, Adv. Mcirob. Ecol., 2000, 16, 4184.
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3. WHO, Iron in Drinking-water Background Document for Development of

WHO Guidelines for Drinking-water Quality WHO/SDE/WSH/03.04/08,
World Health Organization, Geneva, Switzerland, 2003.
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ment of WHO Guidelines for Drinking-water Quality WHO/SDE/WSH/03.04/
104/Rev/1, World Health Organization, Geneva, Switzerland, 2011.
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American Conference on Ozone, Ultraviolet and Advanced Oxidation
Technologies, Toronto, ON, 2011.
8. US EPA, National Primary Drinking Water Regulations EPA 816-F-09-004,
United States Environmental Protection Agency, Washington, DC, 2009.
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13. T. Loegager, J. Holcman, K. Sehested and T. Pedersen, Inorg. Chem.,

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16. L. D. Benefield and J. M. Morgan, in Water Quality and Treatment, ed.
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17. K. L. Rakness, Ozone in Drinking Water Treatment: Process Design, Operation,
and Optimization, American Water Works Association, Denver, CO, 2005.
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Washington, DC, 1999.
19. J. Hoigne and H. Bader, Water Res., 1994, 28, 4555.
20. B. Langlais, D. A. Reckhow and D. R. Brink (ed.), Ozone in Water Treatment:
Application and Engineering, Lewis Publishers, Chelsea, MI, 1991.
21. U. von Gunten, Water Res., 2003, 37, 14431467.
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Works Association, McGraw-Hill, New York, 4th edn, 1990, pp. 229268.
23. M. Deborde and U. von Gunten, Water Res, 2008, 42, 1351.
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26. G. S. Logsdon, Water Filtration PracticesIncluding Slow Sand Filters and

Precoat Filtration, American Water Works Association, Denver, CO, 2008,
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CHAPTER 7
Heavy Metal Pollution

in Water Resources in China
Occurrences and Public Health
Implications
KEISUKE IKEHATA,*a YAO JIN,a NIMA MALEKYa AND
AIJUN LINb
a
Pacific Advanced Civil Engineering (PACE), Inc., 17520 Newhope Street,
Suite 200, Fountain Valley, CA 92708, USA; b College of Chemical
Engineering, Beijing University of Chemical Technology, Beijing 100029,
China
11:26:06.
*Email: kikehata@pacewater.com
7.1 Introduction
Toxic metals (often called heavy metals) constitute one of the groups of
chemicals of major public and environmental health concern due to their
great potency to causing a wide variety of adverse health eects, ranging
from acute toxicity (including mortality) to chronic toxicity such as neuro-
toxicity, developmental toxicity and cancers.1 Despite the fact that many
metals have been used in various industrial applications to improve our
quality of life since the very beginning of civilization, at the same time the
toxicity of metals has been a long-standing issue for human beings.
Metals and metal compounds may be released into the environment
within the lifecycle of metallic products, including: (1) mining, (2) extraction,
smelting and refining, (3) production, (4) use and (5) disposal, recycling and

141
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142 Chapter 7
reuse. They may enter the environment either as a main component of the
metal product or as impurities during any of the stages of the lifecycle, es-
pecially at the beginning (i.e., mining to production) and the end (i.e., dis-
posal) of the cycle.1 The recent rise in the electronics industry has increased
the public health risk due to some heavy metals, such as cadmium, lead,
mercury and chromium, in the environment as they are all linked to both the
manufacturing and recycling of electronics as well as other industries, such as
chemical production and mining.24 The industry-created pollution of heavy
metals is often through the discharge of partially treated or untreated eu-
ents, and can cause possible dangers to the public by contaminating the local
water sources for drinking water supplies and agricultural irrigation water.
Toxic heavy metals have been a universal pollution issue around the world
whenever and wherever heavy manufacturing industries are on the rise and
dominate a countries economy during their rapid development. The Peo-
ples Republic of China (China) is one such country, along with India and
other developing countries, who are currently enjoying a rapid development
and great economic growth. Unfortunately, China is no exception with respect
to environmental pollution and is indeed facing a variety of serious pollution
problems in water, air and soil that are threatening human beings, domestic
animals and wildlife alike and degrading the urban, rural and natural en-
vironments.5,6 Toxic heavy metals, such as lead, mercury, chromium and
arsenic, are considered to be one of the priority pollutants in China.5,7
The hydrosphere (the aquatic environment) is one of the four compartments
of the earth that interconnects with the other compartments, namely the at-
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mosphere, lithosphere and biosphere.1 Water is essential for life and acts
mostly as a vehicle for constituents and pollutants (including toxic heavy
metals) transport between these environmental compartments. In this chapter,
the current status of heavy metal pollution in the water resources in China, with
respect to relevant water quality standards in dierent types of water, including
drinking water, surface water and wastewater, along with recent data on their
occurrences in the water resources in China, are reported and discussed. Spe-
cial attention is made to addressing human health risks associated with heavy
metals in contaminated drinking water, contamination of sediments in rivers
and lakes and the impacts of industrial euents and wastewater irrigation.
7.2 Heavy Metals in Water: Definitions and Their

Health Eects
7.2.1 Brief Discussion on Heavy Metal Definitions
There are many largely inconsistent definitions of the term heavy metals.8
Historically, all metals have been classified into two groups: light metals and
heavy metals, based on densities/specific gravity or atomic number/atomic
weight. For instance, many researchers proposed cut-o numbers for metal
density or specific gravity ranging from 3.5 to 7 g cm3.8 According to this
rather broad definition, the majority of transition metals, poor metals and
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Heavy Metal Pollution in Water Resources in China 143
some metalloids may fall into the category of heavy metals. Others consider
heavy metals as toxic metals and metalloids that tend to accumulate in the
food chain.9 According to the World Health Organization (WHO),10 the
common toxic heavy metals that can be of public health concerns include
beryllium (Be), aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe),
cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se),
molybdenum (Mo), silver (Ag), cadmium (Ca), tin (Sn), antimony (Sb), bar-
ium (Ba), mercury (Hg), thallium (Tl) and lead (Pb). This list includes
beryllium, which is the second lightest metallic element (an alkaline earth
metal) after lithium with an atomic number of four, as well as aluminium,
one of the most widely used industrial light metals with a density of
2.7 g cm3, and arsenic and selenium, which are not even metals, but a
metalloid and a non-metal, respectively.
7.2.2 Fate of Heavy Metals in Water

In the aquatic environment, heavy metals may occur in cationic forms
(e.g., Cd21, Zn21, Cr31, Hg21 and Pb21), oxyanions (e.g., AsO43, SeO42 and
CrO42) or organic forms [e.g., (CH3)2Hg]. While some of the heavy metals,
including arsenic, chromium and selenium, can occur naturally in water
bodies, the majority may have originated from various anthropogenic sour-
ces, including domestic and industrial euents, landfill leachates, urban
and agricultural runos.11 In waters, dry and wet deposition can be a sig-
nificant source of heavy metals that were initially emitted to the atmosphere
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from geological (e.g., wildfires and volcanoes) and anthropogenic sources

(e.g., motor vehicles, manufacturing industries and coal-fired power plants).
Having entered into the aquatic environment, heavy metals go through a
number of physical, chemical and biological reactions, such as oxidation,
reduction, absorption and adsorption, biological uptake and assimilation,
precipitation and complexation, due to the presence of acidbase, aquatic
organisms (microorganisms, plants, fish, small invertebrates) and soil.
Some of these reactions transfer heavy metals from the hydrosphere to other
environmental compartments (e.g., biological assimilation, adsorption to
soil particles), but these reactions and subsequent movements are often
reversible. Biological uptake and assimilation often causes accumulation of
heavy metals in an aquatic organism in the water body (i.e., bioaccumula-
tion) due to their rapid uptake and persistence.1,12,13 The concentration
of certain heavy metals may also be further concentrated in a food chain
(i.e., biomagnifications). These are important considerations when studying
heavy metal pollutions in general.
7.2.3 Toxicological Properties of Heavy Metals with Major

Public Health Relevance
Although there are many toxic heavy metals, such as those listed in
Section 7.2.1 of this chapter, five elements including lead, mercury, arsenic,
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144 Chapter 7
Table 7.1 Basic properties of priority toxic heavy metals.
Standard
Atomic atomic Specific Major toxic eects
Element number weight gravity Category (oral route)
Chromium (Cr) 24 52.00 7.19 Transition Carcinogenicity

metal [Cr(VI) only]
Arsenic (As) 33 74.92 5.73 Metalloid Metabolic
interference,
organ failure,
carcinogenicity
Cadmium (Cd) 48 112.41 8.65 Transition Osteomalacia,
metal nephrotoxicity
Lead (Pb) 80 207.2 11.34 Poor metal Neurotoxicity
Mercury (Hg) 82 200.59 13.53 Transition Neurotoxicity
metal ([CH3Hg]1)
cadmium and chromium (Table 7.1) are more relevant in the present-day,
industrially driven economies, and can carry public health and ecological
concerns when found in the environment. Therefore, these five elements
were selected for further discussion in this chapter. They also coincided with
Chinas five priority key heavy metals.
Four of these priority elements (As, Cd, Pb and Hg) are also listed as
chemicals of major public health concern by the WHO, along with six other
chemicals or groups of chemicals, namely air pollution, asbestos, benzene,
dioxins and dioxin-like substances, inadequate or excess fluoride and highly
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hazardous pesticides.14 Hexavalent chromium [Cr(VI)] is another toxic heavy

metal that has gained much attention in recent years partly due to its known
carcinogenicity and relatively high toxicity with rather controversial tox-
icological relevance in human health risks.15 Because of their high toxicity,
the use of four heavy metals, including lead, mercury, cadmium and hexa-
valent chromium (along with brominated flame retardants) in electronics
has been restricted under the Restriction of Hazardous Substances (RoHS)
Directive by the European Union.16
Heavy metals can present unique toxicological profiles, and with a long
biological half-life for many of these metals, toxicity may occur at what are
traditionally considered as low environmental concentrations. Some of the
important toxicological eects of five heavy metals are summarized in the
following sections.
7.2.3.1 Chromium
Chromium is a transition metal that is widely distributed in the earths
crust. Chromium has many industrial applications such as in alloys
(e.g., stainless steel) and chrome plating due to its excellent corrosion re-
sistance and hardness. It can exist in valences of 2 to 6, and the majority
is present as chromium(III) or chromium(VI) in the aquatic environment
depending on the redox potential.17 While chromium(III) is an essential
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nutrient with no known toxicity, chromium(VI) compounds are known

human carcinogens. Although there is evidence of the carcinogenicity of
chromium(VI) compounds, including calcium, lead, strontium and zinc
chromates, via the inhalation route,17 the toxicological relevance of its car-
cinogenicity via the oral route (i.e., consumption of contaminated food and
water) is inconclusive and controversial, especially at low doses.15,18 Because
chromium(VI) is an oxidizing agent, it can be readily reduced to non-toxic
chromium(III) by reducing agents (i.e., sulfides and thiols) in human gastric
juice and rat liver microsomal fraction. Recent studies suggested that a
cytotoxic mode of action would be dominant in the low-dose region where
exposure of humans to chromium(VI) occurred via drinking water con-
sumption instead of a mutagenic mode of action.15
7.2.3.2 Arsenic
Arsenic has had uses as an anti-corrosive in zinc and lead alloys, a dopant for
semiconductors, in pesticides and wood preservatives.19,20 It is also a by-
product of copper smelting. Arsenic can be found in water either as arsenates
(e.g., AsO43) or as arsenites (e.g., AsO33), depending on the redox potential.
Because these arsenic compounds are oxyanions, they become more soluble
at higher pHs. Arsenic compounds are acutely toxic to humans. In general,
arsenites [arsenic(III)] are more toxic than arsenates [arsenic(V)] and organic
arsenic compounds. Inorganic arsenics are considered as carcinogenic to
humans (Group 1) by the International Agency for Research on Cancer (IARC)
11:26:06.
because of the sucient epidemiological evidence in humans and insucient

evidence in animals. Many studies have suggested an increased risk of can-
cers, such as those of the skin, lung, bladder and kidney, due to high con-
centrations of arsenics in drinking water.21 Various other chronic toxicities,
including cardiovascular diseases, neurotoxicity and developmental toxicity
due to prolonged exposure to arsenic via an oral route, are also well known.
The way that arsenic exhibits toxicity towards humans relates to its ability
to compete with phosphate in various cellular reactions.22 Through this
property arsenic can disrupt adenosine triphosphate production in cell
respiration in various ways, including the inhibition of nicotinamide aden-
ine dinucleotide, disruption of acetyl-CoA production and creating com-
plexes with adenosine diphosphate.22,23 Aside from this, arsenic can also
attack proteins and cause them to cease their proper functions by altering
their folding patterns.22 The carcinogenic properties of arsenics are thought
to be caused by having arsenic down-regulate the p53 protein. Without p53
DNA repair mechanisms cells are disrupted and cancerous cells are not
properly suppressed, increasing the risk of tumour development.24
7.2.3.3 Cadmium
Cadmium can be found in the aquatic environment as Cd21. It is closely
related to zinc (a Group 12 element) and they often occur together.
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146 Chapter 7
The major uses of cadmium include electroplating, anticorrosion agents,

batteries and pigments.25 Cadmium can be found in mining operation run-
os and electronic manufacturing and recycling wastes.26 Although the
acute toxicity of cadmium is relatively low, it is known that cadmium has a
very long biological half-life of 1030 years, depending on the organ and
tissues.12 It accumulates primarily in the kidney.25 According to the IARC,
cadmium is probably carcinogen (Group 2A) via inhalation, although no
evidence of carcinogenicity or genotoxicity via an oral route (i.e., drinking
water and food consumption) has been found.27 Toxic levels of cadmium
seem to cause brittle bones, and put those aected in extreme pain.12,28,29
It is thought that cadmium mediates damage to bones indirectly by its
interactions with organs in the body, and it can eventually lead to death
through organ shut down, especially renal failure.29 One of the most famous
cases of cadmium pollution occurred in Japan, in the early 20th century.
Mining operations produced cadmium polluted run-o that became the
cause of itai-itai disease, and caused severe damage to the aected local
population.12
7.2.3.4 Lead
Lead is abundant, cheap and has various industrial uses, such as leadacid
batteries, alloys, solder and pigments. Alkyl lead compounds including tet-
raethyl lead (TEL) and tetramethyl lead were used extensively as antiknock
agents in gasoline for motor vehicles in the past,3032 although the use of
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lead has been phased out in most countries, including China. However, the
use of TEL in aviation gasoline for aircrafts using reciprocating engines
still continues. Lead compounds may exist in two oxidation states, namely
2 and 4. Lead(II) is more stable and more common in the aquatic en-
vironment.32 Lead compounds may enter the aquatic environment via sur-
face run-os, dry and wet deposition from the atmosphere. Lead has been
used in pipes and fittings, as well as in soldered connections in water dis-
tribution systems, and in plumbing in residences.32
The problem with lead is that its adverse eects on children are quite
profound as it can hinder development in a childs mental capacity. It has
been shown that the levels of lead leaching from soldered connections in
water pipes could be as high as 210390 mg L1, which would be enough to
intoxicate children.33 By inhibiting haem synthesis through the disruption
of iron inclusion in the complex, lead can cause a state of anaemia.34
Furthermore, lead can function as an analogue of calcium, which is one
way it hinders development. As calcium is a crucial part of nerve network
formation and communication, by binding instead of calcium, lead can
prevent the formation of vital pathways and slow the propagation of action
potentials across synapses.26 This aects children in particular, due to
their sensitive developmental stages, and can leave permanent
mental disabilities in aected youths.35,36 Beyond the disruption of
neuronal pathways, lead, being able to react as calcium, would cause it to
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build up in bones in the body, and thus it is dicult to fully purge through
excretion and even treatment.3,35 According to the IARC, although the
evidence for carcinogenicity of lead in humans is inconclusive, inorganic
lead compounds are probably carcinogenic to humans (Group 2A).27
The National Toxicology Program reported that lead compounds are

reasonably anticipated to be human carcinogens based on limited evi-
dence of carcinogenicity in humans and sucient evidence in experi-
mental animals.37 Genotoxicity of some inorganic lead salts has been
suggested.
7.2.3.5 Mercury
Mercury is the only metallic element that is liquid at standard conditions for
temperature and pressure (273.15 K and 100 kPa). It has a vapour pressure of
0.16 Pa at 20 1C.38 It can readily mix with various metals to form amalgams.
Mercury mostly occurs as cinnabar (mercuric sulfide, HgS) in nature, which
was used as a scarlet pigment called vermilion from ancient times to the
Middle Ages. Its modern uses include thermometric materials for thermo-
meters, barometer liquids, conductive materials for electrical switches and
relays, vapour sources in mercury-vapour lamps and fluorescent lamps,
pesticides, pharmaceuticals and dental amalgams, although these uses of
mercury and mercury compounds are decreasing due their toxicity and en-
vironmental concerns.38
Mercury compounds, especially some inorganic mercuric salts and
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organomercury compounds, are highly toxic to humans. The most notable

is the neurotoxicity of methylmercury ([CH3Hg]1).39 This organomercury
is a potent neurotoxin due to several factors, primarily it can cross the
bloodbrain barrier readily and eciently.40, 41 This substance is well
known for being the cause of Minamata disease in the 1950s and 1960s in
Japan.39 While mercury(II) chloride and methylmercury are also readily
soluble in water, elemental mercury vapour and other inorganic mercury
compounds, such as mercury sulfide, have a very low solubility.38 How-
ever, inorganic mercury can be methylated to become more soluble and
the toxic methylmercury through microbiologically mediated reactions by
bacteria such as Pseudomonas spp., some methanogens and fungi in water
and sediments.42,43 Although drinking water is not considered to be a
major source of mercury, microbial methylation, bioaccumulation and
biomagnification in the aquatic food chains (e.g., fish) represent major
public health hazards. The concentration of mercury can increase as it
moves up trophic levels ultimately becoming toxic to human beings.13,39
It is known that, by forming cysteine complexes, methylmercury can
mimic amino acids allowing it to move freely throughout the body, and by
having a biological half-life of 50 days, it may be subject to accumu-
lation.40,41 In addition to the neurological disorders caused by methyl-
mercury, exposure to inorganic mercury compounds can cause renal
damage.38
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148 Chapter 7
7.3 Heavy Metals in Chinese Water Resources

Background
7.3.1 Chinas Recent Industrial Developments and Heavy
Metals in Water
As with many other industrialized nations worldwide, environmental pol-
lution in China has been realized and actively discussed in the past years. In
particular, Chinas environmental problems were getting much attention in
the late 1980s to early 1990s, which coincided with the beginning of the
major industrial and technological development of the country. The eco-
nomic reform and opening up started by the reformists led by Deng
Xiaoping in 1978 took dramatic eect in the early 1980s and stimulated vast
improvement in many industrial sectors, including agriculture, food,
manufacturing, mining, iron and steel and construction. Increase in foreign
trade further accelerated the rate of economic growth and production of
consumer goods, textiles and various commodities, such as agricultural
goods, steel and petrochemicals. In addition to the major cities such as
Beijing and Shanghai, a number of special economic zones (the most not-
able ones include Shenzhen, Zhuhai, Xiamen and Shantou) in southern
China, which were originally established in the 1980s, became the centres of
the economic growth in the early 1990s, in particular the high-tech indus-
tries such as electronics manufacturing, pharmaceuticals and other
biotechnologies.
11:26:06.
Although China has managed to grow so rapidly during the last few dec-
ades, many of the booming industries that have been sustaining the growth
have, at the same time, caused environmental pollution. Among the notable
pollutants, heavy metals constitute a major class that poses serious threats
to humans and the environment.57 For example, with the booming elec-
tronics industry, cadmium is a very relevant issue in wastewater treatment.
Also, being the largest producer of leadacid batteries, and having diculty
enforcing regulations, China has found large quantities of lead in waste-
water euents that contaminate local water sources. This, coupled with
electronic waste (e-waste) disposal and lead mining, has become a great
public health concern in China.3,26 In this subsection, Chinese heavy metal
standards in water and the sources and pollution status are discussed.
7.3.2 Current Water Quality Standards and Recent Trends

The currently enforced Environmental Quality Standards for Surface Water
(GB 3838-2002)44 were released in 2002 by the State Environment Protection
Administration, which is presently called the Ministry of Environmental
Protection (MEP), of the Peoples Republic of China. The Standards include
three tables, classifying basic parameters, supplemental parameters for
centralized drinking water sources and particular parameters for centralized
drinking water sources.44 The Standards employ the single factor index
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evaluation for categorizing the cross sections of a river, that is, the class of
the section is determined by the highest rating among all the parameters
tested.45 If the number of cross sections for a river is less than five, the
average concentration of each parameter will be assessed. When the number
of rated cross sections for a river is more than five, each class percentage will
be evaluated and the class of water body will be classified according to
Table 7.2. The class function for each class is summarized in Table 7.3.
Heavy metals are one of the key pollutant groups in water. In the basic
parameters standards, eight common and toxic heavy metals are included,
as shown in Table 7.4.44 If the surface water body is classified as a drinking
water source, additional heavy metal parameters should be monitored,
which are listed in Table 7.5.
The Class I and II surface water standards, which are applied to drinking
water sources, for hexavalent chromium, arsenic, cadmium, mercury and lead,
are generally in agreement with the WHO Drinking-water Guideline values
Table 7.2 Rivers and Water Systems Qualitative Evaluation.45

Representative
Proportion of class Water quality colour
I to III Z90% Excellent Blue
75% rI to III r90% Good Green
I to III o75%, worse than V o20% Slightly polluted Yellow
I to III o75% and 20% rworse Moderately polluted Orange
than V o40%
I to III o60% and worse than V Heavily polluted Red
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Z40%
Table 7.3 Qualitative Evaluation for Cross Section.45

Representative
Class Water quality colour Class functions
I and II Excellent Blue The first-class protected areas of
drinking water sources;
endangered aquatic organisms
habitat; the spawning zone of
fishes and shrimps; young fish
feeding field
III Good Green The second-class protected areas of
drinking water sources, the
overwintering fields and migration
routes of fishes and shrimps;
aquiculture area; swimming area
IV Slightly Yellow Industry use; recreational water with
polluted no human contact
V Moderately Orange Agricultural water; landscape water
polluted
Worse Heavily Red Not useful except for regionally
than V polluted climatic regulation
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150 Chapter 7
Table 7.4 Comparison of basic heavy metals standards for surface water and
drinking water (mg L1).
Chinese surface water (GB 3838-2002)44 Drinking water
Class
Parameter Class I Class II Class III IV Class V China46 WHO11

Hexavalent r0.01 r0.05 r0.05 r0.05 r0.1 0.05 0.05a
chromium (total
(Cr[VI]) Cr)
Copper (Cu) r0.01 r1 r1 r1 r1 1.0 2.0
Zinc (Zn) r0.05 r1 r1 r2 r2 1.0 N/Ab
Arsenic (As) r0.05 r0.05 r0.05 r0.1 r0.1 0.01 (0.05 0.01
for rural
areas)
Selenium r0.01 r0.01 r0.01 r0.02 r0.02 0.01 0.04
(Se)
Cadmium r0.001 r0.005 r0.005 r0.005 r0.01 0.005 0.003
(Cd)
Mercury r0.00005 r0.00005 r0.0001 r0.001 r0.001 0.001 0.006
(Hg)
Lead (Pb) r0.01 r0.01 r0.05 r0.05 r0.1 0.01 0.01
a
Provisional value.
b
N/A: not applicable
Table 7.5 Supplemental and Particular Heavy Metals

Standard Limits for Surface Water as
Drinking Water Sources (GB 3838-2002).44
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Standard
Parameter limit (mg L1)
Supplemental parameter:
Iron (Fe) 0.3
Manganese (Mn) 0.1
Particular parameter:
Molybdenum (Mo) 0.07
Cobalt (Co) 1.0
Beryllium (Be) 0.002
Antimony (Sb) 0.005
Nickel (Ni) 0.02
Barium (Ba) 0.7
Vanadium (V) 0.05
Titanium (Ti) 0.1
Thallium (Tl) 0.0001
and the most recent Chinese Drinking Water Standards (GB 5749-2006)46
(Table 7.4). Thus, if properly enforced, the Chinese surface water standards are
protective to public health. It can be seen that the surface water mercury
standards are a lot more stringent than the WHO guideline value (0.006 mg L1
as inorganic Hg), while arsenic standards are generally less stringent
(0.01 mg L1 in the WHO guideline). Thus, arsenic removal may be required at
drinking water treatment plants in some cases.
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At present, heavy metal occurrence data in Chinese rivers and lakes are
scarce or unavailable. By reviewing the data presented in the Report on the
State of the Environment in China by the MEP,47 one can get a glimpse at the
current state of surface water quality in China. The water quality in seven
major rivers in China, namely the Yzangtze River, Yellow River, Pearl River,
Huai River, Songhua River, Liao River and Hai River, has been greatly im-
proved over the last ten years (Figure 7.1). Still, a significant portion
(on average 14%) of the sections of these rivers were classified as heavily
polluted (worse than Class V) in 2012. Although the majority of the pollution
problems were reportedly caused by organics (i.e., biochemical and chemical
11:26:06.
Figure 7.1 Change in the proportion of qualitative evaluation of seven major rivers
in China: (a) 2002 and (b) 2012.47,48
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152 Chapter 7
47
oxygen demand), nutrients (e.g., ammonia and phosphorus), those heavily
polluted river sections were aected by heavy metals, which is discussed in
Section 7.4 of this chapter.
7.3.3 Current Discharge Standards for Heavy Metals

in Wastewater
The currently enforced wastewater discharge standard is the Integrated
Wastewater Discharge Standard GB 8978-1996.49 Except for 12 industries
that employ their own standards, such as papermaking, shipbuilding and
iron and steel industries, all other discharging wastewater, including do-
mestic wastewater, should satisfy the requirements established by GB 8978-
1996. The standard categorizes the pollutants into two classes. Each Class
I parameter has only one standard, called the maximum allowable discharge
concentration, regardless of the sources and discharging water bodies, while
each Class II parameter has three standards applicable to dierent receiving
water bodies, depending on the intended use and degree of anticipated
human contact. The five key heavy metals are all listed as Class I pollutants,
as shown in Table 7.6.
It should be noted that older plants may still be permitted to follow higher
discharge standards. For instance, Table 7.7 shows the heavy metals
standards for the non-ferrous metal industry.50 These standards are ap-
plicable to the existing mines and processing plants that were built prior to
1985. Newer mines and plants built after 1985 must follow the requirements
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shown in the Integrated Wastewater Discharge Standard (Table 7.6).
7.3.4 Sources of Heavy Metals in Chinese Water Resources

Heavy metal pollutions in surface water can be caused by multiple point and
non-point sources, including discharges from domestic and industrial
wastewater, urban and agricultural run-os and atmospheric depositions.
However, it has been suggested that heavy metals in surface water in China
Table 7.6 Heavy metals discharge limits from the

Integrated Wastewater Discharge Standard
(GB 8978-1996).49
Maximum
allowable discharge
Parameter concentration (mg L1)
Mercury 0.05
Cadmium 0.1
Total chromium 1.5
Chromium(VI) 0.5
Arsenic 0.5
Lead 1.0
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Table 7.7 Heavy metals discharge limits from the Emission Standards for
Pollutants from Heavy Non-ferrous Metal Industry (GB 4913-85).50
Discharge standards
for plants built
Parameter Process prior to 1985

Mercury Both mining and smelting and 0.05
processing
Cadmium Mining 0.2
Smelting and processing 0.1
Chromium(VI) Both mining and smelting and 0.5
processing
Arsenic Mining 0.5
Smelting and processing 1.0
Lead Both mining and smelting and 1.0
processing
Table 7.8 Key heavy metals discharge quantities in Chinese surface water.53
Parameter (tonnes)
Total
Source Arsenic Lead Cadmium Mercury chromium
Industrial 145.2 150.8 35.1 1.2 290.3
wastewater
Centralized waste 1.4 4.4 0.8 0.2 2.9
control facilitiesa
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a
Wastewater and leachate from domestic waste treatment plants and hazardous waste control
facilities.
are mainly from industrial wastewater discharge.51 The National 12th Five-
Year Plan for Environment Protection identified five key heavy metals,
namely, lead, cadmium, mercury, chromium and arsenic, which should be
under strict control.52 The plan also pointed out major polluting industries,
which consist of non-ferrous heavy metals mining and dressing, the
non-ferrous heavy metals smelting industry, lead batteries manufacturing,
leather manufacturing (including leather tanning process and fur manu-
facturing), chemicals and chemical synthesis products manufacturing (basic
chemicals manufacturing, painting, printing ink, pigment and other com-
parable manufacturing). Non-ferrous heavy metals include copper, lead,
nickel, tin, antimony and mercury. In addition, electroplating industries and
coal-fired power plants should be taken into account.
Based on the most recent statistics presented in the China Statistical
Yearbook on Environment by the MEP,53 the key heavy metals content in
industrial wastewater made up more than 95% of the national discharge in
2011, except for 14% of mercury which came from a centralized treatment
(Table 7.8). Figure 7.2 displays the annual discharge of each key heavy metal
via wastewater from 2000 to 2011.5357 Among these, both arsenic and lead
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154 Chapter 7
Figure 7.2 Key heavy metals annual discharge in China from 2000 to 2011.5357
discharging quantities had been significantly reduced by approximately

11:26:06.
70%, even though several major and minor fluctuations occurred in the last
decade. Cadmium displayed a sharp drop in 2004 while chromium(VI) went
the opposite way, and was then followed by gradual decrease. Mercury dis-
charge also decreased rapidly during 20002004 and became stable at
around 1.3 tonnes after 2007.
Figure 7.3 shows the composition of key heavy metals discharge by dif-
ferent industries. From 2007 to 2009, non-ferrous metals mining and
dressing were the primary sources of heavy metals discharge, followed by
non-ferrous metal smelting and rolling processing, the chemical industry
and ferrous metal smelting. In 2010, metal products manufacturing sur-
passed the ferrous metal smelting industry and became the fourth greatest
contributor. The industry composition had an obvious change in 2011, in
terms of both discharge percentages and composition. The heavy metals
discharge from leather, fur and feather manufacturing and shoe manu-
facturing made up almost 20% of the total discharge, while non-ferrous
metals mining and dressing decreased remarkably to 14%. Additionally, the
heavy metals contribution from metal products manufacturing showed an
upward trend. The cause(s) of the major changes that occurred in the 2011
data in Figure 7.3 (i.e., appearance of leather, fur, feather and shoe manu-
facturing, and the disappearance of the chemical industry) are unknown.
This is possibly due to some changes in statistical data collection methods
and possible industrial restructuring.
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Figure 7.3 The composition of heavy metals discharge from industries in China
from 2007 to 2011.5357
7.4 Recent Heavy Metal Pollutions in Chinese Water

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Resources
This section reviews and discusses examples of the recent investigations on
heavy metal pollutions in the water resources in China. Five important topics
are covered, including: (1) impacts of industrial wastewater, (2) impacts
of wastewater irrigation, (3) pollutions in Beijing, the nations capital,
(4) human health risk assessment and (5) contamination of sediments.
These study locations were spread across the country, as shown in Figure 7.4.
Many of the papers reviewed here were written in Chinese.
7.4.1 Impacts of Mining, Smelting and Other Industrial

Wastewaters
As previously discussed (see Table 7.6 and Figure 7.3), industrial wastewaters
are considered as the major sources of heavy metals in water resources in
China. The Xiang River is the largest river in Hunan Province and one of the
largest tributaries of the Yzangtze River. It flows through one of the main
areas for non-ferrous metals mining and the smelting industry in China.
Especially within the Xiawan drainage area, there are more than 70 smelting
and chemical manufacturing plants. Industrial wastewater has been dis-
charged into the Xiang River through the Xiawan drainage area for dec-
ades.58 It was found that levels of lead, cadmium, chromium, chromium(VI),
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156 Chapter 7
Figure 7.4 Locations of the sites covered in the reviewed articles (the original map
was downloaded at http://d-maps.com/carte.php?num_car 27749&
lang en).
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Table 7.9 Aqueous-phase heavy metals monitoring data at the Xiawan wastewater
discharge outlet (mg L1) (adapted from Qi59).
Total
Sampling date Lead Cadmium chromium Chromium(VI) Mercury Arsenic
8/26/2010 0.132 0.104 0.137 0.079 0.006 0.131
8/27/2010 0.144 0.092 0.105 0.046 0.023 0.051
8/28/2010 0.111 0.028 0.081 0.034 0.008 0.057
mercury and arsenic in the Xiawan drainage area were all rated as Class V.59
Monitoring data are summarized in Table 7.9.
The pollution control for wastewater discharged into the Xiang River at
Xiawan was desired because two major cities of Hunan Province, Changsha
and Xiangtan, are located downstream of Xiawan, which are ecologically
sensitive. The recommendations for improving the water quality included
upgrading the wastewater treatment facilities and separating stormwater
and sewage systems to enable treatment equipment downsizing and low-
ering of the capital costs. In addition, averaged lead contents in the river
sediments downstream of Xiawan were ten times higher than those in other
main rivers or comparable rivers in China, indicating serious lead
pollution.58
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60
Hu et al. also reported the impact of mining activity on another river
in Hunan Province called the Huayuan River. Manganese extraction was
the major on-going mining activity in the area that appeared to be contrib-
uting to elevated concentrations of manganese, cadmium and lead (up
to 2.5, 0.123 and 0.592 mg L1, respectively) in the aqueous phase, which
were well above the WHO and Chinese Drinking Water Guidelines
(Table 7.4), as well as those in the river sediment (12.367, 334, 1.392 and
37.178 mg kg1, respectively).
The impacts of acid mine drainage on groundwater quality have been
studied in the northern Guangdong Province.61 The Guangdong Dabaoshan
Mining Corporation is a state-run mining company that mines and refines
iron and copper. The acid mine drainage was first collected through mud-
retaining impoundment and it then flowed through a stream towards the
Shangba floodplain, which is located about 11 km south of the mine. The pH
of the groundwater in the Shangba floodplain was lower at the monitoring
sites, close to the mine (as low as 4.6) showing the impact of acidic stream
water (pH 2.9) originating from the mine and being used for agricultural
irrigation. Elevated levels of heavy metals were detected in both groundwater
and stream water. For example, high levels of cadmium, copper and zinc
(as high as 0.03, 1.93 and 4.03 mg L1, respectively) were detected in
groundwater samples. Although lead was found in the stream water (up to
1.2 mg L1), this heavy metal was not detected in the groundwater samples.
Based on the results of the Daphnia carinata toxicity test, the groundwater
was found to be very toxic, probably due to the high levels of heavy metals.
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Antimony, a genotoxic metalloid, often occurs simultaneously with arsenic

in sulfide ores.62 Wu et al.63 investigated the health risk associated with
antimony and arsenic in contaminated drinking water and food sources,
including rice, corn, vegetable, fish, meat and poultry that had been aected
by a mine called the Xikuangshan Antimony Mine near Lengshuijian City,
Hunan Province. Drinking water samples contained 54 and 4.8 mg L1 of
antimony and arsenic, respectively. The antimony concentration was more
than ten times higher than the standard value (5 mg L1, see Table 7.5) while
the arsenic level was below the limit (10 mg L1). The contributions of
drinking water consumption to the overall antimony and arsenic intakes
were 19 and 3.2%, respectively. Their results suggested that the overall
dietary health risk was mostly associated with the high level of antimony in
contaminated water and food, although the contribution of arsenic was still
considerably high in the studied area.
Liu et al.64 reported the contamination of river water by elevated levels of
heavy metals, including copper, chromium and nickel, at the downstream of
an electroplating plant in northern Guangxi. As much as 5 mg L1 of these
metals were detected directly after the discharge point. No significant in-
crease in lead and cadmium concentrations due to the wastewater discharge
was recognized (0.02 and 0.03 mg L1, respectively). The water from this
contaminated river has been used in agricultural activities for many years,
although some of the heavy metal concentrations were exceeding the Surface
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158 Chapter 7
Water Quality Standard (Class V for agricultural water; Tables 7.3 and 7.4).
Contamination of paddy soils and rice samples was also confirmed in this
study and a potential health risk to the local residents was suggested. Hang
et al.65 also reported a deterioration of surface water quality by the euent
from an electroplating factory. The euent was characterized by low pH (2.3)

and high concentrations of zinc, manganese, chromium, copper and nickel
(1.34. 3.77, 28.1, 6.40 and 9.37 mg L1, respectively), which all violated the
Integrated Wastewater Discharge Standard (Table 7.6) except for zinc.
In addition to the traditional metal-related industries reviewed here,
e-waste recycling facilities have become a significant source of toxic heavy
metals in southern China.3,26,66,67 The town of Guiyu in Guangdong Province
is one such e-waste recycling centre of China. Many heavy metals, including
copper, lead, nickel, cadmium, mercury and arsenic, were detected in sur-
face water and sediment samples collected from the Lianjiang River area.67
Health risks associated with cadmium, as well as mercury, lead and
copper, were considered significant in the area. Another risk assessment
study conducted by Zheng et al.68 on food, house dust and water from an
unnamed e-waste recycling area demonstrated that the groundwater sources
were contaminated by heavy metals, in particular by lead, and that the
cancer risk could be as high as 5104 to 1103 in a highly exposed
population.
7.4.2 Impacts of Wastewater Irrigation on Water Resources

in China
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Irrigation of farmlands and landscapes, including parks and golf courses,

with wastewater has been widely practiced as an eective wastewater man-
agement method in many nations around the world.69,70 However, the po-
tential health risks associated with this practice have been realized because
of the presence of an array of contaminants in treated and untreated was-
tewater. Heavy metals constitute one of the major groups of contaminants,
besides the excessive nutrients and pathogens. Wastewater irrigation has
been commonly practiced for decades in China, in particular in the north-
western areas where water resources are limited, as well as in some southern
areas such as Wuhan.5,71 It is widely acknowledged that wastewater irri-
gation may cause the transfer and accumulation of heavy metals such as
cadmium, lead, zinc, copper and chromium in soil and crops.7174 At the
same time, the heavy metal contamination of water resources such as
groundwater has been examined. For example, Wu and Cao75 investigated
the groundwater contamination in one of three major wastewater-irrigated
areas in Tianjin where this wastewater irrigation had been practiced for at
least 45 years. They found that although the accumulation of mercury
and cadmium in the wastewater drainage river sediments and wastewater-
irrigated soils were significant, the concentrations of key heavy metals
(Hg 0.016, Cd 0.128, Pb 0.25 and As 4.65 mg L1) were lower than the
Groundwater Quality Standards and WHO Guideline values.
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7.4.3 Heavy Metal Pollution in Rivers and Drinking Water

Sources in Beijing
There are five major rivers in Beijing where point-source pollution was the
primary cause of the deteriorating surface water quality in 2003.76 It was
demonstrated that industrial wastewater brought significantly adverse ef-

fects on the environments, especially in highly industrialized Shijingshan
and Fangshan Districts at that time. The upstream of the Chaobai River
was the cleanest water body in Beijing where the main drinking water
source, the Miyun Reservoir, was located. Most of the river cross sections
belonged to Class II, except for two sampling locations that were identified
as Class III according to the Qualitative Evaluation for Cross Section
(Table 7.3) because of the excessive lead concentration ranging from 0.93
to 4.5 times higher than the Class II standard. The river downstream re-
ceived elevated levels of organic pollutants and ammonia when flowing
through residential and industrial areas and some of the cross sections
were rated as Class V in the midstream. The Daqing River was the most
heavily polluted river at that time. Heavy metals were the main con-
taminants, particularly chromium and cadmium. All cross sections were
either Class V or worse than Class V. Moreover, upstream of the Daqing
River was already polluted by metal mining and smelting industrial was-
tewater euents, which were discharged with partial treatment or without
treatment.
In another long-term monitoring study, Zhang et al.77 showed a persisting
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public health risk due to mercury and total phosphorus in the Miyun Res-
ervoir watershed in Beijing during the period of from 1980 to 2003. However,
other heavy metals including lead and chromium did not exceed the Chinese
Surface Water Standards during the study period. Gao et al.78 performed a
preliminary health risk assessment of heavy metals (Cu, Hg, Cd and As) in
drinking waters using the health assessment model of the United States
Environmental Protection Agency (US EPA) throughout the Beijing area
about the same time. The concentrations of four heavy metals ranged from
0.81 to 6.96 mg L1 for copper, 0.34 to 0.82 mg L1 for cadmium, 0.10 to
0.74 mg 1L for mercury and 0.19 to 3.02 mg L1 for arsenic. The major cancer
risks were associated with arsenic in Tongzhou County (2 105 probability)
and with cadmium in Changping County (2.3 106 probability). These
levels of cancer risk are not considered to be excessive as compared with
background levels (i.e., 1 105 probability).79 The reported highest non-
carcinogenic risk in drinking water in Beijing at that time was associated
with mercury, followed by copper.
7.4.4 Human Health Risk Assessment of Heavy Metals

in Drinking Water Sources in China
A number of recent publications reported the results of human cancer and
non-cancer health risk assessment of heavy metals by ingestion of drinking
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160 Chapter 7
Table 7.10 Summary of recent health risk assessments of water in China.
Locations
(water source) Carcinogenic risk Non-carcinogenic risk Reference
Beijing Ingestion: As Hg and Cu (108 Gao et al.78
(2.0 105), Cd to 109)

(2.3 106)
Henan and Cr and Cd (lower Ba, Cu, Fe, Mn, Mo, Zhang et al.80
Shandong than 5 105) Ni, Pb, Se and Zn
Provinces (drinking:
(Yellow River) 1.13 109 to
6.06 108, dermal:
1.73 1013 to
3.46 1010)
Biyang County, As (drinking: Drinking: 2.1 107 Duan et al.81
Henan 2.5 106 to to 1.7 106,
(Yangtze and 5.2 106, dermal: dermal: 1.0 108
Huaihe Rivers) 1.1 107 to to 6.0 108
2.3 107)
Guangdong Cr (1.14 104 for Acceptable level Wang et al.82
(Dongjiang adults, 2.14 104
River) for children)
water in dierent parts of China. Table 7.10 summarizes the findings of such
recent research works. In addition to the preliminary health risk assess-
ment in Beijing performed by Gao et al.78 discussed earlier, Zhang et al.80
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tested the groundwater samples collected from two irrigation districts in

Henan and Shandong Provinces where water from the Yellow River is used
for irrigation. They found that the concentration of iron, manganese, sel-
enium and zinc in groundwater exceeded the standards in some of the
study areas, including Wucheng County, Donge County, Guan County and
Yucheng City in Shandong, as well as Fan County in Henan. The highest
carcinogenic risk was associated with chromium via drinking water in-
gestion, followed by cadmium, although they were all below the suggested
maximum allowable risk level of 5 105. The non-carcinogenic risks as-
sociated with metals are much lower than the maximum allowable levels.
Another study performed by Duan et al.81 in Biyang County, Henan, also
showed a similar, relatively low carcinogenic and non-carcinogenic
health risks.
On the contrary, Wang et al.82 reported a significantly higher health risk
associated with heavy metals in drinking water sources in townships in the
Dongjiang River Basin in Guangdong Province. The heavy metal of concern
was found to be chromium, followed by arsenic and lead. The cancer risk
associated with chromium in reservoir water was determined to be as much
as 1.14 104 for adults and 2.14 104 for children. The total carcinogenic
risk was higher than the suggested value of 5 105 in reservoir water, river
water and groundwater. It was found that the health risk was the highest in
reservoir water, while spring water posed lesser risks.
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7.4.5 Heavy Metal Contamination in the Sediments

of Rivers and Lakes
Although the concentration of heavy metals in the aqueous phase may be low,
it is well known that these metals have a tendency to accumulate in the bot-
tom sediments of rivers, estuaries and lakes.8385 For example, the significant
accumulation of heavy metals such as lead, copper, nickel and zinc were re-
ported in the Pearl River Delta in Guangdong Province and Hong Kong.85 The
urban rivers in the City of Hangzhou, Zhejiang Province, have been receiving
both industrial and domestic wastewaters, and the pollutants, including heavy
metals, have been found to accumulate in the sediments of the rivers.86 Both
water and sediments were sampled in six targeted rivers. Four heavy metals
were analysed, namely, lead, cadmium, copper and zinc. Based on the in-
vestigation results, water quality of all sampled cross sections were Class V due
to ammonia nitrogen and total phosphorus as the main pollutants. The
aqueous-phase concentrations of four heavy metals were within the range of
Class I to Class II, but sediments contained elevated levels of lead, zinc and
copper compared with the background levels and indicated a slight degree of
hazard according to an ecological risk assessment. Cadmium reached a severe
pollution level. The key pollution sources were identified as machine manu-
facturing, dyeing, papermaking and chemical industries along the rivers.
Lake sediments tend to accumulate more heavy metals than those in rivers
because of the longer hydraulic retention time. Huang et al.87,88 studied the
distribution and accumulation of several heavy metals including lead, cad-
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mium, arsenic, copper and zinc in Baihua Lake, which is one of the source
water reservoirs for Guiyang City in Guizhou Province. The surface area and
capacity of the lake are 14.5 km2 and 190 million m3, respectively. There were
seven headwater streams and most of them were seriously aected by the
development of industrial and agricultural activities, as well as domestic
sewage. The highest concentrations of heavy metals, including lead, cad-
mium, arsenic, copper and zinc, in ten sediments samples from Baihua Lake
were 29.7, 1.23, 74.1, 116.0 and 449.6 mg kg1, respectively. Among the heavy
metals evaluated, the loadings of cadmium and arsenic represented critical
factors in ecological hazards in the lake.
Recently, a significant increase in heavy metal content of surface sedi-
ments over the last 30 years (from 1980 to 2010) has been recognized in
Chaohu Lake in Anhui Province.89 Chaohu Lake is the largest lake in the
province and the fifth largest freshwater lake in China. Besides the heavy
metal pollution, serious water quality issues including algal bloom have
been reported around this lake.90 The sediment samples collected from the
lake showed elevated levels of manganese (44% of the area), zinc (20%), iron
(16%), arsenic (14%), chromium (6%) and nickel (6%). Chromium, copper,
zinc and arsenic concentrations in the lake sediments had increased by
200% as compared with the data from the 1980s in the western lake, where
major urban development in Hefei and agricultural activities had aected
the deteriorating water quality.
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162 Chapter 7
7.5 Concluding Remarks

Owing to their frequent occurrence and high public health relevance, heavy
metals are unquestionably one of the most important pollutants of concern
in the water resources in China. Cadmium, mercury, hexavalent chromium,

lead and arsenic are the key heavy metals and their occurrences have
caused considerable concerns because of the potential impacts on human
health and the environment. In addition to these key heavy metals, elevated
levels of other heavy metals, such as zinc and copper, have often been de-
tected in the water resources in China and regarded as a public health risk
factor. Antimony is another toxic heavy metal that can be of specific im-
portance in China.
The discharge of acidic industrial wastewater such as acid mine drainage
and metal processing wastewater into surface water, as well as the illegal
dumping of solid waste, are by far the most important sources of heavy metal
pollution in China. Drinking water sources, including major rivers, small
rivers, local reservoirs and groundwater aquifers, are contaminated by those
inadequately treated euents from industries in many parts of the country.
Although some of the health risk assessment studies indicated relatively small
carcinogenic and non-carcinogenic risks via drinking water consumption, the
true impacts of heavy metal pollution on public and environmental health
should not be underestimated because of the probable accumulation of these
elements in the other compartments of the environment.
In order to improve the current levels of heavy metal pollution in China,
11:26:06.
the enforcement of current water quality standards and proper implemen-

tation of eective industrial wastewater treatment will be essential. Cost-
eective remediation of contaminated sites will also be necessary. However,
the tension between economic growth and environmental protection always
exists at local, regional and national levels, and the prioritization of en-
vironmental protection over economic growth can be rarely seen, not only in
developing countries, but also in developed ones. In particular, people living
in rural areas may be overlooked intentionally or unintentionally.
There are signs of potential improvement. Chinas most recent 12th Five-
Year Plan (20112015) released in March 2011 includes new initiatives to
protect the environment from chemical risks and to develop a state en-
vironmental protection standard. This Five-Year Plan signifies the import-
ance of environmental protection and pollution control to protect public
health. More specifically, the MEP has completed the plan for heavy metal
integrated pollution control as part of the Five-Year Plan. Although the true
outcome of this progressive plan has yet to be seen, certain improvements in
the environmental quality can be expected. However, data on heavy metals
occurrence in the environment appear to still be scarce, but necessary in
order to properly assess the current public and environmental risks associ-
ated with these pollutants. More work will be needed to understand the true
extent of this important environmental problem in the worlds most popu-
lous country and ultimately solve the problem within a reasonable time.
View Online
Acknowledgements
The authors would like to thank Mr Kun Li at the Chinese Academy of Sci-
ences in Beijing for providing help with data collection. The editorial help of
Ms Kelly M. Huston at PACE is also gratefully acknowledged.
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CHAPTER 8
Heavy Metals Distribution

in Surface Water Samples
of Taihu Lake, China
HOU-QI LIU,a,b YING LIU,a GUANG LIUa,b AND XUE-BIN YIN*a,b
a
Advanced Laboratory of Environmental Research and Technology
(ALERT), Joint Advanced Research Center, USTC-City-U, Suzhou 215123,
China; b Environmental Science Division, School of Earth and Space
Science, University of Science and Technology of China (USTC), Hefei
230026, China
*Email: xbyin@ustc.edu.cn
11:26:23.
8.1 Introduction
Taihu Lake is the third largest freshwater lake in China. The entire area of
the Taihu Lake basin is approximately 36 500 km2, and the actual lake region
is about 2338 km2, with a mean water volume of around 44.297 108 m3.1
The run-o sources of the lake are mostly from the mountainous west and
southwest, and outflows are located throughout East Taihu Lake.24 Taihu
Lake is a large sedimentary shallow lake with a mean depth of 1.9 m, and
there are 172 rivers or channels connected to it.5 As a densely-populated and
highly-industrialized area, the Taihu Lake basin plays an important role in
both the economical and social development of China.68 Taihu Lake is the
most important water supply source and is an attractive site for tourism,
shipping and recreation for Shanghai, Wuxi, Suzhou and other nearby
cities. However, owing to rapid development and industrial and agricultural
production in this region, the lake has been polluted from a range of

168
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Heavy Metals Distribution in Surface Water Samples of Taihu Lake, China 169
sources, such as industrial wastewater, sewage and agricultural waste.9

This waste input has led to a high concentration of organic pollutants, nu-
trients and heavy metals in the lake water. The pollution or contamination
of the lake water has caused algal blooms (which have been studied
extensively10,11) and significantly aect the water supply in this region.12

Thus, the pollution situation of Taihu Lake has become a particularly severe
problem, because of the serious eects on the natural environment and the
economic development in the region.13 Although the Taihu Lake region
accounts for only 0.4% of the total area of China and 2.9% of the nations
population, it contributes more than 14% of Chinas gross domestic pro-
duction (GDP).14,15 In the early 1980s, the water quality of Taihu Lake began
to degrade. By the late 1980s Grade III was met in most areas, however, by
the late 1990s it was Grade IV or V.16
This study aimed to characterize the concentrations of heavy metals (such
as Cr, Pb, Cd, Zn, Cu and As) in surface water samples of Taihu Lake, and to
understand the metal pollution situation of the lake, which could provide a
reference for the utilization of resources and pollution treatment.
8.2 Methods
8.2.1 Sample Collection
Forty-nine surface water samples were collected in February 2010 from
11:26:23.
various locations around Lake Taihu (Figure 8.1 and Table 8.1). All the
samples were stored at 4 1C until the analyses.
Figure 8.1 Map of Taihu Lake showing the distribution of the sampling sites.
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170 Chapter 8
Table 8.1 Details of sampling sites.
Region No. Longitude Latitude No. Longitude Latitude
0 00 0 00 0 00
East Taihu Lake 1 120121 09 31107 30 12 120125 37 31111 0 3400
2 120121 0 5400 31108 0 1800 13 120123 0 5300 31111 0 1100
3 120123 0 2800 31109 0 4300 14 120121 0 3600 31110 0 2800

4 120124 0 0200 31110 0 1700 15 120120 0 5200 31110 0 2300
5 120125 0 2000 31111 0 0200 16 120120 0 2300 31110 0 3600
6 120121 0 2900 31111 0 5500 17 120120 0 5900 31109 0 2300
7 120126 0 0800 31112 0 2300 18 120120 0 1500 31106 0 3100
8 120127 0 4900 31113 0 1700 19 120118 0 3900 31104 0 4900
9 120127 0 5300 31113 0 2200 20 120117 0 2400 31103 0 4600
10 120127 0 5300 31113 0 2500 21 120119 0 0600 31101 0 3700
11 120126 0 5900 31112 0 1700 22 120119 0 1900 31102 0 0900
North Taihu Lake 23 120112 0 0800 31125 0 5300 30 120118 0 3300 31122 0 4200
24 120114 0 5800 31123 0 3700 31 120117 0 2700 31120 0 1200
25 120117 0 0600 31124 0 2400 32 120114 0 0900 31120 0 0300
26 120118 0 5900 31125 0 0300 33 120112 0 3100 31123 0 2400
27 120123 0 2600 31126 0 1800 34 120112 0 1300 31127 0 5400
28 120124 0 5400 31127 0 0000 35 120109 0 0200 31123 0 0900
29 120121 0 2100 31124 0 4800 36 120108 0 2100 31117 0 3900
West Taihu Lake 37 120105 0 1100 31115 0 0800 44 119156 0 1400 31107 0 4000
38 120102 0 2300 31112 0 5200 45 119155 0 0200 31107 0 4000
39 119158 0 1200 31112 0 3300 46 119155 0 5600 31118 0 4100
40 120157 0 1200 31116 0 1900 47 119155 0 3900 31118 0 4700
41 120159 0 3200 31118 0 2500 48 120113 0 2800 31128 0 2100
42 120102 0 4300 31119 0 3800 49 120128 0 0400 31112 0 5800
43 120110 0 1400 31128 0 1500
11:26:23.
8.2.2 Sample Processing and Analytical Procedures

Water samples were filtered through 0.45 mm syringe filters and pure nitric
acid (2%, v/v) was added. All samples were analysed by using an inductively
coupled plasma atomic emission system (Optima 2100 DV, PerkinElmer).
ArcGis software was used for the data processing.
8.3 Results
8.3.1 Chromium (Cr)
The Cr concentrations for all samples taken from Taihu Lake were low
(o0.01 mg L1), which were better than Grade I surface water standards of
China.17
8.3.2 Lead (Pb)

For East Taihu Lake, only in two samples were the Pb concentrations greater
than 0.01 mg L1 and this falls within Grade III water quality. However, all
the other samples showed Pb concentrations below 0.01 mg L1, which fit
with Grade I water quality.17 In two samples the Pb concentration exceeded
View Online
11:26:23.
Figure 8.2 Pb concentration distribution in Taihu Lake.
0.05 mg L1 (water quality level, Grade V), which is above the fishery
water quality standards of China (Pb r 0.05 mg L1).17,18 The other samples
had Pb concentrations below 0.01 mg L1, which qualify for Grade I water
quality.17 In West Taihu Lake, the Pb concentrations of all samples ex-
ceeded 0.01 mg L1, except for two, which were higher than 0.05 mg L1
(Figure 8.2).
8.3.3 Cadmium (Cd)

West Taihu Lake was the region that was most seriously contaminated with
Cd. Nearly half of the collected samples showed Cd concentrations of more
than 0.01 mg L1, and the water quality in this region was below Grade V.17
Except for one sample at North Taihu Lake where the Cd concentration was
0.0019 mg L1, the Cd concentrations in all other regions of the lake were
below 0.001 mg L1.
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172 Chapter 8
8.3.4 Zinc (Zn)

In general, Zn pollution in Taihu Lake was not serious. Only one sample in
East Taihu Lake had a Zn concentration higher than 0.05 mg L1. In the
other samples, the Zn concentrations were less than 0.05 mg L1, which
meets the drinking water standard limits for China (Zn r 1.0 mg L1) and
this level satisfies Grade I water quality17,19 (Figure 8.3).
8.3.5 Copper (Cu)

The Cu concentration in Taihu Lake did not exceed the standards for the
prescribed limits for drinking water in China (Cu r 1.0 mg L1) or the World
Health Organizations (WHO) standards for drinking water (Cu r 2.0 mg L1).19
The Cu concentrations in all samples meet the Grade II surface water standard
or better17 (Figure 8.4).
11:26:23.
Figure 8.3 Zn concentration distribution in Taihu Lake.

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11:26:23.
Figure 8.4 Cu concentration distribution in Taihu Lake.
8.3.6 Arsenic (As)

The As concentration was more than 0.05 mg L1 in the Liangxi River of
North Taihu Lake, which means the water quality was Grade IV.17 The
concentrations of As in other samples were less than the prescribed limits
for drinking water quality standards of China (As r 0.05 mg L1), and meet
the Grade surface water standard. However, the As concentrations in most
samples exceeded the limit for the WHOs drinking water quality standards
(As r 0.01 mg L1)17 (Figure 8.5).
8.3.7 Cobalt (Co)

Co concentrations in all samples in East Taihu Lake were less than
0.001 mg L1. In North Taihu Lake, the Co concentrations ranged from 0.001
to 0.01 mg L1, while in West Taihu Lake they ranged from 0.001 to
0.02 mg L1.
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174 Chapter 8
11:26:23.
Figure 8.5 As concentration distribution in Taihu Lake.
8.3.8 Nickel (Ni)

Ni belongs to the group of general toxicant elements. Except for three
samples in West Taihu Lake (Ni 4 0.02 mg L1), in all the other samples the
Ni concentrations were less than 0.02 mg L1, which meet the specified
limits for the drinking water standard of China (Ni r 0.02 mg L1) and the
limits of the WHOs drinking water quality standard (Ni r 0.02 mg L1).19
8.3.9 Tin (Sn)

Sn concentrations in all samples were less than 0.01 mg L1. In East and
North Taihu Lake, the Sn concentration ranged from 0.001 to 0.005 mg L1.
Sn concentration was a little higher in West Taihu Lake. In this region, only
two samples showed Sn concentrations below 0.002 mg L1, whereas in all
other samples the Sn concentrations ranged from 0.003 to 0.008 mg L1.
View Online
8.3.10 Manganese (Mn)

In East Taihu Lake, only in one sample was the Mn concentration
(0.1009 mg L1) higher than the drinking water standard of China
(Mn r 0.1 mg L1). Mn concentrations in the other sampling locations were
less than 0.1 mg L1.
8.4 Discussion and Conclusions

Cr is an important index for environmental monitoring. Cr compounds are
toxic, which can seriously jeopardize human health and are considered to be
carcinogenic substance by toxicologists.16 Pb compounds are noxious and
can threaten human health, mainly through inhibiting the synthesis of
haemoglobin and causing damage to hematopoietic systems, the cardio-
vascular system, nervous system and kidneys. High concentrations of Zn
may also produce harmful problems to human health. Cu is an essential
trace element for humans, but excessive Cu can be detrimental to humans,
animals and aquatic organisms. In addition, Cu may significantly inhibit the
self-purification capacity of aquatic systems. Arsenic can cause strong toxic
eects on plants and animals. It can enter the aquatic food chain via bio-
logical uptake and be a risk to the health of animals and humans. Arsenic is
considered to be a carcinogenic, mutagenic substance and has endocrine
disrupting eects.12 Co is an essential trace element for nitrogen fixation in
cyanobacteria and other microorganisms, and it is also necessary for ani-
11:26:23.
mals and humans. However, excess amounts of Co are harmful to

humans, animals and plants.2022 Excessive intake of Mn can cause damage
to the human nervous system, and lead to fatigue, headaches and other
symptoms.22
East Taihu Lake had the lowest Pb contamination compared with the
other regions. However, in several samples the Pb concentrations exceeded
the drinking water standard of China and the specified limits of the WHOs
drinking water standard, and the Pb concentrations of all samples also ex-
ceeded the fishery water quality standards of China. In addition, Mn con-
centration in one sample in East Taihu Lake exceeded the drinking water
standard. The concentrations of other elements (Cr, Cd, Zn, Cu, As, Co, Ni
and Sn) in East Taihu Lake were lower.
The North Taihu Lake region has highly-developed industries, intensive
tourism and a dense population, which leads to more severe pollution in this
part of the lake. The Pb concentration in some sites exceeded the drinking
water standard of China and the specified limits of the WHOs drinking
water quality standard. Mn, Cr, Cd, Zn, Cu, As, Co, Ni and Sn concentrations
were also lower in North Taihu Lake.
The West Taihu Lake is wider than the other lake regions, and there are
also sources of high pollution. The discharge of polluted water from in-
dustries, wastewater treatment and agricultural wastes resulted in high
concentrations of Cr, Pb and Ni in this area. In most sampling sites the
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176 Chapter 8
concentrations of Cr in the water exceeded the limits for Grade V surface

water standards of China.
References
1. Y. W. Chen, B. Q. Qin and X. Y. Cai, J. Lake Sci., 2001, 13(1), 63.

2. J. Y. Zhu, H. S. Fang and Y. J. Dou, Shanghai Environ. Sci., 1998,
17(11), 25.
3. H. Z. Liu, Y. Q. Chen and Z. S. Liang, Environ. Protect., 1998, 12, 9.
4. B. Q. Qin, P. Z. Xu, Q. L. Wu, L. C. Luo and Y. L. Zhang, Hydrobiologia,
2007, 581, 3.
5. P. Xu and B. Qin, J. Lake Sci., 2005, 17(3), 213.
6. M. Qiao, C. X. Wang, S. B. Huang, D. H. Wang and Z. J. Wang, Environ.
Int., 2006, 32, 28.
7. S. C. Sun and Y. P. Huang, Taihu Lake, Chinese Ocean Press, Beijing,
1993, 1.
8. Y. Zheng, X. J. Wang and Y. C. Jiang, Geogr. Territor. Res., 2001, 17(1), 40.
9. G. Lai and G. Yu, presented at The American Society of Agricultural and
Biological Engineers, New Bern, NC, 2006, 325.
10. P. P. Shen, Q. Shi, Z. C. Hua, F. X. Kong, Z. G. Wang, S. X. Zhuang and
D. C. Chen, Environ. Int., 2003, 29(5), 641.
11. H. Duan, S. Zhang and Y. Zhang, J. Lake Sci., 2008, 20, 145.
12. P. Pu and J. Yan, J. Lake Sci., 1998, 10(suppl), 1.
13. Q. M. Cai, Taihu Lake Environmental Ecological Research, Meteorological
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Press, Beijing, 1998.

14. L. Shen, G. F. Lin and J. W. Tan, Chemosphere, 2000, 41, 129.
15. G. S. Yang and J. D. Wang, Tai Lake Basin: Economic Development, Water
Environment and Water Disasters, Science Press, Beijing, 2003.
16. X. C. Jiang, S. K. Liu and Z. S. Zhang, China Lake Environment, vol. 1,
Chinese Ocean Press, Beijing, 1995.
17. State Standard of the Peoples Republic of China, Surface Water En-
vironmental Quality Standards, GB 3838-2002, 2002.
18. State Standard of the Peoples Republic of China, Water Quality Standard
for Fisheries, GB11607-89, 1990.
19. State Standard of the Peoples Republic of China, Standards for Drinking
Water Quality, GB5749-2006, 2006.
20. O. Holehensen, Physiol. Plantarum, 1954, 7, 665.
21. H. M. Reisenaner, Nature, 1960, 186(472), 375.
22. A. Kabata Pendias, Inc., Boca Raton Florida, CRC Press, 1984.
CHAPTER 9
Use of Nanotechnology against

Heavy Metals Present in Water
MING ZHANG,a BIN GAO,*a JIN JIN,b HAO CHEN,a YING YAO,a
JUNE FANGa AND ANNE ELISE CREAMERa
a
Department of Agricultural and Biological Engineering, University of
Florida, Gainesville, FL 32611, USA; b Department of Geological Sciences,
University of Florida, Gainesville, FL 32611, USA
*Email: bg55@ufl.edu
9.1 Introduction
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Toxic heavy metals, such as arsenic, cadmium, cobalt, chromium, copper,

mercury, nickel, lead and selenium, are used in industrial manufacturing
and are widely distributed in the earths crust. These metals are found in
electronics, pesticides, batteries, electroplating technology and other ma-
terials,13 so there are a number of ways that they can get into water systems,
especially groundwater aquifers. The contamination of drinking water by
heavy metals has become a serious threat to public health and currently
aects millions of people across the world.4,5 Heavy metal toxicity can cause
damage or reduce mental and central nervous functions, lower energy levels
and damage blood composition, lungs, kidneys, liver and other vital organs.
Long-term exposure may result in slow progressive physical, muscular and
neurological degeneration that mimics Alzheimers disease, Parkinsons
disease, muscular dystrophy and multiple sclerosis.6 Repeated long-term
contact with some metals (or metal compounds) may cause cancer.7 To
prevent deteriorating water quality, the World Health Organization and the
US Environmental Protection Agency have produced standards for heavy

177
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178 Chapter 9
metals in drinking water. The new standards inevitably require many water
utilities to upgrade their current treatment systems or to consider new
purification technologies. During the past decades, much eort has been
spent on developing high-eciency and cost-eective adsorbents for heavy
metal removal, such as metal oxides, modified activated carbons, resins and
gels.810 With the pressures of climate change, population growth and in-
dustrialization of developing countries, the demand for clean drinking water
is increasing. Therefore, ecient treatment of the wastewater is more im-
portant than ever.
In recent years, nanotechnology has successfully introduced dierent
types of nanomaterials for water treatment. Some benefits include increased
eciency for contamination removal, reduced consumption of raw materials
and substitution of more abundant and less toxic materials than ones cur-
rently used.11,12 As absorbents, nanomaterials have been shown to work
eectively against heavy metal contaminants in aqueous systems.1315
9.2 Nanoclays
Clays, or hydrous aluminosilicates, can be broadly defined as the minerals
that make up the colloid fraction (o2 mm) of soils, sediments, rocks and
water. Individual natural clay particles are less than 0.004 mm in diameter;
to be considered nanosized, the clay must be o100 nm in diameter. Most of
the nanoclay for industrial use is extracted from the natural deposits.16
Natural nanoclay, such as montmorillonite, bentonite, kaolinite, hectorite
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and halloysite, can be classified by chemical composition and morphology.

It is common for fine-grained clay minerals to have a sheet-like structure.
These particles are generally referred to as phyllosilicates, a term which
encompasses all hydrous silicates with layered sheets (Figure 9.1).
Figure 9.1 Structure of 2 : 1 phyllosilicates.88

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Use of Nanotechnology against Heavy Metals Present in Water 179
In the environment, clays are important in the adsorption of both heavy

metals and organic contaminants because of their negatively charged ex-
change sites. Most clay minerals acquire a negative charge by a cation-
exchange mechanism, where the silica cation (Si41) is substituted by the
aluminium cation (Al31) in the clay sheet structure. Firstly, isomorphous

substitution produces the capacity in clay sheets to hold positive charges.
Next, because cations, i.e., Fe31 and Al31, are small enough to enter the
tetrahedral coordination with oxygen, they act as a substitute for the silica
cation. Similarly, cations, i.e., Mg21, Fe21, Fe31, Li11, Ni21 and Cu21, can be
substituted for Al31 in the octahedral sheet. Large-sized cations, i.e., K1,
Na1, and Cs1, can be located between the layers and are referred to as
interlayer cations. Anionic substitution is also possible, as the hydroxyl ion
(OH) can be substituted by F. Several types of clay minerals are present in
soils with varying levels of CEC, or cation-exchange capacity. For example,
kaolinite clay found in most soils has a CEC of 35 meq per 100 g, while
smectite and vermiculite CEC can be as high as 100 meq per 100 g. Com-
pared with clay, nanoclay has a higher cation exchange ability due to its
larger surface area and more reactive sites on the surface.17
9.2.1 Nano-Kaolinite
Kaolinite has a plate sheet structure with a diameter of approximately 0.2
10 mm and a thickness of 0.7 nm. The 1 : 1 sheet structure of kaolinite is
made up of an [Si2O5]2 sheet and an [Al2(OH)4]2 sheet. The sheets are so
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tightly stacked that water molecules are unable to pass between them.
Though kaolinite is the least reactive of the clays, its metal adsorption ability
is highly pH dependent. Kaolinite is a common sorbent for heavy metals.18
This adsorption process is usually accompanied by the release of hydrogen
cations from the edge sites of kaolinite. When cations, i.e., Pb21, Zn21 or
Cd21, are adsorbed, the displacement of H1 ions could create swelling,
flocculation or compressibility.19 The substitution of H1 cations for heavy
metal cations could influence the van der Waals forces within the kaolinite
structure.20 Adsorption may also take place on the flat exposed planes of the
silica and the alumina sheets.
9.2.2 Nano-Montmorillonite
Montmorillonite is a member of the 2 : 1 smectite family; it has two tetra-
hedral sheets with an octahedral sheet between them. The silica
aluminasilica units cause a very weak bond and an excellent cleavage
between these units. Owing to the unique structure of montmorillonite,
water and other polar molecules can enter between the layers, causing ex-
pansion. The layers are separated by a regular van der Waals gap due to the
negative charges. The layer thickness is around 1 nm and the other di-
mensions may vary from 300 to several microns. Montmorillonite clay has
excellent sorption and possesses sorption sites that are available within its
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180 Chapter 9
21
interlayer space as well as on the outer surface and edges. Naturally oc-
curring montmorillonite clay has a CEC of between 60 and 100 meq per
100g. The nanocomposites prepared by montmorillonite should have a CEC
of 70150 meq per 100g.22 Compared with kaolinite, montmorillonite has a
very large adsorption capacity; the values may be three times higher.23
9.2.3 Nano-layered Double Hydroxides

Layered double hydroxide (LDH), also called anionic clay, has been known
for a considerable time and is widely studied. The structure is composed of
positively charged brucite-like layers and the interlayer galleries that separ-
ate them (Figure 9.2). The interlayer galleries are made up of charge-
balancing anions and water, which provide significant anionic exchange
capacity.24 This feature makes LDH unique among inorganic materials.
Depending on their constituents, LDH may be hydrophobic or hydrophilic.
They have demonstrated the ability to absorb a wide range of contaminants,
including Cr, Se and As through ion-exchange and complexation mech-
anisms.25,26 LDH clays can even adsorb negatively charged organic con-
taminants between their positively charged layers. LDH nanoparticle clays
have even better potential for remediation because of their increased surface
area. The surface of LDH can be modified to be more hydrophobic with
organics and more compatible with polymers.27 Coatings with ligands in the
clay can alter its charge and further change its ability to sorb heavy metals.28
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9.3 Nanosized Metal Oxides

Nanosized metal oxides, including nanosized titanium oxides, ferric oxides,
aluminium oxides, manganese oxides, magnesium oxides and cerium oxi-
des, provide high surface area and specific anity for heavy metal
Figure 9.2 Schematic structure of layered double hydroxide.89

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adsorption from aqueous systems. Recently, nanosized metal oxides have

become a hot topic. Researchers are striving to develop new technologies to
synthesize the metal oxides, evaluate their removal of heavy metals under
varying experimental conditions, reveal the underlying mechanism respon-
sible for metal removal, based on modern analytical techniques (XAS, ATR-
FT-IR, NMR, etc.) or mathematical models, and develop metal oxide based
materials of better applicability for practical use (such as granular oxides or
composite materials).29
9.3.1 Nanosized Titanium Oxides

The eects, controlling factors and mechanisms of As removal from aqueous
solution by nano-TiO2 have been extensively studied.3032 It was found that
adsorption of As(III) and As(V) on nano-TiO2 obeyed the Freundlich model
and followed pseudo-second order kinetics (Figures 9.3 and 9.4).32 As(V) was
reported to be eectively removed at pH o 8 and maximum removal for
As(III) was observed at pH 7.5.32 The formation of inner-sphere surface
complexes is proposed to be the adsorption mechanism for both inorganic
As and organoarsenic onto TiO2.32,33 Eective removal of As from water
depends on the eciency of oxidization of As(III) to As(V) before adsorption.34
Photocatalytic oxidation is widely employed in the As removal processes
because it is a cheap yet robust technique used to oxidize As(III) to As(V)34,35
with nano-TiO2 under illumination with UV light. Recent eorts have been
made to modify the TiO2 for greater As adsorption. For instance, hydrous
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TiO2 nanoparticles, which were synthesized using TiCl4, were found to have
an adsorption capacity of 96 mg g1 at pH 9.36 FeTi binary oxide nano-
particles were recently produced to remove As from the water with a high
adsorption capability of 33 mg g1 at pH 7.37 In addition to As, nano-TiO2 has
been used to treat other heavy metals in water such as Cd38 and Pt.39
9.3.2 Nanosized Ferric Oxides

Fe-based nanoparticles, such as maghemite, akaganeite and zero-valent Fe,
have been widely used for As removal in water.4042 For instance, strong
adsorption of As(III) and As(V) onto nanoscale Fe oxide has been documented
and the adsorption was found to depend on the As oxidation state, experi-
mental conditions and the mineralogy of the Fe oxide. Mayo et al.42 observed
the removal of both As(III) and As(V) by magnetite nanoparticles and reported
the inverse relationship between adsorption capacities and particle sizes
(Figure 9.5). In addition, nanocrystalline akaganeite has been shown to be an
eective adsorbent for As(III) and As(V).4345 Take As(V) for example, the ad-
sorption capacity of akaganeite for As(V) was found to be 120 mg g1, much
higher than that of goethite.45 Fe-based nanoparticles have also been used to
remediate water contaminated by many additional heavy metals other than
As. Pb,46 Cr,44 Co,46 Zn,47 Cu,48 Cd,46 Ba49 and Pt group metals (Pd, Pt, Rh)50
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182 Chapter 9
Figure 9.3 Arsenic adsorption isotherms in a 1.0 M TiO2 and 0.04 M NaCl suspen-
sion at equilibrium pH 7.0 0.1, equilibrium time 22 h. The lines are
model calculations.32
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Figure 9.4 Arsenic adsorption isotherms in a 1.0 M TiO2 and challenge water at
equilibrium pH 7.0 0.1, equilibrium time 22 h. The lines are model
calculations.32
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Figure 9.5 Adsorption of As(V) on magnetite nanoparticles with dierent sizes

(i.e., 12, 20 and 300 nm) shows the inverse relationship between
adsorption capacities and particle sizes.42
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have all been reported to be removed by maghemite, akaganeite or zero-

valent Fe.
9.3.3 Nanosized Aluminium Oxides

Investigations on heavy metal removal using Al-based nanomaterials have
also been conducted, but less frequently than those using Ti- and Fe-based
nanocompounds. Aluminium oxide nanoparticles incorporated in amine
rich cryogels were found to eectively remove As(V) from water at pH 28,
with an adsorption capacity of 20.3 mg g1.51 Pacheco et al.52 reported that
the adsorption of Hg by alumina nanoparticles could be as high as 100%.
Zhang et al.53 demonstrated that nano-Al2O3 is an eective sorbent to re-
move Tl(III) in water and the adsorption capacity can also reach 100%. The
mesoporous g-Al2O3 spherical nanoparticles have high surface area and high
adsorption capacity for dissolved As; therefore, they have potential for the
treatment of As-contaminated water.54 In addition, modification has been
made on Al-based nanomaterials to improve performance of heavy metal
removal. For instance, Basu et al.55 reported that their synthesized FeAl
mixed oxide nanoparticles have an adsorption capacity of up to 54.6 mg g1
for As(V) in water. Another type of FeAl binary oxide was synthesized by
Hong et al.56 to remove As from water. Their binary oxide presented greater
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184 Chapter 9
As(V) and As(III) adsorption capacity than conventional Fe oxide due to its
large surface area; this may serve as a promising adsorbent for As in water.
9.3.4 Other Nanosized Metal Oxides

The removal of heavy metals from water has also been explored using
nanomaterials made of various metals, such as Zn,57 Mg,58 Sn,59 Ni,60 Zr60
and Mn.61
9.4 Nanostructured Carbon Materials

Nanostructured carbon is a versatile adsorbent that is frequently used in the
removal of various pollutants including heavy metals from aqueous solu-
tions.62,63 In the past decades, carbon nanotubes and graphene are some of
the most intensively explored nanostructured carbon materials among all of
the carbon-based materials.6467 This interest mainly resides in their unique
physical and chemical properties. Carbon nanotubes and graphene were
chosen as absorbents because of their high surface area, excellent mech-
anical strength, light weight and ample number of functional groups.
9.4.1 Carbon Nanotubes

Carbon nanotubes (CNTs) are one of the most commonly used building
11:26:28.
blocks of nanotechnology. CNTs can be visualized as a sheet of graphene

that has been rolled into a tube, and divided into multi-walled carbon
nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs)
(Figure 9.6) according to the carbon atom layers in the wall of the nano-
tubes.68 CNTs, in particular, have received special attention for their ex-
ceptional water treatment capabilities and have been shown to possess great
potential as superior adsorbents for removing many types of heavy metal
contaminations such as Pb21, Cd21, Ni21 and Cu21, etc.64 (Table 9.1).
The mechanisms by which the heavy metal ions are sorbed onto CNTs are
very complicated and appear to be attributed to electrostatic attraction,
sorptionprecipitation and chemical interaction between the metal ions and
the surface functional groups of CNTs.
It is commonly believed that the chemical interaction between the metal
ions and the surface functional groups of CNTs is the major sorption
mechanism. Protons in the carboxylic and phenolic groups of CNTs ex-
change with the metal ions in the aqueous phase. The solution pH drops
once the sorption of metal ions onto CNTs reaches equilibrium. This could
be explained by the release of H1 from the CNT surface where metal ions are
sorbed, consequently decreasing the solution pH. The drop in pH value in-
creases with a rise in initial metal ion concentration, which clearly indicates
that sorption of more metal ion onto CNTs causes the release of more H1
ions from the surface site of CNTs into the solution.69
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Table 9.1 Maximum sorption capacities of metal ions on CNTs.
Heavy
CNTs metal Qm (mg g1) Conditions Reference
Acidified Pb 21
85 [Pb21]initial 50 mg L1 90
MWCNTs with 6 h acidified

MWCNTs
MWCNTsiron Ni21, Ni21 : 9.18 [Ni21]initial 6.0 mg L1, 91
oxide Sr21 Sr21 : NA m/V 0.75 g L1
CNTs Pb21 102.04 pH 5, 40 mg L1 of 92
CNTs, contact time
80 min, agitation
speed 50 rev min1
Oxidized Cd21 25.7 Ultrasonically 45 min at 93
MWCNTs 45 1C
Oxidized Cr(VI) 4.262 m/V 1.0 g L1, 94
MWCNTs T 20 2 1C,
pH 2.05, contact
time 165 h
CNTs Cu21 67.9 Dose of adsorbents 95
immobilized by 0.05 g, pH 5.0,
calcium alginate T 25 1C
MWCNTs Ni21 MWCNTs: m/V 0.2 g L1, pH 6 96
oxidized CNTs 18.08
Oxidized
CNTs: 49.26
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Figure 9.6 Transmission electron microscope (TEM) image of HiPCO SWNT:

(A) unpurified with B35 wt% metal catalyst impurities and (B) purifi-
cation with B2.4 wt% metal catalyst impurities.68
9.4.2 Graphene
Graphene, a rising star among 2D carbon materials, led scientists to being
awarded the Nobel Prize in 2010. It is a one atom thick material made up of
sp2-bonded carbon atoms. Owing to the high conductivity, large surface area,
low mass and excellent mechanical and thermal properties,7072 graphene-
based materials have shown excellent potential for various applications.7375
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186 Chapter 9
Graphene oxides (GO), which are considered as oxidized graphene, contain

oxygen-containing functional groups on the surfaces (Figure 9.7).76,77
Unlike carbon nanotubes, which require special oxidation processes to
introduce hydrophilic groups to improve heavy metal ion sorption, graphene
oxide nanosheets are prepared from graphite using Hummers method to

introduce oxygen-containing functional groups, such as COOH, CO
and OH, on the surfaces of the graphene oxide nanosheets. These
functional groups, along with their large surface areas (theoretical value of
2620 m2 g1), enable graphene oxide and its composites to have a high
sorption capacity in the preconcentration of heavy metal ions from large
volumes of aqueous solutions (Table 9.2).
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Figure 9.7 TEM image of graphene oxides.67
Table 9.2 Maximum sorption capacities of metal ions on graphene.

Heavy Qm
Graphene metal (mg g1) Conditions Reference
Graphene oxides Cu21 46.4 [Pb21]initial 50 mg L1, 97
pH 5.0
Functionalized Cd21 73.42 pH 6.2, contact time 40 min 98
graphene
Functionalized Pb21 406.6 pH 5.1, contact time 40 min 98
graphene
GrapheneMnO2 Ni21 46.6 Agitation speed 50 rev min1 99
for 3 h, T 25 1C
Reduced Ni21 3.0 Agitation speed 50 rev min1 99
graphene oxides for 3 h, T 25 1C
Graphene oxides Co21 68.2 pH 6, [Co21]initial 30 mg L1, 100
T 30 1C, m/V 0.1 g L1
Reduced As(V) 5.83 pH 7, contact time 2 h, 101
GOFe3O4 T 20 1C
Reduced As(III) 13.1 pH 7, contact time 2 h, 101
GOFe3O4 T 20 1C
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The mechanisms of heavy metal ions absorbed onto graphene are pretty
similar to those of heavy metal ions absorbed onto CNTs. The high disper-
sion property of graphene oxide nanosheets in aqueous solution is favorable
for the surface oxygen-functional groups to freely form strong complexes
with heavy metal ions.
9.4.3 Other Nanostructured Carbon Materials

The other nanostructured carbon-based absorbents that have been studied
for adsorption of heavy metal ions include activated carbon, carbon fibers,
nanoporous carbon and their composites.7880 These adsorbents have ex-
cellent removal eciencies for heavy metal ions; the rates are sucient to
meet pollution control requirements. Their large absorption capacity is
linked to well-developed internal pore structures, a large specific surface
area and the presence of a wide spectrum of surface functional groups.
9.5 Potential Negative Environmental Impact

of Nanotechnology
Nanotechnology is an enabling technology that deals with structures with at
least one dimension within the range of from 1 to 100 nm.81 Nanomaterials
possess unique physical and surface properties, which have inspired
plans for a wide spectrum of applications, such as healthcare, consumer
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products like cosmetics, ICT, food and feed, environmental health and
agriculture.82,83 A high surface area to volume ratio provides nanosized
materials with specific physico-chemical characteristics and high reactivity;
however, its applications also pose potential negative environmental
impacts.
One of the most famous examples is nano-silver used in nanoformula-
tions. Owing to the properties of silver at the nanoscale, such as biological
properties and unique optical and physical properties, nano-silver has been
used in an increasing number of consumer and medical products. Of the
more than 800 consumer products that contain nanomaterials, roughly 30%
are claimed to contain silver particles.81 Examples are food packaging ma-
terials and food supplements, odour-resistant textiles, electronics and
household appliances, cosmetics and medical devices, water disinfectants
and room sprays. Some of the applications of nano-silver have resulted in
concern amongst government agencies and the public. A recent study re-
vealed that the silver can easily leak into wastewater during washing and, as
a result, could disrupt helpful bacteria used in wastewater treatment facil-
ities or endanger aquatic organisms in lakes and streams.84 Nano-silver not
only has physical and surface properties that could pose a threat to human
and environmental health,85 but could also serve as a reservoir for toxic
silver ions. Recent research with zebra fish showed that single silver 12 nm
nanoparticles aected early development of fish embryos.85 In addition,
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188 Chapter 9
in vitro and in vivo toxicity studies with mammalian species have shown that
silver nanoparticles have the capability to enter cells and cause cellular
damage.86
Concerns about the safety of emerging nanotechnology have been on the
rise for the past few years. Consequently, more research is urgently needed
to investigate whether nanoparticles present a threat to environmental
health in general, as the direct and indirect exposure to nanomaterials in-
creases. The risk assessments of the engineered nanomaterials prior to their
application in the market and society are critical to ensuring a sustainable
nanotechnology industry.87
9.6 Conclusions
In this chapter, we provide a review of the removal of heavy metal con-
taminants using nanomaterials, including clays, metal oxides and carbon
materials. The chapter briefly addresses important material properties of the
nanomaterials that contribute to heavy metal removal from water, followed
by a critical explanation of the adsorption of heavy metal contaminants on
nanomaterial based on the literature currently available. Finally, potential
negative environmental impacts of nanotechnology are presented.
To date, nanomaterials are widely explored as highly ecient adsorbents
for heavy metal removal from water/wastewater. They exhibit various ad-
vantages such as fast kinetics, high capacity and preferable sorption
towards heavy metals in water and wastewater. Nevertheless, to further
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promote the practical application of nanotechnology in the abatement of

heavy metal pollution, some technical bottlenecks still exist that need to be
solved. For instance, when applied in aqueous solution, nanoparticles tend
to aggregate into large-sized particles and their loss of capacity seems in-
evitable. Furthermore, the unique properties of the nanomaterials may pose
a threat to the environment and to human beings. As a result, the practical
use of nanomaterials as sorbents in water and wastewater treatment de-
pends upon the continuation of research into the development of a cost-
eective method of nanomaterial production and on the toxicity of these
nanomaterials.
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CHAPTER 10
Modified and New Adsorbents

for Removal of Heavy Metals
from Wastewater
M. A. BARAKAT*a,b AND RAJEEV KUMARa
a
Department of Environmental Sciences, Faculty of Meteorology and
Environment, King Abdulaziz University (KAU), Jeddah, Saudi Arabia;
b
Central Metallurgical R & D Institute, Helwan 11421, Cairo, Egypt
*Email: mabarakat@gmail.com
11:26:32.
10.1 Introduction
In last few decades, metallic items or metal-based substances have been in
high demand and their uses are expected to increase day by day. Water
contamination from heavy metals such as Cr, Cd, Hg, Cu, Ni, As, Pb, Zn, etc.,
is a big environmental concern, which is continuing to require significant
attention.1 The major sources of heavy metal pollution are municipal waste,
metal plating facilities, mining operations, fertilizer industries, tanneries,
batteries, paper industries and pesticides, etc.2 Heavy metals are non-
biodegradable and they can be accumulated by living organisms/tissue. If
the metals are ingested beyond the permitted limit, they can cause serious
diseases and disorders.3,4 Therefore, it is necessary to treat metal-
contaminated wastewater prior to its discharge into the environment. Heavy
metal removal from aquatic euent can be achieved using numerous
existing procedures, such as chemical precipitation, ion-exchange and
electrochemical removal. These processes have significant disadvantages,

193
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194 Chapter 10
which are, for instance, incomplete removal, high-energy requirements and

production of toxic sludge.5
Among these methods, adsorption has become one of the alternative
treatments in recent years. The adsorption process implies the presence of a
solid adsorbent that binds molecules/ions by physical attractive forces, ion

exchange and chemical binding.6 To be a good adsorbent, it should be low
cost, available in large quantities, have high adsorption and regeneration
capacity and fast separation eciency. Extensive research work has already
been conducted on dierent types of adsorbents, such as those of mineral,
organic or biological origin, zeolites, industrial by-products, agricultural
wastes, biomass and polymeric materials.7,8 This chapter presents an over-
view of dierent low cost modified adsorbents used for removal of heavy
metals from industrial wastewater. These include materials derived from
natural materials, industrial by-products, agricultural wastes and modified
biopolymers.
10.2 Heavy Metals in Industrial Wastewater and

Toxicity
Heavy metals are generally considered to be those elements having an
atomic weight between 63.5 and 200.6 and density exceeding 5 g cm3.9,10 A
large number of elements fall into this category, but a few of the highly toxic
heavy metals are listed in Table 10.1. The high concentrations of heavy
11:26:32.
metals found in drinking water sources has raised concern in many parts of the
world. These heavy metals have deleterious cytotoxic eects on the biota that
exist there and, consequently, on human health.11 Heavy metals generally enter
the human body through water, in the aquatic food chain. Aquatic species such
as fish or aquatic species based products are the major source of heavy metal
transfer into the human body. Exposure to these toxic metals is associated with
many serious diseases including Alzheimers,12 Parkinsons,13,14 digestive,15
heart disorders16 and liver, kidney, stomach and lung cancers.17,18
In past decades, several studies have been carried out to investigate the
mechanism of toxicity induced by heavy metals and oxidative stress, inter-
ference with essential metals and enzymes, and interactions with cellular
macromolecules, etc., and mechanisms have been described.19 Oxidative
stress is one of the major mechanisms behind metal toxicity.20 The for-
mation of large amounts of reactive oxygen species, such as superoxide
anion (O2), hydrogen peroxide (H2O2), hydroxyl radical ( HO) and singlet
oxygen (1O2), has been reported to promote the induction of oxidative
stress.21 In fact, various studies connect heavy metals with oxidative DNA
damage since these metals may reduce the level of the main antioxidant
compounds in several animal tissues by inactivating enzymes and other anti-
oxidant molecules.22 In humans, oxidative stress is responsible for various
diseases, including cancer, Parkinsons disease, Alzheimers disease, ath-
erosclerosis, heart failure and myocardial infarction.19,23
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 195
Table 10.1 Source, permissible limits and health eects of various toxic heavy
metals.
WHO,
permissible
limit for
portable
Heavy water
metals Sources (mg L1) Potential health eects
As Electronics, metallurgical 0.01 Skin manifestations,
industries, manures visceral cancers,
sewage vascular disease
Cd Metalliferous mining, 0.003 Kidney damage, renal
agricultural materials, disorder, human
fertilizers, waste disposal, carcinogen
landfill leachate,
electronics, metallurgical
industries, manures
sewage
Cr Metal finishing industry, 0.05 Headache, diarrhea,
electroplating nausea, vomiting,
carcinogenic
Cu Metal finishing industry, 2 Liver damage, Wilson
electroplating, disease, insomnia
metalliferous mining
Ni Metalliferous mining, 0.02 Dermatitis, nausea,
metal finishing industry, chronic asthma,
electroplating, manures coughing, human
sewage, sludge, alloys carcinogen
11:26:32.
and steels
Zn Metal finishing industry, 3.0 Depression, lethargy,
electroplating, neurological signs and
metalliferous mining, increased thirst
agricultural materials,
fertilizers, manures
sewage sludge
Pb Electronics, metallurgical 0.01 Damage the fetal brain,
industries, specialist diseases of the kidneys,
alloys and steels, waste circulatory system and
disposal, landfill leachate nervous system
Hg Electronics, waste disposal, 0.001 Rheumatoid arthritis,
landfill leachate and diseases of the
kidneys, circulatory
system and nervous
system
Various agencies have recommended safe levels for heavy metals for the
protection of drinking water and aquatic life, which are given in Table 10.1.
Although, awareness of metal poisoning has been rising in recent years,
removal of metal ions from wastewater in an eective manner has become
an important issue today. Owing to strict regulation and increased concern
about heavy metals, abundant amounts of research have been carried out
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196 Chapter 10
focused on the development of economical technologies for wastewater

purification. In the following sections we will discuss recent technologies
developed for wastewater purification.
10.3 Treatment Processes for Heavy Metals Removal

Dierent conventional processes for removing heavy metals from wastewater,
such as chemical precipitation, coagulationflocculation, adsorption, ion ex-
change and electrochemical deposition, have been developed in recent years.
Chemical precipitation is the method most widely used for the removal of
dissolved heavy metals from wastewater. There are several factors that
control the chemical precipitation process, such as the concentration of the
metal ions present in the aqueous solution, the precipitant used and the
presence of other constituents that may inhibit the precipitation reaction.
Generally, lime, sodium or calcium hydroxides are used as precipitants.24,25
The OH ions react with the metal ions to form the insoluble metal hy-
droxides. The conceptual mechanism of heavy metal removal by chemical
precipitation is presented in Equation (10.1):26,27
Mn1 n(OH)2M(OH)nk (10.1)
n1
where M and OH represent the dissolved metal ions and the precipitant,
respectively, while M(OH)n is the insoluble metal hydroxide. Adjustment of
the pH to basic conditions is the major parameter that significantly im-
proves heavy metal removal by chemical precipitation. Mirbagheri and
11:26:32.
Hosseini24 reported that the maximum precipitation of Cr(III) occurred at pH

8.7 using Ca(OH)2 and the concentration of chromate was reduced from 30
to 0.01 mg L1 while the optimum pH for maximum Cu(II) precipitation was
12.0 for both Ca(OH)2 and NaOH. Charerntanyarak28 used lime for the
chemical coagulation and precipitation of Zn(II), Cd(II), Mn(II) and Mg(II) at
concentrations of 450, 150, 1085 and 3154 mg L1 and the optimum pH was
greater than 9.5. The advantages of using lime precipitation include the
simplicity of the process, inexpensive equipment requirement and con-
venient and safe operations. However, chemical precipitation requires large
amounts of chemicals to reduce metals to an acceptable level for discharge.
Other drawbacks are its excessive sludge production that requires further
treatment, slow metal precipitation, poor settling, the aggregation of metal
precipitates and the long-term environmental impacts of sludge disposal.25
Ion exchange is the most frequently used method for the removal of ionic
pollutants from aqueous euents. Ion exchangers are insoluble solid ma-
terials that remove ions from solution and release these same charged ions
in a chemically equivalent amount, without any changes to the chemical
structure of the ion exchanger.29,30 Commonly used matrices for ion ex-
change are synthetic organic ion-exchange resins, such as Amberlite, Dowex,
Amberjet, Ambersep, Lewatit, Chelex and so forth.30,31 In last decade,
researchers have been focusing on the development new multifunctional
hybrid ion exchangers having selectivity and high separation eciency.
View Online
32
Kolodynska prepared polyacrylate anion exchangers and chelating anion
exchangers for the removal of Cu(II), Zn(II), Ni(II) and Cd(II) complexes with
HEDP (1-hydroxyethylene-1,1-diphosphonic acid) from aqueous solution. The
result reported by Kolodynska shows that modified ion exchangers are more
ecient than the parent one. Despite the several advantages, ion exchangers
have some limitations, such as they cannot handle concentrated metal solu-
tions as the matrix becomes easily fouled by organics and other solids in the
wastewater. Moreover, ion exchange is non-selective and is highly sensitive to
the pH of the solution and the capital and operational costs are high.30
Membrane filtration systems, including ultrafiltration, reverse osmosis,
nanofiltration and electrodialysis, show great potential for the scavenging of
heavy metals from wastewater. The major advantages of these technologies
are high eciency, easy operation and space saving, and membrane fouling
and high operating costs are the major disadvantages of the membrane
process.33 Although there are several methods used for the removal of heavy
metals from wastewater, each method has some advantages and disadvan-
tages, as summarized in Table 10.2. Of the many techniques that can be
Table 10.2 Current treatment technologies for heavy metals removal involving
physical and/or chemical processes.54
Method Advantage Disadvantage
Oxidation Rapid process for toxic High energy costs and formation
pollutants removal of by-products
Ion exchange Good removal of a wide Absorbent requires regeneration
11:26:32.
range of heavy metals or disposal

Membrane Good removal of heavy Concentrated sludge production,
filtration metals expensive
technologies
Adsorption Flexibility and simplicity of Adsorbents require regeneration
design, ease of operation
and insensitivity to toxic
pollutants
Coagulation/ Economically feasible High sludge production and
flocculation formation of large particles
Electrochemical Rapid process and eective High energy costs and formation
treatment for certain metal ions of by-products
Ozonation Applied in gaseous state: Short half-life
alteration of volume
Photochemical No sludge production Formation of by-products
Irradiation Eective at lab scale Requires a lot of dissolved O2
Electrokinetic Economically feasible High sludge production
coagulation
Fentons reagents Eective and capable of Sludge generation
treating variety of wastes
and no energy input
necessary to activate
hydrogen peroxide
Biological Feasible in removing some Technology yet to be established
treatment metals and commercialized
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198 Chapter 10
employed for the treatment of wastewater laden with heavy metals, it is

important to note that the selection of the most suitable treatment for metal-
contaminated wastewater depends on some basic parameters such as pH,
initial metal concentration, the overall treatment performance compared
with other technologies, environmental impact as well as economics par-

ameters, such as the capital investment and operational costs.
10.4 Adsorptive Removal of Heavy Metals

Recently, adsorption has become one of the alternative treatment techniques
for wastewater laden with heavy metals. Adsorption has been found to be a
better technique for the wastewater purification in terms of initial cost,
flexibility and simplicity of design, ease of operation and insensitivity to
toxic pollutants. Adsorption also does not result in the formation of harmful
substances or secondary pollution. Furthermore, adsorption is sometimes
reversible as adsorbents can be regenerated by suitable desorption pro-
cesses. Basically, adsorption is a mass transfer process by which the ad-
sorbate is transferred from the liquid phase into the solid surface and
physical or chemical forces, or both, may be involved. If physical forces are
involved then it is known as physicosorption, and if the adsorbate species is
adsorbed through chemical bonds then it is termed chemisorption.34 In
general, there are three main steps involved in sorption of the pollutant onto
the solid sorbent: (1) the transport of the pollutant from the bulk solution to
the sorbent surface; (2) adsorption onto the particle surface; and (3) trans-
11:26:32.
port within the sorbent particle. Technical applicability and cost-eective-

ness are the key factors that play major roles in the selection of the most
suitable adsorbents to treat inorganic euents. From the literature, a large
variety of adsorbents, such as agricultural waste, industrial by-product,
natural material or modified biopolymers, metal oxides, etc., have recently
been developed and applied for the removal of heavy metals from metal-
contaminated wastewater.3536
10.4.1 Adsorption of Heavy Metals on Modified Natural

Materials
In recent years, natural materials such as zeolites and clay minerals have
been used as adsorbents because of their low cost and the fact that they can
be used as such or after some minor treatment to remove the contaminants.
Natural zeolites are crystalline hydrated aluminosilicates with a porous
framework structure occupied by water, alkali and alkaline earth cations.
Owing to the abundant, low-cost, high cation-exchange ability, as well as to
the molecular sieve properties, natural zeolites have been widely used as
adsorbents for the removal of heavy metals.37,38
Among the most frequently studied natural zeolites, clinoptilolite has
been shown to have high selectivity for certain heavy metal ions such as
Pb(II), Cd(II), Zn(II) and Cu(II).39 In this work the authors observed that the
View Online
Figure 10.1 SEM image of carbonized coconut fiber (left) and carbonized coconut
fiber containing zeolite Y (adapted from reference 40).
cation-exchange capability of clinoptilolite depends on the pretreatment

method and that conditioning improves its ion-exchange ability and removal
eciency. Ramirez et al.40 prepared novel hierarchical porous structures
based on carbonized olive seeds, coconut shells and coconut fibres coupled
with zeolite Y, and applications were investigated for the removal of As and
Co. Figure 10.1 shows the successful deposition of zeolite Y into the porous
carbon structure. Carbonzeolite Y showed excellent adsorption for both
metal ions. The ability of dierent types of synthetic zeolite for heavy metals
11:26:32.
removal is highly dependent on the solution pH.4143 Basaldella et al.41 used

NaA zeolite for removal of Cr(III) at neutral pH, while Barakat43 used 4A
zeolite, which was synthesized by dehydroxylation of low-grade kaolin.
Barakat reported that Cu(II) and Zn(II) were adsorbed at neutral and alkaline
pH, Cr(VI) was adsorbed at acidic pH while the adsorption of Mn(IV) was
achieved at high alkaline pH values. Nah et al. prepared synthetic zeolite
magnetically modified with iron oxide (MMZ).44 MMZ showed high ad-
sorption capacities for the Pb(II) ion and a good chemical resistance over a
wide pH range 511.
The natural clay minerals such as kaolinite, montmorillonite, bentonite,
beidellite, etc., are widely used as low-cost adsorbents because clay minerals
have large surface areas, good ion-exchange capacities and layered struc-
tures. Generally, van der Waals type weak bonding, hydrophobic eects and
H-bonding forces are mainly involved in the adsorption of adsorbate onto
clay.45 In the last decade, focus has been on modified clay minerals to re-
move heavy metals from aqueous solutions.4648 Various phosphates, such
as calcined phosphate at 900 1C, activated phosphate (with nitric acid) and
zirconium phosphate, have been employed as new adsorbents for the re-
moval of heavy metals from aqueous solution.4951 Kim et al.52 synthesized
an alginatealuminacollagen fibre adsorbent for the removal of organic and
inorganic pollutants. They observed that the amounts of Cu(II) and Pb(II)
removed in 1740 h were 1690 and 414 mg kg1, respectively, and the
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200 Chapter 10
Table 10.3 Adsorption capacities of modified natural materials for heavy metals.
Adsorption capacity (mg g1)
Adsorbent Pb21 Zn21 Cu21 Ni21 Cr61 Reference
Modified zeolite 123 44
HCl-treated clay 63.2 83.3 80.9 46

Clay-poly(methoxyethyl)acrylamide 81.02 47
Calcined phosphate 85.6 20.6 29.8 49
Activated phosphate 155.04 50
Zirconium phosphate 398 51
Polypyrrole-momo-morillonite 209.6 53
adsorption followed pseudo-second order kinetics. Setshedi et al.53 syn-

thesized a polypyrrolemontomorillonite nanocomposite via in situ poly-
merization and used it as an adsorbent for the removal of Cr(VI). It was
observed that modified clay has a higher potential than the parent one and
the maximum adsorption was found to be 209.6 mg g1 at pH 2 and at 318 K.
Moreover, desorption experiments revealed that the nanocomposite can be
reused eectively for two consecutive adsorptiondesorption cycles without
any loss of its original capacity. Table 10.3 presents the maximum metal
adsorption capacities of several low-cost adsorbents from various modified
natural materials.
10.4.2 Adsorption of Heavy Metals on Industrial By-products

11:26:32.
The eective utilization of industrial by-products as potential adsorbents is

also associated with waste management. A number of studies have shown
that industrial wastes can be directly, or after some modification, used as
low cost alternative adsorbents.54 Industrial by-products, such as fly ash,
waste iron, iron slags, hydrous titanium oxide, etc., can be chemically
modified to enhance its removal performance for metal removal from was-
tewater. Gupta et al. used rubber-tyre waste for the preparation of activated
carbon (RTAC) for the removal of Pb(II) and NI(II), and approximately 96 and
87% Pb(II) and NI(II) removal, respectively, was achieved by RTAC from a
simulated electroplating industry wastewater.55 Blast furnace slag (BFS), a
by-product from the iron manufacturing industry, was used as a low-cost and
abundant precursor for preparing a high surface area (219 m2 g1) calcium
silicate hydrate.56 The synthesis of slag-made calcium silicate hydrate
(slagCS) was achieved via a facile two-step dissolutioncoprecipitation pro-
cedure using HCl and NaOH, respectively, as shown in Figure 10.2. The thus
synthesized slagCS showed good adsorption properties for removal of Cu21,
phosphate ions and model protein from wastewater. The maximum ad-
sorption capacity of synthesized and pure slag is stated in Table 10.4. Lee
et al.57 studied green sands, another by-product from the iron foundry in-
dustry, for Zn(II) removal. Feng et al.58 investigated Cu(II) and Pb(II) removal
using iron and steel slag; pH ranges of from 3.5 to 8.5 [for Cu(II)] and from
View Online
Figure 10.2 Schematic of synthetic routes from blast furnace slag (BFS) to various
mineral compounds (adapted from reference 56).
Table 10.4 Adsorption capacities of industrial by-products for heavy metals.

Adsorption
Adsorbent Metal capacity (mg g1) Reference
Red mud Cu(II) 106.44 1
Cd(II) 66.67
Tea industry waste Cu(II) 11.29 2
Cd(II) 8.64
11:26:32.
Waste rubber tire (carbon) Pb(II) 327.87 55

Ni(II) 138.89
Raw blast furnace slag Cu(II) 2.41 56
Pure calcium silicate Cu(II) 127.09
Slag calcium silicate Cu(II) 118.18
Iron slag Cu(II) 88.50 58
Pb(II) 95.24
Cu(II) 16.21
Pu(II) 32.26
5.2 to 8.5 [for Pb(II)] were optimized. The iron slag had a much higher
sorption capacity for metals than the steel slag due to its higher surface area,
higher porosity and higher ion-exchange ability.
Fly ash from industries also showed good potential for the removal of
heavy metals from industrial wastewaters. Gupta et al.59 explored bagasse fly
ash, a solid waste from the sugar industry, for Cd(II) and Ni(II) removal from
synthetic solutions at pH ranging from 6.0 to 6.5. Mohan and Gandhimathi
used fly ash for the removal of heavy metals in a batch process.60 The uptake
behaviour of fly ash for heavy metal ions follows the order
Pb214Cd214Zn214Cu214Mn21, and the Freundlich isotherm fitted well
for the adsorption of heavy metals on the fly ash. The fly ash contains oxi-
dized functional groups as SiO2 and Al2O3 and above pH 6.9 these groups
acquire negative charge. The negative charges at an active site on the surface
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202 Chapter 10
21
of the fly ash, which allow cationic metals (M ) and metal hydroxides
[M(OH)2] to be complexed at the surface, are as follows:
SiOH OH-SiO H2O (10.2)
AlOH OH-AlO H2O (10.3)
2(SiO) M21-(SiO)2M (10.4)
2(AlO) M21-(AlO)2M (10.5)
SO M(OH)2-SOM(OH)2 (10.6)

where SO are the free surface sites on the fly ash.
Although, industrial waste showed great potential for the removal of heavy
metals, the following measures/steps should be taken before any industrial
waste material is used as an adsorbent for the treatment of wastewater:54 (1)
a leaching test of the industrial wastes as an adsorbent should be performed
for the investigated water system; (2) forced extraction of mobile/labile
substances present in the industrial waste; and (3) destruction or ultimate
disposal of persistent heavy metals from industrial waste (adsorbent)-loaded
heavy metals.
10.4.3 Adsorption of Heavy Metals on Modified Agriculture

11:26:32.
and Biological Wastes (Biosorption)

The potential of an agricultural based adsorbent for the removal of heavy
metals has been widely investigated in the last two decades. Agricultural
waste materials are eco-friendly and available in abundance, either free or at
very low cost. Cellulose, hemicellulose, lignin, lipids, protein, sugars, starch
and hydrocarbons are the basic components of agricultural waste ma-
terials.61,62 Generally these components act as active sites for the inter-
actions with the heavy metals. The use of agricultural by-products in
bioremediation of heavy metal ions is known as biosorption. This utilizes
inactive (non-living) microbial biomass to bind and concentrate heavy
metals from waste streams by purely physico-chemical pathways (mainly
chelation and adsorption) of uptake.63
Various types of biosorbent such as hazelnut shell, rice husk, pecan shells,
jackfruit, maize cob and husk have been used as they are, or after chemical
modification or conversion into carbon, activated carbon, for the decon-
tamination of heavy metals. Ajmal et al.64 used orange peel for the removal
of Ni(II) from aqueous solution and the maximum adsorption was found to
be at pH 6.0. Minamisawa et al.65 investigated the adsorption of Pb(II), Cu(II),
Cd(II) and Zn(II) by biomaterial gels synthesized in cross-linked reactions
from agricultural wastes such as lemon, yuzu (Citrus junos) and coee. The
adsorption mechanism involved acid ion-exchange reactions between the
View Online
Figure 10.3 Adsorption mechanism of heavy metals on yuzu and lemon cellulose
matrix gels (adapted from reference 65).
heavy metal and the carboxylic acid of pectic acid in the lemon and yuzu
11:26:32.
gels, improving the amounts of Pb(II), Cu(II), Cd(II) and Zn(II) adsorbed onto
the lemon and yuzu gels by approximately 5- and 6-fold, respectively. The
binding mechanism for the adsorption of heavy metals onto the biosorbent
surface is shown in Figure 10.3.
Surface modifications of coconut shell charcoal (CSC) and commercial
activated carbon (CAC) with chitosan and/or oxidizing agents, such as sul-
furic acid and nitric acid, respectively, are also carried out to improve
Cr(VI) removal performance.3 CSC and CAC chemically modified with nitric
acid showed higher Cr(VI) adsorption capacities (CSC 10.88 and CAC
15.47 mg g1) than those oxidized with sulfuric acid (CSC 4.05 and CAC
8.94 mg g1) and non-treated CSC coated with chitosan (CSCCC 3.65 mg g1),
respectively, suggesting that surface modification of a carbon adsorbent with
a strong oxidizing agent generates more adsorption sites on their solid surface
for metal adsorption.
Cu(II) and Zn(II) removal from real wastewater were studied using pecan
shells activated carbon.66 Bishnoi et al.67 conducted a study on Cr(VI) re-
moval by rice husk activated carbon from aqueous solution. They found that
the maximum metal removal by rice husk took place at pH 2.0. Rice hull,
containing cellulose, lignin, carbohydrate and silica, was investigated for
Cr(VI) removal from a simulated solution.68 To enhance its metal removal,
the adsorbent was modified with ethylenediamine. The maximum Cr(VI)
adsorption of 23.4 mg g1 was reported to take place at pH 2.
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204 Chapter 10
Three dierent cortex fruit wastes, including banana, lemon and orange
peel treated with NaOH, were evaluated as biosorbents by Vargas et al.69 It
was found that for Pb and Cu removal, lemon and orange cortex showed
better biosorption capabilities when compared with banana cortex (up to
15% less for Pb and 48% less for Cu). For Cd, banana cortex showed better
biosorption capability of 57% (67.2 mg g1 of cortex) more than orange
(28.8 mg g1 of cortex) and 82% more than lemon (12 mg g1 of cortex).
Baki and Shemirani70 used sodium dodecyl sulfate (SDS) coated micro-
particles of walnut sawdust modified with dimethylglyoxim for the de-
termination and preconcentration of Ni(II) from real samples. The eects of
solution pH and initial metal ion concentration, contact time, etc., were
investigated, as shown in Figure 10.4. The equilibrium time was found to be
30 min and maximum adsorption was at pH 7.5. The maximum monolayer
adsorption capacity was 22 mg g1.
In recent years, biological materials such as bacteria, algae, yeasts and
fungi have received increasing attention for heavy metal removal and re-
covery due to their good performance, low cost and the large available
quantities.7175 The biosorbent contains a variety of functional sites, in-
cluding carboxyl, imidazole, sulfhydryl, amino, phosphate, sulfate, thio-
ether, phenol, carbonyl, amide and hydroxyl moieties.76 Several algal
biomass such as Spirogyra species,71 Ecklonia maxima,72 Ulva lactuca,73
Oedogonium sp. and Nostoc sp.74 and brown alga Fucus serratus75 have
been utilized as adsorbents for the removal of heavy metals. The adsorption
capacities of these biosorbent are reported in Table 10.5. The mechanism for
11:26:32.
the uptake of heavy metal ions can take place by metabolism-independent

metal binding to the cell walls and external surfaces. This involves ad-
sorption processes such as ionic, chemical and physical adsorption. Metal
ions can be adsorbed by complexing with negatively charged reaction sites
on the cell surface.
Ozdemir et al.77 used thermophilic bacteria species for the biosorption of
Cd21, Cu21, Ni21, Zn21 and Mn21 using Geobacillus toebii ssp. decanicus (G1)
and Geobacillus thermoleovorans ssp. stromboliensis (G2) in a batch process.
Figure 10.4 Eect of solution pH (a) and adsorption isotherm of nickel ions on
modified walnut sawdust (b) (adapted from reference 70).
View Online
Table 10.5 Adsorption capacities of some agriculture and biological wastes for
heavy metals.
Adsorption capacity (mg g1)
Adsorbent Pb21 Cd21 Zn21 Cu21 Ni21 Cr61 Reference
Coconut shell charcoal 3.65 3

Maize cob and husk 456 493.7 495.9 63
Orange peel 158 64
Pecan shells activated 13.9 31.7 66
carbon
Rice husk 2.0 0.79 67
Modified rice hull 23.4 68
Walnut sawdust 22 70
Spirogyra (green algae) 133 71
Ecklonia maxima marine 235 90 72
alga
Ulva lactuca 112.3 73
Oedogonium species 145 74
The experimental results fitted well to Scatchard, Langmuir, Freundlich,

DubininRadushkevich (DR) plots and the maximum biosorption capaci-
ties of Cd21, Cu21, Ni21, Zn21 and Mn21 for G2 were 38.8, 41.5, 42, 29 and
23.2 mg g1, respectively, with 29.2, 48.5, 21, 21.1 and 13.9 mg g1 for G1,
respectively.
Recently, Gohari et al.78 cultivated cells from S. cerevisiae (yeast sp.) and
used them as an adsorbent for the removal of Cu(II) from wastewater. Copper
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uptake capacities were 10.36 and 15.33 mg g1, respectively, for intact and
disrupted biomass at an initial concentration of 100 ppm, pH 5, biosorbent
dosage 0.3 g, biomass drying temperature 180 1C and contact time 120 min.
FTIR analysis revealed that disulfides (SS) and ester (SOR) bonds con-
tribute to Cu(II) removal in addition to the carboxyl and hydroxyl functional
groups, which play important roles in metal removal.
10.4.4 Adsorption of Heavy Metals on Modified Biopolymers

and Hydrogels
The biopolymers such as starch, cellulose, chitin chitosan and so forth are
emerging adsorbents for the removal of heavy metal ions, even at low con-
centrations. The properties of these biopolymers such as biodegradability
and non-toxicity are the major advantage of the adsorbents. Another at-
tractive feature of biopolymers is that they posses a number of dierent
functional groups, such as hydroxyls and amines, which increase the e-
ciency of metal ion uptake and the maximum chemical loading possibility.79
The adsorption capacity of various polysaccharide based-materials are
summarized in Table 10.6. There are two main methods for the preparation
of sorbents containing polysaccharides: (1) cross-linking reactions, by a re-
action between the hydroxyl or amino groups of the chains with a coupling
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206 Chapter 10
Table 10.6 Adsorption capacities of modified biopolymers for heavy metals.
Adsorption
Adsorbent Metal capacity (mg g1) Reference
Modified cellulose Cu21 153.5 83
Cd21 250
Pb21 500
Oxidized cellulose Cu21 268.2 85
Cs1 133.8
Magnetic cellulosechitosan Cu21 44.7 5 89
Fe21 94.1 7
Pb2 28.1 3
agent to form water-insoluble cross-linked networks (gels); and (2) immo-

bilization of polysaccharides on insoluble supports by coupling or grafting
reactions in order to give hybrid or composite materials.80
Starch is an economical, biodegradable, abundant and environment
friendly material but the adsorption capacity for heavy metals cannot pro-
vide a satisfactory removal eect to meet the demands for pollution control.
Wang et al.81 modified the dialdehyde starch (DAS) using o-phenylenedi-
amine (PDA), m-phenylenediamine (MPA) and phenylhydrazine, which are
designated as DASPDA, DASMPA and DASPH, respectively. The adsorption
properties of the three adsorbents towards Ni21, Zn21 and Cd21 were
studied and the results indicated that DASPH had a good adsorbability to
Cd21 among the various metal ions. Further adsorption studies revealed that
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the adsorption of Cd21 increased with the increasing degree of substitution

of the DASPH and maximum monolayer adsorption was found to be
12.319 mmol g1.
Cellulose is the most abundant organic raw material in the world, present
in natural cellulosic materials such as paper, cotton and cloth, and cellulose
chains are organized through multiple hydrogen bonding in a well-defined
cellular hierarchical structure with a large surface area.82 To use cellulose as
a heavy metal ion adsorbent, chemical modifications such as esterification,
etherification and oxidation targeting the hydroxyl groups present in cellu-
lose are essential.83,84 Isobe et al.85 used a TEMPO oxidation process (nitroxy
radical catalyzed oxidation with hypochloritebromide) for the treatment of
cellulose hydrogel using an LiOHurea solvent. TEMPO oxidation success-
fully introduced carboxyl groups onto the surface of the cellulose hydrogel
with retention of the gel structure and its nanoporous property. The TEMPO-
oxidized cellulose hydrogel showed high adsorption capacity for other toxic
metal ions, such as Cu21, Zn21, Fe31, Cd21 and Cs1 as shown in Table 10.6.
Chitin is a naturally abundant mucopolysaccharide extracted from crust-
acean shells, (wastes product of seafood processing industries). It is a linear
polysaccharide of N-acetyl-d-glucosamine (GlcNAc) connecting through an
ab (1-4) glycosidic linkage.86 Chitosan is a deacetylation product of chitin,
which is the structural element in the exoskeleton of crustaceans and cell
walls of fungi.87 Chitin has been extensively investigated as an adsorbent for
View Online
Figure 10.5 Scheme of the preparation of magnetic chitosancellulose hydrogels

and adsorption of heavy metals (adapted from reference 89).
the removal of metal ions from wastewater.79 Recently, researchers worked

on the modification of chitin to enhance its adsorption capacity and easy
handling during the adsorption process. Tang et al.88 synthesized a chitin
cellulose membrane and used it as a potential adsorbent for the removal of
Cu21, Pb21 and Hg21. The amounts of metal ions adsorbed onto a unit
amount of the membrane were in the order of Hg21 (3.85 mmol g1)4Pb21
(3.85 mmol g1)4Cu21 (3.85 mmol g1). The adsorption equilibrium could
be well described by Langmuir adsorption isotherms, indicating monolayer
adsorption of metal ions onto the membrane.
Magnetic cellulosechitosan hydrogels prepared using ionic liquids
(Figure 10.5) as a reusable adsorbent for the removal of heavy metal ions
Cu21, Fe21 and Pb21 have been investigated by Liu et al.89 Results demon-
strated that the magnetic hydrogels had a limited anity to Mn21, Zn21 and
Ni21, but exhibited excellent and selective anity to Cu21, Fe21 and Pb21,
11:26:32.
and the corresponding equilibrium adsorption capacities were 44.7 5,

94.1 7 and 28.1 3 mg g1, respectively. Cu21 and Pb21 can form metal
chelates with chitosan easier than other metals and Fe21 can be readily
hydrolyzed and oxidized to Fe(OH)3, which could interact with the hydrogels.
The sorption mechanism of polysaccharide-based materials is dierent
from those of other conventional adsorbents. These mechanisms are com-
plicated because they implicate the presence of dierent interactions. Metal
complexation by chitosan may thus involve two dierent mechanisms
(chelation versus ion exchange) depending on the pH, since this parameter
may aect the protonation of the macromolecule.80 Chitosan is character-
ized by its high percentage of nitrogen, present in the form of amine groups,
which are responsible for metal ion binding through chelation mechanisms.
Amine sites are the main reactive groups for metal ions though hydroxyl
groups. However, chitosan is also a cationic polymer and its pKa ranges from
6.2 to 7. Thus, in acidic solutions it is protonated and possesses electrostatic
properties. Therefore, it is also possible to sorb metal ions through anion-
exchange mechanisms.
10.5 Batch Equilibrium Studies

The experimental data and the models obtained for any adsorption study
can be used in designing a large scale batch system for liquids containing
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208 Chapter 10
heavy metals. For given initial metal ions concentration and a finite liquid
volume, in order to achieve the desirable removal of heavy metals on a large
scale, the amount of adsorbent to be used and the residence time of the
liquid in the batch need to be determined. For a given equilibrium con-
centration, Ce, the amount of metal ions adsorbed onto the adsorbent at
equilibrium, qe, can be estimated from the Langmuir isotherm model. The
required amount of adsorbent, mD, to treat a volume of liquid, VD, can then
be calculated as follows:
mD (Ci Ce)VD/qe (10.7)
where Ci is the initial metal ion concentration in the liquid. In practice, there
would be a trade-o between the maximized utilization of the adsorbent and
the adsorption time since the adsorption rate is very low when the equi-
librium is approached. The adsorption system would thus usually be de-
signed at less than 100% saturation of the adsorbent, such as 9095%
saturation.90,91 The residence time (cycle time) of the liquid in the batch
could then be estimated using pseudo-second order kinetics. The design
amount of heavy metals removal qt, can be estimated as:
qt (Ci Ct)VD/mD (10.8)
where Ct is the specified (or design) heavy metals concentration remaining
in the liquid at the end of the adsorption cycle.
10.6 Summary
11:26:32.
Although all the heavy metal wastewater treatment techniques can be em-
ployed for the detoxification of water containing heavy metals, adsorption
technology is receiving the greatest attention because of its easy operation
and it is eco-friendly and low cost. It is important to note here that the
maximum adsorptive removal of heavy metals mainly depends on the ex-
perimental conditions, nature of adsorbent and metal ions. The use of agro-
industrial waste materials as low-cost adsorbents for removing metallic
pollutants from water and wastewater presents many attractive features,
especially their contribution in the reduction of costs for waste disposal.
However, dierent types of modified materials have been summarized in
this chapter, which show great potential for the scavenging of heavy metals
from industrial wastewaters. However, there is still a need to investigate
more materials with better adsorption capacity and fast separation.
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11:26:32.
CHAPTER 11
Natural Clays/Clay Minerals

and Modified Forms for Heavy
Metals Removal
ALFIN KURNIAWAN, SURYADI ISMADJI,*
FELYCIA EDI SOETAREDJO AND ANING AYUCITRA
Department of Chemical Engineering, Widya Mandala Surabaya Catholic

University, Kalijudan 37, Surabaya 60114, Indonesia
*Email: suryadiismadji@yahoo.com
11:26:35.
11.1 Introduction
The worlds supply of clean and safe waters for human consumption and
needs is becoming more and more scarce due to various anthropogenic and
industrial activities. Such activities have inevitably released substantial
amounts of wastewater containing toxic substances, thus accounting for
great environmental concerns for many years. Heavy metals are broadly
defined as those metals and metalloids of relatively high specific gravity (at
least five times that of water) or of high relative atomic weight, which are
considered to be of sucient dissemination and prevalence as to be in some
way environmentally or biologically significant as poisonous elements. Such
a substance is highly life-threatening towards living organisms due to its
high toxicity even at a very low concentration, non-biodegradability and
persistent nature and it is bio-accumulative (passed up the food chains to
humans).1 Heavy metal poisoning of humans via inhalation, ingestion and
skin absorption can result in reduced mental and central nervous functions,
changes in numerous metabolic body processes and damage to blood

213
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214 Chapter 11
composition, kidneys, lungs, liver and other vital organs. Long-term ex-
posure may result in degeneration of physical, muscular and neurological
functions that mimics Parkinsons disease, Alzheimers diseases, muscular
dystrophy and multiple sclerosis.24 Heavy metals rich euents are dis-
charged from many industries worldwide, such as electroplating, mining,

metal finishing, photographic, ammunition, leather tanning, textile and
dyeing, fertilizers, batteries, alloys and electronic goods manufacturing as
well as from agricultural activities to a lesser extent. Several types of toxic
heavy metals frequently pollute surface water bodies and their maximum
permissible limits according to the WHO and US EPA are presented in
Table 11.1.5,6 In order to meet environmentally acceptable concentrations,
metal euents that are discharged from municipal and industrial activities
should be treated properly before entering surrounding water bodies
and/or soils.
Chemical precipitation, electrodialysis, ion exchange, ultrafiltration, co-
agulation, reverse osmosis, microbial bioremediation, phytoremediation
and solvent extraction are some examples of conventional technologies for
purifying metal-contaminated euents. The advantages and disadvantages
of these technologies are summarized in Table 11.2.79 So far, the appli-
cations of these methods have encountered major obstacles and are un-
sustainable, particularly in the developing nations due to high operational
costs, generation of toxic waste sludge, complicated installation of waste-
water treatment units and poor removal eectiveness for the handling of
wastewater containing trace levels of metal ions. Lately, adsorption has be-
11:26:35.
come a frequently used technique and a viable option for controlling the
fate, transport and bioavailability of heavy metals in terrestrial and aquatic
environments due to its simple design and operation, cost-eectiveness,
wide adaptability and high removal eciency, which produces high-quality
euents. Nowadays, special attention has been focused on the pursuit of
Table 11.1 Maximum acceptable limits of several toxic heavy metal ions in the
surface waters based on WHO and US EPA regulations.
Heavy metal Toxicity rank WHO (mg L1) US EPA (mg l1)
As 1 10 10
Pb 2 10 15
Hg 3 1 2
Cd 8 3 5
Cr, hexavalent 17 50 100
Co 52 NRa 100
Ni 57 70 100
Zn 75 NGLb 5000
Cu 125 2000 1300
Mn 140 400 50
Fe 300
a
NR, not recorded.
b
NGL, no guideline.
Table 11.2 The advantages and disadvantages of several conventional technologies for the treatment of heavy metal contaminated
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal
euents.
Working
Technology Advantages Disadvantages concentration
Chemical Ready availability of equipment Large volumes of sludge are generated, incurring 410 mg L1
precipitation and many chemicals additional waste-disposal costs
Convenient, self-operating and Extra coagulationflocculation is compulsory for
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low maintenance the complete precipitation of light tiny flocs

Low metal concentration in the Regulation requirements are not always met
euent is achieved using hydroxide and carbonate precipitation
alone
Non-selective
Long-term environmental impacts of sludge
disposal
Safety concerns due to working with corrosive
chemicals
Electrodialysis Little chemical consumption High cost of electrodes and ion exchange 410 mg L1
Recovery of pure metal is the membranes
added economic value Relatively short lifetime of membranes,
especially when working in a high-density
electrical field
Energy intensive
The formation of metal hydroxides can clog the
membranes
Low removal eciency at dilute concentrations
Ion exchange Highly eective for removing High cost of ion exchanger o100 mg L1
metal ions to a very low Partial removal of certain metal ions and highly
concentration sensitive to the pH of the solution
Cannot handling concentrated metal solutions
as the ion-exchanger matrix gets easily fouled by
organics and other solids in the euent
Disposal of exhausted ion exchangers
215
216
Working
Technology Advantages Disadvantages concentration
Reverse osmosis High eectiveness (over 99% of High procurement and operating cost of the 410 mg L1
all dissolved minerals can be membranes
removed) The use of elevated pressures makes this
The capability to reduce the technique costly and sensitive to operating
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concentration of ionic conditions

contaminants, as well as
dissolved organic compounds
Biological treatment Fairly inexpensive and moderate Limited to those compounds that are
capital investment biologically degradable
Environmentally safe and The biodegradation products may be more
acceptable by the public persistent or toxic than the parent compound
Can be conducted on site, often Considerable experience and expertise may be
without causing a major required to design and implement a successful
disruption of normal activities bioremediation process
The resulting residues after Dicult to be adapted because the success of
treatment processes are usually this process highly depends on the presence of
harmless products, which metabolically capable microbial populations,
include carbon dioxide, cell suitable environmental growth conditions
biomass and water and appropriate levels of nutrients and
Self-sustaining process contaminants
Solvent extraction Selective heavy metals removal High capital cost 4100 mg L1
Continuous concentrated metal Discharge of harmful solvent to environments
solution recovery
Phytoremediation Diculty for the regeneration of the plant in the mg L1
further remediation
Time consuming
Chapter 11
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 217
natural adsorbents that possess high loading capacity, fast kinetics, a large
availability and are renewable and economically viable.
Numerous kinds of natural adsorbents ranging from industrial by-
products to agricultural waste have been explored for the remediation of
aquatic environments that are polluted by heavy metals and they may be an
alternative to more costly materials such as commercial activated carbons
or synthetic ion-exchange resins.1025 Despite their abundant availability
and cheapness, most of these solids show unimpressive results, associated
with poor removal capacity. Of particular interest are clays and clay min-
erals, which are highly valued for their ion sorption/exchange capacity, low
permeability, swelling ability, chemical and mechanical stability, large
specific surface area and ubiquitous presence on earth in the geological
deposits, terrestrial weathering environments and marine sediments.26 In
the terrestrial environments, clay deposits may act as a natural scavenger
by taking up pollutants from water passing through the soil by ion ex-
change and/or adsorption mechanisms. Many types of clay materials have
been tested for the removal of heavy metal ions from waters and waste-
waters, including diatomite, illite, sepiolite, bentonite, kaolinite, clin-
optilolite, halloysite and palygorskite.2741 These clays and clay minerals
possess important surface reactivity, which stems from the permanent
negative charge within the layers. Furthermore, the natural exchangeable
alkali and alkali earth metal cations, such as Na1, K1, Ca21 and Mg21
located between two adjacent layers, can be replaced with larger molecular
mass cations, expanding the interlayer space and consequently the
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internal volume. Surface modifications of the acidbase chemistry are

therefore, the main aspect for broadening potential applications of clays
and clay minerals as an engineered material in new technologies. Over the
past few years, research devoted to surface modification of clays/clay
minerals as promising heavy metal sorbents, through thermal and chem-
ical activations as well as pillaring, grafting and intercalation techniques,
has been steadily growing and yet recent advances in this area have not
been well reported.
Starting from the environmental background previously outlined and the
urgent need to combat problematic heavy metal pollutions, this chapter
critically provides up-to-date information focusing on the fundamental
structural and surface chemistry of natural clays and clay minerals and their
various modified forms as heavy metal adsorbents. The adsorption per-
formance of natural and modified clays/clay minerals for removing heavy
metal ions from synthetic and real wastewaters has been discussed at great
depth in a large number of published studies. Considering the process de-
sign and its optimization, the knowledge of the single and multicomponent
adsorption behaviour of clayheavy metal pairs, covering isotherms, kinetics
and thermodynamics, will be presented in detail. Finally, future perspectives
on the development of clay-based adsorption systems for industrial-scale
wastewater treatment is described with respect to technical and economic
feasibility.
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218 Chapter 11
11.2 Structural Features of Clays and Clay Minerals

as Heavy Metals Sorbent
Clays are chemically a layer-type hydrous aluminosilicate material consisting
of a mixture of micrometre-sized clay minerals and other microscopic crys-

tals of quartz, feldspars, carbonates and metal oxides.42 They are often re-
ferred to as earthy material that becomes plastic when mixed with limited
amounts of water and will harden upon drying or firing. To date, clays have
found applications in various industrial areas such as drilling fluid, foundry
sand, extenders in aqueous-based paints, natural fillers in paper making,
decolorizing agents in the oil industries, filtering and deodorizing agents in
the petroleum refineries, building material, catalysts and adsorbent.4345
The origin of clays may be from gradual surface weathering and secondary
sedimentary processes of a variety of minerals, typically silicatealumina
bearing rocks or low temperature hydrothermal alteration over long periods
of time.46 The properties of dierent clays, including specific gravity,
hardness, elasticity, plasticity, swelling ability, crystallinity, etc., vary con-
siderably, depending on the place of origin and weathering conditions.
Generally, clay minerals can be categorized as 1 : 1 or 2 : 1, based on the layer
structure. The 1 : 1 clay mineral consists of one silica tetrahedral sheet and
one alumina octahedral sheet and belonging to this type are serpentine,
halloysite and kaolinite. This type of clay mineral can also be classified as a
non-expanding clay because H-bonding holds the sheets tightly together.
The alternative type, known as a 2 : 1 clay mineral, has two tetrahedral sheets
11:26:35.
sandwiching one octahedral sheet. Some examples of 2 : 1 clay minerals are

talc, vermiculite, smectite, chlorite and illite/hydrous mica. Several well-
known classes of clay minerals and the related information including
chemical formula, cation-exchange capacity and the layer charge per unit
cell are given in Table 11.3.47,48
Electronically, clay minerals possess a net negative layer charge due to
isomorphous substitution between Al31 and Si41 in the tetrahedral co-
ordination and between Mg21, Fe21, Zn21 or Ca21 and Al31 in the octa-
hedral coordination.49 The negative layer charge imparts surface reactivity
towards the surrounding environment, for example the clay mineral surface
Table 11.3 Several well-known classes of clay minerals and their structural
properties (adapted from reference 47).
Layer
CEC charge
Clay Layer (meq/ per unit
mineral Chemical formula type 100 g) cell
Kaolinite [Si4]Al4O10(OH)8 nH2O (n 0 or 4) 1:1 315 o0.01
Illite Mx[Si6.8Al1.2]Al3Fe0.25Mg0.75O20(OH)4 2:1 1040 1.42.0
Smectite Mx[Si8]Al3.2Fe0.2Mg0.6O20(OH)4 2:1 70120 0.51.2
Vermiculite Mx[Si7Al]AlFe1.5Mg1.5O20(OH)4 2:1 100150 1.21.8
Chlorite Mx[Si6.8Al1.2]Al3.4Mg0.6O20(OH)4 2 : 1 : 1 1040 Varied
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can form an electrical double-layer when exposed to aqueous electrolyte

environments (i.e., natural waters).50 Therefore, water molecules can be
intercalated between two adjacent layers to form an interlayer ionic solution
that contributes to the swelling phenomenon related to electrical double-
layer properties.51,52 The negative layer charge from isomorphous substi-

tution is permanent and pH independent, which is compensated by ex-
changeable alkali and alkali earth metal cations, such as Na1, K1 or Ca21,
within the mineral framework. Additionally, the location of whether the
layer charge derives from isomorphic cation substitutions in the tetrahedral
or octahedral sheet is also an influencing factor of both hydration and cat-
ionic speciation in the interlayer spacing. Sposito demonstrated that
H-bonding between basal oxygen atoms and water molecules is enhanced by
tetrahedral rather than by octahedral sheet substitution.52 The adsorbed
waters, together with hydrated interlayer exchangeable cations, give rise to
the clays/clay minerals surface hydrophilic character and swelling ability.
According to the theory of hard and soft acids and bases (HSAB) intro-
duced by Pearson,53 the 2 : 1 silicate layers and hydrated interlayer cations in
the clay minerals structure can be considered as a Lewis base (electron donor
or nucleophilic group) and a Lewis acid (electron donor or electrophilic
group), respectively. Given this, clay minerals can be categorized as a soft or
hard base, depending on how the location of the layer charge is derived. The
soft base clay minerals are those whose layer charge derives from octahedral
sheet substitutions (e.g., Mg21 or Fe21 - Al31) while for hard base clay
minerals, the layer charge originates from tetrahedral sheet substitutions
11:26:35.
(e.g., Al31 - Si41).54 Among the soft base 2 : 1 silicate clay minerals are
montmorillonite, hectorite, glauconite and celadonite, while among the
hard base are vermiculite, saponite, beidellite and illite. Brigatti et al. have
proven that the layer charge location at a 2 : 1 layer type clay mineral aects
the hydration of the layers and, more importantly, the sorption process of
the cationic species.55 In general, hard acids (e.g., metal cations) complex
with hard bases and soft acids (e.g., organic cations) complex with soft bases.
The SiOSi bonds of silica tetrahedrons form a reactive surface called a
siloxane, while the OAlOH bonds of alumina octahedrons form an oxy-
hydroxy surface. The siloxane surface, typical of 2 : 1 silicate clay minerals,
can be classified as inner-sphere or outer-sphere in terms of cation ad-
sorption complexes.50 In the inner-sphere surface complex, water molecules
will not be able to penetrate siloxane ditrigonal cavities (each being nearly
0.26 nm in diameter), whereas the adsorption of cations may be still feasible
due to their smaller sizes than the cavity size. Meanwhile, the outer-sphere
surface complex has at least one water molecule interposed between the
surface functional group and the bound ion or molecule,50 in other words, a
hydrated adsorbed cation is accommodated. The reactivity of the siloxane
surface towards cationic species (e.g., heavy metal ions) may stem from the
negative charge-bearing patches arising from isomorphic substitution of an
aluminium atom in place of a silicon atom. In this regard, the molecular
interaction between metal cation and inner-sphere surface complex can be
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220 Chapter 11
monodentate (the ion is bonded to one oxygen atom), bidentate (the ion is
bonded to two oxygen atoms), mononuclear or multinuclear.56
The oxyhydroxy surface is characterized by a plane of exposed hydroxyl
sites underlying Mg, Al or Fe atoms in the centre of the octahedrons. Clays
with a 1 : 1 layer type structure such as kaolinite and rectorite usually consist
of a siloxane surface on one basal plane and an oxyhydroxy surface on an-
other basal plane. The exposed basal hydroxyl groups are subject to dis-
sociation, therefore they are reactive toward positively charged ions.
Considering those properties, it can be implied that the sorption of cationic
species onto siloxane and oxyhydroxy surfaces takes place through surface
complexation phenomena.
The location of cation complexation (i.e., inner-sphere or outer-sphere)
and its modes are the major area that is still continuously studied to date
due to the lack of theoretical understanding and incoherent data in the
literature. Therefore, a number of molecular-scale investigations and com-
putational studies have sought to investigate the adsorption mechanisms of
heavy metal ions onto the surfaces of siloxane and oxyhydroxy groups and
the modes of cation-surface complexes using various in situ molecular-scale
spectroscopy techniques, such as X-ray absorption fine-structure spec-
troscopy, neutron scattering spectroscopy, nuclear magnetic resonance
spectroscopy and Fourier transform infrared spectroscopy.50,56 The study
of Sposito and coworkers reported that excess negative charge density in
the siloxane surface makes it possible for this surface to create strong ad-
sorption complexes with cations and water molecules.50 Electron spin
11:26:35.
spectroscopy and quasielastic neutron scattering spectroscopy can be used

to probe metal ions bound in surface complexes and its adsorption modes
whether inner-sphere complex (ISC), outer-sphere complex (OSC) or diuse-
layer (DL) based on the molecular time-scale.50 The immobilization time-
scale for cationic species on 2 : 1 layer-type clay minerals for ISC, OSC and DL
lies between 1 and 100 ns, 10 and 100 ps and 4 and 10 ps, respectively.50
Systematic molecular simulation studies using Monte Carlo (MC) com-
puter simulations have recently been conducted to examine the stability of
an aqueous ionic system in the case of charge-bearing hydrated clay min-
erals with phasespace sampling strategies introduced by Skipper and
coworkers57,58 and Chang et al.59,60 Experimental works of Wang et al.,61
Sheng et al.62 and Strawn et al.63 have proven that the responsible adsorption
mechanisms of cationic species onto surface complexes at low pH and weak
ionic strength were outer-sphere complexation (i.e., interlayer adsorption of
hydrated cations) and ion exchange, while at high pH and ionic strength, the
predominant adsorption mechanisms were inner-sphere complexation (i.e.,
electrostatic attractions onto ligand functional groups located at the mineral
discontinuities) and surface precipitate formation.
Dubbin and Goh studied the sorptive capacity of montmorillonite toward
hydroxyCr polymers and revealed the inner-sphere complexation mode of
interlayer Cr by forming covalent bonding with the basal siloxane oxygen
atoms at pH of about 6 and ionic concentrations (I) of 12002400 cmol()
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64
per kg of clay. Based on previous studies, one can conclude for conveni-
ence that alkali and alkali earth metal cations primarily bound to the surface
complexes by forming outer-sphere complexes or through an ion-exchange
process (categorized as non-specific adsorption), while trace and heavy metal
cations primarily form inner-sphere complexes with surface hydroxyl groups

(categorized as specific adsorption). Furthermore, the modes of cationic
sorption complexes also depend on other factors, in addition to solution pH,
such as surface loading, contact time and types of sorbent, which are all
specific for each system.
The edge hydroxyl groups of clay minerals in particular are more active
than basal hydroxyl groups and play important roles in the sorption pro-
cess of cationic species, the two most important being silanol (SiOH) and
aluminol (AlOH) groups. These surface hydroxyl groups resulted from
transformation of broken SiOSi and AlOAl bonds, carrying residual
negative charges along the edges of the clay mineral particles. Upon
contact with water, the anhydrous Fe- or Al-oxide surfaces can form ferrol
(FeOH) or aluminol groups, respectively. The defect sites of silanol and
aluminol groups are amphoteric and pH-reactive, in which these groups
carry a net positive charge at low pH (i.e., Lewis acid sites), neutral at the
isoelectric point (iep) and negative at high pH (i.e., Lewis base sites). Many
studies have investigated the ionizable properties of silanol and aluminol
surface groups as a function of pH, associated with protonation and
deprotonation reactions. At solution pHs lower than the pH of point zero
charge (pHpzc) of the sorbent, both silanol and aluminol edge sites are
11:26:35.
protonated due to excessive concentration of H1 ions in the bulk solution,

while at solution pHs higher than pHpzc of the sorbent, both silanol and
aluminol groups are deprotonated. The protonation and deprotonation
mechanisms of silanol and aluminol surface hydroxide groups are given as
follows:
Protonation reactions (at solution pHopHpzc of the sorbent):
SiOH H3O12SiOH21 H2O (11.1)
AlOH H3O12AlOH21 H2O (11.2)

Deprotonation reactions (at solution pH4pHpzc of the sorbent):
SiOH2SiO H3O1 (11.3)
AlOH2AlO H3O1 (11.4)

Yet Sposito et al. revealed that only the aluminol hydroxyl surface groups
can accept or donate protons, while the silanol hydroxyl groups is only
capable of dissociating its proton due to the larger valence of the silicon
atom.50 In another recent study, Liu and coworkers investigated the acidity
constant of surface groups on the (0 1 0)-type edge sites of montmorillonite
and kaolinite clays using the first principles of molecular dynamics (FPMD)
based on the vertical energy gap technique.65 This study concluded that the
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222 Chapter 11
values of acidic constants of silanol groups of montmorillonite and kaolinite

are 7.0 and 6.9, respectively. In acidic constants (pKa) the sorption of metal
cations onto surfaces of clays and clay minerals is favourable at elevated pH,
associated with deprotonation of surface hydroxyl groups on the broken
edge sites, which provide negatively charged ligands for the binding of
metal cations.
The cation-exchange capacity (CEC), expressed in milliequivalents per
100 g of clays/clay minerals, or centimoles of charge per kilogram [cmol()
per kg], is defined as the maximum holding capacity to which a clay/clay
mineral can adsorb and exchange cations from the clay suspensions at a
specific pH,55 therefore it directly determines the eectiveness of clay/clay
mineral sorbents in removing metal cations. Each clay/clay mineral has a
specific range of exchange capacities, as shown in Table 11.3, because of
structural dierences and the variation of chemical compositions. The
higher this number, the higher the negative charge and the more cations the
clays and clay minerals can hold through electrical attraction. Generally
speaking, the exchange capacities of clays and clay minerals can be en-
hanced by either adding organic matter or increasing the suspension pH.
The latter is preferred and adopted in most sorption studies for eective
removal of heavy metal ions from aqueous solutions. Increasing the pH
would provide negatively charged surface sites for the binding of heavy metal
ions, resulting from deprotonation of structural hydroxyl groups, mainly
silanol and aluminol groups. Thus, one can infer that the acting uptake
mechanism, in connection with cation-exchange capacity, is a reversible
11:26:35.
exchange reaction between cations held near a mineral surface by un-

balanced electrical charges and cations in a solution in contact with the
mineral. The tetrahedraloctahedraltetrahedral (T-O-T) layer structure of
2 : 1 silicate clay minerals is also more advantageous for the sorption of
heavy metal ions compared with tetrahedraloctahedral (T-O) clay, associ-
ated with a larger internal volume and a higher number of edge hydroxyl
groups exposed on the surface,66 providing more vacant spaces to accom-
modate higher amounts of metal cations. Other beneficial features of clays
and clay minerals as heavy metal sorbents are the high specific surface area
that arises from the tiny size of the particles (in the nanoscale) and good
interconnectivity of the pore structures consisting of mesopores and
micropores, and macropores to a lesser degree.
11.3 Surface Modification Techniques of Clays

and Clay Minerals for Enhanced Heavy
Metals Sorption
Improving the performance and surface compatibility of clays and clay
minerals as heavy metal sorbents has becoming the hot subject area for
much environmental engineering research in recent years. Surface modifi-
cations of clays/clay minerals are conducted in order to: (1) enhance metal
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loading capacity and (2) alter the mineralogy, adsorptive and electrokinetic
properties of the minerals so that they become widely applicable. In their
native state, clays and clay minerals are potential sorbents for removing
cationic species (e.g., heavy metal ions) because they readily sorb onto un-
altered colloidal surfaces through ion exchange or complexation mech-

anisms. Many eorts have been made to investigate the performance of
natural clays and clay minerals to sorb various heavy metal ions.
Table 11.4 lists several studies dealing with adsorption processes of vari-
ous heavy metal ions from synthetic and real euents using natural clays
and clay minerals over a six-year period from 2007 to 2012. A comparative
study on lead adsorption potential on three local natural clays,
namely perlite, dolomite and diatomite, has been recently conducted by
Irani et al.67 The removal capacities of lead ions ranked as follows: diatomite
(25.01 mg g1)4dolomite (19.69 mg g1)4perlite (8.91 mg g1), which
agreed well with the decreasing surface properties of clays, including the
BET surface area and total pore volume. Natural kaolin and montmorillonite
are both able to treat metal-contaminated waters eectively with an ad-
sorption extent reaching 37.6% for kaolinite and 78.7% for montmorillonite,
as studied by Bhattacharyya and Gupta.68
In another study, Chen and Wang revealed that natural palygorskite, a
silicate clay with talc-like units arranged alternately along the c-axis of a fi-
brous structure, had a relatively high sorption capacity toward Pb(II) ions
with a maximum uptake value of 104.28 mg g1.69 The adsorption feasibility
of expanded perlite (EP) clay for the removal processes of toxic Ag(I), Cu(II)
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and Hg(II) cations has been studied by Ghassabzadeh et al.70 They observed
excellent performance of expanded perlite in removing Ag(I) and Cu(II) ions
at near-neutral pH with a removal percentage that reached 92% for Cu(II) and
100% for Ag(I), while for Hg(II) it was 35%. Natural clinoptilolite and ben-
tonite clays have also been utilized as a low-cost material for fast uptake of
bivalent lead ions from aqueous solutions in a batch mode.71 It was found
that bentonite clays were able to sorb higher amounts of Pb21 ions with a
removal percentage that reached 100% at ambient temperature with mild
agitation. Under the same conditions, the removal percentage of clin-
optilolite with particle sizes ranging between 2.5 and 5 mm and in a dust
form were about 42 and 55%, respectively. This dierence is due to the
higher specific surface area of clinoptilolite dust than that of granular
clinoptilolite, which facilitates the mobilization of transport with respect to
the incoming lead ions.
The adsorption potential of two volcanic rock grains, namely Scoria (VSco)
and Pumice (VPum), towards Ni(II) ions has been tested by Alemayehu and
Lennartz.72 The maximum uptake capacity of Ni(II) ions was 980 mg kg1 for
VSco and 1187 mg kg1 for VPum at room temperature under weak acidic
conditions (pH of 5). The potential application of Turkish illitic clay for re-
moving Cd21 and Pb21 ions has been evaluated by Ozdes et al.73 A removal
eciency of nearly 100% for Pb(II) ions and 78% for Cd(II) ions was obtained
in their study.
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224 Chapter 11
Table 11.4 The removal capacity of various natural clays and clay minerals towards
various heavy metal ions.
Heavy Maximum sorption
Clays/clay minerals metals capacity (mg g1)a Reference
Palygorskite Pb(II) 104.28 Chen and Wang69

Montmorillonite Pb(II) 31.05 Bhattacharyya and
Gupta68
Kaolinite Pb(II) 11.52 Bhattacharyya and
Gupta68
Cankiri bentonite Zn(II) 80.64 Veli and Alyuz74
Illitic clay Cr(III) 39.9 Ghorbel-Abid et al.75
Cd(II) 52.50
Expanded perlite Ag(I) 8.46 Ghassabzadeh et al.70
Cu(II) 1.95
Hg(II) 0.35
Brazilian smectite Cr(VI) 60.32 Guerra et al.76
Brazilian sepiolite As(V) 5.44 Guerra et al.77
Brazilian kaolinite U(VI) 0.77 Guerra et al.78
Clinoptilolite Pb(II) 80.93 Gunay et al.79
Kaolinite Pb(II) 11.50 Bhattacharyya and
Gupta68
Cd(II) 6.80
Ni(II) 7.10
Montmorillonite Pb(II) 31.10 Bhattacharyya and
Gupta68
Cd(II) 30.70
Ni(II) 21.10
Palygorskite Co(II) 8.88 He et al.80
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Diatomite Pb(II) 25.01 Irani et al.67

Dolomite Pb(II) 19.69 Irani et al.67
Perlite Pb(II) 8.91 Irani et al.67
Apatite Pb(II) 82.88 Kaludjerovic-Radoicic
and Raicevic81
Sericite Ni(II) 44 Kwon and Jeon82
Kaolinite Cr(III) 2.013.44 Turan et al.83
Sericite Cu(II) 1.67 Tiwari et al.35
Pb(II) 4.69
Cankiri bentonite Cu(II) 44.84 Veli and Alyuz74
Diatomite Th(IV) Sheng et al.63
a
Prediction by Langmuir adsorption isotherm model.
Boron impurity (BC), a heterogeneous waste material containing clay

mixtures from a boron enrichment plant, has been examined for the removal
of lead and nickel ions from aqueous solutions.84 About 81.86 and 74.28% of
lead and nickel ions, respectively, were adsorbed onto the BC surface from a
single-component solution within 90 min. The eectiveness of extruded clay
mixtures consisting of zeolitekaolinbentonite for the sorption of lead ions
was investigated by Salem and Sene.85 The obtained results indicated that
the simultaneous addition of bentonite and kaolin could substantially im-
prove the compression strength and adsorption capacity. The Raschig ring-
shaped adsorbent prepared at an optimum mixing ratio of 66.67 wt% zeolite,
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29.17 wt% bentonite and 4.16 wt% kaolin, displayed a maximum sorption
capacity of 140.9 mg g1. Natural clays and clay minerals are also acquiring
prominence for nuclear waste management. In the study of Zhao et al.,
laboratory-grade MX-80 bentonite was used to treat tetravalent thorium ions
in aqueous solution; the adsorption is dominated by surface complexation

between cationic species [Th41 and Th(OH)31] and negatively charged sur-
face sites.86
Despite these results, not all natural clays and clay minerals demonstrate
appreciable metal sorption capacity, which is attributed to the low specific
surface area, inaccessible inner pore channels responsible for adsorption/
exchange, non-expanding characteristics of the minerals and poor cation-
exchange capacity. Therefore, various modification techniques have been
employed to ameliorate the layer structure and surface chemistry of clays
and clay minerals while preserving its crystal lattices for an enhanced metal
removal process. The following sections will discuss pillaring, grafting and
intercalation as common techniques as well as thermal (physical) and
chemical activation methods, to a lesser extent.
11.3.1 Thermal Activation

Surface modification of clays and clay minerals through thermal activation is
mostly conducted by subjecting the materials to high temperature treat-
ment, up to 1000 1C. The general purposes of thermal activation processes
are to remove any impurity (e.g., organic matter) and moisture attached to
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the clay particles. The resulting material, termed calcined or sintered clay,
possesses a lower degree of crystallinity, which is cluster-shaped or
amorphous with coarse-shaped pores, poor dispersibility in aqueous solu-
tions (e.g., water) and a generally lower sorption capacity in conjunction with
a reduced specific surface area.
Talaat et al. studied the performance of Egyptian kaolin and bentonite
clays and their heat-treated forms for the removal of five heavy metal ions,
namely chromium, cadmium, nickel, zinc, copper and lead.87 The experi-
mental results showed that all modified kaolinite clays displayed lower re-
moval capacities towards Cr(III) and Cd(II) ions, although Na-bentonite
exhibited the highest adsorptivity towards Cd(II), Cu(II), Zn(II), Pb(II) and Ni(II)
cations. The calcination of Turkish bentonite clay to remove the radio-
nuclide U(VI) ions from synthetic euent has been conducted by Aytas
et al.88 They observed a strong correlation between calcination temperatures
and U(VI) removal capacity in which the adsorptivity of uranyl ions (UO221)
onto thermally treated bentonite (TAB) surfaces gradually fell at extreme
calcination temperatures, typically above 400 1C, due to the distortion of the
internal structure of clay. In this regard, a calcination temperature of 400 1C
was selected as the optimum point that gave the highest adsorption capacity
of uranyl (UO221) ions.
Similar attempts were made by by Alkan and colleagues to investigate the
sorption performance of calcined kaolin for preconcentrating copper ions
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226 Chapter 11
89
from aqueous solutions. They found that the phase transition from kao-
linite to the metakaolinite phase took place by calcinating clay at 600 1C.
Another useful finding in their study is that the extent of copper sorption
onto the clay surface decreased with increasing activation temperature due
to the removal of most micropores and structural hydroxyl groups during

calcination, typically at activation temperatures beyond 400 1C. The application
of heat-treated palygorskite clay to sorb cadmium ions from aqueous solutions
has been conducted by Wang et al.90 The gradual increase in the specific
surface area of heat-treated palygorskite clay from 48.66 to 128.9 m2 g1 was
observed for calcination temperatures up to 300 1C, thereafter, the specific
surface area gradually decreased to 64.87 m2 g1 when the calcination tem-
perature reached 600 1C. The decreasing surface area of heat-treated clay was
followed through the lower amount of adsorbed cadmium ions at equilibrium
from 46.49 mg g1 at an activation temperature of 300 1C to 8.56 mg g1 at an
activation temperature of 600 1C. Calcined and flux-calcined diatomite clays
also displayed remarkable sorption performance for treating euents con-
taining radioactive waste.91 Both these clays exhibit high selectivity and fast
kinetics to sorb Th(IV) ions. With a specific surface area of 21.93 m2 g1 for
calcined diatomite and 1.25 m2 g1 for flux-calcined diatomite, the removal
percentage of Th(IV) ions reaches 99 0.1 and 91 0.4%, respectively, under
optimum pH conditions (pH 4). The responsible adsorption mechanism under
these conditions was an electrostatic interaction between positively charged
thorium acetate ion complexes (i.e., [ThCH3COO]31 and [Th(CH3COO)2]21)
and deprotonated hydroxyl edge groups.
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During the calcination process, two types of reactions, namely de-

hydration and dehydroxylation, take place, which are responsible for the
changes on structural, textural (e.g., pore size distribution) and adsorptive
removal of calcined clay materials. A dehydration reaction causes the lib-
eration of hydrated and intercalated water moieties from the clay framework,
resulting in the denser packing structure. Meanwhile, dehydroxylation re-
actions (i.e., the evolution of water from hydroxyls belonging to the clay
skeleton) take place at higher temperatures than those of dehydration re-
actions, typically ranging from 500 to 600 1C. This reaction can be accom-
panied by the movement of octahedral cations within the octahedral sheets,
causing phase transformation of clays/clay minerals into a meta-phase and
further recrystallization of the meta-phase into a crystalline phase.89 Cal-
cination of clays and clay minerals at an extreme temperature causes dis-
tortion of the crystalline structure, which results in a notable decrease of
adsorption capacity. Therefore, it must be taken into account that sucient
heat should be applied in order to remove impurities and adsorbed waters in
the external surface and clay matrix as well as to make the octahedral layers
remain intact during the treatment process. On the other hand, very high
temperature treatment will deteriorate the interior structure of the mineral,
leading to amorphization.
The loss of chemical constituents and any thermal reaction occurring
during calcination can be monitored by simultaneous application of
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thermogravimetric analysis (TGA) and dierential scanning calorimetry

(DSC), which record the amount and rate of change in the mass of sample as
a function of temperature or time in a controlled atmosphere. These ther-
moanalytical techniques can dierentiate between peaks associated with
mass loss and those associated with phase transformation in many solids.
The distinctive characteristics of endothermic and/or exothermic peak
temperatures that appear at a certain temperature region represent any
thermal reaction or phase transition in the solid phase and the corres-
ponding percentage of mass loss. In the study by Alkan et al.,89 the structural
distortion of silica tetrahedral and alumina octahedral of kaolinite clay
could be identified at four temperature points: (1) removal of physically
bound water in pores and on the surfaces at 100 1C; (2) mass loss associated
with dehydration of a surface hydroxyl group in the alumina octahedral
sheet at about 400 1C; (3) dehydroxylation of kaolinite and formation of a
metakaolinite phase between 400 and 650 1C; and (4) decomposition of a
metakaolinite phase at 950 1C to form an AlSi spinel phase.
11.3.2 Chemical Activation/Conditioning

Surface modification of clays and clay minerals through chemical activation
is performed by impregnating or immersing the solids in inorganic acid
solutions, such as hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid
(HNO3) or aluminium sulfate [Al2(SO4)3], base solutions such as alkali
and alkali earth metal hydroxides [e.g., NaOH, KOH, Ca(OH)2 or Al(OH)3] or
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anion salts such as potassium dihydrogen phosphate (KH2PO4), orthopho-

sphate, tri-polysulfate and sodium tetraoxosulfate(VI). Chemical treatment
with inorganic acids has been widely used to improve surface and catalytic
properties of fibrous clays with respect to increased surface area, porosity
and number of acid sites compared with the parent clays. Acid leaching of
clays and clay minerals causes disaggregation of the clay particles, elimin-
ation of impurities and dissolution of the external layers.92 In this context,
the solubility characteristics of clays and clay minerals in acids reveal certain
attributes of the mineral itself and are of fundamental importance for de-
termining the utility of various clay minerals as aluminium sources and to
produce porous and high surface area materials for catalyst supports or
adsorbents. Generally, the acid-modified clays consist of a mixture of non-
attacked clay layers and a hydrous, amorphous and partially protonated
silica phase.92
The physico-chemical characteristics of H2SO4-leached kaolin have been
evaluated by Panda and colleagues.93 The eect of acid molarity on the
structural and chemical properties of the resulting materials were charac-
terized using a series of techniques, including XRF, XRD, FTIR, TGA, DTA
and N2 physisorption. The results show the leaching of interlayer and
octahedral cations upon acid treatment in which high acid strength treat-
ment provoked amorphization and structural transformation to form an
amorphous silica type phase. The specific surface area and pore volume were
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228 Chapter 11
found to increase after acid leaching, which is beneficial for removal pur-
poses. Sulfuric acid-activated Tunisian green (RGC) and red (RRC) clays have
been tested for the adsorption of lead metal from aqueous solution in a
batch system.94 The surface properties of acid-treated RGC and RRC clays,
including specific surface area, total pore volume, internal porosity and
pore size, increased and they showed maximum retention capacities of
27.15 mg g1 for H2SO4 treated RRC and 40.75 mg g1 for H2SO4 activated
RGC, as predicted with the Langmuir adsorption model.
Jiang et al. also obtained Al2(SO4)3 modified kaolin with excellent ad-
sorption capacity and high selectivity to remove Pb(II) ions from synthetic
and plating factory wastewater.95 Compared with the parent clay, the sorp-
tion capacity of Al2(SO4)3 modified kaolin is almost 5-fold higher with a
Langmuir monolayer adsorption capacity of 32.2 mg g1. It could be that
modification of kaolin clay by aluminium sulfate octadecahydrate in this
study revealed that the modifying chemical did not impregnate the clay in-
terior, but might exist on the outer surface and provide more available ex-
change sites for enhanced adsorption. During activation of clays/clay
minerals with inorganic acids, the exchangeable cations are substituted by
protons and part of the octahedral cations (mainly Al31) dissolve, creating
new acid centres in the solid structure and making them amorphous, more
porous and acidic. Furthermore, the acid treatment method is eective for
minimizing the possible decomposition of the crystalline structure, thus
generating the desired features for further thermal activation of clay ma-
terials to prepare an eective adsorbent towards heavy metals.
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The influence of acid treatments on the adsorption capacity of sepiolites

was evaluated by Kilislioglu and Aras to sorb radioactive uranium ions
(UO221).96 The acid-treated forms of the clays termed SS200 and SC200 show
a dramatic increase in the specific surface area, but the uranium adsorption
capacity was not solely related to the specific surface area of the materials.
This study found a lower amount of UO221 ions adsorbed onto SS200 (SBET of
568.5 m2 g1) than that adsorbed onto untreated sepiolite (SBET of 325.2 m2
g1), probably due to the leaching of all Mg21 interlayer ions and the col-
lapse of the octahedral layer. Acid-activation of kaolin clay at dierent molar
concentrations and acid to solid impregnation ratios was conducted by
Alkan et al. for removing copper ions.89 This study obtained a lower uptake
of Cu21 ions onto acid-activated clay, possibly due to partial distortion of the
layer structure and specific adsorption of H1 ions onto the clay surface that
reduced active patches.
Chaari et al. modified Tunisian smectite-rich clay using two inorganic
acids, namely HCl and H2SO4 with an equimolar concentration for lead(II)
ions adsorption.97 They found that H2SO4 activated clay (labelled as AYDs)
demonstrated a significantly higher loading capacity towards Pb21 cations
than HCl activated clay (labelled as AYDh). This might be attributed to the
greater solubility of clay minerals in sulfuric acid than in hydrochloric acid,
which resulted in the dissolution of a sucient number of octahedral central
atoms required to increase the specific surface area and the formation of
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non-crystalline Si-rich phase with a three-dimensional cross-linked structure.

Compared with non-activated clay, both acid-activated clays have a higher
number of active surface sites for the binding of lead cations. Spent
bleaching earth (SBE), a waste by-product from an edible oil refining factory
also has value for the elimination of lead ions from water in the study by
Mana et al.98 The SBE, after being thermally treated at a mild temperature
(100 1C) following NaOH impregnation treatment to form SBTE material,
exhibited a significantly higher sorption capacity than those of virgin
bleaching earth and pristine SBE, as well as faster kinetics uptake at the same
metal concentration. Modification of bentonite using phosphate and sulfate
anion salts has been carried out by Olu-Owolabi and Unuabonah.99 Although
the modification process causes the specific surface area of bentonite clays to
decrease due to blockading of the pores, the CEC, as well as adsorption
capacity towards bivalent zinc and copper ions, increased due to the presence
of more binding sites introduced from the physisorbed sulfate and chemi-
sorbed phosphate anions, in which the latter were preferentially adsorbed
onto the AlOH and AlH2O surface functional groups of bentonite clay.
Another ecient pathway to chemically tailoring the surface chemical
nature of clays and clay minerals is through chemical conditioning. Chem-
ical conditioning is a technique with the aim of removing certain ex-
changeable cations from the clay layers and locating more easily removable
ones that are more willing to undergo ion-exchange processes. Lihareva et al.
studied the behaviour of natural and sodium-loaded clinoptilolite as a cation
exchanger of monovalent silver ions.100 The Na form of clinoptilolite showed
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an improved ability for cation exchange of Ag1 ions due to the more
monoionic character of modified clay from the replacement of K1, Ca21 and
Mg21 interlayer cations. The introduced exchangeable Na1 cations from the
conditioning treatment help to increase the exchange performance to
remove Ag1 ions.
Similar work dealing with chemical conditioning of clinoptilolite using
NaCl and HCl solutions has been conducted by Coruh for the removal of zinc
ions.101 They found that the conditioned clays, irrespective of the types of
chemicals, exhibit higher eective ion-exchange capacity due to lower Si to Al
ratios. Chemical conditioning with saturated NaCl solution resulted in the
exchange of tightly bound K1 and Ca21 cations from the zeolitic lattice and
removal of fine dust particles, making the channel apertures more easily
accessible for incoming metal cations. Pretreatment of clinoptilolite with four
dierent chemicals, namely NaCl, KCl, HCl and CaCl2 has been carried out by
Gedik and Imamoglu.102 The results of this study reveal that pretreatment
with NaCl can be adopted as an ecient way to obtain the monoionic form of
clinoptilolite, which shows more than 2-fold enhancement in the metal re-
moval capacity compared with that of the as-received form.
Alkaline Ca-bentonite (ACB) was utilized in the study by Zhang et al. by
treating raw bentonite clay with calcium hydroxide as a cheap sorbent to
remove zinc(II) ions.103 The ACB sorbent displayed a monolayer sorption
capacity 2-times greater than raw bentonite and a more eective
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230 Chapter 11
performance in terms of shorter equilibrium time and broader pH range for

metal removal. In this study, adsorption (cation exchange and fixation) and
formation of Zn precipitates on the outer surface were the two main
mechanisms for Zn(II) removal using ACB sorbent over a pH range of 17.
The adsorbed Zn21 ions were found to intercalate between the clay layers,
causing structural changes and generation of micropores in the sorbent wall.
In another work, Dimirkou conditioned natural clinoptilolite using an
Fe(NO3)3 solution under strong basic conditions to prepare a fully iron ex-
changed form of clinoptilolite, designated as a Clin-Fe-oxide system.104 The
hardness as well as the concentrations of alkali and alkali earth metal cat-
ions of the Clin-Fe-oxide system dramatically dropped after Fe conditioning,
nevertheless the Si to Al ratio of the clay system remained intact compared
with the respective ratio of the parent clay. The synthesized Clin-Fe-oxide
system contains high iron concentrations, exceeding the practical and the-
oretical cation-exchange capacity of the parent clay, characterizing the over-
exchanged feature. The non-crystalline iron clusters (as FeOH) deposited
in the zeolite channels and on the external sites give rise to the Clin-Fe
system higher specific surface area as well as extra-framework positions for
Zn(II)-exchange through outer-sphere complexation.
Abu-Eishah synthesized a chemically modified local clay (termed Sarooj
clay) by saturating the solid phase with 0.01 M NaNO3 solution.105 The Na-
saturated clay was employed to sorb three heavy metal ions, namely Zn21,
Cd21 and Pb21, and showed an eective performance due to its higher
surface properties, including BET surface area, specific micropore surface
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area, external surface area and total pore volume. During chemical treat-
ment, more than half of the interlayer Ca21 cations were exchanged with
Na1 ions, while other metal cations (in the oxide forms) such as Al2O3,
Fe2O3, MgO and K2O were increased. From several of the previous studies
discussed earlier, it can be concluded that the final monoionic and near-
monoionic nature of the clays was found to enhance their eective exchange
capacity and performance in ion-exchange applications, including heavy
metals sorption. Recently, surface modification processes of clays and clay
minerals have been switched to pillaring, grafting or intercalation techni-
ques because they are simpler, and provide cost and energy savings.
11.3.3 Pillaring, Grafting and Intercalation Techniques

Many studies are currently interested in functionalizing the surface chem-
istry of clays and clay minerals through pillaring, grafting and intercalation
techniques rather than conventional thermal and chemical activation pro-
cesses, due to the simpler procedures, cost reduction in respect of prepar-
ation of adsorbents and energy saving. Generally, all these techniques aim to
increase the adsorption potential of clays/clay minerals for removing heavy
metal ions either by increasing the specific surface area and/or tailoring the
chemical nature of the mineral surface so that particular metal species can
be selectively sorbed. The modified clays/clay minerals are well defined as
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organoclays in which the organofunctionalization is normally used to

introduce basic groups on anchored pendant chains.106,107 Typical examples
of guest molecules that have been used for the surface modification pro-
cesses are long-chain ionic surfactants [e.g., cetyltrimethylammonium
bromide (CTAB), lauryl alkyl sulfate (LAS), sodium dodecyl sulfate (SDS),
cetylpyridinium bromide (CPBr), tetramethylammonium bromide (TMAB),
phenyl trimethylammonium bromide (PTMAB) and hexadecyltrimethyl
ammonium (HDTMA)], metal salts that are Lewis acids (e.g., FeSO4, NaNO3,
NaCl and ZnCl2), amino acids or polypeptides, chelating agents (e.g., chit-
osan, chitin, citric acid, succinic acid and organosilanes) and metallic/
composite oxides (e.g., Al2O3, Fe2O3, Fe3O4, TiO2, ZnO, MnO2, SiO2 and
MnFe2O4).
Nowadays, pillared clays (PILCs) have become a well-known class of por-
ous materials with properties exceeding those of zeolitic clays. The pillaring
of clays and clay minerals involves intercalation of bulky inorganic and or-
ganic clusters, such as polynuclear complex inorganic ligands (e.g., hydroxo
and chloro ligands), large metal complex ions with organic ligands and
polyhydroxy cations (e.g., AlCl3 6H2O, ZrOCl2 8H2O and hydroxyl zir-
conium) to exchange interlayer cations. Upon high-temperature treatment
(calcination), the intercalated polyoxycations convert into their metal oxide
forms, which expand the internal pores and create a solid with a stable two-
dimensional microporous structure and large surface area. Some important
factors in the clay pillarings include the size and amount of pillars and their
configuration in the interlayer space, which are highly sensitive to the clay
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characteristics (e.g., the layer charge and its location) and hydrolysis con-
ditions under which the polyoxycations are formed.108,109 The resulting
pillared clays also inherit properties specific to the chemical nature of the
pillaring species, in addition to their improved permanent porosity.
Karamanis et al. studied the application of Al-pillared montmorillonite for
the fast uptake of strontium and caesium ions from aqueous solutions.110 In
the study of Bhattacharyya and Gupta,111 kaolinite and montmorillonite
pillared with polyoxo-Zr ions were used for the removal of Fe(III), Co(II) and
Ni(II) ions in single batch systems. After the pillaring and calcination pro-
cesses, the exchange capacity of clays substantially fell due to dehydroxyla-
tion and interlayering of positively charged cations. Accordingly, the
sorption capacity of pillared clays was lower compared with the parent clays,
possibly due to the blockade of negatively charged adsorption sites and
probably some pore networks by bulky polyoxycations.
The surface modification of clays and clay minerals with cationic sur-
factants involves both a cation-exchange process and the bonding of a
hydrophobic moiety in the clay layers. In this regard, the concentration of
the loaded surfactant crucially determines the types of adsorptive layer
formed. Cationic surfactants can form two types of adsorptive layers:
monolayers and bilayer/patchy bilayers.112,113 At low loading levels, sur-
factant cations eventually create an adsorptive monolayer, while at higher
loading levels, the formation of a bilayer, patchy bilayer or bilayer with a
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232 Chapter 11
paran-type structure may take place. In the study by Atia, commercial

bentonite was loaded with cetylpyridinium bromide to prepare organo-
bentonite for sorbing chromate and molybdenum oxyanions from water.114
From this study, the configuration of surfactant cations in the interlayer
space of the clay depends on the amount of surfactant adsorbed and is a

CEC-function. The formation of a surfactant monolayer was observed when
the amount of surfactant in the interlayer space slightly exceeds the CEC,
while a bilayer and a bilayer with a paran-type arrangement are formed
when the adsorbed amount of surfactant cations were lower than twice and
several-fold higher than the CEC, respectively.
The results of the study conducted by Ouellet-Plamondon et al. demon-
strated that the maximum sorption capacities were 29 mmol/g for Al-pillared
bentonite and 158 mmol/g for QAC-intercalated bentonite toward Pb(II)
ion.115 The amounts of Pb adsorbed by Al-pillared bentonites were higher
than those for untreated bentonite. Faghihian and Kabiri-Tadi modified
natural clinoptilolite using three dierent chemicals, namely NaNO3, KNO3
and Ca(NO3)2 to prepare Na, K and Ca-exchanged forms of zeolitic clays.116
The adsorptive properties of natural and cation-exchanged clinoptilolite to
treat Zr-bearing aqueous euents were contrasted and higher eectiveness
for the latter adsorbent was found under identical conditions. Chemical
modification of kaolin and montmorillonite with tetrabutylammonium
bromide (TBAB) has been carried out to eectively sorb Fe(II), Ni(II) and Co(II)
metal cations.117 However, an intercalation process following calcination
resulted in the decreasing adsorption capacity due to the blockade of some
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parts of the surface pores and negatively charged sites by bulky ammonium
cations. The intercalation of Algerian halloysites with saturated sodium
acetate solution has been conducted by Mellouk et al.118 In their study, the
intercalation process causes the basal spacing of halloysite to increase from
7.6 to 10.1 and the specific surface area from 58 to 884 m2 g1, of which the
increase in basal spacing was found to be unaected with an increase in
contact time during the modification process. The CH3COONa intercalated
halloysite was used thereafter for removing Cu21 ions and shows a max-
imum uptake capacity of 52.3 mg g1.
Silane coupling agents are a family of organosilicon monomers with the
general structure of RSiX3 where R and X refer to the organo-functional
group attached to silicon and hydrolysable alkoxy groups are typically
methoxy (OCH3) or ethoxy (OC2H5), respectively.119 This coupling agent
has found many applications related to uses involving site-specific inter-
actions because of its capability of providing chemical bonding between an
organic and an inorganic material. In the case of surface modification of
clays/clay minerals, the organosilanes (e.g., organosiloxanes and organo-
chlorosilanes) are attached to the clay edge sites through condensation re-
actions between surface hydroxyl groups (SiOH or AlOH) and the
chloro or alkoxy groups of the organosilane.120122 Dogan et al. functiona-
lized sepiolite with [3-(2-aminoethylamino)propyl]trimethoxysilane for the
preconcentration of six metal ions from aqueous solutions namely Co21,
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21 21 21 31 21 123
Cu , Mn , Zn , Fe and Cd . The functionalized material was
characterized using FT-IR, XRD and zeta potential measurements to investi-
gate its surface and electrokinetic properties. It was revealed from their study
that the anchored pendant chains contain basic nitrogen active sites that
facilitate the uptake of metal ions. The intercalated clays exhibit dierent
sorption characteristics, including higher selectivity and sorption capacity.
A low cost chemical sensor for detecting various toxic heavy metals
was prepared from sepiolite grafted with 3-aminopropyltriethoxysilane
(3-APT).106 The grafted sepiolite clays acquire basic amino centres that are
favourable for retaining more metal cations. The specific adsorption of
metal cations onto the grafted sepiolite imparts more positive charges and
shifts the isoelectric point (iep) of the modified clay to higher pH. The fol-
lowing sequence of metal adsorptivity onto the grafted sepiolite surface
(Fe4Mn4Co4Cd4Zn4Cu4Ni) may reflect that basic amino centres
preferentially sorb hard cations such as iron and manganese.
Three dierent intercalation methods of montmorillonite with aluminium
hydroxypolycation and cetyltrimethylammonium bromide (CTAB) have been
performed by Hu and Luo.124 Based on the combined characterization
analyses, including X-ray diraction analysis, Fourier transform infrared and
zeta potential measurements, it was found that the modifying agent had
either entered the interlayer spaces or sorbed onto the external surface of the
clay. Furthermore, they also studied the intercalation orders of surfactant
agents for batch adsorption process of hexavalent chromium. Modification
of various clay minerals such as zeolite, bentonite, exfoliated vermiculite and
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attapulgite using a cationic surfactant (hexadecylammonium bromide) to

sorb hexavalent chromium ions was studied by Thanos et al.125 The results
show that the intercalation of cationic surfactant expands the lamellar space
and changes the negative zeta values of clays to positive, which are
favourable for the adsorption of chromate anions. The maximum adsorption
capacity followed the order of vermiculite (27.06 mg g1)4bentonite
(24.16 mg g1)4attapulgite (15.25 mg g1)4zeolite (13.22 mg g1). The
intercalated clays also exhibit a dierent thermal stability compared with
untreated clays.
The potency of Na-montmorillonite intercalated with a long-chain amine
(i.e., dodecylamine) has been evaluated by Kumar et al.126 They observed
a significant enhancement on the sorption capacity of dodecylamine-
intercalated clay due to the presence of protonated amine and surface sila-
nol groups as well as changes on the surface properties of the modified clay
to organophilic. A series of characterizations, including infrared spec-
troscopy and X-ray diraction, revealed that the organic group bound to
interlayer spacing of montmorillonite via cation exchange mechanism with
Na1 cations and also H-bonding interaction between protonated N in the
primary amine and the OH groups in the silica tetrahedral layer.
The application of bentonite modified with a commercial alkyl ammo-
nium surfactant known as Arquads 2HT-75 for the removal of hexavalent
chromium ions was studied by Sarkar et al.127 The results obtained indicated
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234 Chapter 11
that the organoclays loaded with higher amounts of surfactant exhibited a

more ordered structure and a remarkable increase in the sorption capacity.
The maximum monolayer Cr(VI) adsorption of 14.64 and 8.51 mg g1 at 37 1C
was obtained by loading the clay with surfactant to clay mass ratios of 4.75 : 1
and 2.38 : 1, respectively. Modified bentonites have also proved their worth
for the remediation of water polluted by antimony ions from aqueous so-
lutions. Polyvinyl alcohol (PVA) modified kaolinite was also employed to
remove Pb21 ions in a two-stage counter-current batch adsorber design.128
Although PVA-modified kaolinite had lower specific surface area and ex-
change capacity, it showed higher adsorptivity toward Pb21 ions due to more
active sorption sites donated from the deprotonation of hydroxyl group of
PVA species. In another study, the functionalizing of 2 : 1 clay minerals (i.e.,
vermiculite and montmorillonite) with an amino acid [e.g., cysteine,
H2NCH(CH2SH)CO2H] has been undertaken by Malferrari et al.129 They de-
scribed the modification to the structure of clay minerals addressing the
sorption behaviour of Cd(II) ions onto both untreated and treated clays.
Chelating agents or natural polysaccharide materials have also now been
widely used to modify surface characteristics of clays, with the aim of ren-
dering the clay surface to be more hydrophobic or hydrophilic, at will, de-
pending on the chelating functionalities and, more importantly, to improve
the selectivity and sorption capacity of the sorbents towards specific metal
ions. Moreover, the incorporation of clays/clay minerals into polymeric
networks can strengthen the swelling properties, gel strength and reduce the
production costs of the corresponding adsorbents. Some common func-
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tionality inserted into the clays/clay minerals platelets are amine (NH2) and
hydroxyl (OH) groups. Natural polymer materials with high amino or hy-
droxyl contents have been found to possess good sorption capacity for many
heavy metal ions through surface complexation with these active surface
groups. Chitosan, a hydrophilic and cationic polymer product of chitin has
been used as a chelating agent of zeolite to prepare a chitosanzeolite
composite adsorbent with a weak basic nature.130 The optimum pH for Cu(II)
sorption using a chitosanzeolite composite was 3, when electrostatic ions
were sorbed onto the solid surface by forming electrostatic attractions.
Similar work employing chitosan to prepare a magnetically separable
composite adsorbent was taken by Chen et al.131 The composite adsorbent,
termed chitosanmontmorilloniteFe3O4 microspheres, showed a notable
maximum sorption capacity of 74.2 mg g1 towards Cr(VI) at low pH. In this
study, the separation of composite microspheres from metal solution after
the adsorption process was easily performed with the aid of an external
magnetic force. Natural Wyoming montmorillonite embedded with dierent
chelating functional groups (e.g., NH2, COOH, SH and CS2) from
ammonium organic derivatives was tested for the removal of Pb21, Cd21 and
Zn21 ions from aqueous solutions by Sathi et al.132 When compared with the
unmodified montmorillonite, the resulting organoclays showed considerable
improvement in terms of sorbing selectivity and metal loading capacity. The
insertion of four guest organic functionalities into the lamellar space of clay
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minerals causes the increase in organophilicity and the presence of more

negatively charged ligands from the intercalated organics. Abou-El-Sherbini
and Hassanien immobilized Na-montmorillonite clay with a 2-oxyhydrazino-
N-(2-methylen-yl-hydroxyphenyl)pyridinium (OHMP) hydrazone derivative
chelating agent to remove copper ions from spiked natural water and granite
samples.133 The intercalated clay possessed good chemical tolerance in acids,
bases and common ionic species such as Na1, K1, Ca21, Cl or SO42 as well
as good removal eciency towards Cu(II) ions (119 meq per 100 g) at pH 6.
They also found that the grafted MMT-clay also found potential application
for the treatment of real contaminated euent.
The possibility to use natural chitinbentonite biocomposites for re-
moving toxic chromium(VI) ions in batch mode was conducted by Saravanan
et al.134 The results showed that the prepared biocomposite materials were
able to sorb more than 80% Cr(VI) ions at pH 4 with fast uptake in the initial
30 min and the sorption tends to slow after 45 min. From this study, one can
conclude that the negatively charged nitrogen or oxygen ligands of chitin
macromolecules serve as ancillary sites that are responsible for chelating
higher amounts of metal ions.
The preparations of clays/clay minerals modified with metallic/composite
oxides have gained increasing awareness because they are specifically
functional for sorbing dierent heavy metal ions. The following are several
reasons for employing metal/composite oxides to modify clays/clay minerals:
(1) the surface groups of metal/composite are amphoteric in nature and can
function as an acid or a base, depending on the suspension pH; (2) metal/
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composite oxides have relatively high surface energy and reaction activity
stemming from the large specific surface area; and (3) favourable physical
and chemical properties such as swelling ability, stiness, catalytic, optical,
electronic and magnetic properties. Despite these advantages, most metallic/
composite oxides possess low durability and mechanical strength so they
often aggregate due to lack of dispersibility, which reduces the specific
surface area and eectiveness to sorb pollutants in aqueous suspensions.
The aggregated metal oxides also possess diculties in the separation
process after the metal sorption. To address this challenging issue, various
immobilization techniques are being developed for improving stability and
dispersibility of metal/composite oxides and one of the convenient, cost-
eective methods is by loading with clays and clay minerals as a support
material. Among the metal oxides, iron (Fe) oxides and manganese oxide are
the two most widely used because they have high anity towards metal ions,
large surface area and microporous structure. Clays/clay minerals pillared
with metal oxides exhibit superior structural and chemical properties, such
as high thermal stability, large surface area, intrinsic catalytic activity and
significant sorption capacity over a wide pH range. For example, kaolin
loaded nanoscale zero-valent iron, nZVI (sizeo100 nm), was synthesized
and tested in the removal process of Pb(II) ions from aqueous solution.135
Kaolin-loaded nZVI showed higher specific surface area than untreated
kaolin (26.11 m2 g1 versus 3.67 m2 g1), which may be ascribed to the kaolin
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236 Chapter 11
support preventing agglomeration of iron particles and therefore presenting

a higher specific surface area of available iron to the aqueous phase. The
removal percentage of nearly 100% was observed for kaolin-supported nZVI,
while those of nZVI and kaolin are only 15.8 and 8.6%, respectively. This
observation is in good agreement with the study by Uzum et al. for Cu(II) and
Co(II) removal using Turkey kaolinite-supported nZVI.136
According to the study carried out by Sari and Tuzen, the surface area of
MnO2-modified vermiculite increased about 10-fold from 0.84 to 8.42 m2 g1
after the modification process.137 The MnO2-modified vermiculite also
demonstrated higher sorption capacity than the parent vermiculite (46.2
versus 69.2 mg g1). The optimum concentration of MnO2 deposited onto
the clay surface ranged between 0.2 and 0.3 g g1 while at higher loading
concentrations, the adsorption eciency levels o due to obstructed
micropores, which reduced the number of active adsorption sites.
Manganese oxide coated zeolite has been tested for the removal of Mn21
ions in a batch adsorption system.138 The coating of manganese oxide on the
surface of zeolitic clay provides more available sites for the sorption of Mn(II)
ions at suspension pHs higher than the point of zero charge of the sorbent.
The MnO2 species bound on the zeolite surface (mainly as vernadite) are also
responsible for higher adsorption capacity compared to untreated zeolite for
removing metal ions, which might be ascribed to the increased anity of
MnO2 particles toward Mn21 ions in solution arising from specific equi-
librium reaction Mn21 MnO2 2 H2O22 MnOOH 2 H1. The interfacial
reactions of surface hydroxyl groups are also responsible for the enhanced
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sorption process of metal cations. Similar results were obtained by Eren for
the removal of copper ions using MnO2-modified bentonite.139 After modi-
fication, the maximum sorption capacity of raw bentonite was enhanced
significantly from 42.41 to 105.38 mg g1. Incorporation of manganese oxide
was evidence of increasing the specific surface area and the resultant surface
charge of raw bentonite giving rise to eective removal of Cu(II) ions.
In another study, the preparation of low-cost ceramisite consisting of three
raw materials, namely sintering bentonite, hematite powder (Fe2O3) and ac-
tivated carbon, and its adsorption performance towards zinc and lead metals,
has been tested by Yuan and Liu.140 The presence of fine hematite particles
on the outer surface of the ceramisite composite were found to react and
enhance the removal percentage while the increase of activated carbon dos-
age led to decreasing bulk density. The maximum removal capacity of cer-
amisite was found to be 17.5 mg g1 for Pb21 ions and 7.4 mg g1 for Zn21
ions at pH 5. Additionally, the chemical reaction between the hydroxyl group
and heavy metal ions occurred during metals removal, forming new pris-
matic and spherical crystalline grains containing Pb(II) and Zn(II), respect-
ively, that accumulated and piled up onto the surface of the adsorbent.
Therefore, it can be concluded that the incorporation of metal/composite
oxides enhances removal eciency due to the increase in the surface area
and negative surface charge associated with the formation of deprotonated
oxides on the sorbent surface.
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11.4 Isotherms, Kinetics and Thermodynamics

Evaluation of Heavy Metals Sorption onto Clays
and Clay Minerals
Considering the sorption process of heavy metal ions onto the surface of
clays and clay minerals, some crucial information such as adsorption
equilibria, kinetics and thermodynamics are of great importance for reliable
prediction of adsorption parameters and behaviour, eective design of the
sorption system and optimization of the sorption mechanism pathways.
Given this, adsorption isotherms are invaluable for the adsorption studies
because they describe the equilibrium relationship of adsorbate concen-
tration in the bulk liquid phase (i.e., aqueous solution) and in the solid
phase (i.e., adsorbent surface) at a constant temperature and pH. Adsorption
equilibrium is established when an adsorbate-containing phase has been in
contact with the adsorbent for sucient time, with both the adsorption and
desorption rates being equal.141 This knowledge is not only indispensable
for the process design and optimization, but also in understanding the
adsorption kinetics and thermodynamics of single and multicomponent
systems. Typically, the mathematical models describing such phenomenon
are usually depicted by graphically expressing the solute concentration in
the solid phase (qe, mg g1 or mmol g1) against its residual concentration
in the liquid phase (Ce, mg L1 or mmol L1).
Over the years, a wide variety of empirical and semi-empirical adsorption
equations have been widely used to correlate experimental isotherm data of
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various adsorbateadsorbent pairs, including heavy metal ions. The earliest

model to be known was introduced by Langmuir in 1918 to address the
adsorption of gases onto planar surfaces of mica, glass and platinum, based
on the kinetic principle.142 He developed an empirical adsorption equation
based on the three assumptions as follows:143
a. Adsorption is limited to monolayer surface coverage (the adsorbed

layer is one molecule in thickness) without further adsorption can take
place on the occupied sites.
b. The adsorbate molecules can only accommodate one localized site
without lateral interactions between the adsorbed species, even on the
neighbouring sites.
c. The surface of the solid is ideal with definite localized sites that are
identical in terms of adsorption heat and anity.
Graphically, a Langmuir isotherm is characterized by a plateau curve, which

means that no further adsorption and desorption can take place when the
saturation point is established. This isotherm equation describes Henrys law
behaviour when the solute concentration in the liquid phase is fairly low; on
other hand, at a high-end concentration, the saturation point of adsorption
will be established and the Langmuir isotherm model equals the maximum
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238 Chapter 11
1 1
sorption capacity for a given solid (qmax, mg g or mmol g ) or characterizes
the monolayer surface coverage. The essential characteristic of a Langmuir
equation can be characterized with a dimensionless equilibrium constant
called the separation factor (RL), as defined by Weber and Chakravorti:144
RL (1 KL C0)1 (11.5)
Various RL values indicate the types of adsorption to be unfavourable
(RL41), linear (RL 1), favourable (0oRLo1) or irreversible (RL 0). The
applications of this isotherm model have found reasonable success for
correlating various heavy metalclay sorption systems15,16,18,8998 with
favourable adsorption nature and can be implied as the platform and most
useful isotherm model for describing physical and chemical adsorption
phenomena, both in gas and liquid phases.
The Freundlich equation is another adsorption isotherm model that has
been frequently used to describe non-ideal and reversible adsorption phe-
nomena,145 specifically for complex solids with non-uniform distribution in
terms of adsorption energy and anity, such as activated carbons or mo-
lecular sieves. In this isotherm perspective, the amount of adsorbate re-
tained in the solid phase continually rises with increasing concentration in
the bulk solution, which means that infinite adsorption can take place
on the solid surface. Generally, a Freundlich isotherm gives accurate pre-
dictions in the intermediate range of adsorption equilibrium data, typically
at moderate solute concentrations. In some cases, the favourability of the
adsorption process can also be evaluated from the Freundlich empirical
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constant, called the intensity factor (nF), in which the characteristic of the
adsorption process is poor (nFo1), moderately dicult (1onFo2), feasible
(2onFo10) and approaching a rectangular or non-reversible isotherm when
nF value is larger than 10, respectively.143 However, this model is criticized
due to the lack of a fundamental thermodynamic basis and not approaching
Henrys law at the vanishing concentration and saturation adsorption limit at
high-end concentrations. The same as for the Langmuir isotherm model, the
successful applications of Freundlich isotherms have been reported in many
sorption studies involving heavy metal ions and clays/clay minerals, apart
from the limitation and lack of fundamental thermodynamics in this model.
In the past few years, much eort has been paid to formulating various
empirical or semi-empirical adsorption equations, either to overcome some
drawbacks in the predecessor equations (e.g., Langmuir and Freundlich
equations) or to propose new adsorption models featuring adequate fun-
damental kinetics and thermodynamics as well as satisfactory agreement
over a wide range of concentrations. Some examples are Hill, Temkin, Flory
Huggins, DubininRadushkevich, LangmuirFreundlich or Sips, Toth,
RedlichPeterson and BrunauerEmmettTeller adsorption equations.146
Table 11.5 presents several studies with successful applications of the two-
parameter or three-parameter adsorption equations mentioned here for
describing liquid phase adsorption behaviour for heavy metalclays/clay
mineral systems.
Table 11.5 Several two-parameter and three-parameter isotherm models used for liquid phase heavy metals adsorption equilibria
correlation.
Isotherm models Mathematical form Adsorption parameters Systems References
Langmuir KL Ce qm maximum adsorption Sarooj clay Zn(II) 105
qe qm
1 KL Ce capacity (mg g1 or Sarooj clay Cd(II)
mmol g1) Sarooj clay Pb(II)
KL Langmuir adsorption VSco Ni(II) 72
anity (L mg1 or VPum Ni(II)
L mmol1)
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Kaolinite Cu(II) 89
CPBr/bentonite Cr(VI) 114
CPBr/bentonite Mo(VI)
TBA/kaolinite Co(II) 117
TBA/montmorillonite
Co(II)
Smectite Pb(II) 97
Clinoptilolite Zn(II) 101
Functionalized sepiolite 123
Co(II)
Functionalized sepiolite
Mn(II)
Tunisian clay Pb(II) 94
Na-exchanged 100
clinoptilolite Ag(I)
Spent bleaching earth 98
Pb(II)
Halloysite Cu(II) 118
Attalpugite Cr(VI) 125
Diatomite Th(IV) 91
Chitosan/zeolite Cu(II) 130
MnO2-coated zeolite 138
Mn(II)
Chitosan/montmorillonite 131
Cr(VI)
239
Organo montmorillonite 126
Cr(VI)
240
Isotherm models Mathematical form Adsorption parameters Systems References
Alkaline Ca-bentonite Zn(II) 103
Polyvinyl-modified kaolin 128
Pb(II)
Expanded perlite Hg(II) 70
Palygorskite Pb(II) 69
Organobentonite Cr(VI) 127
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Freundlich 1=n
qe KF Ce KF Freundlich adsorption Bentonite U(VI) 27
anity (mg g1)(L mg1)1/n Clinoptilolite Zn(II) 101
or (mmol g1)(L mmol1)1/n Na-exchanged 100
clinoptilolite Ag(I)
n dimensionless intensity Spent bleaching earth Pb(II) 98
factor characterizing the Halloysite Cu(II) 118
surface heterogeneity degree Attalpugite Cr(VI) 125
Diatomite Th(IV) 91
Chitosan/zeolite Cu(II) 130
MnO2-coated zeolite Mn(II) 138
Chitosan/montmorillonite 131
Cr(VI)
Organo montmorillonite 126
Cr(VI)
Alkaline Ca-bentonite Zn(II) 103
Chitin/bentonite Cr(VI) 134
Palygorskite Cd(II) 90
Boron-containing clay Ni(II) 84
Kaolinite Cu(II) 89
Dubinin qe qm exp(be2) qm the maximum Organo montmorillonite 126
Radushkevich (DR) adsorption capacity Cr(VI)
(mg g1 or mmol g1) Diatomite Th(IV) 91
Chapter 11
b the Dubinin Attalpugite Cr(VI) 125
Radushkevich constant of Sepiolite U(VI) 96
adsorption energy (mol2 Perlite Pb (II)
kJ2) Dolomite Pb(II)
e the Dubinin Unye clay Cu(II) 67
Radushkevich constant of 139
the Polanyi potential, with
e equal to RTln[1/(1 Ce)]
RedlichPeterson (RP) K1 Ce K1, K2 RedlichPeterson Chitosan/zeolite Cu(II) 130
qe
1 K2 Ceb isotherm constants, in Halloysite Cu(II) 118
(mg g1) or (mmol g1) and Organo montmorillonite 126
(mg g1)b or (mmol g1)b Cr(VI)
11:26:35.
b RedlichPeterson
isotherm exponent which
lies between 0 and 1
Temkin RT RT A Temkin isotherm constant Organo montmorillonite 126
qe ln A ln Ce
b b of adsorption anity Cr(VI)
(L mg1 or L mmol1) Diatomite Th(IV) 91
b Temkin isotherm constant
of heat of sorption
(kJ mol1)
FloryHuggins (FH) Y KFH FloryHuggins Diatomite Th(IV) 91
log ln KFH adsorption equilibrium
Ci
constant
nFH log1 Y nFH the FloryHuggins
model exponent
Y the degree of surface
coverage, expresses as
1 Ce/Ci
Elovich qe qe KE Elovich adsorption Organo montmorillonite 126
ln lnKe qm equilibrium constant Cr(VI)
Ce qm
(L mg1 or L mmol1)
qm the maximum
adsorption capacity
(mg g1 or mmol g1)
241
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242 Chapter 11
Considering the adsorption parameters associated with solute adsorptivity

and maximum sorption capacity of a given solid, several environmental factors
such as temperature and initial solute concentration all play crucially im-
portant roles. Generally speaking, the adsorptivity of solute molecules towards
the adsorbent surface increases with increasing temperature because of the

greater magnitude of kinetic energy in the system, which allows the solute
molecules to move around faster and it is then easier to sorb onto the solid
surface. The increasing adsorption anity of heavy metal cations towards the
solid surface with increasing temperature can be found in several studies.
Moreover, the increasing amount of metal ions adsorbed at higher tempera-
ture may reveal that chemisorption is the dominant mechanism by forming
chemical bonding between positive and negative charge clusters. Among the
well-known adsorption models, Langmuir and Freundlich are the two most
popular equations used for the correlation of liquid phase equilibrium data in
many heavy metalclay systems. These two isotherm equations have found
reasonable success and correlations of copper adsorption isotherm data
onto clays has been studied by Irani et al.,67 Alkan et al.,89 Mellouk et al.,118
Wan Ngah et al.,130 Weng et al.,147 Yu et al.,148 Komy et al.149 and Dizadji et al.150
Adsorption kinetics is also one of the most crucial factors for the eective
design of sorption systems since it predicts the rates of adsorption and de-
sorption of pollutants in a given solid/solution system. The overall sorption
rate may be mainly controlled by any or a few of the following steps:151
(1) transport of solute in the bulk solution; (2) diusion of solute across the
so-called liquid film surrounding the solid particles; (3) diusion of solute in
11:26:35.
the liquid contained in the pores of the solid particles and along the pore
walls (intraparticle diusion); and (4) adsorption and desorption of solute on/
from the solid surface. In this context, some extensively used mathematical
models for describing the kinetics of sorption for a particular system are
pseudo-first order (Lagergren), pseudo-second order, intraparticle diusion
and the Elovich equations. These formulae have usually been associated with
surface reaction kinetics as the rate-controlling step and oer some advan-
tages, such as compactness and simplicity with few computer resources re-
quired to solve the rate equations. The common procedure used to verify
whether the best kinetic models are suitable to fit experimental data is
through best-fit either using linear or non-linear regression techniques.
11.5 Conclusions
Clays and clay minerals are promising low-cost materials for the cost-eec-
tive and ecient remediation of synthetic and real waste euents con-
taminated by toxic heavy metal ions. Considering several previous studies
dealing with the adsorption of heavy metal ions using clays and clay min-
erals, the following conclusions can be deduced:
a. The layer characteristics with structural negative charge and the sur-
face chemical nature of natural clays and clay minerals are both
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suitable for the eective removal of cationic pollutant species such as

heavy metal ions.
b. The edge hydroxyl groups, namely silanol and aluminol, are pH-
dependent and are important in the sorption of metal cations by
providing negatively charged ligands at high pH.

c. Thermal activation of clays and clay minerals is essentially eective for
increasing the surface area and porosity by removing adsorbed waters
(dehydration) and other impurities while the layered structures of
clays/clay minerals remain intact. Extreme activation temperature
causes structural distortion (e.g., dehydroxylation, recrystallization,
shrinkage, fracture and sintering) and amorphization of the solid,
which means the adsorptive removal of the solid decreases.
d. Chemical activation with inorganic acids (e.g., HCl and H2SO4) can
improve the sorption capacity of clays/clay minerals considerably by
introducing additional centres that are active for metal ions binding
and increasing surface area that resulted from the elimination of
octahedral central atoms, delamination of card-house structure and
generation of microporosity.
e. Surface modification of clays/clay minerals through pillaring, grafting
or intercalation techniques can be employed in an eective way to
increase chemical stability and provide additional sorption sites with
exceptional anity toward metal cations by covalently intercalating
guest molecules into the interlayer surfaces.
11:26:35.
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CHAPTER 12
Heavy Metals in Tannery

Wastewater and Sludge:
Environmental Concerns
and Future Challenges
GIUSY LOFRANO,*a MAURIZIO CAROTENUTO,b
RAVINDRA KUMAR GAUTAMc AND
MAHESH CHANDRA CHATTOPADHYAYAc
a
Department of Environment, Waste Division, Salerno Province, via Mauri
61, 84129 Salerno, Italy; b Department of Chemistry and Biology University
11:26:38.
of Salerno, via Giovanni Paolo II, 84084 Fisciano (Sa), Italy;

c
Chemistry, University of Allahabad, Allahabad211 002, India
*Email: glofrano@unisa.it
12.1 Introduction
The tanning process aims to transform skins into stable and imputrescible
products, namely leather.1 Production of leather can be performed by both
vegetable and chrome tanning. The vast majority of leather production relies
on chromium(III) based tanning processes, nevertheless leather production
based on vegetable tanning (VT) is utilized extensively by traditional tan-
neries in developing countries.2 Chrome-tanned leather tends to be softer
and more pliable than vegetable-tanned, has higher thermal stability, is very
stable in water and takes less time to produce than vegetable-tanned leather.
Almost all leather made from lighter-weight cattle hides and from the skin of

249
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250 Chapter 12
sheep, lambs, goats and pigs is chrome tanned. The first steps of the process
(soaking, fleshing, liming/dehairing, deliming, bating and pickling) and the
drying/finishing steps are essentially the same as in vegetable tanning.
However, in chrome tanning, the additional processes of re-tanning, dyeing
and fat liquoring are usually performed to produce usable leathers, and a
preliminary degreasing step may be necessary when using animal skins,
such as sheepskin. A re-tanning bath procedure applied for production of
clothes in one of main industrial Italian leather districts is shown in
Figure 12.1.
When the chromium salts are used as tannage, only 60% of the total
chromium reacts with the hides and about 40% of the chromium remains in
the solid waste and spent tanning solutions. The tanning wastewaters con-
tain the highest concentration of total chromium (up to 4950 mg L1). Al-
though the leather tanning industry is known to be one of the leading
economic sectors in many countries, there has been an increasing en-
vironmental concern regarding the release of various recalcitrant pollutants
and metals in tannery wastewater and sludge.1 Now, as ever, its future de-
pends on the challenge of making the process environmentally friendly and
recovering primary resources.
12.2 Heavy Metals in Tannery Wastewater

and Sludge: Treatment Options
12.2.1 Characteristics
11:26:38.
Wastewaters from tanneries contain a large range of substances that are

either derived from hides and skins or are present through the addition of
reagents during the processing, including high concentrations of chlorides,
aliphatic sulfonates, sulfates, aromatic and aliphatic ethoxylates, sulfonated
polyphenols, acrylic acid condensates, fatty acids, dyes, proteins, soluble
carbohydrates and also heavy metals, mainly chrome. Chromium ion in li-
quid tanning wastes occurs in two forms: trivalent Cr(III) and hexavalent
Cr(VI). The hexavalent form is 500 times more toxic than the trivalent and can
cause or increase the rates of certain cancers.4 The characteristics of tannery
wastewaters vary depending on the nature of the tanning process adopted,
the amount of water used, the process of hide preservation, the hide pro-
cessing capacity and the in-plant measures followed.5 Table 12.1 reports the
average composition of mixed euents from leather tanneries. The average
influent chromium(III) concentration varies from 30 to 260 mg L1.1 The
toxic eect of chromium in leather tannery wastewater has been demon-
strated in various studies. Lofrano et al.6 showed that the raw wastewater
collected from the equalization tank of a central leather tanning wastewater
plant (Campania, Italy) displayed 100% immobilization on Daphnia Magna
even at 25% dilution.
As a consequence of wastewater treatment, the tannery sludge contains a
considerable amount of organic matter and heavy metals, as well as
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Heavy Metals in Tannery Wastewater and Sludge 251

11:26:38.
Figure 12.1 A re-tanning bath procedure applied for production of clothes; percent-
ages are for 100 g of leather product, which proceeds in the tumbler (6 l
of water are used for production of 12 kg raw pre-pickled leather (600%
of water for 100% of leather) (reprinted from Lofrano et al.3 with kind
permission of Taylor and Francis).
pathogenic or disease-causing microorganisms, which are harmful to the

environment and human health. Both the wastewater and sludge contain
levels of heavy metals, especially chromium, that are high enough to warrant
252
Table 12.1 Characteristics of tannery wastewater (mg L1)a (reprinted from Lofrano et al.1 with kind permission of Elsevier; data has been
compiled from references6,19,3955).
pH COD BOD5 TSS TS SS TDS Alk. Chloride Sulfate Sulfide NH4-N Phosph. Cr Iron
11:26:38.
8.4 4947 2239 665 7601 95 4

10.5 3114 1126 18 884 1147 17 737 55 33 83
7.79 2155 915 35.8 168 50.9
7.59 5000 1500 100
10 000 2000
8 1803 106 526 9435 2251 70
8000 930 2004 15 152 228 11.2
7.4 2227 1800 578 3430 1210 137
8.28.5 5650 19 775 5025 14 750
10.72 11 153 2906 6810 507 162 32.87
7.7 2200 5003 36 800
7.7 2426 286 335 29.3
6.6 6855 2700 2865 1010 2835 745 70.5 140
7.08 10 265 2820 128 90100
7.2 2810 910 1520 6400 89 130 62 0.62
8.3 3100 1195 1010 4150 54
7.088.7 4100 630 600 13 300 11.5
6700 975 955 19 700 14.3
7.2 2102 576 3260 118
7.99.2 2533 977 1244 21 620 6528 860 118 62 258 2.56
7.4 3700 1470 2690 440 180
a
COD, chemical oxygen demand; BOD, biochemical oxygen demand; Alk., alkalinity; TS, total solids; TSS, total suspended solids; SS, suspended solids; TDS,
Chapter 12
total dissolved solids; Phosph., phosphorus.
View Online
investigation into recovery and possible reuse of wastewater and decon-

taminated sludge.7
12.2.2 Treatment Options: Removal and Recovery

12.2.2.1 Wastewater
Removal of metals from tannery wastewater is achieved by the application of
several processes, such as chemically assisted sedimentation,8,9 coagulation/
flocculation,10 electrochemical processes,11,12 ion exchange,13 ad-
sorption,1417 filtration and membrane processes7 and their combinations.18
The coagulationflocculation (CF) process, generally using inorganic co-
agulants such as aluminium sulfate (alum), ferric chloride (FeCl3) or ferrous
sulfate (FeSO4), has been applied to leather tanning wastewater to reduce the
organic load and suspended solids in addition to removing chromium be-
fore biological treatment. Ates et al.19 investigated the eectiveness of alum
and FeCl3 based CF for the treatment of a homogenized inlet of a central
treatment plant in a leather tanneries district. All experiments resulted in
470% of COD removal. Total chromium was also eectively (o5 mg L1)
removed by the alum, while it was almost completely removed using FeCl3,
as seen in Figure 12.2.
Kabdasli et al.20 also reported 4070% removal of COD and 499% of total
chromium from leather tanning wastewater using FeSO4, FeCl3 and alum.
According to Song et al.10 7499% removal of chromium with an initial
concentration of 12 mg L1 can be achieved by using the optimum coagulant
11:26:38.
dosage (FeCl3 800 mg L1) in the optimum pH range (around 7.5). The initial
chromium concentrations and pH values of the wastewater have a great ef-
fect on the chromium removal eciency. Low chromium concentrations and
high pH produce a more eective result for chromium removal than high
chromium concentrations and low pH. Higher dosages do not significantly
increase pollutant removal and are not economical.
Among the various adsorbents, bentonite clay has been found to be
eective in the removal of chromium from tannery wastewater by Tahir and
Naseem.16 Natural materials that are available in large quantities or certain
10000 1000
[mg L-1]
[mg L-1]
5000 10
0 0.1
A B C D A B C D
COD in Cr in
Figure 12.2 The chemical settling of a homogenized raw wastewater from a central-
ized leather tanning district: A, alum polyelectrolyte (600 2) mg L1;
B, alum polyelectrolyte (400 2) mg L1; C, FeCl3 polyelectrolyte
(1000 2) mg L1; D, FeCl3 polyelectrolyte (750 2) mg L1 (data
from Ates et al.19).
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254 Chapter 12
waste products from industrial operations and agricultural by-products

that may have potential as inexpensive adsorbents have also been tested.15,17
The percentage of Cr(III) removal as a result of adding shrimp shells to
the tanning wastewater was higher than 99% in the studies by Fabbricino
et al.17
The selection of the best treatment options needs to take into account
discharge limits. To this eect, Table 12.2 provides a comparison between
the legal discharge limits for Cr(III) adopted in several countries.
Chromium recovery from tanning exhausted baths represents a significant
economic advantage for the leather industry in terms of its reuse and for the
simplification of the polishing process of global wastewaters. The exhausted
baths from chromium tanning contains about 30% of the initial salt and it is
normally sent to a clean-up plant. The traditional method for chromium
recovery is based on the precipitation of the chromium salt with NaOH
followed by the dissolution of Cr(OH)3 in sulfuric acid. However, the quality
of the recovered solutions is not always optimal with respect to the presence
of metals, lipidic substances and other impurities. Therefore in recent years
membrane technology has become increasingly attractive for chrome re-
covery and recycling. The main advantage of a membrane process is that
concentration and separation are achieved without changing the physical
state or the need to use chemical products. Crossflow microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and supported
liquid membranes (SLMs) can be applied in the leather industry for the
recovery of chromium from spent liquors. The application of these mem-
11:26:38.
brane systems (MF, NF, UF and RO) and dual schemes MFUF, UFNF and
NFRO for the treatment of tannery wastes and for the recovery of chromium
and other chemicals has been experimentally investigated by several
Table 12.2 Total chromium legal discharge limits in sewers

and surface waters in several countries.
Surface water Sewers
Country Cr (mg L1) Cr (mg L1)
Italy 2 4
France 1
Greece 0.5 0.5
Portugal 2 2
Spain 2 4
Austria 4 15
Denmark 2a 2a
The Netherlands 0.05a 2a
Poland 0.5
Switzerland 2a 2a
New Zealand 550
United Kingdom 2 510
Brazil 0.5 0.5
India 0.05 2
a
Limits refer to trivalent chromium only.
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7,21,22
researchers oering interesting perspectives for improving the sus-
tainability of the leather tanning industry and for recovering and recycling of
the primary resources.
12.2.2.2 Sludge
The management of mixed physico-chemical and biological tannery slud-
ges pose a serious environmental concern and a health risk for humans.
Thermal incineration is considered as the cheapest alternative and the
most attractive method because of its simultaneous energy production and
volume reduction of the sludge. However, special attention is required with
respect to issues such as release of toxic chromium(VI), halogenated organic
compounds, polyaromatic hydrocarbons, etc., into the environment. The
high concentration of heavy metals (Cu, Cr, Zn and Pb) causes chronic air
pollution.23 The major species formed from Cr(III) during thermal in-
cineration of solid waste are Cr2(SO4)3(s), CrOCl2(g) and Cr2O3(s), which
subsequently account for a path to the formation of Cr(VI). Sludge com-
position and oxygen concentration in the incinerator determine the extent
of conversion of Cr31 to Cr61. Attempts have been made to inhibit the
formation of these species under a supply of a reduced oxygen atmos-
phere.24 However, in this case bottom-ash containing toxic heavy metals
and partially burnt carbon, which need to be carefully managed, are also
produced. An eective solidification and stabilization of bottom-ash has
been resorted to in order to change potentially hazardous solid wastes into
11:26:38.
less hazardous or non-hazardous solids before it is disposed of as

landfill.24
Illegal dumping and uncontrolled landfills are still common practice in
many developing countries.25 In Italy, every year 120 000 tons of such sludge,
as dry solid, are wasted. Because of their high chromium content
[Cr(III) ranges from 1 to 5%, while Cr(VI) is practically absent], according to
the current Italian regulations, the disposal of these sludges calls for con-
trolled landfilling.26 On the other hand, owing to the progressive exhaustion
of such landfills and the diculty in obtaining authorization for new sites,
land disposal of such sludge is increasingly attractive, providing an eco-
nomical and attractive alternative for the final disposal of tannery sludge
because it consists largely of organic substances and also contains nitrogen
and phosphorus. However, spreading tannery sludge on land (raw or after
composting with urban solid wastes) is not allowed as chromium could af-
fect the metabolism of, and/or accumulate in, living organisms. The un-
avoidable oxidation of Cr(III) to more soluble and toxic Cr(VI) species could,
moreover, cause groundwater pollution.
Therefore, removal of Cr and the other heavy metals from tannery sludge
results is indispensable for safe sludge management, especially in land-use
application. Among the chemical and microbiological methods investigated
to leach chromium and other metals from tannery sludge and other wastes,
in the last decade, bioleaching has arisen and is growing in interest.
View Online
256 Chapter 12
The removal of heavy metals from sewage sludge using Acidithiobacillus

ferrooxidans (an iron and sulfur oxidizing bacterium) or Acidithiobacillus
thiooxidans (an sulfur oxidizing bacterium) has been widely investi-
gated.25,2729 This process used biological reduction of sludge pH and phase
separation to remove toxic metals from sewage sludge. It was demonstrated

that sludge pH was decreased to 2.0 and more than 80% of Cu, Zn, Cd and Ni
were leached from the sludge. In microbiological methods, metals can be
readily solubilized by oxidation of metal sulfide to soluble sulfate or via acid
dissolution with sulfuric acid formed by oxidation of elemental sulfur. The
released chromium can be eciently removed or recovered for reuse in
many ways. The main procedure in the chromium recovery from spent
tanning solutions is the precipitation of the chromium as chromium hy-
droxide by the addition of an alkali to the spent tanning solution. Sub-
sequently, the chromium hydroxide is redissolved by H2SO4 and basic Cr(III)
sulfate is obtained. This compound is reused in tanning.30 Thus treatment
of tannery sludge with sulfur-oxidizing bacteria is expected to be advan-
tageous for the tanning industry with respect to environmental and eco-
nomic considerations.
12.3 Environmental Concerns

12.3.1 Exposure Pathways and Health Eects
11:26:38.
Chromium is commonly used in paints and tanning salts, and as a con-

sequence finds its way into air, soil, food and water. Workers in tanning
facilities are exposed to chromium by inhalation of dust or fumes as well as
by dermal contact from improper handling. Ingestion or contact with con-
taminated water are other ways of chromium exposure. Inhalation of chro-
mium(VI), which occurs most frequently among workers, has been found to
cause cancer for respiratory systems. Inhalation of dust contaminated with
chromium can also lead to eye damage, ulcerations, swelling, asthmatic
bronchitis and irritation to the throat and nose. Sores develop in the nose
and the formation of holes in the nasal septum have also been associated
with chronic exposure to chromium(VI). It is also known that chromium(VI)
can cause stomach problems, such as ulcers, damage to the kidneys and
aect liver functions. Dermal contact causes a number of skin problems,
including rashes, sores and ulcers. Several studies showed that the chro-
mium accumulation in the body can damage a persons ability to metabolize
iron, producing an iron deficiency: anemia.31,32 According to the infor-
mation collected for an inventory of sites prepared by the Blacksmith In-
stitute,33 95 polluted sites have been estimated around the world
(Figure 12.3).
As shown in Table 12.3, South Asia, and in particular India and Pakistan,
has the highest number of tanning industries, and the largest populations
being exposed to chromium contamination.
View Online

Figure 12.3 Populations estimates are preliminary and based on an on-going global
assessment of known polluted sites.33
Table 12.3 Regions most impacted by chromium pollution from

tannery operations.
11:26:38.
Estimated
Number of sites in impacted
Country Blacksmith database33 population
South Asia 62 1 147 400
Central America 3 310 500
South America 11 205 000
Africa 9 143 000
12.3.2 Phytotoxicity
When present in small amounts, the metals that accumulate in tannery
sludge, Cr, Cd, Cu, Pb and Zn, may be essential for plant growth; however, in
higher concentrations they are likely to have a detrimental eect. The ac-
cumulation of heavy metals in vegetables resulting from irrigation with
contaminated water obtained from industrial euents may create a poten-
tial public health risk.
Chromium (Cr) naturally occurs in rocks, soils and plants. Owing to its low
solubility, only a little chromium is bioavailable. As a consequence crops
grown on soils treated with sludge relatively high in Cr rarely show any
phytotoxicity eect. Zinc (Zn) is essential for plants and animals. A Zn tissue
concentration of less than 15 mg kg1 (dry weight) leaves a plant deficient,
whereas a concentration over 400 mg kg1 (dry weight) is potentially
View Online
258 Chapter 12
34
phytotoxic. The tolerance of animals to Zn strictly depends by the presence
of Cu, Mn, Fe, Pb and Cd. Zinc can be accumulated in plants tissues, which
can be used for human consumption. However, its toxicity in plants occurs
before reaching the level that is harmful to humans who ingest the plant.
Toxicity of Zn is seldom observed until plant tissue levels in excess of

1000 mg kg1 are reached.34
Copper (Cu) is a micronutrient for plants and animals. Its natural con-
centration in plants usually ranges from 5 to 25 mg kg1 (dry weight). Lower
levels will render the plant deficient in Cu, higher levels (above 25 mg kg1)
might promote phytotoxicity. However, the land application of biosolids and
compost with normal Cu concentrations, even at very high cumulative
loading rates, did not produce Cu phytotoxicity.34 Only when concentrations
of more than 2000 mg kg1 were applied to strongly acidic soils was Cu
phytotoxicity observed in sensitive crops.34
Plant tolerance to soil lead (Pb) is very high because it is easily adsorbed.
However Pb is not essential for plants or animals and can be toxic to both.
The potential risk from Pb in compost is not through plant uptake of
compost-applied Pb, but rather through direct soil ingestion of Pb by chil-
dren or livestock.34
Cadmium (Cd) is not essential for plants or animals, however it has not
been found to be toxic to plants under natural conditions35 but when added
to acidic soils. Various species of plants show dierent levels of cadmium
accumulation, while accumulation varies in dierent plant organs as fol-
lows: leaves4storage roots4fruits and grains.35
11:26:38.
12.4 Future Challenges

The processing methods in tanning industries have been dominated by
traditional practice. Conventional tanning methods are known to con-
tribute more than 98% of the total pollution load from the processing of
leather.36 The pollution control of the leather tanning process is now of
high and immediate priority to enable this industry to survive. Research
studies on the possibility of rendering the process eco-sustainable foresee
recovering and recycling of the primary resources.7,21,37,38 Stream segre-
gation is the initial step in implementing in-plant controls. Owing to the
dierence in wastewater characteristics from the beamhouse (high pH and
sulfides), tanning and re-tanning (low pH and chromium) operations, more
ecient control could be achieved through the use of a treatment process
specifically designed for the relevant pollutant. Furthermore, the segre-
gation could lead to the reuse or recycling of spent liquors and the recovery
of materials.56
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CHAPTER 13
Fluorides in Dierent Types

of Aquatic Systems and their
Correlation with Metals
and Metalloids
C. CHRISTOPHORIDIS,*a I. PASIAS,b E. MITSIKA,a
S. VELOUTSOUa AND K. FYTIANOSa
a
Environmental Pollution Control Laboratory, Department of Chemistry,
Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece;
b
Laboratory of Analytical Chemistry, Department of Chemistry, University
of Athens, Zografou, 15771 Athens, Greece
11:26:40.
*Email: cchrist@chem.auth.gr
13.1 Heavy Metals and Fluorides in the Environment

Heavy metals represent one of the most important classes of pollutants,
since they are non-degradable, highly toxic and commonly found in many
environmental matrices. Their main sources are well studied and include
natural processes, such as rock weathering, dissolution and volcanic erup-
tions, as well as anthropogenic activities, such as smelting, plating, mining
processes, production of paints and pigments, etc.1
Fluorides (F) comprise a common constituent of groundwater, mainly
originating from the dissolution of fluorine-bearing minerals. Nevertheless,
fluorides can enter the environment through various pathways: natural or
anthropogenic.2

261
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262 Chapter 13
13.1.1 Natural Sources

Fluorides enter the environment through three main natural sources. The
first source, with the highest contribution, is the weathering of fluoride-
rich minerals. Fluorapatite [Ca5(PO4)3F], fluorite (CaF2), cryolite (Na3AlF6),
biotite K2(Mg,Fe)4(Fe,Al)2[Si6Al2O20](OH)2(F,Cl)2, amphiboles (Ca,Na,K)01

(Ca,Fe,Li,Mg,Mn,Na)2(Al,Cr,Fe,Mg,Mn,Ti)5(Al,Si,Ti)8O22(OH,F,Cl)2, micas
(K,Na,Ca,Ba)(Al,Cr,Fe,Li,Mg,Mn,V,Zn)23(Al,Be,Fe,Si)4O10(OH,F)2, topaz (Al2
(F,OH)SiO4) and cryolite (Na3AlF6) are the most common inorganic fluoride
minerals in the earths crust.3 The presence of fluorides can influence
mineral solubility, therefore substituted apatites with high fluorine content
are more soluble than pure (high-temperature) apatites.4 The presence of
fluorides in groundwater aquifers depends on the geological, chemical and
physical characteristics of the aquifer, the porosity and acidity of the soil and
rocks, the temperature, the action of other chemical elements, the contact
time and the depth of the aquifer. Because of the large number of variables,
the fluoride concentrations in groundwater can range from well under
1 mg L1 to more than 35 mg L1.5
Fluorides can be leached out and dissolved in groundwater and thermal
gases from natural minerals. Fluoride concentrations are frequently pro-
portional to the degree of waterrock interaction, especially in granitic and
metamorphic terrains.6 Metamorphic rocks have a fluorine concentration
ranging from 100 mg L1 (regional metamorphism) up to more than 5000
mg L1 (contact metamorphism). In these rocks the original minerals are
enriched with fluorine by metasomatic processes. Chae et. al.4 examined the
11:26:40.
deep bedrock groundwater of South Korea and reported that the median
fluoride concentration in groundwater is related to the mineral composition
of granitoids, metamorphic and complex rocks, where the basic minerals are
biotites and the granite intrudes into deeper parts of the aquifer.4,5 Sedi-
mentary rocks have a fluorine concentration of 200 mg L1 (limestone) up to
1000 mg L1 (shales). In carbonate sedimentary rocks the fluorine is present
as fluorite. Clastic sediments have higher fluorine concentrations as the
fluorine is concentrated in micas and illites in the clay fractions. High
concentrations may also be found in sedimentary phosphate beds (shark
teeth) or volcanic ash layers.
In general, groundwater contains higher fluoride concentrations than
surface water due to higher contact times with fluoride-bearing minerals
in rockwater interactions.2,5 These types of groundwater formations are
usually associated with deep aquifer systems and a slow groundwater
movement. Shallow aquifers, which contain recently infiltrated rainwater,
usually have low fluoride concentrations. Exceptions can occur in shallow
aquifers situated in active volcanic areas aected by hydrothermal
alteration.
Volcanic activity constitutes the second and most persistent source of
fluorides. Volcanic aerosols and ash, emitted during eruptions, are crucial
factors for the enrichment of the fluoride content in drinking waters.
View Online
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 263
Volcanic plumes are a turbulent mixture of gases, solid particles and

aqueous acid droplets710 emitted at high temperature from craters dur-
ing eruptive episodes. Magmatic fluorine is released as hydrogen fluoride
through volcanic degassing; either at a short-lived volcanic eruption,
where large amounts of hydrofluoric gas and high fluoride containing

magma are released, or as a slow permanent release during the period
volcanoes remain quiescent (passive degassing). Nevertheless, hydrogen
fluoride gas is highly soluble in magmas, resulting in only 20% release of
HF in its gaseous form.11 It is estimated that the global annual inorganic
fluoride volcanic emissions are between 60 and 6000 kilotonnes,3,12 which
are in the same order of magnitude as anthropogenic emissions.13
Furthermore, geothermal sites constitute great sources for fluoride in
the environmental waters and in the drinking water. Under such con-
ditions, the solubility of fluoride increases with increasing temperature
and fluorides may be also added to groundwater by dissolution of
HF gas.6
The third natural source of fluoride is marine aerosols, which is esti-
mated to contribute approximately 20 kilotonnes of inorganic fluorides
annually.3,12
13.1.2 Anthropogenic Sources of Fluorides

Fluorides are also released into the environment (air, soil, water) through
various human activities. Exhaust gases, processed water and waste from
11:26:40.
industrial processes, such as steel manufacturing, primary aluminium

manufacturing, copper and nickel production, phosphate fertilizer pro-
duction and use, glass production, brick and ceramic manufacturing, as well
as glue and adhesive production, lead to an increase of the natural back-
ground fluoride levels of fresh waters (Table 13.1).14 The application of
pesticides containing fluoride and the fluoridation of potable water adds to
the overall amount of fluoride that is being released from anthropogenic
sources.12
Fluorides are either dissolved directly in the groundwater systems or are
emitted as gaseous fluorides through the type of ash produced. Aluminium
metal industries are among the dominant industrial fluoride producing
activities, since various fluoride-containing salts are used for preparing
appropriate electrolyte solutions for the reduction of alumina, which causes
generation of hydrogen fluoride (HF) as well as perfluorocarbons, such as
CF4, C2F6, etc. In a recent study, by Kumar and Rani,15 it is mentioned that
gaseous fluoride forms as fugitive particulate fluoride are also generated
and aect the flora and fauna of the interconnected rainfall. The denoted
composition of produced particulate matter is: alumina (Al2O3) 23%;
cryolite (Na3AlF6) 82%; aluminium fluoride (AlF3) 9.7%; spar (CaF) 67%. All
these forms of fluoride are easily dissolved in water and rainfall and can
lead to an excess fluoride concentration in drinking water.15 Furthermore,
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264 Chapter 13
Table 13.1 Manufactured chemicals containing fluoride, their use and sources.
Chemical Use Source
Hydrogen fluoride Synthetic cryolite Calcium fluoride
(HF) Aluminium fluoride (AlF3) (CaF2)
Motor gasoline alkylates

Chlorofluorocarbons
Nuclear industry
Semiconductor devices
Cleaning and etching glass
Cleaning brick and aluminium
Tanning leather processes
Petrochemical manufacturing
processes
Commercial rust removers
Calcium fluoride Flux in steel, glass and enamel Mineral fluorite
(CaF2) production (or fluorospar)
Raw material for the production of
hydrofluoric acid and anhydrous
hydrogen fluoride
As an electrolyte in aluminum
production
Sodium fluoride Fluoridation of drinking water Hydrofluoric acid
(NaF) Preservative in certain glues and sodium
In glass and enamel production carbonate or
As a flux in steel and aluminium sodium
production hydroxide
Insecticide
Wood preservative
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Fluorosilicic acid Fluoridation of drinking water Co-product from

[(H3O)2SiF6] the manufacture
of phosphate
fertilizers
Sodium Fluoridation of drinking water Fluorosilicic acid
hexafluorosilicate and sodium
(Na2SiF6) chloride or
sodium sulfate
Sulfur hexafluoride Insulation and current interruption
(SF6) medium in electrical switchgear
Protective inert gas over molten metals
Calcium Source of phosphates in the fertilizer Mineral
fluorophosphate industry fluorapatite
[Ca5(PO4)3F]
Phosphate fertilizers Soil fertilization Rock phosphates
(3.5% fluorine)
Gonzalo and Camargo proposed Echinogammarus calvus as a suitable

bioindicator of fluoride pollution (for even less than 1 mg L1 F) in
freshwater ecosystems due to the fact that they have the ability to bioac-
cumulate fluoride ions.16
View Online
The use of fluorides for dental health reasons has been a controversial
issue. Fluoridation of drinking water was introduced after early studies on
the link between caries and low fluoride water content. Today around 10%
of the population in Britain is supplied with fluorinated water.5 As of
2000, 42 out of the 50 largest US cities received fluoridated water.17 At

lower levels, they can promote dental quality, however in excessive
amounts and long-term exposure, fluorides can be held accountable for
dental fluorosis and damaging dental bone tissues, resulting in teeth
discolouration and deterioration of the teeth enamel.18 In a review of 214
studies overall reduction in the incidences of caries were found, but they
were less than previously reported. The prevalence of fluorosis (mottled
teeth) is highly associated with the concentration of fluoride in drinking
water. Adverse eects such as bone fracturing are heterogeneously dis-
tributed among the studies, and no clear conclusion can be made. There
are no definite patterns of association with incidences of fractures on
bones.19
13.1.3 Fluoride Content in Environmental Samples

Surface waters naturally contain fluoride ranging from 0.01 to 0.3 mg L1,
depending on the geographical location, although seawater fluoride
concentration is much higher (1.21.5 mg L1). At areas with fluoride rich
rocks (e.g., volcanic magma) or nearby industrial activities (e.g., phos-
phate fertilizer plants), much higher concentrations have been reported.12
11:26:40.
A short review of fluoride presence in various types of water is given in

Table 13.2. In areas not close to emission sources, the fluoride concen-
tration in ambient air does not exceed 0.1 mg m3. Near emission sour-
ces, levels of gaseous and particulate fluoride are usually between 2 and 3
mg m3. Most soils contain naturally occurring fluoride in their com-
position, usually ranging from 20 to 1000 mg g1. However, in mineral
soils with fluoride depositions, the concentrations can reach several
thousand mg g1.2
13.1.4 Health Eects of Fluorides

13.1.4.1 Health Eects to Humans
Fluorine is one of the few elements that can cause health problems by both
its deficiency and excess intake. For example, low fluorine intake can cause
dental problems, while high intake rate may lead to skeletal fluorosis.5
Acute Toxicity. Acute oral exposure to fluoride may produce eects in-
cluding nausea, vomiting, abdominal pain, diarrhoea, fatigue, drowsiness,
coma, convulsions, cardiac arrest and death. Also, it has been reported
that exposure through dermal contact to hydrofluoric acid can cause
266
Table 13.2 Major compounds chemical composition in mg L1 of dierent types of waters.
Reference ID pH F HCO3 Cl SO42 Na NH41 Mg Ca Al As
72 Drinking water 6.59.5 1.5 250 250 200 0.5 0.2 0.01
maximum
permissible levels
bdla
11:26:40.
49, 50 Far from the 5.7 bdl 0.33 1.12 1.08 0.27 0.14 1.18 0.003 bdl
Nyamuragira volcano
area
Near the Nyamuragira 4.2 8.3 25.3 15.8 6.6 3.4 3.3 12.6 2.66 0.0019
volcano area
20, 41 Geothermal waters 1.67.52 3.3648.6 bdl232 2.86802 21.63490 310576 bdl86.6 bdl9.12 0.86736.8 0.1681.6 0.003714.6
47 Kolar District (drinking 6.297.91 0.363.34 156634 26462 15153 18369 10.783 30254
water)
Tumkur District 6.678.33 0.785.35 157869 18582 15206 26350 4.894 15.2248
(drinking water)
73 Natural spring water, 5.68.2 0.0060.9 0.1540 135.9 0.0430 bdl 0.01217.4 0.4897.1 bdl0.38 bdl0.01
Turkey
Natural mineral water, 5.37.9 0.031.52 7.3760 bdl702 1.611770 bdl0.44 9.24447 46420 bdl2.5 bdl0.01
Turkey
Drinking water, Turkey 6.08.2 bdl1.0 10.773.8 2.431 7.350 bdl 0.98.5 625 bdl0.05 bdl0.001
Processed drinking 5.88.0 bdl0.7 2.914 2.315.2 bdl 0.0486 0.98.2
water, Turkey
39 Na-HCO3 water sample 8.29.1 0.88.2 337484 3.512.6 13213 109298 0.52.1 0.82.4 4.07.5 bdl0.0015
type
Ca-Na-Mg-SO4-HCO3 6.77.6 0.42.9 173571 4.174.4 144512 44.1173 bdl3.1 9.482.1 6.6217 bdl0.00006
water sample type
Ca-HCO3 water sample 7.07.7 0.20.4 261462 2.616.4 37.0129 9.780.6 bdl0.6 9.222 79.0153 bdl0.0013
type
55 Groundwater 7.318.85 0.512.0 460913 28.6369 35.4602 235687 3.962.9 3.250.4 bdl0.25
74 Nanital District 5.98.1 0.010.66 2.213 2.5140 1.214 7.750 17120
Chapter 13
(drinking water)
a
bdl: below detection limit.
View Online
severe tissue damage, respiratory eects, cardiac arrest and death. In-
gestion of toxic amounts of fluoride may result in gastrointestinal eects
due to the corrosive action of the HF produced within the acidic environ-
ment of the stomach.21,22 Toxicity levels dier according to the fluoride
species. In general higher solubility of a fluoride salt leads to higher toxi-

city levels. For example, highly soluble sodium fluoride is more toxic than
the insoluble calcium fluoride.23
Fluorosis. The term fluorosis refers to a widespread disease caused by

high fluorine ingestion through water and food. Fluorosis is most com-
monly related to natural fluoride sources, although sometimes it can be of
anthropogenic origin. Dental fluorosis is characterized by discoloured,
blackened, mottled or chalky-white teeth, while skeletal fluorosis by severe
and permanent bone and joint deformations.2 Humans ingest fluorine
mainly through drinking water and rarely through fluorine rich vege-
tables.24 Absorption through the skin or inhalation of fluoride species are
unlikely to contribute to the fluorine body burden.
There is evidence that fluorosis is more widespread through third world
populations because of malnutrition. Clinical data show that low protein,
calcium and vitamin C and D intake can lead to an elevated fluorosis risk.
It is estimated that tens of millions of people are aected by fluorosis
globally.25 Unfortunately, dental or skeletal fluorosis eects have been ir-
reversible, leaving prevention as the only cure.26
The World Health Organization2 established a maximum limit of
11:26:40.
1.5 mg L1 for fluorides in drinking water. The limit must be lowered to
1 mg L1 for fluorides in areas with a warm climate due to higher water
consumption.
The US Environmental Protection Agency (USEPA)23 has set the primary
standard (enforceable limit) at 4 mg L1 for fluoride in drinking water,
although the secondary standard (non-enforceable) for the United States
drinking water is 2 mg L1. In countries with special fluoride problems
and high occurrence in the drinking water supply, higher standards have
been implemented (8 mg L1) reflecting the problems and diculties to
eectively remove the higher fluoride content, complying with WHO
guidelines. It is estimated (not accurately) that more than 200 million
people consume water with fluoride content higher than the established
WHO guidelines.2
13.1.4.2 Health Eects on Animals and Plants

Microorganisms. Concentrations of fluorides up to 100 mg L1 seem to
have no eect on the growth or the chemical oxygen demand degrading
capacity of activated sludge, although when fluoride was added continu-
ously, poor sludge settleability was observed, probably due to enhanced
growth of filamentous organisms.27 In another study by Van Wensem and
Adema (1991) it was found that fluorides can be toxic for microbial
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268 Chapter 13
processes at concentrations found in moderately fluoride polluted areas

with 0.51.0 mg L1.80
Algae and Aquatic Plants. According to Camargo,14 fluoride can aect ei-
ther positively or negatively the growth of algae, depending on the ex-

posure time, the algae species and the fluoride concentrations; some algae
can live in waters with F concentration up to 200 mg L1. It is believed
that the growth inhibition of fluoride ions on some algae is due to their
negative eect on nucleotide and nucleic acid metabolism.28 On the other
hand, some algae species require fluorides for optimal growth.29 Also,
some aquatic plants were found to enhance the removal of fluorides from
polluted waters.14
Terrestrial Plants. Weinstein and Alscher-Herman13 studied fluoride toxi-

city on plants in great depth. Inorganic fluorides phytotoxicity (fluorosis)
can be evident by signs of chlorosis, necrosis and decreased growth rates,
especially in the young, expanding tissues of broadleaf plants and elong-
ating needles of conifers.30 Also, Weinstein and Alscher-Herman13 reached
the conclusion that calcium and magnesium concentrations aect signifi-
cantly the response of plants to fluoride. A type of detoxification seems to
occur because of the fluoride immobilization when it reacts with calcium.
Studies have shown that F ions can be toxic for cultivating plants in a
range of 50 to 2000 mmol L1, depending not only on the plant species but
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also on ionic fluoride species. It was additionally found that the soil type
can have a great eect on the uptake rates and the toxicity potential of
fluorides.
Aquatic Invertebrates and Fish. Aquatic animals, such as invertebrates

and fish, absorb fluorides directly from water than from food. However,
toxicity also depends on fluoride concentration, time of exposure and
water temperature.3133 In contrast, the toxic eects decrease as the intras-
pecific organism size and the water concentration of calcium and chloride
increase.31
As Camargo14 reports, fluorides tend to accumulate on the exoskeleton of
invertebrates and the fish bone. Neuhold and Sigler31 suggest that
the fluoride accumulation in the hard tissues might be a defence mech-
anism to high fluoride concentrations. In addition, fluoride that accumu-
lates on the hard tissue of invertebrates can combine with calcium and
phosphorus to give fluorapatite, thus hardening their exoskeleton
significantly.32,33
Acute intoxication in fish, due to lethal doses of fluorides, presents
symptoms of fluorosis before death. Other symptoms are lethargy and
apathetic behaviour, anorexia, hypoexcitability, decreased respiratory rates,
increased fluoride levels in the blood, darkening of the skin (dorsal side) and
increased mucus secretion from the respiratory and integumentary
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3436
epithelium. It has been reported also that high fluoride concentrations
can delay the hatching of fertilized fish eggs.37,38
Terrestrial Invertebrates and Animals. Fluoride toxicity on terrestrial in-

vertebrates varies greatly among dierent species. Some species are not af-
fected living in or feeding on a fluoride-rich environment, while others are
aected in various ways, such as excessive egg production, growth and co-
coon building inhibition. Herbivorous animals accumulate fluorine in the
form of fluoroapatite to their skeleton either through direct ingestion par-
ticulates (e.g., volcanic ash) deposited over grass or by feeding on fluoride
rich vegetation. Thus, carnivores will not accumulate fluoride through
their feed.11 Another fluoride source for animals is contaminated water.
Symptoms of toxicity include emaciation, stiness of joints, abnormal
teeth and bones, decreased milk production and detrimental eects on
the reproductive capacity of animals.2
13.2 Relation Between Fluorides and Metals/

Metalloids
13.2.1 Role of Physico-chemical Parameters and Ions
As far as hydrogeological and geochemical processes are concerned, the
temperature and pH values are the main factors controlling the dilution of
fluoride in groundwater, especially when dierent anion-exchange media are
11:26:40.
present such as certain clay minerals, illite, chlorite, smectite and also or-
ganic matter. For this reason, igneous (such as granites, gneisses and bas-
alts), volcanic rocks and sedimentary rocks (such as shales, limestone and
sandstone) are mainly associated with high fluoride contents.39,40
Drinking water is also aected by the presence of hydrothermal water
systems in the nearby area. Hydrothermal waters are generally alkali chlor-
ide solutions with high temperatures of from 50 to 90 1C and neutral pH
values, thus leading to easy fluoride dissolution from minerals in ground-
water. Deng et al.41 studied the correlation between the fluoride content
and the hydrothermal water samples from Yellowstone National Park, USA.
It was proven that high fluoride concentrations are found consistently
in waters with field pH values higher than 6 and temperatures higher
than 50 1C.
Among all its fluoride forms, fluorite (CaF2) seems to be the main mineral
that controls the geochemistry of fluoride in most environments42 and the
amount of fluoride ions released into the groundwater is dependent on the
degree of saturation of fluorite and calcite (CaCO3). Fluoride concentration
is inversely related to calcium and directly related to bicarbonate concen-
tration in groundwater.4345 Fluorite dissolution in groundwater seems to
be increased in sodium bicarbonate waters, whereas it appears to be in-
hibited in calcium rich water,46 especially when the calcium concentration is
above the limit for fluorite solubility owing to a common ion eect.42,46,47
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270 Chapter 13
48
Rosborg et al. also proved that the highest fluoride values were associated
with low Ca : Al ratios and HCO32 values and were related to acid soils.
Cuoco and coworkers49,50 proved that the eruption of Mount Nyamuragira
during January 2010 had a significantly negative impact on the drinking
water quality of the Virunga Volcanic Province, since rain water is the essential
drinking water resource for most inhabitants in this region. The results indi-
cated that the Nyiragongo Volcano severely aected the chemistry of the sur-
rounding atmosphere. The pH of the drinking water was significantly aected
due to the production of several volcanic acids, among them HF. The content
of fluoride anions was enormously increased and was linearly correlated
with the content of Cl and SO42 anions. The team found that the ratios of
Cl : F, SO42 : F and SO42 : Cl could be indicative of the contaminated and
non-contaminated toxic rains and directly related to the quality of the drinking
water. By measuring these parameters they divided the rainwater samples
into two main categories: (1) uncontaminated, with higher values of 20, 40
and 5, respectively, and (2) contaminated acid rain showing values as low as
1.5, 5.0 and 0.5, respectively. They also concluded that the relative enrichment
factor of high field strength elements such as Al, Fe, Hf and Th is also
correlated with the sum of the fluoride and chloride anions concentration.
Similar results were achieved also by Ruggieri et al.51 who investigated the
environmental geochemical behaviour of the rhyolitic ashes from the 2008
eruption of the Chaiten volcano, Southern Chile. They concluded, after
conducting leaching experiments, that fluoride anion concentrations was
extremely high.51
11:26:40.
The solubility of fluoride in waters therefore depends on the presence of

other elements, such as Ca, Na, B, Li, K and Cl. Fluorine is the most elec-
tronegative halogen compound rendering fluoride a strong ligand factor,
leading to the formation of strong complexes with polyvalent cations such as
Al31, Mg21, Fe31 and Ca21 or other components such as B, Si, Be, Li and V.
For example, in the hot springs of Yellowstone National Park the concen-
trations of boron, silica and lithium were unusually high, ranging from
2350, 650800 and 58 mg L1, respectively. In this area the concentrations
of fluoride and arsenic were also increased, up to 50 and up to 15 mg L1. In
South Korea, positive correlations between fluoride and SiO2 supported the
silicate origin of fluoride in the groundwater bedrocks52,53 while in the
Ruapehu volcano, CaSiF6 was the most important F-bearing compound,
along with the highly soluble NaF in purely magmatic eruptive systems.
The complexation of fluorides was also an interesting conclusion dis-
seminated by Deng et al.41 They found a direct correlation between the
fluoride content and aluminium content. They concluded that the main
fluoride species (free F, HF and AlF complexes) are controlled not only by
pH but also by the ratio of F and Al concentrations. The fluoride aqueous
speciation variation was simulated using 0.1 and 1 mM concentrations of
F and 0.01, 0.1 and 1 mM concentrations of Al and ratios of 10, 1 and 0.1.
At low concentrations of Al, fluoride is found as HF in the range of pH 03.
As the Al concentration increases (1 mM), the AlF21 form predominates up
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to a pH of 6 where free-fluoride ion is mainly found. As the pH value in-

creases further, at constant F concentration, the species AlF21 becomes a
more prominent fraction but limited to a narrow pH window close to 6. With
an increase in both Al and F concentrations, the AlF3 form increases in
importance briefly at pH 7. In alkaline water with pH values greater than 6,

the free to total fluoride ratio was 499% because elevated concentrations of
OH ions outcompeted F in complexes with cations (Figures 13.1 and 13.2).
Occasionally fluoride may also interact with Fe, Mg and B leading to some
complex forms, such as FeF21, MgF1 and BF2(OH)2.
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Figure 13.1 Fluoride speciation in water varies with pH in the absence of Al.41
Figure 13.2 Fluoride aqueous speciation varies with pH and F and Al

concentrations.41
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272 Chapter 13
The presence of ion-exchange media in the aquifer often also leads to high
fluoride contents. For example, reduction in calcium ions due to precipi-
tation of calcite may increase the sodium to calcium ratio, which in turn
increases the soluble fluoride concentration in the groundwater. Waters that
are sodium (Na)-, potassium (K)- and chloride (Cl)-rich but calcium (Ca)
poor, tend to contain high fluoride concentrations. In the geothermal waters
from Thailand,20 the mean fluoride concentration of 18.5 mg L1 was in-
fluenced by the salinity and sodium concentration in particular, as for the
same samples, sodium (Na) concentration was the highest and ranged from
49.0 to 95.8 mg L1. For the same water types the conductivity was also in-
creased ranging from 250 to 553 mS cm1 while the Ca21 concentration was
estimated at approximately 3.5 mg L1.
It was therefore observed that solubility of fluoride was increased at a
high concentration of sodium in groundwater. This process has been stud-
ied in the sedimentary basin of the Aigion area, Greece, where during the
1980s several fluorosis incidents had been detected due to consumption of
groundwater with fluoride content exceeding 8 mg L1.39 The researchers
showed that the groundwaters from the broader area can be identified as
belonging to three main hydrochemical types (Ca-HCO3, Na-HCO3 and
Ca-Na-Mg-HCO3-SO4). Concerning their quality, it is shown that elevated
fluoride concentrations are related to the second water type (Table 13.2).
They concluded that the water uprising through fractures, due to hydrostatic
pressure, deposits a significant quantity of fluoride in lignite lenses hosted
in the Plio-Pleistocene sediments of the area. The process that follows is the
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leaching of fluoride by the Ca-HCO3 groundwater, which recharges the

aquifer resulting in Ca-Na-Mg-HCO3-SO4 type. As also defined by other re-
searchers, fluoride concentration is generally less in Ca-HCO3 type waters
when compared with NaHCO3 type waters.3,43,54 Similar conclusions were
also reached by Gomez et al. who observed that there is a positive linear
relationship between fluoride content and the ratio of Na : Ca.55
13.2.2 Fluoride and Arsenic Correlation

Another interesting correlation55 is between arsenic and fluoride content,
which has been investigated along with the geochemical conditions associ-
ated with the presence of these elements in the phreatic aquifer of Coronel
Moldes, in the central sector of the Argentinean Chacopampean plain. Ac-
cording to the authors, the studied aquifer is composed of silty sand sedi-
ments of aeolian origin, typically loess-like sediments, while the water type
varied from sodium bicarbonate to sodium sulfatechloride.55 A significant
correlation between As and F was found (R2 0.84), which is interpreted as
an indicator of the common natural origin of these elements, which, due to
the subsaturation in amorphous silica, is attributed to the dissolution of
volcanic glass.
Furthermore, they concluded there is a moderate positive correlation be-
tween As and F with the relationship Na : Ca (R2 0.55 and R2 0.61,
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respectively). They also defined that the higher contents of As and F are
related to the presence of NaHCO3 water type, in which amorphous silica
(e.g., volcanic glass) dissolves, together with the dissolution of calcite. In
non-bicarbonate water, there is no dissolution of glass, therefore when cal-
cite precipitation occurs, the adsorption of As and F is promoted.56 They

finally assumed that the geochemical environment of sodium bicarbonate
water and high pH are responsible for the negative correlation between As
and F with Ca and Mg as well as with the positive correlation with Na.
Correlation and high levels of arsenic and fluoride in groundwater have
also been reported in many countries around the world.41,5761 Deng and
Nordstrom and their team41 reported that in the thermal waters of the
Yellowstone National Park, the fluoride concentrations ranged from 0.04 to
99.32 mg L1 while the arsenic concentration reached 14.6 mg L1.
Table 13.3 summarizes briefly the presence of these ions in various aquifers.
Blanes et al.57 indicated that the mobility of As and F and consequently
their distribution in groundwater from aquifers are dependent on their
adsorption onto Fe and Al oxides and oxy-hydroxides. However, their ad-
sorption is limited under conditions of high pH and high HCO3 concen-
tration. Also, high pH values and high HCO3 concentrations facilitate the
dissolution of volcanic glass, releasing As and F into groundwater. It was
reported that in the shallow and deep groundwaters in the CentralWest
region of Chaco, pH may control As and F mobility. At the same aquifer, low
Ca21 and high Na1 concentrations were detected, indicating a cation-
exchange reaction in which Ca21 (originally in the water) has been ex-
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changed by Na1, or removed due to precipitation of carbonate minerals
Table 13.3 Fluoride and arsenic concentrations in various water aquifers.

Reference Country Water aquifer F (mg L1) As (mg L1)
41 USA, Yellowstone Thermal water 0.0499.32 o0.0514.6
45 Kenya, Malawi Groundwater 9.5 No data
45 Kenya, Malawi Lake Nakuru water 2800 No data
45 Kenya, Malawi Groundwater 0.57.0 No data
75 Mexico Drinking water 12.97 No data
58 Mexico Geothermal water 17.0 24.0
58 Mexico Surface water 8.0 16.3
3 South Korea Groundwater 4.4 No data
76 India Surface water 0.0313.2 No data
76 India Thermal water 420.0 No data
20 Thailand Drinking water 0.12.3 No data
77 China, Wamiao Drinking water 0.574.5 No data
78 China, Wamiao Drinking water 0.43.7 No data
79 India, Delhi, Bhalswa Groundwater 50.0 No data
59 Turkey, Kirsehir Geothermal water 9.5 0.28
48 Sweden Drinking water 0.230.87 o0.05
18 Saudi Arabia Drinking water 0.52.8 No data
57 Argentina, Chaco Groundwater 4.2 o0.05
60 Ghana Drinking water 19.0 0.028
61 Argentina Groundwater 0.529.0 0.22.0
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274 Chapter 13
under high alkalinity and consequent pH increase. This process results in

the formation of Na-HCO3 in groundwater thus providing favourable con-
ditions for high mobility of anionic complexes of As and F species.57
It has to be mentioned that the co-exposure to As and F in drinking waters
is of great importance although the exact eects on human health are yet
unknown. As summarized in Chouhan and Floras review62 there is no
conclusive experimental evidence as to whether the combined exposure will
lead to synergistic or antagonistic eects in humans and animals. For ex-
ample, there are some studies showing that co-exposure can lead to distinct
damage on the nerve system of osprings, leading to decreased learning
ability, and some others have reported altered histology of the cerebral
hemisphere following combined arsenicfluoride exposure.63,64 On the other
hand, fluoride may be able to minimize the toxic eects of arsenic either
through strong bonding or perhaps decrease its anity for active cell
components.62
13.3 Fluoride Removal Techniques

The purpose of treating fluoride-contaminated water is to reduce the fluor-
ide concentration to levels below the acceptable and safety limits. In general,
the suitable removal methods can be divided into two categories: membrane
and adsorption techniques.65 Table 13.4 summarizes the main methods of
fluoride removal from water.
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13.3.1 Membrane Methods

Reverse osmosis, nanofiltration, dialysis and electrodialysis are the main
membrane methods that can be used for fluoride removal. Reverse osmosis
can produce water of high quality with experiments showing fluoride re-
moval up to 98%.66
Nanofiltration is similar to a reverse osmosis technique. The dierence is
in the size of the membrane pores. In the case of nanofiltration, the mem-
brane pores are a bit wider, resulting in a lowered resistance to the passage
of both solvents and solutes. Therefore, there is less need for high pressures
and energy consumption, the removal of solutes is much less exhaustive and
the flows are increased. Another advantage of nanofiltration over reverse
osmosis is the selectivity of the former.65
Dialysis uses membranes preferably to separate solutes than to retain
them. In this case membrane pores are looser than those of nanofiltration
and the solutes penetrate them either by the Donan eect or by an applied
electric field.65 Hichour et al.,67 taking advantage of the Donan dialysis ef-
fect, managed to reduce the fluoride concentration from highly contamin-
ated water to about 1.5 mg L1 using anion-exchanging membranes loaded
with sodium chloride. In the electrodialysis method, the ionic constituents
of an aqueous solution are removed when they are forced through an ion-
exchange membrane due to an applied electric field.65
Table 13.4 Popular removal methods for fluoride from drinking water.5
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals
Relative
Removal method Capacity/dose Working pH Interferences Advantages Disadvantages cost
Precipitation:
Alum (aluminium 150 mg per mg F Non-specific Established process Sludge produced, treated water in Medhigh
Sulfate) acidic residual Al present
Lime 30 mg per mg F Non-specific Established process Sludge produced, treated water in Medhigh
alkaline
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Alum lime 150 mg alum 7 mg Non-specific Low-tech, Sludge produced, high chemical Medhigh
(Nalgonda) lime per mg F established dose, residual Al present
process
Gypsum fluorite 5 mg gypsum Non-specific Simple Requires trained operators. Low Lowmed
o2 mg fluorite eciency, high residual Ca21,
per mg F SO42
Calcium chloride 3 mg CaCl2 per mg F 6.58.0 Simple Requires trained flocculent Medhigh
(e.g., FeCl3)
Adsorption exchange:
Activated carbon Variable o3.0 Many Large pH changes before and after High
treatment
Plant carbon 300 mg F per kg 7.0 Locally available Requires soaking in potassium Lowmed
hydroxide
Zeolites 100 mg F per kg Non-specific Poor capacity High
Defluoron 2 360 g F per m3 Non-specific Alkalinity Disposal of chemicals used in resin Medium
regeneration
Clay pots 80 mg F per kg Non-specific Locally available Low capacity, slow Low
Activated alumina 1200 g F per m3 5.5 Alkalinity Eective, well- Needs trained operators, chemicals Medium
established not always available
Bone 900 g F per m3 47.0 Arsenic Locally available May give taste, degenerates not Low
universally accepted
Bone char 1000 g F per m3 47.0 Arsenic Locally available Not universally accepted. May give Low
high capacity adverse colour, taste
Other:
Electrodialysis High Non-specific Turbidity Can remove other Skilled operators, high cost. Not used Very high
ions. Used for much
high salinity
Reverse osmosis/ High Non-specific Turbidity Can remove other Skilled operators, high cost Very high
275
nanofiltration ions. Used for
high salinity
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276 Chapter 13
13.3.2 Adsorption Methods

Even though membrane methods are capable of decreasing fluoride con-
centrations within the desirable limits and have been studied and improved
a lot in the last decade, adsorption techniques are preferred because of the
easier accessibility and the lower cost of the materials used. Researchers are
still trying to develop new more eective adsorbents, improve the ones
currently used and lower the treatment costs.68,69
In theory, fluoride adsorbs onto solid particles in three main steps:70
(1) F ions are diused or transported to the external surface of the adsorbent
from bulk solution, crossing the boundary layer surrounding the adsorbent
particle (called external mass transfer); (2) F ions adsorb onto particle sur-
faces; and (3) the adsorbed F ions probably replace some of the structural
elements inside the adsorbents particles, if the chemistry of the solids allow
it, or the adsorbed F ions are transferred through the porous material to the
internal surfaces of the particles (intra-particle diusion).
In order for an adsorbent to be eligible for practical use, one must take
into consideration the adsorption capacity in dilute solutions, pH, time for
fluoride removal, stability of adsorbent, regeneration and loading capacity in
the presence of other anions and cations and, finally, the overall cost for
fluoride removal. Until now a wide variety of adsorbents have been used for
F removal from water. Some of these are activated and impregnated alu-
mina, rare earth oxides, activated clay, impregnated silica, carbonaceous
materials, solid industrial wastes like red mud, spent catalysts and fly ash,
zeolites and related ion exchangers, biosorbents, alum, alum sludge and
11:26:40.
modified chitosan.57 Many adsorbents have been studied so far, but only a
few can lower the fluoride concentration in water below the established
WHO limits for drinking water or for euent water that might find its way
into drinking water sources.71 Nevertheless, higher limits for euents that
are not discharged in sensitive areas are easily reached.
Industrial euents with high fluoride content are usually treated with a
calciummagnesiumbarium hydroxide slurry, in order for the fluorides to
precipitate in the form of CaF2, MgF2 or BaF. By this method fluoride con-
centration is brought down to about 30 mg L1.57
13.4 Conclusions
Fluorides can be found in the environment through various anthropogenic
and natural sources. Volcanic activity and underground mineral weathering
are the most common natural sources of pollution. Their presence in
surface- and groundwater is dependent on various factors, such as the
prevailing physico-chemical properties, the minerals present, the contact
time and depth of aquifer. Heavy metal industries, aluminium and
steel production, phosphate fertilizer production and glue/adhesive pro-
duction are among the most widespread anthropogenic sources. Depending
on the pollution source and its proximity to the examined water, samples
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can contain varying fluoride concentrations ranging up to more than

40 mg L1.
Fluorides are responsible for various eects on humans, plants and ani-
mals. Although fluorides exhibit low acute toxicity, nevertheless they have
been reported to promote fluorosis and bone deterioration. Fluoride can act
as an inhibitory factor for the growth of algae and microorganisms, while it
can be a decisive factor for plant toxicity, depending on the available calcium
and magnesium concentrations.
Studies have explicitly shown the correlation between the presence of
fluorides and various physico-chemical parameters. As far as hydro-
geological and geochemical processes are concerned, the temperature and
pH values are the main factors controlling the dilution of fluoride in
groundwater. Fluoride is mainly released by fluorite dissolution in ground-
water, which is controlled by the presence of calcium and bicarbonate ions.
A linear correlation has been observed between fluoride content and Cl and
SO42 concentrations. Moreover, the ratios of Cl : F, SO42 : F and SO42 :
Cl could be indicative of water quality and are directly related to fluoride
concentrations. Fluoride concentrations can be aected by the formation of
strong complexes with polyvalent cations such as Al31, Mg21, Fe31 and Ca21
or other components such as B, Si, Be, Li and V. There is also a direct cor-
relation between fluoride and aluminium content, under various pH values.
The interaction leads to complex formations and changes in fluoride
solubility.
The presence of ion-exchange media can also aect the presence of
11:26:40.
fluorides, since those media retain other ionic species, which in turn aect
fluoride dissolution. Fluoride presence is strongly positively related to so-
dium concentrations and negatively related to calcium and magnesium
concentrations, due to the formation of compounds with varying solubility.
Finally a significant correlation between arsenic and fluoride concentrations
has been proven in numerous studies, and in various groundwater types,
due to the common source of these pollutants and their positive relation to
the presence of sodium.
The main removal techniques, such as adsorption and membrane meth-
ods are presented, highlighting their advantages and technical aspects.
References
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2. World Health Organization, Fluorides, in Environmental Health Criteria,
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3. CEPA, Priority Substances List Supporting Document for Inorganic
Fluorides, Act CEP (ed.), Prepared by Eco-Health Branch & Environment
Canada, Ottawa, Ontario, 1994.
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278 Chapter 13
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91.082, NIPG-TNO, 1992.
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CHAPTER 14
Use of Industrial and

Agricultural Waste in Removal
of Heavy Metals Present in
Water
JUNE FANG,a BIN GAO,*a YINING SUN,a,b MING ZHANGa
AND SANJAY K. SHARMAc
a
Department of Agricultural and Biological Engineering, University of
Florida, Gainesville, FL 32611, USA; b State Key Laboratory of Pollution
Control and Resource Reuse, School of the Environment, Nanjing
University, Nanjing 210046, China; c Department of Chemistry, JECRC
11:26:43.
University, Jaipur-303905, India

*Email: bg55@ufl.edu
14.1 Introduction
Heavy metal contamination of water is a major concern throughout the
world due to the ecological and health risks it poses. Heavy metals com-
monly released into water include lead, arsenic, mercury, cadmium, chro-
mium, copper and nickel. These metals are discharged into water bodies by
industries such as mining operations, tanneries, paper mills, electronics,
batteries, textile mills and electroplating.1,2 Even though maximum allow-
able concentrations for these contaminants have been established by several
agencies (with those of the EPA listed in Table 14.13), these concentrations
are often exceeded as a result of industrial activity. Table 14.2 shows the
metal concentrations of two rivers contaminated with mine tailings

281
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282 Chapter 14
Table 14.1 EPA established maximum concentration
limits for heavy metals.3
Maximum
concentration
limit (mg L1)
Heavy metal
Arsenic (As) 0.01
Lead (Pb) 0.015
Mercury (Hg) 0.002
Cadmium (Cd) 0.005
Chromium [Cr(VI)] 0.01
Zinc (Zn) 5.0
Manganese (Mn) 0.05
Copper (Cu) 1.3
Table 14.2 Heavy metal concentrations (ppm) for two mine waste contaminated
rivers (Pilcamayo and Tarapaya) and an uncontaminated river (Cachi
Mayu).4
Area Lead (Pb) Cadmium (Cd) Zinc (Zn) Copper (Cu)
Pilcomayo, 0.0022 0.00015 0.028 0.0006
Poituco reach (0.0006 (0.00008 (0.011 (0.0001
0.0042) 0.00028) 0.058) 0.0016)
Pilcomayo, 1.399 (0.911 0.0592 6.021 0.304
Potosi reach 2.111) (0.0199 (1.490 (0.098
0.101) 10.557) 0.463)
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Pilcomayo, 0.0198 0.00077 0.186 0.017

Villa Montes (0.0093 (0.00022 (0.040 (0.0056
reach 0.0301) 0.00203) 0.408) 0.037)
Pilcomayo, 0.002 (0.0005 0.00012 0.009 0.0025
Argentina 0.0029) (0.00005 (0.002 (0.0002
reach 0.00019) 0.015) 0.0052)
Tarapaya 2.291 (1.101 0.315 (0.0789 12.416 1.709
3.980) 5.13) (7.772 (1.101
22.980) 2.880)
Cachi Mayu 0.001 (0.0006 0.00011 0.008 0.0018
0.0017) (0.00007 (0.002 (0.0003
0.00014) 0.013) 0.0041)
compared with those of a nearby uncontaminated river in Bolivia.4 Since

heavy metals have high mobility in aqueous ecosystems and do not naturally
degrade easily, it is of utmost importance to develop methods that actively
remove them.5 Some of the methods currently being used are flocculation,
reverse osmosis, neutralization, ion exchange, chemical precipitation, ad-
sorption using commercial activated carbon, membrane filtration and flo-
tation.6,7 However, these methods are expensive, and some produce sludge
as a by-product, for which disposal is also a costly endeavour.8,9
An alternative method for heavy metal removal from water is adsorption
using industrial and agricultural waste products. Unlike commercially
View Online
Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 283
available activated carbon, the source material is inexpensive.10 In addition,

waste products are renewable and abundant, and using them as adsorbents
also provides a solution to the problem of their disposal.11,12 When used as
sorbents, industrial and agricultural waste products have a high removal
eciency, produce less toxic waste products as an end product and have the
potential to recover metals for reuse. Some common waste products include
bagasse, sawdust, fruit peels, nutshells, shellfish, yeast and fly ash.8 These
products may be used as is, or can be physically and chemically modified
(such as heat or acid treatment) to improve their adsorption eciency.
Biosorption using waste products is not yet used on a commercial scale, but
the studies conducted so far prove it is a promising method for heavy metal
removal from aqueous solutions. This chapter describes the mechanism
behind adsorption and summarizes select studies that have been conducted
so far on the use of industrial and agricultural waste products as adsorbents
for heavy metals.
14.2 Sorption Mechanisms

14.2.1 Biomass Sorbents
Biosorption is a physico-chemical process where contaminants such as
heavy metals are bound onto the cellular structure of the biomass.7 The
intricate nature of the biomass cellular structure results in biosorption being
a complex process driven by multiple mechanisms, which include
11:26:43.
adsorption, diusion, chemisorption, complexation, ion exchange and

precipitation.2
Functional groups in organic waste products are responsible for their
uptake of heavy metals. Some of the functional groups they contain are
amino, amido, sulfhydryl, phenolic, carboxylic and hydroxyl functional
groups.13 Most functional groups are located in plant cell walls, which
are composed of cellulose molecules surrounded by a layer of lignin,
hemicellulose, pectin and protein. Other components that contain func-
tional groups include extractives, lipids, simple sugars, starches,
water, hydrocarbons and ash. Functional groups bind metal ions in solu-
tion by forming complexes with them through the donation of electron
pairs.14
14.2.2 Inorganic Sorbents

In inorganic materials, heavy metal uptake occurs mainly through the pro-
cess of surface adsorption. Some of the mechanisms involved in adsorption
are cation exchange, precipitation and electrostatic attraction.15 Clays con-
tain exchangeable cations such as sodium, magnesium, potassium and
calcium.15,16 Since these elements are nontoxic, they can be safely released
into the solution when substituted with other cations such as heavy metals
during the wastewater treatment process.16,17
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284 Chapter 14
14.3 Adsorption Models

When an adsorbent is added to an aqueous solution, equilibrium between
the amount of contaminant adsorbed and the amount remaining in the
solution will eventually occur. Equation (14.1) is used to calculate the

amount of contaminant removed by an adsorbent for a system under equi-
librium conditions:
X V
C0 Ce (14:1)
M M
where X is the mass of the contaminant, M the mass of the adsorbent, C0 the
initial contaminant concentration, Ce the concentration of contaminant in
the solution after equilibrium has been reached and V the volume of solu-
tion to which the adsorbent has been added to.14 X/M is usually expressed in
mg g1.
Several isotherm models have been developed to describe the adsorption
process, such as the Langmuir and Freundlich equations. An adsorption
isotherm describes the amount of contaminant adsorbed by a unit weight of
adsorbent as a function of the amount of contaminant remaining in the
solution at equilibrium.18 The Freundlich model is shown in Equation
(14.2):
X
KF Ce 1 = n (14:2)
M
where KF is the Freundlich anity constant and n is the Freundlich linearity
11:26:43.
constant.
The Langmuir model is defined by Equation (14.3):
X KL QCe
(14:3)
M 1 KL Ce
where KL is the Langmuir bonding term and Q is the Langmuir maximum
capacity.19
14.4 Modification Methods

Although agricultural and industrial waste materials can be used as ad-
sorbents when raw, modifying them can improve them in major ways. Raw
materials pose environmental risks, since they tend to release soluble or-
ganic compounds such as lignin, tannin, pectin and cellulose into aqueous
solutions. The release of these compounds results in high chemical oxygen
demand, total organic carbon and biological chemical demand. These
problems can decrease the oxygen content of water, which negatively
impacts aquatic organisms.20 By modifying the materials, these problems
can be reduced due to extraction of soluble organic compounds, and the
adsorptive capacity increases as well.21 Some common treatment methods
are described in the following sections.
View Online
14.4.1 Physical
Physical modification of waste materials includes heating and grinding to
increase the surface area. One of the most popular methods for the physical
modification of biomass is pyrolysis. Pyrolysis is the process of heating
biomass to high temperatures in the absence of oxygen, and the resulting

solid product is known as char.22 Pyrolysis causes low volume pores to form
on the surface of biomass, which increases its surface area. The increase in
surface area subsequently increases the percentage of heavy metals adsorbed
due to the availability of more active surface sites on the adsorbent for heavy
metals to bind to. The properties of char are dependent on the pyrolysis
temperaturethe higher the temperature, the more the surface area in-
creases.23 In some cases, the surface area will start to decrease with further
increases in temperature, as is the case with palm stone char in a study
conducted by Guo and Lua in 1998 (Figure 14.1).24 This is due to pore wall
collapse as well as formation of volatile products in the pores.25,26
Figure 14.2 shows SEM images of raw palm stone and palm stone chars
that were pyrolysed at 600, 800 and 900 1C.
The char can be further modified to form a product known as activated
carbon. This process is termed either activation or oxidation, where the
material may be heated to high temperatures in the presence of
oxygen. Activated carbons typically have surface areas ranging from 500 to
1500 m2 g1, which is significantly higher than that of char.26
Grinding biomass into smaller particles also increases its surface area.
Agarwal et al. found that the amount of Cr(VI) adsorbed by tamarind seeds
11:26:43.
increased as the particle size decreased.27 Ozimen and Ersoy-Meriboyu

had similar findings in that chestnut shell activated carbon had higher
Figure 14.1 BET surface areas of the chars pyrolysed at 400900 1C for various
retention times.24
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286 Chapter 14
Figure 14.2 SEM images of (a) raw oil palm stones, (b) oil palm stone char produced
at 600 1C, (c) oil palm stone biochar produced at 800 1C and (d) oil palm
11:26:43.
stone biochar produced at 900 1C.24
adsorption capacities for Cu(II) than grape seed activated carbon due to
chestnut shell having a greater surface area than grapeseed.28
14.4.2 Chemical
Many chemical solutions can be used to modify raw waste materials in order
to improve adsorption capacities for heavy metals. They may be basic solu-
tions, mineral and organic acid solutions, organic compounds or oxidizing
agents.12 Figure 14.3 shows the dierence between the surface structures of
raw and various chemically modified soybean straws.29 Passion fruit skin
also displays a dierence between raw and modified forms,30 as shown in
Figure 14.4. Modified materials can also be pyrolysed to create chemically
activated charcoals. Chemical activation is preferred to physical activation
because it is more time and energy ecient.31
14.5 Sorption Studies

Table 14.3 summarizes the results of a small selection of studies conducted
on the heavy metal adsorptive capacity of various waste materials. Materials
are indicated to be either raw or treated, and if treated, the treatment
View Online
11:26:43.
Figure 14.3 FESEM micrographs of soybean straw before and after citric acid (CA)
modification: (a) raw, (b) milled, (c) water washed, (d) base (NaOH)
washed, (e) water washed, CA modified and (f) base washed, CA
modified.29
method is listed. Experimental conditions are also listed when given by the
original study.
14.5.1 Dierences Between Materials in the Adsorption Rate

of a Metal
A waste material may display dierent adsorptive capacities for dierent
heavy metals. Some waste materials are more ecient at adsorbing certain
heavy metals than others, and some heavy metals are better sorbed by
certain waste materials than others.
Reddy et al. tested the adsorptive capacity of HNO3 treated honeycomb
biomass on Pb(II), Cd(II), Cu(II) and Ni(II). The adsorptive capacity is highest
for Pb(II).1 Xu et al. found that dairy manure biochar showed much higher
adsorptive capacity for Cu and Cd than it did for Zn, both about 40%
higher.32 Apricot stone activated carbon was least eective at sorbing Pb(II)
288
11:26:43.
Figure 14.4 From left to right: micrographs of raw passion fruit skin, passion fruit skin modified with NaOH and passion fruit skin
modified with NaOH and citric acid.30
Chapter 14
View Online
Table 14.3 Summary of sorption capacity of various waste materials to heavy
metals.
Adsorptive
Temperature capacity
(mg g1)
Feedstock Raw or modified Metal pH (1C) Reference

Agave bagasse Raw Cd(II) 5 25 13.27 12
Raw Zn(II) 5 25 35.6
Raw Pb(II) 5 25 7.84
NaOH Cd(II) 5 25 18.32
NaOH Zn(II) 5 25 50.12
NaOH Pb(II) 5 25 20.54
HCl Cd(II) 5 25 12.5
HCl Zn(II) 5 25 42.31
HCl Pb(II) 5 25 12.40
HNO3 Cd(II) 5 25 13.5
HNO3 Zn(II) 5 25 54.29
HNO3 Pb(II) 5 25 14.43
Ananas Raw Cd(II) 7 18.21 10
comosus peel
Apricot stone Activated Ni(II) 5 25 26.97 33
carbon
Activated Co(II) 6 25 30.07
carbon
Activated Cd(II) 6 25 33.57
carbon
Activated Pb(II) 4 25 22.85
carbon
Activated Cu(II) 6 25 24.21
11:26:43.
carbon
Activated Cr(III) 6 25 29.47
carbon
Activated Cr(VI) 1 25 34.70
carbon
Banana peel Raw Cr(VI) 2 40 131.56 38
Canna indica Raw As(V) 7 1.717 39
pulp
Carrot Raw Cr(III) 4 25 45.09 40
residues Raw Cu(II) 5 25 32.74
Raw Zn(II) 5 25 29.61
Chestnut shell Activated Cu(II) 2 25 38.76 28
carbon
carbon
carbon
Activated Cu(II) 5 35 100
carbon
Coconut Activated Pb(II) 6 30 94.35 41
buttons carbon
Activated Hg(II) 7 30 82.09
carbon
carbon
View Online
290 Chapter 14
Adsorptive
Feedstock Raw or modified Metal pH (1C) (mg g1) Reference
Corn straw Biochar Cu(II) 5 Room 12.52 42

temperature
Biochar Zn(II) 5 Room 11
temperature
Dairy manure Biochar Cu(II) Room 54.4 32
temperature
Biochar Zn(II) Room 32.8
temperature
Biochar Cd(II) Room 51.4
temperature
Grapeseed Activated Cu(II) 2 25 31.84 28
carbon
carbon
carbon
carbon
Hardwood Biochar Cu(II) 5 Room 6.79 42
temperature
Biochar Zn(II) 5 Room 4.54
temperature
Hibiscus Raw As(V) 7 1.938 39
rosasinensis
11:26:43.
pulp
Honeycomb HNO3 Pb(II) 5 50 74.17 1
HNO3 Cd(II) 5 50 61.16
HNO3 Cu(II) 5 50 56.52
HNO3 Ni(II) 5 50 52.71
Maple sawdust Raw Cu(II) 7 23 1.79 43
Mosambi peel Raw Cr(VI) 2 40 250 36
Orange peel Raw Cu(II) 6 30 44.28 20
Methyl acrylate Cu(II) 6 30 289
Parkia speciosa Raw Cd(II) 7 25.64 10
pods
Passion fruit Raw Pb(II) 4 85.68 30
skin NaOH Pb(II) 4 112.99
NaOH and citric Pb(II) 4 204.08
acid
Peanut hull Hydrochar Pb(II) Room 1.04 44
temperature
Hydrochar, Pb(II) Room 22.82
modified with temperature
H2O2
Pistachio hull Raw Cr(VI) 2 40 116.3 45
Psidium Raw Cd(II) 7 39.68 10
guajava peel
Red mud H2O2, activated Pb(II) 4 30 88.20 46
H2O2, activated Cr(VI) 2 30 75.00
View Online
Adsorptive
Feedstock Raw or modified Metal pH (1C) (mg g1) Reference
Romanian Raw Cu(II) 5 20 14.7 47

pine bark Raw Zn(II) 5 20 13.01
Rosa rosa pulp Raw As(V) 6 1.966 39
Saccharomyces Raw Cu(II) 5 25 6.08 37
cerevisiae Methanol Cu(II) 5 25 3.36
Formaldehyde Cu(II) 5 25 2.2
Glutaraldehyde Cu(II) 5 25 6.23
Sugarcane Raw Pb(II) 5 11.63 48
bagasse NaOH Pb(II) 5 30.68
Citric acid Pb(II) 5 52.63
NaOH and citric Pb(II) 5 35.09
acid
Tagetes erecta Raw As(V) 6 1.887 39
pulp
Tea waste Raw Cu(II) 7 22 48 49
Raw Pb(II) 5 22 65
Walnut Raw Pb(II) 25 6.54 34
sawdust Raw Pb(II) 45 6.68
Raw Pb(II) 60 6.66
Raw Cd(II) 25 4.39
Raw Cd(II) 45 4.65
Raw Cd(II) 60 4.90
Raw Ni(II) 25 2.40
Raw Ni(II) 45 2.68
11:26:43.
Raw Ni(II) 60 2.79
while most eective at sorbing Cr(VI) with sorption capacities of 22.85 and
34.7 mg g1, respectively.33 Walnut sawdust shows highest adsorption for
Pb(II) and agave bagasse for Zn(II).34
14.5.2 Eect of pH on Adsorption

The pH of the solution influences the surface characteristics of sorbents and
is thus a major factor in determining the eectiveness of a sorbent. Most
heavy metals are cations, so the more anionic an adsorbent is, the more
metal ions that can be sorbed onto its surface. At low pH levels, there are
more protons available to protonate with active groups on the sorbents
surface so they compete with the heavy metals when it comes to ad-
sorption.35 This has been confirmed in many studies. Feng et al. found that
when using orange peel as an adsorbent for Cu(II), the removal rate was
lowest at a pH of 1 and increased to a high at a pH of 6, as shown in
Figure 14.5. Kobya et al. studied the usage of apricot stone activated carbon
as a sorbent for various heavy metals and adjusted the pH of the solutions to
determine how that aects the sorption rate. They found that as pH in-
creased, the amount of Ni(II), Co(II), Cd(II), Pb(II), Cu(II) and Cr(II) removed by
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292 Chapter 14
Figure 14.5 The eect of equilibrium pH on the adsorption of Cu(II). Conditions: C0,
50 mg L1; contact time, 3 h; temperature, 30 1C; adsorbent concen-
tration, 2 g L1.20
apricot stone activated carbon also increased. However, they found that the
opposite occurred for Cr(VI), as the removal rate was highest at a pH of 1 and
decreased as pH increased. This is because the predominant form of Cr(VI) at
low pH levels is HCrO4, which is the active form of Cr(VI). At higher pH
levels, Cr(VI) is shifted towards the CrO4 and Cr2O7 forms, which do not sorb
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as well.33 Saha et al. also observed this phenomenon when they tested Cr(VI)
removal using mosambi peel as the adsorbent. They found that adsorption
was most eective at a pH of 2.36
14.5.3 Raw versus Modified Materials

Treated sorbents display dierent sorption capacities from those of
raw materials, and dierent treatments are eective for dierent metals.
Velazquez-Jimenez et al. investigated how modifying agave bagasse aects its
ability to sorb Cd(II), Pb(II) and Zn(II). The agave bagasse was treated with
HNO3, HCl and NaOH; the sorption capacities were then compared with
those of raw agave bagasse. NaOH was found to increase sorption capacity
for Cd(II) and Zn(II) the most, while HCl increased sorption capacity for Pb(II)
the most.12
Feng et al. compared the Cu(II) adsorption capacities of raw and methyl
acrylate modified orange peel. The methyl acrylate modified orange peel
displayed an adsorptive capacity of 289 mg g1, much higher than that of the
raw orange peel, which was 44.28 mg g1. This is due to the fact that
modification with methyl acrylate increases the number of carboxyl groups
on orange peel.20
Jianlong compared the ability of raw and chemically modified
Saccharomyces cerevisiae, a type of yeast, to adsorb Cu(II). S. cerevisiae was
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modified using methanol, formaldehyde and glutaraldehyde. The result

was that the sorption capacity of S. cerevisiae was not improved after
modification, and some chemicals actually hindered its ability to adsorb
Cu(II). Raw S. cerevisiae had an adsorption capacity of 5.98 mg g1; methanol,
formaldehyde and glutaraldehyde modified S. cerevisiae had adsorption

capacities of 4.13, 2.07 and 6.03 mg g1, respectively. These results are ex-
plained by the fact that carboxylic and amino groups are responsible for the
majority of Cu(II) adsorption that occurs. Methanol causes esterification of
the carboxylic groups and formaldehyde causes methylation of the amino
groups, both of which are processes that prevent those functional groups
from participating in heavy metal adsorption. While glutaraldehyde did not
decrease the adsorption capacity, the increase was insignificant.37
14.5.4 Eect of Temperature on Adsorption

Ozimen and Ersoy-Meriboyu tested the adsorption capacities of grapeseed
and chestnut shell activated carbons at two dierent temperatures, 298 and
308 K. Increasing the temperature of the solution improved the adsorption
capacity of both sorbents.28 Bulut and Tez had similar results with walnut
sawdust. Temperatures of 25, 40 and 60 1C were tested on the ability of
walnut sawdust to adsorb Pb(II), Cd(II) and Ni(II). For all three metals, ad-
sorption increased as temperature increased. At higher temperatures,
chemical endothermic reactions occur more and the number and size of
active pores on the adsorbents surface increase, allowing for more copper to
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be adsorbed to its surface.34
14.6 Conclusions
The sorption of heavy metals onto industrial and agricultural waste ma-
terials is a complex process, as sorption capacity varies according to a
combination of the types of sorbents and sorbates, whether or not the sor-
bents are raw or modified, modification methods and sorption conditions
such as pH and temperature. Chemically modified materials are shown to be
much more eective at enhancing heavy metal sorption than the raw or
physically modified ones. In order to determine the best way to use or to
modify an adsorbent, it is important to identify the functional groups on its
surface that are responsible for the binding of heavy metals. This is further
emphasized by the fact that some chemical treatment methods may actually
decrease the adsorption capacity of a material because they alter the surface
functional groups. Overall, waste materials prove to be eective at heavy
metal removal in most cases. With more comprehensive research conducted
on these waste materials and more experimentation with dierent types of
modification procedures to pinpoint the best production method, creating
low-cost and eective sorbents to use on a commercial basis will become
more convenient.
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294 Chapter 14
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CHAPTER 15
Biosorption of Metals From

the Basics to High Value
Catalysts Production
TERESA TAVARES* AND CRISTINA QUINTELAS
IBB Institute for Biotechnology and Bioengineering, Biologic Engineering

Department, University of Minho, Campus de Gualtar, 4710-057 Braga,
Portugal
*Email: ttavares@deb.uminho.pt
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15.1 Introduction
Increasing awareness of environmental pollution with heavy metals and its
long-term and xenobiotic eects has instigated growing research and de-
velopment eorts towards pollution abatement. The application of dierent
biological materials in the removal and recovery of metals from wastewater
has been reported in numerous studies.15 Usually, the mechanisms of
biosorption are defined as being metabolic independent, but some authors2
have defined biosorption as the ability of biological materials to accumulate
heavy metals from waste streams by either metabolic mediation or by purely
physico-chemical uptake pathways. These dierent perspectives will be
presented. It is important to identify and evaluate extensively the factors that
aect the performance of biosorption systems in order to optimize their
practical application. The main operational conditions that significantly
influence the biosorption of heavy metals are the solution pH, the biomass
and the metal concentrations, the temperature, age of the cells, contact time
and the competitive presence of other metals in solution. All these points

296
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Biosorption of Metals From the Basics to High Value Catalysts Production 297
will be discussed, as well as some application perspectives that will be

presented.
15.2 Metals of Environmental Concern

Metals are widespread in the environment and results from both natural and
anthropogenic sources (Table 15.1). Certain metals are essential elements
for plant growth and for animal and human health. However, if present
in excessive concentrations they may become toxic and even xenobiotic.
According to Roberts et al.,6 metals are usually classified into categories such
as light, heavy, semimetal (i.e., metalloids), toxic and trace, depending on
several physical and chemical criteria such as density, atomic weight, atomic
number and degree of toxicity. Sparks7 suggested that there are 13 trace
metals and metalloids that should be considered as priority pollutants
(Ag, As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Tl and Zn) and they can be derived
from both natural and anthropogenic sources. Natural sources may include
parent rocks and metallic ores and, on the other hand, agriculture (fertil-
izers, animal manures, pesticides), metallurgy (mining, smelting, metal
finishing), energy production (leaded gasoline, battery manufacture, power
plants), microelectronics, sewage sludge and scrap disposal may be included
in the anthropogenic sources.8
Metals such as arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu),
lead (Pb), mercury (Hg), nickel (Ni) and zinc (Zn) are commonly found at
contaminated sites and in aqueous systems. A brief description of the
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chemistry, toxicity and remediation strategies will be discussed here.
15.2.1 Arsenic
Arsenic is the 20th most abundant element of the earths crust and con-
tamination of aqueous sources is known to occur naturally, although human
activity also contributes to the release of this metal into the environment.9,10
Table 15.1 Sources of heavy metals pollution.

Pollution Source
Atmospheric Forest fires
Volcanic activity
Dust particles
Anthropogenic emissions
Aqueous systems Erosion of rocks
containing metals
Surface runo up naturally
formed and anthropogenic
metals particles
Contaminated waste dumping
Industrial discharges
Sewage
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298 Chapter 15
It is mobilized through a combination of natural processes such as wea-

thering reactions, biological activity and volcanic emissions,11,12 as well as
through a range of anthropogenic activities such as gold mining, non-
ferrous smelting, petroleum refining, combustion of fossil fuel in power
plants and the use of arsenical pesticides and herbicides.11,13,14

Arsenic occurs in 3, 0, 3 and 5 oxidation states. As(V) is dominant in
aerobic environments, usually in the form of arsenate (AsO4)3. It behaves as
a chelate and can co-precipitate with or adsorb into Fe oxy-hydroxides under
acidic conditions. As(III) dominates under reducing conditions, existing as
arsenite (AsO3)3, which is soluble in water and can be adsorbed/co-
precipitated with metal sulfides.15,16
The toxicity of an arsenic-containing compound depends on its valence
state, its form and the physical aspects governing its absorption and elimin-
ation. In general, inorganic arsenic is more toxic than organic arsenic and
trivalent arsenite is more toxic than penta-valent and zero-valent arsenic.1720
The typical remediation strategies for arsenic include ion exchange,2123
membrane separation,24,25 chemical precipitation or coagulation,2628 lime
softening29,30 and adsorption.31,32 Biosorption emerges as a promising
strategy to solve the problem of As deposition and recently several reports
have been published where the authors present removal percentages higher
than 95%.3335
15.2.2 Cadmium
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Cadmium is a transition element and together with Hg and Pb, it is one of

the big three heavy metal poisons that not known to have any essential
biological function. In its compounds, Cd occurs as the divalent Cd(II) ion.9
Natural, as well as anthropogenic sources of cadmium, including industrial
emissions and the application of fertilizer and sewage sludge to farm land,
may lead to contamination of soils and to increased cadmium uptake by
crops and vegetables grown for human consumption. The uptake process of
soil cadmium by plants is enhanced at low pH.36
Cd occurs in 0 and 2 oxidation states. At high pH, the hydroxide
[Cd(OH)2] and carbonate (CdCO3) species dominate, whereas Cd21 and
aqueous sulfate species dominate at lower pH (o8). It precipitates in the
presence of phosphate, arsenate, chromate, sulfide, etc., and shows mobility
at a pH range of between 4.5 and 5.5.16,19
According to Mudhoo et al.,37 cadmium is one of the most toxic heavy
metals and is considered non-essential for living organisms. Cadmium
pollution has induced extremely severe eects on plants, microorganisms
and animals, including man. The maximum intake by humans recommended
by the WHO is 0.40.5 mg per week, and the maximum admissible concen-
tration in drinking water specified by the U.S. EPA is 0.005 mg L1.31,32
Rao et al.38 described a series of various techniques such as precipitation,
cementation, membrane separation, ion exchange, solvent extraction and
adsorption that have been employed to remove cadmium pollutants from
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37
contaminated euents. According to Mudhoo et al., most of these tech-
niques are ineective or extremely expensive in terms of energy and reagent
consumption, especially when concentrations of dissolved metals are in the
order of 1100 mg L1. An alternative, using the biomass of microorganisms,
leads to biosorption that is an eective, ecofriendly and economic technol-

ogy for the removal and recovery cadmium from wastewater streams.
Biological removal of Cd(II) with live or dead microorganisms has emerged
as a potential alternative method to conventional treatment techniques
during recent years.14,39
15.2.3 Chromium
Chromium is the sixth most abundant element of the earths crust40 and its
deposition results from its widespread use in various activities, such as
electroplating, leather tanning, cement, mining, dyeing, fertilizers and
photography industries.37 Owing to these industrial processes, large quan-
tities of Cr compounds are discharged in liquid, solid and gaseous wastes
into the environment and can ultimately have significant adverse biological
and ecological eects.
Chromium exists in a series of oxidation states from 2 to 6 valence, the
most important stable states being 0 (element metal), 3 (trivalent) and 6
(hexavalent). Cr(VI) is the dominant and toxic form of Cr in shallow aquifers.
Chromate CrO42 and dichromate Cr2O72 are major Cr(VI) species but Cr(III)
is the dominant form of Cr at pH lower than 4. Under anaerobic conditions,
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Cr(VI) can be reduced to Cr(III) by soil organic matter, S2 and Fe21 ions.
Chromium is very toxic when in the hexavalent state. Metallic Cr does not
present significant toxicity while Cr31 is an essential trace element for living
beings. In humans, it assists the metabolism of glucose and cholesterol.41
Cr61 forms oxyanion compounds in aqueous media. These species are
highly soluble and mobile in both aquifers and soils, which renders Cr61
compounds very accessible to life forms.41
The conventional methods for chromium removal from industrial waste-
water are similar to known methods for removing other metals in general
and include coagulation, precipitation, ion exchange, cementation, electro-
winning, electrodialysis, electrocoagulation and reverse osmosis.42 These
technologies are often inecient and/or expensive, mainly when applied to
dilute solutions, and they usually generate huge volumes of sludge con-
taining high levels of heavy metals. Owing to these limitations, new pro-
cesses and technologies are necessary and biosorption is gaining relevance
as one such process.4345
15.2.4 Copper
Copper has been known since ancient times. The early use of copper prob-
ably resulted from its natural occurrence in native form. Copper is mainly
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300 Chapter 15
37
employed in electrical and electroplating industries, smelting, metal pro-
cessing, machine manufacturing, organic synthesis and tanning industries.
Cu occurs in 0, 1 and 2 oxidation states. In aerobic alkaline systems,
CuCO3 is the dominant soluble species and, in the presence of sulfur, CuS(s)
will form in anaerobic environments. Cu is able to form strong solution

complexes with humic acids.46,47
The cupric ion (Cu21) is the most toxic species of Cu as Cu(OH)1 and
Cu2(OH)221. However, in large amounts, all forms of Cu are extremely toxic
to living organisms. In surface water, copper can travel great distances and it
strongly attaches to organic matter and minerals and accumulates in plants
and animals.37 According to this author, copper toxicity is a much over-
looked contributor to many health problems, including anorexia, migraine
headaches, allergies, childhood hyperactivity and learning disorders.
As for all the other heavy metals, Cu can be removed using the typical
removal technologies for heavy metals, and biosorption is an eco-friendly
alternative technology to remove these metals from dilute aqueous solutions
using inactive and dead biomass.37,48 Hence, there has been a growing
interest in the search for low-cost, easily available and environmentally
friendly biological materials suitable for the ecient removal of heavy metal
ions.49,50
15.2.5 Mercury
Mercury, the seventh most abundant toxic element is released into the
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environment as a result of both natural processes as well as due to an-

thropogenic activities51,52 and these activities include the refining of
mercury-containing ores, the burning of fossil fuels, industrial processes
such as chlorine production, electronics manufacturing and through mining
and any related activities that utilize mercury in metal recovery pro-
cesses.53,54 As a result, large amounts of mercury are included in the wastes
produced by these industries. Owing to its toxicity, there is a need to elim-
inate mercury from these industrial wastes.
Hg occurs in 0, 1 and 2 oxidation states and it may occur in an
alkylated form (methyl/ethyl mercury) depending upon the pH and Eh of the
system. Sorption on soils, sediments and humic materials is pH-dependent
and increases with pH.15 It exists in several forms: inorganic mercury, in-
cluding metallic mercury and mercury vapour (Hg0) and mercurous (Hg221)
or mercuric (Hg21) salts, and organic mercury, which includes compounds
in which mercury is bonded to a structure containing carbon atoms (methyl,
ethyl, phenyl or similar groups).55 Hg21 and Hg221 are more stable under
oxidizing conditions.
Hg has been reported as one of the most potent toxic heavy metals in the
environment. In response to Hg toxicity, bacteria have developed a surprising
array of resistance mechanisms to overcome the eect of Hg toxicity.50
Mercury in any form is poisonous to humans, with mercury toxicity most
commonly aecting the neurologic, gastrointestinal and renal organ systems.
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Poisoning can result from mercury vapour inhalation, mercury ingestion,

mercury injection and absorption of mercury through the skin.55
Various bioremediation technologies such as biosorption,49,56 bio-
transformation and bioprecipitation of Hg have been suggested, but their
applications are limited to removal of Hg from the environment. However,

some strategies based on the modern aspects of biological technologies
employing mer operon genes in dierent combinations have proved to
be quite interesting in the remediation of mercury contaminated
environments.51,53
15.2.6 Lead
Lead is one of the most dangerous contaminants, which is released into the
environment by various anthropogenic activities. Process industries such as
battery manufacturing and metal plating and finishing are prime sources of
Pb(II) pollution.57 In recent years lead contamination has decreased because
some anthropogenic sources of lead, most notably leaded gasoline, lead-
based paint, lead solder in food cans, leadarsenate pesticides, shot and
sinkers, have been eliminated or strictly regulated due to leads persistence
and toxicity.37
Pb occurs in 0 and 2 oxidation states and this last one is the most
common and reactive form of Pb. Low solubility compounds are formed by
complexation with inorganic (Cl, CO32, SO42, PO43) and organic ligands
(humic and fulvic acids, EDTA, amino acids).58
11:26:47.
Lead is very toxic for living organisms. In animals, Pb21 accumulates

mainly in bones, brain, kidney and muscles and may cause many serious
disorders like anemia, kidney diseases, nervous disorders, sickness and even
death.57
Traditionally, lead can be removed by chemical precipitation, ion ex-
change, reverse osmosis, electrokinetic remediation, phytoremediation and
adsorption/biosorption. Research has shown that adsorption is the simplest
and the most cost-eective method. Various adsorbents have been tested
and the main focus is now on the biological adsorbents. Biosorption pro-
cesses oer the advantages of low operating costs, the possibility of metal
recovery and potential biosorbent regeneration.59 The search for novel and
less expensive biosorbents, for example agricultural/industrial wastes, is the
aim of the work by Parvathi et al.60 and Qaiser et al.61
15.2.7 Nickel
Nickel occurs naturally in various mineral forms. Nickel contamination of
the environment occurs locally from emissions of metal mining, smelting
and refining operations, from combustion of fossil fuels, from industrial
activities, such as nickel plating and alloy manufacturing, mordents for
dying and textile printing and battery manufacturing industries, from land
disposal of sludge, solids and slags and from disposal of euents.37
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302 Chapter 15
In its compounds, nickel exhibits oxidation states of 1, 0, 1, 2, 3

and 4, though the 2 state is by far the most common.62 Ni21 forms a
large number of complexes, encompassing coordination numbers 4, 5 and 6
and all of the main structural types, e.g., octahedral, trigonal bipyramidal,
tetrahedral and square. The absorption of nickel is dependent on its

physico-chemical form but it is easier with water-soluble forms.
Nickel is a nutritionally essential trace metal for several animal species,
microorganisms and plants, and therefore either deficiency or toxicity
symptoms can occur when, respectively, too little or too much Ni is taken
up.62 Most nickel enters the body via food and water consumption, although
inhalation exposure in occupational settings is a primary route for nickel-
induced toxicity. Toxic eects of nickel to humans and laboratory mammals
are documented for respiratory, cardiovascular, gastrointestinal, musculo-
skeletal, hepatic, renal, dermal, ocular, immunological, developmental,
neurological and reproductive systems.37
The typical methods to remove this metal are ion exchange, precipitation,
reverse osmosis, adsorption and biosorption. Among various treatment
methods, biosorption method has been extensively used due to the re-
markable properties of living and non-living microorganisms in the trans-
formation and detoxification of inorganic pollutants. Quintelas et al.63 have
presented very promising work using biosorption to remove nickel.
15.2.8 Zinc
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Zinc and its compounds are found in the earths crust and are present in
most rocks, certain minerals and some carbonate sediments. As a result of
weathering of these materials, soluble compounds of zinc are formed and
may be released into water.64 Zinc is one of the metals found in euents
discharged from industries involved in galvanization, electroplating,
manufacture of batteries and other metallurgical industries.
Zn occurs in 0 and 2 oxidation states and it forms complexes with anions,
amino acids and organic acids. Zn is bioavailable at high pH and it hydrolyses
at pH 7.07.5, forming Zn(OH)2. Under reducing conditions Zn readily pre-
cipitates and may coprecipitate with hydrous oxides of Fe or manganese.65
Zinc in its metallic form has limited bioavailability and poses no eco-
logical risk. However, zinc can react with other chemicals such as acids and
oxygen to form compounds, which can be potentially toxic and can cause
serious damage to biological systems.65,66 Zn is an essential and beneficial
element for humans and plants. Complete exclusion of Zn is not possible
due to its dual role, an essential microelement on the one hand and a toxic
environmental factor on the other.37
The removal of Zn21 from euents is a major problem due to the diculty
in treating such wastewaters by conventional treatment methods.37,67,68
Biosorption could be the appropriate alternative and several studies re-
ported in the literature for the removal of this metal support the feasibility of
this removal technique.67,68
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15.3 Biosorption Mechanisms: Physical

and Biochemical Aspects
The simplest definition of biosorption is that it is the entrapment of sub-
stances from solution by biological material. Although true, it is not that

simple as biosorption is a complex physico-chemical process that includes
such mechanisms as absorption, adsorption, ion exchange, surface com-
plexation and precipitation.69
Metal biosorption can be performed by both, live and dead biomass and
also by its excreted and derived products. The complex structure of micro-
organisms allows many ways for the metal to be taken up by the microbial cell.
The biosorption pathways can be divided into metabolic and non-metabolic
mechanisms. As the transport of the metal across the cell membrane, yielding
intracellular accumulation, is dependent on the cells metabolism, the use of
live biomass is mandatory for the establishment of a metabolic mechanism.70
For the non-metabolic processes dead or live microorganisms may be used.
The main reaction paths used by the microorganisms can be divided into
three groups: assimilation, adsorption and biodegradation.71 A description of
all the processes involved in the biosorption mechanism will be given. A brief
overview of these mechanisms is presented in Figure 15.1.
15.3.1 Assimilation
Assimilation of metals by microorganisms or other biosorbents involves the
11:26:47.
uptake of these elements and their incorporation into the structure of the
Biosorption Mechanisms
Assimilation Adsorption Biodegradation
Physical Adsorption
Complexation
Precipitation
Co-ordination
Reduction
Ion exchange
Figure 15.1 Brief overview of the main mechanisms involved in a biosorption

process.
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304 Chapter 15
microorganism/biosorbent and generally refers to intracellular accumu-

lation. Consequently, nutrients are removed from the water streams.71,72
Several authors refer to this process in their works, as Sousa et al.,73 who
studied the selenium assimilation and Suzuki et al.,72 who used nonliving
Ulva seaweed as a biosorbent for various heavy metals.
15.3.2 Adsorption
The adsorption phenomena include physical adsorption, complexation,
precipitation, ion exchange, reduction and co-ordination, as the main
reaction steps.
15.3.2.1 Physical Adsorption

This type of adsorption is a result of intermolecular forces of attraction
between the adsorbent and the adsorbate. The molecular attractive forces
that retain the adsorbate can be a result of Van der Waals forces, inter-
molecular potential and dispersion forces. This is a readily reversible phe-
nomenon. The energy of interaction between the adsorbate and adsorbent
has the same order of magnitudes as, but is usually greater than, the energy
of condensation of the adsorbate.74,75 The physical adsorption was well
characterized in the works developed by Chojnacka76 who studied the bio-
sorption of Cr(III) ions by wheat straw and grass and more recently by Din
et al.75 who established the thermodynamics of biosorption of Co(II) ions by
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an ecient and ecofriendly biosorbent, Saccharum bengalense.
15.3.2.2 Complexation
Complexation plays an important role in the fixation of heavy metals by
microbial aggregates. This process can take place by complex formation on
the cell surface after the interaction between the metal and the active surface
groups. Many functional groups in the extracellular polymeric substances
(EPS), such as carboxyl, phosphoric, sulfhydryl, phenolic and hydroxyl
groups, can complex with heavy metals.71 The complexation as a biosorption
step was investigated by Schiewer77 who modeled the complexation and
electrostatic attraction in heavy metal biosorption by Sargassum biomass and
by Allaboun and Al-Rub78 who reported the dynamics, mechanistic
and equilibrium studies for the biosorption of nickel on palm tree leaves.
15.3.2.3 Precipitation
Metal precipitation is usually involved in biosorption and it may be either
dependent on the cellular metabolism or not. The precipitates may be
formed and remain in contact with or inside the microbial cells but they also
may be independent of the solid phase of the microbial cell. Precipitation
may be a consequence of the chemical interaction between the metal and the
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70
cell surface when there is no dependence on the cellular metabolism. The
presence of the solid phase microbial cell or biofilm also enhances
precipitation.
Precipitation usually refers to the formation of insoluble inorganic metal
precipitates. However, organic metal precipitates may also be formed in the

case of metal biosorption by microbial cells as metals are easily bound
to extracellular polymeric substances (EPS) excreted by some prokaryotic
(bacteria, archaea) and eukaryotic (algae, fungi) microorganisms. Purified
products such as glucan, mannan and chitin, obtained from isolated cells,
accumulate greater quantities of cations than the intact cells, proving that
biomolecules can form metal precipitates.79 These last authors studied the
mechanism of metals precipitation by biologically generated alkalinity in
biofilm reactors.
15.3.2.4 Co-ordination
Tsezos et al.80 arm that metal atoms have preferences for specific donor
atoms (hardhard/softsoft) and for the stereochemical arrangements that
play an important role in the binding with the available ligands on the
microbial cell. It is suggested that there is limited information on surface
complexation models to describe metal biosorption, based on the theory of
surface co-ordination chemistry. Nevertheless, metal biosorption capacities
and biosorption mechanisms may be explained by the preferences of the
metal species.
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Studies developed by Al-Qunaibit81 about divalent Cu, Cd and Pb bio-

sorption in mixed solvents confirmed metal coordination to carboxylate
ligands. Similar findings were described by Garcia et al.,82 with spectro-
scopic studies of vanadium biosorption on dierent types of carbohydrate
biomass and the spectroscopic data indicates co-ordination with the metal
ion through the oxygen atoms of COO and sugar OH donors.
15.3.2.5 Reduction
Reduction is a well-known path for biosorption. A typical example is the
removal of toxic hexavalent chromium from aqueous solution using dier-
ent types of biomass. This removal is often associated with the simultaneous
reduction of Cr(VI) to Cr(III), and then incorporation of Cr(III) in the biomass,
Figure 15.2. Quintelas et al.83 investigated the biosorption of Cr(VI) by dif-
ferent bacteria and asserted that some bacteria can detoxify chromium
wastewater, by either chemical reduction of the ion or by surface adsorption
and accumulation inside the cells. Once inside a cell, Cr(VI) can be reduced
to Cr(V/IV/III) by dierent nonspecific reductants such as glutathione, glu-
tathione reductase, cysteine, carbohydrates, NADH, NADPH, nucleotides
and ascorbic acid. The reactive oxygen species (ROS) by-products of the Cr(VI)
reduction process, can attack and damage DNA and proteins. Considering
the composition of the bacterial cell wall (teichoic acids, polycarbohydrates
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306 Chapter 15
Figure 15.2 New method of chromium removal from wastewater and catalytic
reutilization in VOCs oxidation.
and other diol-containing substances that possess reducing ability) and the
activity of dierent specific and nonspecific membrane associated reduc-
tases, the authors suggested that Cr(VI) can be partly reduced on the bacterial
cell wall.
15.3.2.6 Ion Exchange

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Ion exchange is an important concept in biosorption, because it explains

many of the observations made during heavy metal uptake experiments. Cell
walls of microorganisms contain polysaccharides or ions as Ca, Na or P, and
bivalent metal ions may exchange with those counter ions of the cells. The
process of ion exchange is presented in studies developed by Williams and
Edyvean84 who established an ion-exchange relationship between the se-
questration of nickel ions and the concomitant release of calcium ions. Pino
et al.85 used biomass to remove Cd(II) and the results proved the presence of
cadmium in the biomass particles after biosorption and the absence of Cl, K,
Na and Mg bands in the biomass particles after biosorption of Cd(II) ions,
suggesting a possible involvement of ionic exchange mechanism interaction.
15.3.3 Biodegradation
Although biodegradation it is not applied to metals but only to organic
compounds, it was decided to make a reference to this process in this
chapter because usually the euents are a cocktail of metals, organic
compounds and other pollutants. Some of the processes to remove metals
originate as metalcomplexes and these can be removed by biodegradation.
Biodegradation is the capability of microorganisms to degrade hazardous
compounds, producing less toxic substances. In some cases complete deg-
radation of compounds is achieved. Thomas et al.86 investigated the
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biodegradation of metalEDTA complexes by an enriched microbial popu-

lation and obtained very good results for seven dierent metalEDTA com-
plexes. Similar findings were obtained by Joshi-Tope and Francis,87 who
studied the mechanisms of biodegradation of metalcitrate complexes by
Pseudomonas fluorescens, and more recently Okello et al.88 confirmed the

biodegradation of hexavalent chromium using naturally derived flavonoids.
15.4 Factors Aecting Biosorption

Investigation of the equilibria of biosorption by the dierent microbial
biomass is essential for the industrial applications, as it gives information
about the metal uptake of the process, necessary for the design of the
equipment. The following factors aect the biosorption process: pH, tem-
perature, contact time, competing ions/co-ions, initial concentration of
metal ions and biomass, composition of cultural medium and cell age
(Figure 15.3). Comments on each of these factors will be provided.
15.4.1 Solution pH
This pH is one of the most important environmental factors aecting bio-
sorption processes. The pH value of a solution strongly influences not only
the site dissociation of the biomass surface, but also the solution chemistry
of the heavy metals. It determines possible hydrolysis, complexation by or-
ganic and/or inorganic ligands, redox reactions, precipitation, the speciation
11:26:47.
and the biosorption availability of the metals.89

The biosorptive capacity for metal cations increases with increasing pH of
the sorption system, but not in a linear relationship. On the other hand, a
too high pH value can cause precipitation of metal complexes, so it should
be avoided during the process. For dierent biosorption systems of metal
ions, the optimal pH is dierent.
Hundreds of works have been published about the influence of pH on
the biosorption of metals. The works of Pagnanelli et al.90 on the metal
Initial pH
Factors Temperature
Cell Age Affecting
Biosorption
Contact Time
Competing
Ions
Figure 15.3 Factors aecting biosorption.

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308 Chapter 15
speciation and pH eect on Pb, Cu, Zn and Cd biosorption onto Sphaerotilus

natans should be highlighted.
15.4.2 Bulk Temperature

Temperature also has an influence on the biosorption of metal ions, but to a

limited extent and within a certain range of values. Biosorption processes are
not operated at high temperature because that will increase the operational
cost. Adsorption reactions are normally exothermic, so biosorption capacity
increases with a decrease of temperature.91 Overall, the temperature is be-
lieved to have a smaller eect on the biosorption than the other factors.92
15.4.3 Contact Time

Generally speaking, the biosorption capacity and the removal eciency of
metal ions became higher on prolonging the contact time until an equi-
librium state is reached. This equilibrium is a consequence of saturation of
the biomass. Several works have been published about this subject and
two of the more recent studies are the ones developed by Dina and Mirza,93
who evaluated the eect of contact time on the biosorption of Ni(II) using a
novel green biosorbent Saccharum bengalense, and the one published by
Khoramzadeh et al.,52 who investigated the same eect on the mercury
biosorption from aqueous solutions by sugarcane bagasse.
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15.4.4 Competing Ions Present on Solution

The eect of competing ions on the overall biosorption eciency is well
known. Other sorbable ions in solution may compete with the metal ion of
interest for sorption sites. The binding of this metal ion is then disturbed.
The inhibition depends on the binding strength of the protagonist ions to
the biomass. This eect was investigated by Zvinowanda et al.,94 who used
maize tassel for the removal of Pb, Se, Sr, U and V from borehole water
contaminated with mine wastewater in the presence of alkaline metals and
concluded that the concentration of other ions had a negative impact on the
uptake of lead. The eect was also considered by Hana et al.95 who in-
vestigated the eects of anion species and concentration on the removal of
Cr(VI) by a microalgal isolate, Chlorella miniata.
15.4.5 Initial Concentration of Metal Ions and of Biomass

The literature shows that the initial metal ion concentration seems to have
an impact on biosorption, with a higher concentration resulting in a higher
solute uptake. This is due to the fact that at lower initial solute concen-
trations, the ratio of the number of moles of solute to the available surface
area is low; subsequently, the fractional sorption becomes independent of
the initial metal concentration. However, at higher concentrations, the sites
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available for sorption become fewer compared with the number of moles of
solute present; hence, the removal of solute is strongly dependent upon the
initial solute concentration.
According to Das,96 the dosage of a biosorbent strongly influences the
extent of biosorption. An increase in the biomass concentration generally

increases the amount of solute biosorbed, due to increased surface area of
the biosorbent, which in turn is proportional to the number of binding sites.
Dina and Mirza93 and Manzoor et al.97 are two recent reports where the focus
is on the eect of adsorbent dosage.
15.4.6 Cell Age

Wang and Chen91 arm that cell age of biomass has an influence on metal
biosorption because, usually, the cells at the lag phase or early stages of
growth have a higher biosorptive capacity for metal ions than that of sta-
tionary phase. These dierences are related to the dierence in the cell walls
composition. Anagnostopoulos et al.98 investigated the subject with a contri-
bution to the interpretation of uranium uptake dependence upon the growth
phase of microorganisms, and concluded that the metal retention capacity of
exponential cells is higher than that of stationary phase cells. Ngwenya99 also
studied this eect and concluded that enhanced adsorption of zinc is asso-
ciated with aging and lysis of bacterial cells in batch incubations.
15.5 New Perspectives

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Environmental awareness identified the need for developing green pro-

cesses, whereas the current economic constraints favour the demand for
recoveryreuse technologies. The recovery of biosorption supports is pos-
sible as an alternative process of benign production of heterogeneous
catalysts for oxidation reactions under mild conditions. An advantage of
using a biosorption system supported on zeolites for the treatment of was-
tewater contaminated with metals is the reutilization of the obtained metal-
loaded zeolites as catalysts in oxidation reactions of organic compounds.
Zeolites are low cost ion exchangers and have peculiar properties that result
from the presence of positively charged exchangeable ions. The lack of anity
of the zeolite for Cr(VI) species can be overcome by the use of bacteria, such as
A. viscosus, that have the capacity of transforming toxic Cr(VI) compounds
through reduction into cationic Cr(III) species that are much less harm-
ful.99102 Cr-containing catalysts have found application in the oxidation of
several organic substrates, including cyclohexene and cyclohexanol.
15.6 Conclusions
Biosorption of heavy metals has proved to be a competitive alternative to
conventional technologies to concentrate metals from wastewater. It is easy
to implement, demands low investment and may be considered as a green
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310 Chapter 15
process with little environmental impact. Moreover, it allows the recycling of

water and metals and eventually the production of high value catalysts to be
used in the mild oxidation of VOCs starting with an industrial waste. Two
lines of research and development have gained momentum in the mean-
while: the application of living biomass, where molecular biology may im-
plement the biosorptive characteristics of the cells to be used, and the use of
inactive biomaterials that demand a deeper optimization of supports,
operational parameters and modeling tools. A broad array of microorgan-
isms have been tested up till now as biosorbent materials and the present
tendency is focused on the biosorption application for detoxifying high
volumes of low concentrations of complex euents. Furthermore, other
approaches are also under investigation, including food enrichment with
complementary elements or purification and enrichment of high-value
pharmaceuticals.
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2008, 158, 615.
96. N. Das, Clean Soil, Air, Water, 2012, 40, 16.
97. Q. Manzoor, R. Nadeem, M. Iqbal, R. Saeed and T. M. Ansari, Bioresour.
Technol., 2013, 132, 446.
98. V. A. Anagnostopoulos, A. Bekatorou and B. D. Symeopoulos, J. Radio-
anal. Nucl. Chem., 2011, 287, 665.
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314 Chapter 15
99. B. T. Ngwenya, Chemosphere, 2007, 67, 1982.

100. H. Figueiredo, I. C. Neves, C. Quintelas, T. Tavares, M. Taralunga,
P. Magnoux and J. Mijoin, Appl. Catal. B: Environmental, 2006, 66, 274.
101. H. Figueiredo, B. Silva, C. Quintelas, M. F. R. Pereira, I. C. Neves and
T. Tavares, Environ. Eng. Manage. J., 2010, 9, 305.

102. B. Silva, H. Figueiredo, I. C. Neves and T. Tavares, Int. J. Chem. Biomol.
Eng., 2009, 43, 59.
11:26:47.
CHAPTER 16
Chromium in Tannery
Wastewater
MARILIZ GUTTERRES* AND BIANCA MELLA
Federal University of Rio Grande do Sul, Chemical Engineering

Department, Laboratory for Leather and Environmental Studies,
Porto Alegre, Brazil
*Email: mariliz@enq.ufrgs.br
16.1 Introduction
The tanning process in Brazil, and worldwide, is of great economic im-
11:26:49.
portance. Brazil has the second largest herd, representing approximately

210 million heads of cattle, and has the largest marketable herd in the world.
The country is also the second largest producer and exporter of leather and
aims at excellence with investments, qualification and technology.1 The
global leather industry is giving increasing attention and making eorts to
treat liquid euents and provide proper disposal for the sludge and residues
generated in the processes.
There is great concern regarding the level of treatment and the final
destination of the euents and about what will be the consequences for the
environment with regards to the quality of the receiving waters. Considering
these aspects, studies, criteria and projects relating to the treatment and
disposal of the euents must proceed with special care to ensure adequate
decontamination of the euents, and, equally, the maintenance and im-
provement of the uses and of the quality of the receiving bodies.2
Tanning with chromium salts is the most widely employed method;
usually chromium used in leather processing is in the form of basic chro-
mium sulfate (CrOHSO4) and is analysed in the form of chromium oxide.

315
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316 Chapter 16
The chrome tanning process is relatively economic and is a well-established

technology. The chromium tanned leather has a good anity to most
chemical products used in post-tanning stages. Currently, no tanning agent
is capable of completely replacing basic chromium sulfate in the production
of the entire range of articles with respect to quality, competitive manu-

facturing costs and with the same ease of performance of the tanning.3,4
Considering the level of chromium in wastewater, it is relevant the de-
velopment of appropriate techniques looks into the recovery and recycling of
the residual chromium. Residues containing chromium are classified as
dangerous residues in Brazil and must be disposed of in dangerous indus-
trial residues landfills. This applies to wet-blue leather shavings and trim-
mings, semi-finished and finished, and the sludge generated in the
wastewater treatment plants.
Chromium is an essential element for human nutrition. However, doses
above the adequate level can be toxic and cause a number of diseases in
humans.5 Environmental eects and interactions of chromium present in
the soil, air and water with living species have been studied.
The management of the use of chromium in tanneries involves the con-
trolled application of the tanning technologies, ecient treatment of eu-
ents generated in these process stages, the adequate disposal of solid
residues containing chromium and the reuse of chromium in the tanning
process itself.
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16.2 Forms of Chromium in Nature

Chromium is present in all physical states in the environment, i.e., in air,
water and soil. It is found naturally in rocks, animals, plants, soil, dust and
volcanic mists. Chromium has atomic number 24 and atomic mass 52, it is a
transition chemical element and the most common oxidation states of
chromium are 2, 3 and 6; however, the main forms are: metallic Cr,
identified as Cr(0); trivalent chromium, identified as Cr(III) or Cr31; and
hexavalent chromium, identified as Cr(VI) or Cr61. The bivalent form is un-
stable in many compounds, because it is easily oxidized to the trivalent form
by air. Chromium in its trivalent form is the more stable state of the element,
followed by the hexavalent, in addition to the elemental form, and appears
in the composition of oxides, sulfates, chromates, dichromates, basic salts
and in the elemental form covering metal and plastic parts in surface
treatment processes.58
Thus, only two states are found in nature, Cr(III) and Cr(VI). The relation-
ship between the hexavalent and trivalent oxidation states of chromium is
shown in Equation (16.1):5
Cr2O72 14H1 6e - 2Cr31 7H2O 1.33 V (16.1)
The electric potential dierence between these two states reflects the
oxidizing property of hexavalent chromium and the substantial energy
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Chromium in Tannery Wastewater 317
required to oxidize the trivalent form to the hexavalent one. The reduction
of Cr(VI) occurs spontaneously, unless the species is in the insoluble
form.6,9
Under normal conditions, Cr(III) and metallic chromium are relatively
non-reactive in the atmosphere, but Cr(VI) in the air can react with particu-
late materials or gaseous pollutants to form Cr(III).6 The conversion between
trivalent and hexavalent chromium states is an important feature. The Cr(III)
is the less mobile, less toxic form and is found mainly bound to organic
matter in soil and in aquatic environments.10 In contrast to the low mobility
observed for Cr(III) in soils, plants, animals and natural waters, Cr(VI) is more
soluble, mobile bioavailable and toxic than Cr(III).11,12
Cr(III) acts as an essential micronutrient for carbohydrate and lipid me-
tabolism in humans. Trivalent chromium is an essential element for human
nutrition. This nutrient plays an important role in the metabolism of glu-
cose, fats and proteins. It is believed that the biologically active form of
organic Cr(III) complex facilitates the interaction of insulin with its cellular
receptors. Also, cases of atherosclerosis and aorta injuries related to chro-
mium deficiency in rats and rabbits have previously been identified.5
However, the beneficial eects of this element should be considered with
caution. Doses above the adequate level can cause intoxication and a
number of diseases.
Cr(III), once absorbed, combines with plasma proteins, being distributed
in the tissues depending on its quantity.13 Absorption of Cr(VI) is influenced
by the acidity of the gastric juices, which can favour its reduction to Cr(III),
11:26:49.
and the presence of other food components, which can act as reductors
(ascorbic acid, sulfhydric compounds) or blockers. Once inside the cell,
Cr(VI) is rapidly reduced to Cr(III), for example, by hemoglobin and the
endoplasmic reticulum.14 Cr(III) is an active component of the glucose tol-
erance factor and thus enhances the insulininsulin receptor interaction
with consequent biologic response.13 A deficiency of chromium in man15
can cause a glucose intolerance (the most sensitive indicator), an inability to
use glucose for energy, neuropathies with normal insulin levels, increase of
free fatty acids and serum cholesterol in the blood, low respiratory quotient,
abnormalities in nitrogen metabolism, with the consequent reduction in
growth and longevity.16
Cr(III) is considered an essential nutrient and relatively non-toxic to
humans and mammals, however, it can be oxidized in nature, thus be-
coming its most toxic form Cr(VI).5
Cr(VI) is considered to be the most toxic chromium type and commonly
occurs in association with oxygen in the form of chromate (CrO42) or
dichromate (Cr2O72). Cr(VI) acts as a carcinogen and genotoxic agent.17,18 In
man, acute exposure to Cr(VI) produces nausea, diarrhea, liver and kidney
damage, internal bleeding, dermatitis and respiratory problems, while acute
exposure to Cr(III) is rarely reflected in toxic eects. For man, Cr(VI) is
considered a carcinogen substance. Several studies have confirmed the
appearance of lung cancer due to exposure of workers to Cr(VI).
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318 Chapter 16
16.2.1 Chromium in the Environment

In the most important deposits of the planet, chromium is in the elemental
form or in the trivalent oxidation state. The concentration of chromium in
rocks ranges from 2 to 90 ppm in granitic rocks, 1000 to 3400 ppm in
ultramafic rocks and from 30 to 590 ppm in shale and clay.19 In most soils,
chromium is found in low concentrations (260 mg kg1) and only a fraction
of that chrome is available to plants. In areas where significant deposits of
chromium occur, water sources may present concentrations greater than
50.0 mg L1, values that exceed the national and international standards for
drinking water of 0.05 mg L1. In atmospheric air, the chromium concen-
trations found are lower than 0.1 mg m3 , and uncontaminated water
values are in the region of 1.0 mg L1. In seawater, concentrations are in a
range of between 1 and 10 mg kg1, and the permitted level in drinking
water is 50 mg kg1.6
The concentration of chromium in the soil depends on specific factors
such as the type of industrial process present in the region and the in-
adequate disposal of residues containing heavy metals on the site. The most
common route to chromium contamination in soil is a consequence of the
inadequate method of disposal of the residues containing this metal. The
factors intervening in the transport of substances in soils are: (a) charac-
teristics of the contaminant (solubility, density, concentration, pH, BOD,
COD, etc.); (b) soil characteristics by which it percolates (granulometry, clay
fraction mineralogy, permeability, organic matter, etc.); and (c) character-
istics of the environment (time of soil exposure to the contaminant, presence
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of microorganisms, hydrogeological conditions, aerobic/anaerobic con-

ditions and temperature). Temperature can alter the permeability of the
soil (it changes the fluid viscosity), the speed of chemical reactions and
solubility of the contaminant. The area aected by the contaminant as well
as the way it moves underground characterizes the so-called contamination
plume.20
In plants the concentration of chromium is mainly associated with the
presence of soluble forms of the element in the soil. In the hexavalent form
chromium appears as a soluble anion that penetrates easily through the cell
membrane, having a strong toxic action since it is a powerful oxidizing
agent. In its turn, Cr(III) is only present in the soluble form at pH values lower
than those normally found in biological systems or when complexed with
organic molecules with low molecular weight, which have little mobility
across the cellular membrane. The absorption of the chromium species by
plants occurs by dierent mechanisms.5
Chromium is present in all plants, but there is no scientific evidence that
it is essential to them. Plants growing in soils containing high concen-
trations of chromium retain chromium in their roots and only a small
portion is transported to their superior parts, probably not bioaccumulating
in these parts. Most microorganisms (protozoa, fungi, algae, bacteria) are
capable of absorbing chromium.21
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The main route to exposing the population in general to chromium is the

intake of food and water, while occupational exposure is through inhalation,
but it also may occur by contact dermatitis. The main human activities in
which chromium and its compounds are released into the environment are:
emissions from cement manufacturing; civil construction, due to residues

from cement; metal alloy welding; mines and foundries; steel and alloys
manufacturing; electroplating industry; lamps; urban and industrial waste;
waste incineration; coal ash; tanneries and fertilizers; and wood preserva-
tives.6,9,19 In these processes or sources of contamination, chromium ap-
pears in the trivalent, hexavalent and elemental forms.5
Forest fires and volcanic eruptions are natural sources of environmental
contamination of air. Cr(VI) is released into the atmosphere from industrial
sources such as, for example, in ironchrome production plants, chrome-
plating plants, power plants, incinerators, cement plants and welding
processes.22
16.2.2 Chromium in Water

The majority of the chromium in surface water bodies may be in the form
of particulate materials or deposited in the sediment. Some particles may
remain as suspended matter and subsequently be deposited in the sedi-
ments. The hexavalent chromium can be reduced to Cr(III) by organic
substances present in water and can, eventually, be deposited in
sediments.19
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Industrial euents containing chromium, some in the hexavalent form,

are led to rivers and air.6 As chromium compounds are nonvolatile, the
transport of chromium from water to the atmosphere does not occur, except
through the mists of marine waters. Most of the chromium released in water
is deposited in the sediments. A small percentage of it can be present in
water in both soluble and insoluble forms. Soluble forms are found as Cr(VI)
and Cr(III) complexes. In the aqueous phase, Cr(III) occurs as a solid adsorbed
to clay particles, organic materials or iron oxide.9
The hexavalent chromium reduction and Cr(III) oxidation in water have
been well studied. The reduction of Cr(VI) to Cr(III) by sulfide ions and iron(II)
ions, under anaerobic conditions, occurs rapidly, with a half life ranging
from instant to a few days.9 Oxidation of Cr(III) to Cr(VI) by oxygen dissolved
in natural waters is practically nonexistent. Cr(III) added to a lake water23
suers a slow oxidation to Cr(VI), corresponding to a half life of the oxidation
of nine years; it can be reduced to two years with the addition of 50 mg L1 of
manganese oxide. Thus, the oxidation process may be insignificant in nat-
ural waters.5 Oxidation of Cr(III) to Cr(VI) during water chlorination was
shown to be higher at a pH of between 5.5 and 6.0. However, this phe-
nomenon rarely occurs during the chlorination of water distributed to the
general population, due to the fact that metal concentrations are low and
because of the presence of organic matter, favoring the complexation of
Cr(III) and protecting it against oxidation.9,11
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320 Chapter 16
The environmental consequences of the increase of chromium concen-

trations fall mainly on aquatic species from algae to higher organisms
through passive diusion. Chromium is normally accumulated in the
gills, bronchus and bowels about 1030 times more when compared with
the accumulation in the heart, skin, scales and muscles of fishes.

Ecological factors, the state of the species and its activity can determine this
bioaccumulation.21 The concentration of chromium in aquatic plants is
generally low, less than 5 mg kg1 of dry weight. Near sources of pollution,
the residues increase to 50 mg kg1 of dry weight. Terrestrial species
also contain low levels, between 0.1 and 45.2 mg kg1 with an average of
2.7 mg kg1.24
The formation of chromium species in deep water depends on the redox
potential and on the pH of the aquifer. The Cr(VI) species predominates at
high oxidizing conditions, which does not happen with the Cr(III). In sea-
water, the predominant species is the Cr(VI), which is generally stable. In
these waters the chromium concentrations are found in a range between 1
and 10 mg kg1, the permitted level in drinking water being 50 mg kg1. In
natural subterranean water, with a pH of between 6 and 8, the predominant
species are CrO42 and Cr(OH)1. These and other species of Cr(III) pre-
dominate at acidic pH and Cr(OH)3 and Cr(OH)4 in alkaline waters.25
The results of several studies are a warning for the need to control the
public supply of water in rural zones, and particularly in industrial areas,
considering that the inappropriate disposal of chromium may contribute to
the contamination of groundwater.
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Many nations use the potability standard recommended by the World

Health Organization (WHO) of 0.05 mg L1; in this case it is assumed
that Cr(VI) is the dominant species. The Environmental Protection Agency
(EPA) (1989) of the United States developed a less restrictive standard of
0.12 mg L1, which was derived based on chronic ingestion of water con-
taining Cr(III) and Cr(VI). The World Health Organization has recommended,
since 1958, a maximum concentration of 0.05 mg L1 of Cr(VI) in drinking
water. The Brazilian Resolution CONAMA 357 of 2005 recommends a max-
imum concentration of 0.05 mg L1 for total chromium for human water
consumption.24
The EPA has set the following parameters for chromium in water:9,26
maximum concentration level, 0.1 mg L1; maximum concentration in
subterraneous water, 0.05 mg L1; standard for drinking water, 0.1 ppm;
criteria for environmental quality of the water, Cr(III) 170 mg L1 and
Cr(VI) 0.05 mg L1.
16.3 The Processing of Leather

Leather processing consists in transforming skin or hide (green or con-
served) into leather and it includes its finishing, defined according to the
final leather article to be manufactured. The fabrication technology requires
several processing steps, with additions of water and chemical products to
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the skins/hides being processed in drums, intercalated by weighing, washing

and mechanical operations (Figure 16.1). The drums I, II, III and IV of the
figure indicate the four dierent drums used for corresponding steps.
Salty hides
Weighing I Green hides
Salt shake-off Weighing I

(Drum I)
Presoaking Prefleshing
Soaking
Dehairing/Liming
Washing
(Drum) II
Fleshing/Splitting
Weighing II
Deliming/Bating
Pickling
Tanning
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(Drum III)
Samming
Shaving
Weighing III
Deacidification
Retanning
Dyeing
Fatliquoring
(Drum IV)
Mechanical
Treatments/Drying
Operations
Finishing Operations
Classification
Leather Expedition
Figure 16.1 Flow chart of the stages of leather processing.

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322 Chapter 16
The processing steps of the transformation of hide into leather are

grouped into the beamhouse (salt shake-o to pickling), the tanning and the
finishing (wet finishing, pre-finishing and final finishing) and are presented
as follows:
(a) Salt shake-o. This is performed on hides conserved with salt (so-
dium chloride), with the objectives of removing the salt that is de-
posited (free) in the hide and decreasing the salinity of the euents
from the soaking step. It is performed in an open drum designed
especially for this situation.
(b) Presoaking. This is the step in the process where the hide is placed on
a drum with water to take away any dirt and salt as well as being
subjected to the first hydration.
(c) Pre-fleshing. This is performed in a fleshing machine with the aim of
eliminating the material adhered to the carnal, the subcutaneous
tissue and adipose material.
(d) Soaking. This cleans and re-hydrates the hides in order to eectively
interrupt the salt conservation eects and replenish skin moisture for
its processing. It is done in the soaking drum with the addition of
water, tensoactive, alkali and other chemical products.
(e) Dehairing and liming. This step has finally to take away the hair from
the skin, remove the epidermis, open the fibrous structure for
cleaning through the swelling of the hide, continue the degreasing
which started during soaking and facilitate the stripping through
11:26:49.
hide swelling. This is done in a drum with the addition of water, lime,
sodium sulfide and other chemical agents.
(f) Fleshing. This takes away the residues from subcutaneous material
(hypodermis). If well conducted, the prefleshing is enough and
fleshing is not necessary;
(g) Splitting. The hide is divided into two layers, where the top layer is called
grain or top split (considered to be the noblest part, which contains
the grain or thermostatic layer and part of the reticular layer) and the
bottom layer is called flesh or bottom split (only the reticular layer).
(h) Deliming. Removes alkaline substances introduced into the hide in
the liming by means of delimer chemical products and it reverses the
swelling of the hide.
(i) Bating. Enzymes are added to remove residues of epidermis, hair and
fat leaving the hide clean and the grain thin and smooth.
(j) Pickling. This is the stage that interrupts the action of deliming and
bating and the collagen fibers are prepared for easy penetration of
tanning agents by acidification of the skin in a saline solution.
(k) Tanning. This is the main stage of leather processing, where the hide is
modified by reaction with tanning agents for leather transformation.
(l) Samming and shaving. The leather is dried out in the drying machine
(samming) and after that adjustment is made to the uniformity of its
thickness on a shaving machine.
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(m) Acid washing and deacidification. A mild acid washing removes

surface chromium (not fixed) that is on the hide surface. The deaci-
dification neutralizes residual acids present in wet-blue leather.
(n) Retanning. This is the stage in which the physicalmechanical, tex-
ture and surface characteristics of the leather are defined through the
use of retanning substances.
(o) Dyeing. Gives colour to the leather through the use of dyes.
(p) Fatliquouring. The fibers are lubricated with oils to give softness to
the leather.
(q) Mechanical and drying operations. The mechanical treatments of
leather after drumwork in the float are samming, stretching and
setting out followed by the operations of air drying, vacuum drying,
paste drying and wet toggling.
(r) Softening and prefinishing. Leather is made soft by feeding to staking
machines or by milling in rotating drums. The prefinishing oper-
ations are conditioning, toggling, sanding, stucco application, dust
removal, trimming and grain impregnation.
(s) Leather finishing. Surface treatments give the leather presentation
and definitive aspects by means of application of covering and top
layers with film-forming chemical products (polymer resins), pig-
ments and auxiliary agents in water base or solvent base.
(t) Quality control, classification, measurement and leather expedition.
16.3.1 Tanning with Chromium Salts

11:26:49.
After the beamhouse operations, the hide is ready to receive the tanning
agent. During the tanning the actual transformation of the skin collagen
structure into leather occurs. This modification is achieved by chemical
bonds and transverse links of the collagen chains with the tanning agents.
The tanning provides stability of the hide to putrefaction (microbial and
enzymatic), chemical stability and hydrothermal stability as well as pro-
viding porosity to the material. The eects of the chemical modifications
performed in the hide eliminate its shrinkage through the action of hot
water (or boiling in the case of tanning with chromium), eliminate its ability
to swelling by water absorption, improve its mechanical resistances and the
leather acquires flexibility.
Most classic tannings are those that employ chromium or vegetable tan-
nin. The vegetable tanning provides, in general, a less flexible material and
with brown coloration that is characteristic of vegetable tannin and is aimed
at specific markets, while chromium tanning is more versatile in terms of
properties of the articles produced.
It is also common practice for the association of tanning substances, the
so-called combined tannings. The proportion of the products employed
varies with their function and with the process as a whole. Vegetable tanning
is usually preceded by treatment with phenolic synthetic tannins. There are
tanning systems that combine vegetable tannins with mineral tanning
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324 Chapter 16
agents such as vegetable tanning combined with oxazolidine, combinations

of chromium with other metal salts (in order to reduce the supply of
chromium or to give lighter shades); combinations of vegetable tannins with
metal salts (aluminium and titanium, in order to increase the hydrothermal
stability); and various retanning systems with naphthalene and phenolic

synthetic tannins, resins and polymers.27
Chromium is the main tanning agent used worldwide, from which wet-
blue leather is obtained, allowing several types of leather to be obtained
through wet finishing, drying and final finishing treatments. About 80% of
all leathers in the world are tanned with chromium.
In the search for new tanning systems there is much well developed re-
search and technology that is being applied industrially. Demand for chro-
mium free tanning systems is growing, not only for automotive leathers, but
also for footwear and leather goods. From the 20% of free tanning systems,
one-third is for the automotive industry, the main sector that is driving the
search for these technologies.
Even so, chromium tanning remains the dominant tanning system, due to
the properties of this type of leather and due to the optimal performance of
the tanning system employing a single tanning agent. Chromium tanning is
relatively economic and has a well-established technology. Leathers treated
with chromium are cationic and have good anity with most chemical
products used in the post-tanning stages (retanning, dyeing and greasing).
This implies that they will respond well to any finishing or surface treat-
ment, giving finished leathers with good resistances during use.
11:26:49.
Highlights of the properties of chromium tanned leathers are its good

chemical stability, versatility in physical properties (softness, elasticity),
dyeing and finishing with bright colours, high dimensional stability and
good resistance to heat in the presence of water (hydrothermal stability) in
water with temperatures of 1001C, suering no retraction. The leathers with
chromium are lightweight, soft, solid to light, allow themselves to be dyed
giving intense colours, have good resistance to traction and use, elasticity,
firm and smooth flower and high hydrothermal stability. However, they have
poor filling, are hard to sand due to their elasticity and do not allow pattern
recording. Even so, these characteristics can be changed with appropriate
retanning agents, which means that the wet-blue leather obtained is quite
versatile when treated in the wet finishing in order to obtain dierent types
of leather articles.
The process of tanning with chromium is performed in drums in two
steps: the diusion and the fixation of the chromium salt. Both steps are
intimately linked to the basicity of the chromium salt used. The more well
distributed and fixed the tanning agent in the structure of the fibers is, the
better is the quality of the leather obtained.
During the hide pickling process many constituent carboxylic ions of the
collagen structure become electrically neutral (COO H1 2 COOH),
thus decreasing the anity of the chromium complex to collagen. This de-
crease of anity is convenient, because it enables diusion of the complexes
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of chromium(III) throughout the depth of the hide thickness, fibers and fi-
brils. If the hide has too much anity with chromium, at the very beginning
of the tanning the fixation only occurs in the outer layers, blocking the
chromium penetration to the whole skin depth.28
The chromium salt widely used in tanning is basic chromium sulfate, a

compound that possesses chromium in the trivalent state and whose bas-
icity is variable. The basicity is the number of valences of chromium co-
ordinated with hydroxyl groups (OH). The non-occurrence of combination
with hydroxyl groups results in a compound with zero or null basicity. The
incidence of only one chromium valence linked to the hydroxyl group results
in a chromium salt with 33% basicity, of two valences in a chromium salt
with 66% basicity and, finally, if all the chromium valences are linked to
hydroxyl groups, the chromium salt has 100% basicity. The basicity increase
of the chromium salt decreases its diusion into the hide, while it increases
its fixation and tanning power. In high basicity, above 66%, tanning is not
performed because chromium tends to precipitate.
On the market there are chromium salts of dierent basicities, the most
common of which have basicities of 33, 40, 48 and 50%.
The chromium salt that is most used in a tannery has 33% basicity and
26% chromium oxide. Usually, the process of tanning begins with chromium
salts at a basicity of 33% or less with the objective of ensuring the pene-
tration of chromium and to avoid a superficial tanning and, in the next
steps, the basicity of chromium salts is increased in order to fix the chro-
mium agent in the hide, by adding alkaline compounds, until basicity
11:26:49.
between 50 and 60% is reached. The most common basifying agents are
sodium bicarbonate and magnesium oxides. The increase in basicity of the
tanning agent decreases the diusion of the salt, but increases the fixation of
it to the hide, enhancing the tanning power.
The chromecollagen anity depends on the factors: electric charge, di-
mensions of tanning molecules, pH and temperature of the bath, as well as
the characteristics of hide pH and its treatment in the beamhouse
operations.
The chromium salt employed in the tanning is anionic, moving to cationic
over time. As the compound is anionic, it has no tanning action and a
higher diusion rate. The charge change of the complex from anionic to
cationic increases its fixation. This change is a function of time, of alkalinity
(pH) and temperature. The cationization occurs with the basification. The
compound formed by chromium reaction with protein is represented by
Figure 16.2.
According to the ABNT NBR 11054 specification, leather must have a
minimum of 3.5% of Cr2O3 on a dry basis. In leather it can be fixed close to
6% of chromium oxide, which varies according to the supply of salt, the
kinetic conditions of the process and mechanical action.
The excess tanning substances remain in the residual bath or are present
in the structure, but they are not chemically bound to collagen (soluble
chromium in leather).25 The residual liquid euents in the tanning bath
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326 Chapter 16
Figure 16.2 Chromium complex with collagen.
contain chromium as well as the treatment sludge of these euents. In

tanning tests with chromium salt supplies of 6 and 9%, the chromium
contents in the residual baths not fixed were 0.27 and 4.07 g L1, respect-
ively. In a tanning analysis done with a supply of 5.5% of Cr2O3 on the hide
in a set of 4200 kg of skin in a tannery,29 there was 83% absorption of
chromium, leaving 1.61 g L1 of Cr2O3 in the bath.
Even if trivalent chromium salt is used in leather tanning, there is concern
about the possible oxidation of the actual chromium into the hexavalent
form. The internationally accepted method for Cr(VI) analysis in leather is
ISO 17075:2007. The lower detection limit of the method is 3 mg of Cr(VI) per
kg of dry leather; and this value is adopted as the maximum acceptable for
leather by many companies.30
The greatest eect of oxidation of chromium in leather is verified when
the leather fatliquoring with sulfated and sulfited fish oils and products with
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single or multiple unsaturated fatty acids (free or esterified) are employed.

Natural or synthetic greaser agents without the substances discussed pre-
viously do not form Cr(VI).30,31 The increase in the supply of chromium in
tanning and the performance of chromium retanning show a tendency to an
increase in the formation of hexavalent chromium.30 To avoid the trans-
formation of Cr(III) into Cr(VI) it is recommended32 to end the leather wet
finishing treatments with an acidic pH, of between 3.5 and 4.0, by addition
of formic acid. In the deacidification of leather with pH from 5.5 to 6.0, there
was little further influence on the formation of Cr(IV).30,33 In general, vege-
table tannins, such as mimosa, quebracho and tara, when applied in
retanning prevent the formation of hexavalent chromium even when the
leathers are exposed to extreme ultraviolet radiation conditions and high
temperature.31 The use of antioxidants and the application of 13% of
vegetable tannin (calculated on the weight of wetblue leather) in the
retanning step are enough to ensure that the leather resists the accelerated
aging process without formation of hexavalent Cr.30,32
The influence of the following conditions on the oxidation of Cr(III) to
Cr(VI) was evaluated:30 the supply of chromium in tanning (6 or 9% of
chromium salt), the eect of retanning (with chromium and with vegetable
tannin), the deacidification pH and the types of fatliquoring oils (synthetic,
fish and sulfited calfs foot jelly oils. Cr(VI) was analysed in samples under
natural conditions and after accelerated aging. The increase in chrome
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supplies in tanning and retanning resulted in a greater tendency towards the

formation of Cr(VI). The synthetic oil causes less formation of Cr(VI), while
fish oils and sulfited calfs foot jelly oils led to increased formation of Cr(VI).
The re-tanning with 5% of vegetable tannin inhibited the formation of Cr(VI).
16.4 Unitary Operations in Tannery Euents

Treatment
The physical properties and chemical and biological characteristics of waters
and wastewaters are interrelated, e.g., physical and chemical characteristics
of water bodies aect the abundance, species composition, stability, prod-
uctivity and biological conditions of populations of aquatic organisms.34 The
important constituents that deserve consideration in wastewater treatment
are included in the following categories:35 suspended solids, biodegradable
organic pollutants, pathogens, nutrients, priority pollutants, refractory organic
pollutants, heavy metals and dissolved inorganic solids. Secondary treatment
standards for wastewater are concerned with the removal of biodegradable
organic agents, total suspended solids and pathogens. Most strict standards
that have been recently developed concern the removal of nutrients, heavy
metals and priority pollutants. When wastewater is to be reused, standards
generally include additional requirements for the removal of refractory or-
ganic pollutants, heavy metals and sometimes dissolved inorganic solids.
The study of the concept of water reuse eectively started at the beginning of
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the 1980s. It was an attempt to solve the problem of wastewater allocation

planning, which consists in the determination of water flow through an inter-
connected network in the processes where the consumption of fresh water is
minimized, where the processes are supplied with water that meets standards.
The physico-chemical indicators of tannery euents depend on the
technologies and processes employed. Table 16.1 shows parameters of
wastewater analysed after completion of each processing step.
The treatment of tannery euent is basically performed in the following
steps: (1) preliminary treatment, such as the removal of course materials and
fats of wastewaters or segregating liming baths; (2) primary (or physico-
chemical) treatment that aims to remove settleable solids and treatment of the
tanning baths in a segregated procedure in some tanneries; (3) secondary (or
biological) treatment that results in the biological oxidation of organic matter;
(4) tertiary treatment (advanced or polishing treatment), is not used very often,
but its objective is to remove pollutants that could not be eliminated in pre-
vious treatments; and (5) sludge treatment.38
16.4.1 Preliminary Treatment

Screens are made with racks that can be hand-cleaned or mechanically
cleaned by static, vibrating and rotating sieves. The purpose of this treatment
is to retain solid residues, like fibers, leather wastes and other materials.
328
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Table 16.1 Characterization of wastewater from tannery process.36,37

Total
Conductivity Turbidity COD BOD NTKa Chrome Chlorides Calcium solids
Processing steps (mS cm1) pH (NTU) (mg L1) (mg L1) (g L1) (g L1) (g L1) (g L1) (g L1)
Presoaking 78 7.74 87 1264 5533 1.69 152.78 132
Soaking 65 9.10 306 10 146 1.48 78.68 69
Dehairing/liming 36 12.3 41000 57 182 2515 7.37 o0.20 1.955 80
Deliming 53 8.90 102 8608 1459 10.82 0.465 47
Fleshing 9 8.90 59 1087 6.10 4
Pickling 44 3.16 82 1201 800 4.57 49.30 70
Tanning 42 4.01 26 6649 1.02 1.297 94
Deacidification 1 14 5.05 2 2935 800 0.75 0.939 16
Deacidification 2 15 6.55 2 4403 600 14
Retanning 4 3.39 36 7028 400 0.50 0.033 2
Dyeing 13 3.98 9264 873 19
Fatliquoring 6 3.44 10 392 1020 7
a
NTK Total Kjeldahl Nitrogen.
Chapter 16
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Homogenization aims to equalize the variations in flow and pollutant

concentrations in the euent, with the objective of generating an euent
with constant characteristics and to facilitate the treatment. The mixture is
produced by mechanical surface aerators, diusers and air mixers. The
dosing with chemicals (acid or base) for pH adjustment is also performed in

this operation.
16.4.2 Primary Treatment

During coagulation and flocculation of the euents, chemical products are
added that interact with the solids in order to destabilize suspended colloidal
particles or those in suspension to form flocs, which are liable to sedimen-
tation. In this process step the following chemical products are commonly
employed: aluminium sulfate [Al2(SO4)3] and ferric chloride (FeCl3), as
coagulants; and anionic polyelectrolytes, as flocculants. These are diluted in
the chemical products mixing tanks and are dosed to the euent in a rapid
mixing tank or directly into the sedimentation tank. The flocs formation
occurs in slow mixing equipment or in the sedimentation tank itself.
The primary decantation aims to remove the floc material separating the
sedimentable part (sludge) of the clarified euent, which then follows
through the treatment process.
When precipitation is performed it is carried out in tanning wastewater
treated separately. The wastewaters are poured into a separate tank and
specific chemicals are dosed to react with the metal, the objective being to
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take away the chromium in the form of a precipitate for reuse or to be dis-
charged to industrial dangerous residues landfill. To accomplish the pre-
cipitation of chromium the following alkaline agents are used: calcium
hydroxide [Ca(OH)2], sodium hydroxide (NaOH), ammonium hydroxide
(NH4OH), magnesium oxide (MgO) or sodium bicarbonate (NaHCO3).
16.4.3 Secondary Treatment

Among the biological processes, this one is aimed at the removal of the
organic load from the euents in colloidal and/or suspended form. This
process is developed biochemically in the presence of oxygen, where a cul-
ture of microorganisms degrades the organic matter of the euent turning it
into cell mass and metabolic products.
The most frequently used secondary treatment is activated sludge in a
system consisting of a biological reactor provided with aeration, which
functions as a biological reactor, followed by a secondary sedimentation
tank and a pump that performs partial recycling of the biological sludge to
the biological reactor with the object of increasing the microbial mass and
keeping it alive. The microorganisms feed, reproduce and move with the
energy obtained through biological reactions from the consumption of or-
ganic matter and nutrients. Oxygen normally comes from injected air bubbles,
through surface mechanical aeratorsmost frequently employedinside a
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330 Chapter 16
solidliquid mixture under turbulent conditions, through diusers or other

types of aeration equipment.
16.4.4 Tertiary or Advanced Treatment

In order to meet the new standards set by environmental legislations, the use
of advanced treatments after secondary treatment has been studied. The
choice of a treatment method depends on a general balance, which involves
the cost of the process, the concentration of the pollutant to be removed and
the flow rate of the euent.
Tertiary treatment incorporates some operations aimed at the removal of
specific pollutants that have not met the euent emission standards and/or
the increase of the eciency of the processes used in the treatment of the
euents. This treatment has been employed in tanneries for the removal of
nitrogen, as the destination of this component in the receiving bodies involves
the risk of eutrophication, and also to reduce the toxicity of the euents.
Generally, the techniques of advanced treatment are not employed too
often in tanneries. Some individual initiatives for these treatment levels in
tanneries have been found, such as physico-chemical post-treatment, sta-
bilization ponds, subsequent filtration, constructed wetlands and ad-
sorption with activated carbon, among others.
16.4.5 Sludge Treatment

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As for sludge treatment, no thickening processes are employed, just direct

dewatering. To remove moisture from sludge, drying beds and mechanical
dewatering systems as centrifuges, filter presses and dewatering belt presses
are employed.38
A promising alternative that has been studied for the degradation of this
sludge and of the residues from leather processing is anaerobic bio-
degradation of this material. This process occurs by microbial action, where
the residues that are degraded produce leachate and gases, which can go on
for many years in dangerous industrial residues landfills. The generated gas
(biogas) is a mixture of compounds, mainly methane (CH4) and carbon
dioxide (CO2); both gases are causes of the greenhouse eect, methane being
21 times more active at retaining heat compared with carbon dioxide.
Therefore, the use of generated methane as a source of energy through the
burning of it proves to be an environmentally and energetically interesting
alternative, helping to reduce the environmental impact of the leather
sector.39
The technique of segregation of sludge that contains chromium
represents an economy in the costs of depositing in dangerous industrial
residues landfills, because this sludge containing chromium, according to
the Brazilian norm ABNT NBR 10.004, is classified as dangerous solid
residue (Class I), while chrome-free sludge is classified as non-dangerous
(Class II).
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16.4.6 Wastewater Reuse

Water is essential to life. However, its indiscriminate use may lead to the
shortage of this precious natural resource. Wastewater reuse is a rational
practice that contributes to environmental protection. This technique is
being implemented to reduce water consumption and the high costs of water
treatment. The implementation of reuse requires the establishment of
quality guidelines, criteria and standards and procedures that regulate the
practice of wastewater reuse. Wastewater reuse is the process of reusing
treated or non-treated water for the same or another purpose. This reuse can
be direct or indirect, planned or unplanned, according to the following
classification:34
Direct reuse: Occurs when the water used for a given purpose can be reused
without previous treatment to be applied in a less noble purpose. Some
examples include wastewater use in industries or in irrigation.
Indirect wastewater reuse: Occurs when wastewater used for domestic or
industrial purposes is treated in order to be available for another use.
Water recycling: Involves reusing water for the same application for which it
was originally used. In this case, the water is treated (regenerated).
The types of wastewater reuse are classified into four main categories:
urban, industrial, agricultural and groundwater recharge, as is described.
In tanneries, the stages of conditioning and preparation of the hide for
tanning, as well as the transportation and fixation of tanning substances, are
all carried out in aqueous media. Most of the steps of these processes are
carried out with fresh water, which is used as a vehicle for the diusion of
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chemical products and the extraction of undesirable materials from

the hide.
Processing waters from liming/dehairing and tanning operations are often
reused as input for the same respective operations in industry, most of all by
liming/dehairing operations in the case of Brazil. One study40,41 provided
tools for the minimization of water consumption at tanneries by applying
the reuse of water at some stages of the process. Water consumption and
concentration of some contaminant parameters for each stage of beam-
house, tanning and post-tanning operations were given and alternatives of
water reuse were evaluated. A study was carried out on pilot and industrial
scales to demonstrate the viability of reuse practices in the tannery industry,
which has shown the feasibility of wastewater streams reuse in beamhouse
steps of leather processing.
Process integration is a holistic methodology used in process design, and
the modification and improvement of already existing processes and oper-
ations, to improve the exploitation of mass and energy, with emphasis on the
process units.34 Mathematical programming was applied41 to the formu-
lation of the problem of water reuse in a tannery processing a 4,200 kg batch
of hides in beamhouse steps, which requires 25,200 L of freshwater. On
selecting calcium as the limiting factor for the reuse, the decrease in fresh
water demand was 32% for the first integration and 26% for the second
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332 Chapter 16
integration. The combination of more contaminants did not aect the water
saving result.
The recycling of wastewater from dehairing and liming consists of the
recovery of the residual bath used for hide processing and in its use in the
dehairing process of the next batch, replacing the amount of water and
chemical inputs needed to complete the formulation. In general, the fil-
tering is performed for the removal of hair and solids and the sedimentation
process is performed to remove precipitates and lime. The separation of fat
is carried out in retention tanks, where the floated material is retained. This
material and fat removal, besides reducing the volume and organic load of
the euents, generates a saving of chemical products, as well as enables the
reuse of these baths.
The recycling of baths of dehairing and liming can be total or partial,
according to the demands of the depilation process. To reuse these baths,
the concentration of dissolved salts is controlled, analytically or by meas-
urement of the Baume degree, which is directly related to the saline
solution density (g cm3 ). After measurement, addition of new water is
made to replenish the baths and when it is needed, an entire replacement
is done. The advantages of this practice are: savings in chemical inputs
consumption, reduction in the quantity of oxygen required to oxidize the
residual sulfides or thiosulfates and decreasing the toxic load on the total
euent.
It is possible to recycle the tanning wastewater, passing them through a
sieve, do a chromium solution analysis and replenish the amount of chro-
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mium salt and chemical inputs required for the process. Tests were con-
ducted on an industrial scale for reuse of tanning wastewaters in a tannery in
Brazil.25,41 Before the baths were recycled the pH value, the concentration of
Cr2O3 and the content of oils and greases were measured. It was possible to
reduce the supply of salt (sodium chloride) in tests through recycling. As the
recycled wastewaters already contained a certain amount of salt (necessary to
avoid the swelling of the hide) 3.04.5% of sodium chloride was added in
relation to the mass of hides, while usually 5.5% of sodium chloride is added
to a new bath. In the recycling of tanning wastewater the supply of chro-
mium, from 5.5 to 4.0%, was achieved.
16.4.7 Chromium Recovery for Tanning by Chemical

Precipitation
Chemical precipitation is used to remove heavy metals in inorganic eu-
ents. After pH adjustment to basic conditions, the dissolved metal ions are
converted into an insoluble solid by chemical reaction through the addition
of an alkaline agent. Generally, the metal (M) precipitates in the form of a
hydroxide, according to Equation (16.2):
M21 2(OH)2M(OH)2 (16.2)

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In the case of chromium, the metal precipitates as chromium hydroxide

and, after sedimentation, it is redissolved with strong acid and can be em-
ployed again as input in the tanning process.
The chemical products most employed in chromium precipitation in
tanneries are:42 calcium hydroxide [Ca(OH)2], sodium hydroxide (NaOH),

magnesium oxide (MgO) and calcium carbonate (CaCO3), magnesium car-
bonate (MgCO3) and sodium carbonate (Na2CO3).
Magnesium oxide is significant for making the chromium precipitate in a
shorter time, but has the disadvantage of being the product with the highest
cost. The most widely used compound is sodium hydroxide (NaOH), having
the lowest cost of all. In tests performed,43 chromium precipitated more
quickly with calcium oxide and magnesium oxide when compared with so-
dium hydroxide.
The indirect reuse of the tanning wastewaters through chemical precipi-
tation consists basically of three steps: chromium precipitation with alkali
such as, for example, sodium hydroxide, calcium hydroxide, magnesium
carbonate or sodium oxide; chromium hydroxide separation by sedimen-
tation, filtration or centrifugation; and dissolution of chromium hydroxide
with sulfuric acid for its reuse.
The precipitate may be separated in sedimentation tanks, where a dry
matter content of between 4 and 5% is obtained, or by filtration, providing a
dry matter content of up to 32%,35 or by disposal on drying beds with a dry
matter content of 1525%.44 After this separation, a re-dissolution with
sulfuric acid is carried out to obtain chromium sulfate, according to the
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stoichiometric reaction given in Equation (16.3):

2Cr(OH)3 3H2SO4-Cr2(SO4)3 6H2O (16.3)
From this reaction the necessary volume of sulfuric acid to add to the
precipitated chromium hydroxide is calculated to give the formation of
Cr2(SO4)3. This formation occurs at pH around 1.0.38
Chromium decantation with magnesium oxide (MgO), when it is properly
designed and operated, can remove levels of chromium in the euents
above 99% and achieve a recovery in process of 9598%.45 A treatment46
based on the precipitation of chromium with sodium hydroxide (NaOH)
followed by a filtration of the chromium hydroxide formed, then dissolving
it with sulfuric acid, produced a concentrated solution of chromium sulfate,
and the optimal precipitation pH was between 9.5 and 9.7. In tests con-
ducted by chemical precipitation in tanning residual water47 a removal of
98.7% of Cr2O3 was obtained. The process of chromium precipitation with
magnesium oxide (MgO) and its dissolution in sulfuric acid (H2SO4)48 was
responsible for removing practically 99% of chromium from liquid euents
from a tannery in Spain.
The system at an industrial plant recycling the chromium contained in the
final tanning baths, to be used in pickling, was tested on a tannery in
Colombia that processed 500 leathers per day. The chromium present in
wastewaters was precipitated as chromium hydroxide and diluted with sulfuric
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334 Chapter 16
acid to be subsequently reused in the pickling bath. The system saved

chromium sulfate and sodium chloride.49 The technology met the require-
ments of the process, which were: a clear and homogeneous colour of lea-
ther, an absence of stains and the concentration of oils and greases in the
leather of less than 0.5%.

However, chemical precipitation requires large amounts of chemical
products to reduce the concentrations of metals for disposal.50 Another
disadvantage is that if chromium is not going to be reused in the tanning,
additional treatment and adequate final disposal will be necessary.51,52 One
problem of the process is that the quality of the chromium liquor may
change with each batch.53
A study was conducted in order to characterize the sludge generated in
four tanneries in the State of Rio Grande do Sul, Brazil54 (Table 16.2). Re-
garding the chromium analysis (standard deviations of the analyses per-
formed in triplicate) in the sludge collected in the tanneries, it was verified
that the large dierence between the chromium levels is a consequence of
the segregation of the tanning baths; while in tanneries III and IV the sludge
is the result of the treatment of the wastewaters of only the tanning stage and
have higher chromium concentrations, the sludge from tanneries I and II is
derived from mixtures of all residual waters from the tanneries, where
chromium is diluted and, therefore, the sludge has lower chromium con-
centration. The eciency in the precipitation of chromium in the euent is
greater in tannery IV (higher chromium content) that uses sodium hydroxide
for its precipitation, which is shown to be a more suitable chemical product
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for this function, while at tanneries I, II and III aluminum sulfate was em-
ployed as coagulant. The sludge sedimentation tank of the tanning waste-
water from tannery II, as well as the drying bed used for sludge drying, is
shown in Figure 16.3.
In chemical precipitation assays of chromium with sodium hydroxide
(NaOH), at a concentration of 12 M, in tanning residual baths, chromium
removals above 98% were reached and the best result was 99.74%, with a
final concentration of 5.3 mg L1 of Cr2O3 in the clarified euent at pH 9.98
(Figure 16.4).54
Besides the aforementioned tanneries of the State of Rio Grande do Sul
(Brazil) that segregate and treat the euents from tanning separately, other
tanneries also do this, such as a tannery in the state of Mato Grosso do Sul,
Table 16.2 Characterization of tannery sludge.

Chromium oxide
Samples in the ash (%) TS (%) FST (%) VST (%)
a
Tannery I 3.58 0.05 20.63 0.0 10.76 0.04 9.87 0.04
Tannery IIa 1.95 0.02 32.75 0.22 20.83 0.29 11.92 0.52
Tannery IIIb 12.18 0.6 9.98 0.49 6.49 0.06 3.50 0.55
Tannery IVb 27.10 1.38 20.46 0.47 14.03 0.04 6.43 0.51
a
Mixed sludge from euents treatment (without segregation of streams containing chromium).
b
Sludge only from treatment of the streams containing chromium.
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Figure 16.3 (a) Drying bed sludge with chromium; (b) precipitation of the chro-
mium in the form of hydroxide.
100%
90%
80%
Efficiency of removal
70%
60%
50%
40%
30%
20%
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10%
0%
1 2 3 4 5 6 7 8 9 10 11 12
pH
Figure 16.4 Influence of pH on the removal of Cr2O3 from the residual tanning bath
for chemical precipitation.55
which has reported the recovery and reuse all the chrome in the process of
leather tanning55 and another tannery in the State of Goias that employs
good practices in its leather processing, where about 90% of chromium used
in the process is recycled.56
16.4.8 Electrocoagulation of Chromium

The electrocoagulation process occurs when the sacrificial anode undergoes
oxidation, releasing metal ions, and the cathode undergoes reduction, re-
sulting in the formation of hydroxyl ions, through the hydrolysis of water.
The metal ions combine with hydroxyl ions, forming metal hydroxide
compounds that favour the formation of flocs by destabilization of con-
taminants or suspended particles. The flocs formed can be separated from
the liquid by sedimentation or flotation depending on their density.57
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336 Chapter 16
Electrocoagulation consists of the formation of metal hydroxides that form

in the residual water by electrodissolution of soluble anodes, usually made
of iron or aluminium.58 The coagulating agent is gradually released when a
potential dierence is applied to the metal electrodes. As the sacrificial
anode corrodes, the active cation is released for the solution.59

In the mechanisms associated with the electrocoagulation process, using
iron as the constituent material of the electrodes, reactions occur according
to Equations (16.4) to (16.9):
Iron oxidation reaction:
Fe-Fe12 2e (16.4)
Anode:
2Fe21 5H2O 12O2-2Fe(OH)3 4H1 (16.5)
Fe21 2OH-Fe(OH)2 (16.6)

Cathode:
2H2O 2e-2OH H2 (16.7)
Global reaction:
2Fe 5H2O 12O2-2Fe(OH)3 2H2 (16.8)
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Fe 2H2O-Fe(OH)2 H2 (16.9)
Because electrocoagulation is an alternative treatment without the add-
ition of chemical products it has been shown to be very promising in the
treatment of euents from various industrial sectors. In tannery euents
electrocoagulation was studied60 at low currents (less than 1 A) with electrodes
of steel and aluminium. For the removal of sulfides, steel electrodes led to
removal above 90%, compared with those of aluminium, which had an e-
ciency below 12%. For removal of chemical oxygen demand (COD), ammonia,
total organic carbon (TOC), sulfide and colour, a system was tested where the
euent was first treated with steel electrodes, followed by the filter and, fi-
nally, with aluminium electrodes, resulting in 68.0, 43.1, 55.1, 96.7 and 84.3%,
respectively. Recovery of 99% of residual chromium was reached61 from a
residual tanning wastewater after 2 h of electrolysis of 1.0 V, at pH 5.0 and an
agitation speed of 500 rpm using lead as the cathode and copper as the anode.
Electrodes made of dierent materials,54 aluminium, copper and iron,
were used to assess the influence of these and the extent of the chromium
removal from residual tanning wastewater. The best removal eciencies
were obtained with aluminium electrodes at 3.0 V of 97.76%, with copper
electrodes at 2.0 V of 69.91% and with the iron electrodes at 2.5 V of 90.27%.
All hide had good chromium crossing during the tanning and adequate pH
values and ash contents; hide tanned with chromium recovered by chemical
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Table 16.3 Chromium removal eciency (%) with time for experiments on
electrocoagulation with electrodes of aluminium, copper and iron.
Time Al-Al (%) Cu-Cu (%) Fe-Fe (%)

(min) 2.5 V 3.0 V 1.5 V 2.0 V 2.5 V 3.0 V
0 0.00 0.00 0.00 0.00 0.00 0.00

10 14.86 12.37 35.94 45.85 15.52 4.56
20 22.95 18.03 40.42 52.71 14.34 8.57
30 33.23 30.32 47.65 58.72 31.43 31.90
40 43.90 38.44 56.67 63.82 46.42 41.87
50 49.88 50.30 68.08 64.46 57.39 48.81
60 57.55 56.04 61.61 66.38 65.31 56.84
70 63.25 59.75 60.45 67.31 66.29 60.76
80 67.84 66.60 61.01 68.23 74.16 70.54
90 71.08 73.72 56.80 68.57 84.04 73.28
100 75.19 79.19 57.17 69.91 90.27 82.57
110 90.14 97.76 61.93 69.10 68.22 51.99
precipitation and electrocoagulation with copper electrodes showed good

hydrothermal stability (Table 16.3).
There are some parameters associated with the electrocoagulation process
that must be controlled for better eciency of the removal of pollutants and
lower operational cost. The eects of pH of the residual water influence the
current eciency, as well as the solubility of metal hydroxides. Generally, the
eciency of the currents in aluminium plates are higher in acidic or alkaline
conditions compared with the neutral condition. The energy consumption
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is, however, superior to a neutral pH due to the variation in conductivity.

When the conductivity is high, the eect of pH is not significant.62 The
electrical conductivity of the euent considerably influences the eciency
of removal of pollutants and the consumption of electric energy. This par-
ameter can be increased by adding salt compounds to the treatment system.
In general, sodium chloride (NaCl) is used because it is a low-cost and non-
toxic product; but at high concentrations the release of a large amount of
Cl ions occurs, making the formation of organochlorine compounds of
considerable toxicity a possibility. The electric current applied to the elec-
trocoagulation process will determine the amount of metal (used in the
electrodes) that will be oxidized at the anode. Regarding the origin of the
eletrodes,63 there are two types that can participate in the electrochemical
processes: the inert and the reactive ones. Reactive electrodes participate in
the process leading to wear, by oxidation or reduction, the simplest ones
being those formed by metals such as iron, aluminium or copper, which may
contribute to the formation of metal ions in the solution. Inert electrodes do
not suer wear from the passage of electric current, for example, those
formed by materials such as titanium, platinum, graphite and ruthenium
oxide, among others. Agitation increases the homogeneity across the whole
reactor and is usually due to a mechanical source or a magnetic agitator. In
electrocoagulation, batch electrolytic reactors produce gas bubbles of oxygen
and hydrogen in situ, which can help in the agitation.
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338 Chapter 16
The use of the electrolytic process for euent treatment points to some
advantages, such as: it does not generate odours, uses a small area for its in-
stallation, is easy to operate, requires less time for treatment and disinfection
of the euent from the perspective of reusing some compounds recovered
from residual waters.64 There are some disadvantages to using electro-

coagulation, such as the regular exchange of sacrificial electrodes that are
dissolved in residual water flows, the use of electrical energy can be expensive
in some places, high conductivity of the euent is required, a waterproof oxide
film may be formed on the cathode leading to loss of eciency of the unit and
a gelatinous hydroxide tends to solubilize in some cases.65
16.4.9 Other Treatment Techniques for Chromium Recovery

Many methods are used to remove heavy metals such as: chemical precipi-
tation, ion exchange, adsorption, reverse osmosis, coagulationflocculation,
electrocoagulation, flotation, etc.6668
Adsorption is a transfer process of one or more constituents (adsorbates)
of a fluid phase (adsorptive) to the surface of a solid phase (adsorbent). In
the adsorption process, molecules present in the fluid phase are attracted to
the interfacial zone due to the existence of uncompensated attractive forces
at the surface of the adsorbent.69 Recent studies have shown good results for
adsorption of tannery euent trivalent chromium70 and removal of dyes
from leather dyeing.68
Researchers have studied adsorbents using more economical materials for
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chromium removal from water, such as cellulose adsorbents,71 beet pulp,72

polyacrylonitrile fibers,73 coal developed from residual materials,74,75 bio-
sorbents,76,77 ash residue78 and zeolites.79
The biggest advantages of the adsorption process for euent treatments
are in its low initial investment, simplicity of design and operation, non-
toxicity, lower energy use and superior eciency relative to both con-
ventional and other non-conventional processes.80,81
Ion exchange is a process very similar to adsorption, because it retains the
solutes in the solids through several actions. The adsorbate is retained by a
chemical reaction with an ion-exchanger solid (zeolites, resins, activated coal,
etc.). The ion-exchange resin can be solid in synthetic or natural form and has
the specific capacity to exchange its cations with metals present in residual
waters. Among the materials used in the processes of ion exchange, synthetic
resins are generally preferred because they are eective at removing heavy
metals from the solution.82 Ion-exchange processes have been widely used to
remove heavy metals from residual water, due to the many advantages, such
as high treatment capacity, high removal eciency and quick kinetics.83
Reverse osmosis and membrane filtration technologies with dierent
types of membranes show the greatest promise for removal of heavy metals
because of the high eciency, ease of operation and economy of space.66
The process of reverse osmosis (RO) uses a semi-permeable membrane,
allowing the fluid that is to be purified to pass through it, while rejecting the
contaminants. RO is one of the techniques capable of removing a variety of
View Online

84
species dissolved in water. The RO process stands out from other solute
separation techniques and is a technique widely used in the process of de-
salination of sea water.85 RO is responsible for more than 20% of the de-
salination capacity of the world.84
Flotation is used to separate solid or liquid dispersed in a liquid phase

from the bubble-particle adhesion.86 Bubble particles that contain heavy
metals are separated as they ascend to the surface. Flotation may be
classified as: (1) dispersed air flotation, (2) dissolved air flotation (DAF),
(3) vacuum air flotation, (4) electroflotation and (5) biological flotation.
Among the various types of flotation, DAF is the one used most for treating
residual water contaminated with metals.87 DAF allows micro air bubbles
to attach to suspended particles in the water and to form agglomerates of
density lower than water, causing the flocs to ascend and accumulate on
the surface, where they can be removed as muds.88 The advantages are:
better removal of small particles, smaller hydraulic detention times and
low cost.89,90
16.5 Conclusions
There is concern from society regarding the use and provision of the metal
chromium therefore there is an eort by tanneries in order to implement
clean technologies and treat the euents and residues generated in the
industrial process. In Brazil it is now usual practice to recycle liming baths,91
water reuse in other stages of beamhouse has been proposed and tested41
11:26:49.
and biotechnology has been applied in leather processing.9294 The state of

implementation of clean technologies to avoid water pollution in tanneries,
guidelines to improve water management and alternatives available to tan-
neries aimed at their improvement have been described.95 New euent
treatment techniques, such as adsorption of dyes from leather dyeing, have
been shown to be successful.68
As for the euents from the tanning stage, the recycling of these is still
not practiced comprehensively in the industry and there are uncertainties
about the actual necessary dosage of chemical reagents responsible for the
precipitation of chromium. The precipitation for chromium removal from
tanning wastewater enables the reuse of the metal when it is redissolved to
be used again in the process. The techniques for chromium recovery54 by
chemical precipitation to form chromium hydroxide or by electrocoagula-
tion showed satisfactory results in terms of euent removal eciency and
hide tanned, with the chromium recovered showing a higher amount of
chromium oxide than the minimum required by the technical specifications.
Nevertheless, considering the excellent properties of chromium tanned
leather and the necessary environmental precautions for the use of chrome
due to exposure of its euents and residues in the environment, the solu-
tion is to control the tanning processes and to ensure an adequate man-
agement of its euents and residues to improve the processes and prevent
any type of environmental pollution, since there are appropriate and highly
ecient technologies available for this purpose.
View Online
340 Chapter 16
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11:26:49.
Subject Index
acid washing, in leather processing, pseudo-second order, 74
323 WeberMorris, 7475
activated carbons, and iron removal, and metal biosorption, 304306
1617 complexation, 304
acute toxicity, 265, 267 co-ordination, 305
adsorption. See also biosorption; ion exchange, 306
metal biosorption physical, 304
and arsenic contamination, precipitation, 304305
110113 reduction, 305306
and batch equilibrium studies, and physico-chemical
207208 treatments of heavy
equilibrium isotherm metals, 48
modeling, 7577 and sorption
11:26:52.
Freundlich isotherm, eect of pH on, 291292

7577 temperature eect on,
Langmuir isotherm, 77 293
other two-parameter and tannery euents
isotherms, 77 treatment, 338
as fluoride removal technique, advanced oxidation processes, for
276 heavy metal removal, 2729
and heavy metal removal, advanced treatment, and tannery
198207, 284 euents, 330
biosorption, 202205 agriculture waste (modified), and
on industrial by-products, adsorption, 202205
200202 air, arsenic contamination in, 9698
on modified agriculture algae, and fluorides, 268
and biological wastes, aluminium oxides, nanosized,
202205 183184
on modified biopolymers animals health eects, and
and hydrogels, 205207 fluorides, 267269
on modified natural anthropogenic sources, of arsenic,
materials, 198200 9495
kinetic studies for, 7375 aquatic invertebrates, and fluorides,
pseudo-first order, 74 268269
View Online
346 Subject Index
arsenic, 297298 biomass of metal ions, and heavy

and fluorides, 272274 metals, 1315
and photocatalytic process, biomass sorbents, and heavy metal
3940 removal, 283
in Taihu Lake surface water, biopolymers (modified), and

173 adsorption, 205207
arsenic contamination biosorption
chemical characteristics, 8790 and adsorption, 202205
description, 8687 metal (See metal biosorption)
distribution in environment, of metal ions, and heavy
90105 metals, 1315
anthropogenic sources, biota, arsenic contamination in,
9495 98100
in foods and drugs,
100102 cadmium, 298299
metabolisms and toxicity and photocatalytic process,
of, 102105 3739
natural groundwater, 105 in Taihu Lake surface water,
natural sources, 9094 171
in plants and biota, carbon nanotubes, 184185
98100 charge separation, 29
in water, air and soil, 9698 chemical activation/conditioning,
removal from water and and clays/clay minerals, 227230
wastewater, 105117 chemical modification methods,
11:26:52.
adsorption, 110113 and heavy metal removal, 286

advanced and integrated chemical precipitation
technologies, 116117 and physico-chemical
coagulation and treatments, of heavy metals,
flocculation, 107110 4647
combined processes, 117 and tannery euents
constructed wetlands, treatment, 332335
114116 chemistry, of iron and manganese
electrocoagulation, oxidation and removal, 124129
116117 Chinese water resources, heavy
membrane filtration, metals in. See also Taihu Lake
113114 surface water, and heavy metals
photochemical and current discharge standards,
photocatalytic 152
oxidation, 117 current quality standards and
recent trends, 148152
bating, in leather processing, 322 recent industrial
bio-based separation, for heavy developments, 148
metal removal, 4950 recent pollutions in, 155161
biologically active carbon (BAC), 136 contamination in
biological waste (modified), and sediments of rivers and
adsorption, 202205 lakes, 161
View Online
Subject Index 347
human health risk pillaring, grafting and

assessment of, 159160 intercalation, 230236
mining, smelting and thermal activation,
other industrial 225227
wastewaters, 155158 coagulation. See also

rivers and drinking water electrocoagulation
sources in Beijing, 159 and arsenic contamination,
wastewater irrigation, 107110
158 as physico-chemical
sources of, 152155 treatment, 47
chromium, 299 cobalt, in Taihu Lake surface water,
forms in nature, 316320 173
in environment, 318319 combined processes, and arsenic
in water, 319320 contamination removal, 117
and photocatalytic process, constructed wetlands, and arsenic
3537 contamination, 114116
salts, tanning with, 323327 contamination
in Taihu Lake surface water, of arsenic (See arsenic
170 contamination)
tannery euents treatment in sediments of Chinese rivers
and adsorption, 338 and lakes, 161
by chemical copper, 299300
precipitation, 332335 in Taihu Lake surface water,
electrocoagulation of, 172
11:26:52.
335338 coprecipitation, and magnetic

and flotation, 339 nanoparticles, 6568
and ion exchange, 338
and membrane filtration, dehairing, in leather processing,
338339 322
and reverse osmosis, deliming, in leather processing,
338339 322
clays/clay minerals dierential scanning calorimetry
as heavy metals sorbent, (DSC), 227
218222 drugs, arsenic contamination in,
and isotherms, kinetics and 100102
thermodynamics evaluation, drying operations, in leather
237242 processing, 323
overview, 213217 DSC (dierential scanning
as remediation technology, calorimetry), 227
1213 dyeing, in leather processing, 323
structural features of, 218222
surface modification ecosystems. See environment
techniques of, 222236 euents treatment, tannery. See
chemical activation/ tannery euents treatment
conditioning, 227230 electrochemical precipitation, of
description, 222225 heavy metals, 47
View Online
348 Subject Index
electrocoagulation. See also risks, and heavy metals, 47

coagulation sources of heavy metals in,
and arsenic contamination, 5862
116117 toxicity on, 6264
and heavy metals, 1112 environmental concern metals,

remediation technologies, 297302
heavy metals, 1112 arsenic, 297298
and tannery euents cadmium, 298299
treatment, 335338 chromium, 299
electronhole scavenger eect, and copper, 299300
photocatalytic process, 33 lead, 301
engineering considerations, mercury, 300301
oxidation and removal nickel, 301302
for iron and manganese, zinc, 302
129138 equilibrium isotherm modeling,
source water quality 7577
analysis, 130133 Freundlich isotherm, 7577
treatment process Langmuir isotherm, 77
considerations, other two-parameter
133138 isotherms, 77
groundwater
treatment, fatliquouring, in leather processing,
133135 323
surface water ferric oxides, nanosized, 181183
11:26:52.
treatment, filtration techniques. See membrane

136138 filtration
environment fish, and fluorides, 268269
and arsenic contamination, fleshing, in leather processing, 322
90105 flocculation
anthropogenic sources, and arsenic contamination,
9495 107110
in foods and drugs, as physico-chemical
100102 treatment, 47
metabolisms and toxicity flotation, and tannery euents
of, 102105 treatment, 339
natural groundwater, 105 fluorides
natural sources, 9094 in environment, 261269
in plants and biota, anthropogenic sources,
98100 263265
in water, air and soil, content in environmental
9698 samples, 265
and chromium forms in natural sources, 262263
nature, 318319 health eects of, 265269
fluorides in, 261269 acute toxicity, 265, 267
nanotechnology impact on, algae and aquatic plants,
187188 268
View Online
Subject Index 349
on animals and plants, health eects

267269 of fluorides, 265269
aquatic invertebrates and acute toxicity, 265, 267
fish, 268269 algae and aquatic plants,
fluorosis, 267 268

to humans, 265267 on animals and plants,
microorganisms, 267268 267269
terrestrial invertebrates aquatic invertebrates and
and animals, 269 fish, 268269
terrestrial plants, 268 fluorosis, 267
and metals/metalloids, to humans, 265267
269274 microorganisms, 267268
and arsenic, 272274 terrestrial invertebrates
physico-chemical and animals, 269
parameters and ions, terrestrial plants, 268
269272 and heavy metals, 47
removal techniques, 274276 toxicity to human, 6264
adsorption, 276 tannery wastewater and sludge
membrane methods, treatment, 256257
274 heavy metal removal
fluorosis, and fluorides, 267 adsorption models, 198207, 284
foods, arsenic contamination in, biosorption, 202205
100102 on industrial by-products,
Freundlich equation, 7577, 238, 284 200202
11:26:52.
on modified agriculture
genetically modified and biological wastes,
microorganisms, and heavy metal 202205
removal, 52 on modified biopolymers
grafting, and clays/clay minerals, and hydrogels, 205207
230236 on modified natural
graphene, 185187 materials, 198200
groundwater advanced oxidation processes
arsenic contamination, 105 for, 2729
treatment, for iron and application of photocatalytic
manganese removal, process for, 3540
133135 group 6 metal
group 6 metal (chromium), and (chromium), 3537
photocatalytic process, 3537 group 15 metalloid
group 15 metalloid (arsenic), and (arsenic), 3940
photocatalytic process, 3940 group 10 metals (nickel
group 10 metals (nickel and and platinum), 37
platinum), and photocatalytic group 12 metals (zinc,
process, 37 cadmium and
group 12 metals (zinc, cadmium and mercury), 3739
mercury), and photocatalytic and batch equilibrium studies,
process, 3739 207208
View Online
350 Subject Index
heavy metal removal (continued) and nanotechnology (See

bio-based separation for, 4950 nanotechnology, and heavy
and genetically modified metals)
microorganisms, 52 physico-chemical treatments
isolated strains and eciency, of, 4648

5052 adsorption, 48
modification methods, 284286 chemical precipitation,
chemical, 286 4647
physical, 285286 coagulationflocculation, 47
sorption mechanisms, 283 electrochemical
biomass sorbents, 283 precipitation, 47
inorganic sorbents, 283 ion exchange, 46
sorption studies, 286293 membrane filtration, 4748
dierences between regulatory limits of, 45
materials, 287291 remediation technologies, 717
eect of pH on biomass and biosorption
adsorption, 291292 of metal ions, 1315
raw vs. modified clays/layered double
materials, 292293 hydroxides, 1213
temperature eect on electrocoagulation, 1112
adsorption, 293 heterogeneous catalysts
treatment processes for, and catalysis, 10
196198 and magnetic
heavy metals. See also specific types nanoparticles as
11:26:52.
adsorptive removal, 198207, nanosorbents, 15

284 membrane filtration, 78
biosorption, 202205 and photocatalysts, 1011
on industrial by-products, phytoremediation, 810
200202 removal of iron and manganese
on modified agriculture from water, 1517
and biological wastes, activated carbons, 1617
202205 ion exchange, 16
on modified biopolymers sorbent, clays/clay minerals as,
and hydrogels, 205207 218222
on modified natural sources of, 24
materials, 198200 in environment, 5862
environmental and health toxicity of
risks, 47 acute, 265, 267
industrial sources of, 26t of arsenic, 102105
in industrial wastewater and and industrial
toxicity, 194196 wastewater, 194196
kinetic modeling for toxicological properties of,
adsorption of, 7375 143147
pseudo-first order, 74 arsenic, 145
pseudo-second order, 74 cadmium, 145146
WeberMorris, 7475 chromium, 144145
View Online
Subject Index 351
lead, 146147 iron removal, from water, 1517

mercury, 147 activated carbons, 1617
in wastewater, 4445 ion exchange, 16
in water, 142143 isolated strains and eciency, and
heterogeneous catalysts and heavy metal removal, 5052

catalysis, and heavy metals, 10 isotherms evaluation, and clays/clay
heterogeneous photocatalytic minerals, 237242
process, 29
humans health eects, and kaolinite, 179
fluorides, 265267 kinetic modeling, for adsorption of
hydrogels (modified), and heavy metals, 7375
adsorption, 205207 pseudo-first order, 74
hydrothermal syntheses, and pseudo-second order, 74
magnetic nanoparticles, 68 WeberMorris, 7475
kinetics evaluation, and clays/clay
industrial by-products, and minerals, 237242
adsorption, 200202
industrial wastewater, and toxicity, Langmuir isotherm model, 1517,
heavy metals in, 194196 75, 77, 208, 237, 238
initial metal ion concentration layered double hydroxides, 1213,
eect, and photocatalytic process, 180
3132 lead, 301
inorganic sorbents, and heavy metal in Taihu Lake surface water,
removal, 283 170171
11:26:52.
intercalation, and clays/clay leather finishing, in leather

minerals, 230236 processing, 323
invertebrates, and fluorides, 268269 leather processing, 320327. See also
ion exchange tanning
and iron removal, 16 flow chart of, 321f
and tannery euents steps of, 322323
treatment, 338 tanning with chromium salts,
iron oxidation and removal 323327
chemistry of, 124129 light intensity eect, and
in natural waters, 124125 photocatalytic process, 33
engineering considerations for, liming, in leather processing,
129138 322
source water quality
analysis, 130133 magnetic nanoparticles
treatment process (MNPs), 64
considerations, 133138 and equilibrium isotherm
groundwater modeling, 7577
treatment, Freundlich isotherm,
133135 7577
surface water Langmuir isotherm, 77
treatment, other two-parameter
136138 isotherms, 77
View Online
352 Subject Index
magnetic nanoparticles (continued) as fluoride removal technique,

kinetic studies for adsorption, 274
7375 and heavy metals, 78
pseudo-first order, 74 remediation technologies,
pseudo-second order, 74 heavy metals, 78

WeberMorris, 7475 and tannery euents
metal recovery and treatment, 338339
regeneration of, 78 mercury, 300301
synthesis of, 6469 and photocatalytic process,
coprecipitation, 6568 3739
hydrothermal metabolism, of arsenic, 102105
syntheses, 68 metal biosorption, 303307
microemulsions, 69 and adsorption, 304306
thermal decomposition, 69 complexation, 304
thermodynamic analysis, co-ordination, 305
7778 ion exchange, 306
in wastewater treatment, 6973 physical, 304
as nanosorbents, 15, precipitation, 304305
7073 reduction, 305306
manganese and assimilation, 303304
removal from water, 1517 and biodegradation, 306307
in Taihu Lake surface water, factors aecting, 307309
175 bulk temperature, 308
manganese oxidation and removal cell age, 309
11:26:52.
chemistry of, 124129 competing ions, 308

in natural waters, contact time, 308
124125 initial concentration of
engineering considerations for, metal ions and of
129138 biomass, 308309
source water quality solution pH, 307
analysis, 130133 metals/metalloids. See also specific
treatment process types
considerations, biosorption of, 303307
133138 (See also metal biosorption)
groundwater adsorption, 304306
treatment, assimilation, 303304
133135 biodegradation, 306307
surface water factors aecting, 307309
treatment, of environmental concern,
136138 297302
marine aerosols, 263 arsenic, 297298
mechanical operations, in leather cadmium, 298299
processing, 323 chromium, 299
membrane filtration copper, 299300
and arsenic contamination, lead, 301
113114 mercury, 300301
View Online
Subject Index 353
nickel, 301302 nanoclays, and heavy metals,

zinc, 302 178180
and fluorides, 269274 kaolinite, 179
and arsenic, 272274 layered double hydroxides, 180
physico-chemical montmorillonite, 179180

parameters and ions, nanoparticles, magnetic. See
269272 magnetic nanoparticles (MNPs)
group 15 (arsenic), and nanosized aluminium oxides,
photocatalytic process, 183184
3940 nanosized ferric oxides, 181183
group 6 (chromium), and nanosized metal oxides, and heavy
photocatalytic process, metals, 180184
3537 aluminium oxides, 183184
group 10 (nickel and ferric oxides, 181183
platinum), and titanium oxides, 181
photocatalytic process, 37 nanosized titanium oxides, 181
group 12 (zinc, cadmium and nanosorbents, magnetic
mercury), and photocatalytic nanoparticles as, 15, 7073
process, 3739 nanostructured carbon materials,
microemulsions, and magnetic 184187
nanoparticles, 69 nanotechnology, and heavy metals
microorganisms environmental impact of,
and fluorides, 267268 187188
genetically modified, and nanoclays, 178180
11:26:52.
heavy metal removal, 52 kaolinite, 179

minerals, clays/clay. See clays/clay layered double
minerals hydroxides, 180
MNPs. See magnetic nanoparticles montmorillonite,
(MNPs) 179180
modification methods, and heavy nanosized metal oxides,
metal removal, 284286 180184
chemical, 286 aluminium oxides,
physical, 285286 183184
modified agriculture waste, and ferric oxides, 181183
adsorption, 202205 titanium oxides, 181
modified biological waste, and nanostructured carbon
adsorption, 202205 materials, 184187
modified biopolymers, and carbon nanotubes,
adsorption, 205207 184185
modified hydrogels, and adsorption, graphene, 185187
205207 nanotubes, carbon, 184185
modified natural materials, and natural groundwater, arsenic
adsorption, 198200 contamination, 105
modified vs. raw materials, and natural materials (modified), and
heavy metal removal, 292293 adsorption, 198200
montmorillonite, 179180 natural sources, of arsenic, 9094
View Online
354 Subject Index
nickel, 301302 photocatalytic oxidation, and arsenic

and photocatalytic process, 37 contamination, 117
in Taihu Lake surface water, photochemical oxidation, and
174 arsenic contamination, 117
photoreactor development, and

oxidation and removal. See iron photocatalytic process, 34
oxidation and removal; photoreduction thermodynamics,
manganese oxidation and removal 3031
physical modification methods, and
pH eect, on adsorption, 291292 heavy metal removal, 285286
photocatalysis physico-chemical treatments
application for removal of and fluorides, 269272
heavy metals, 3540 of heavy metals, 4648
group 6 metal adsorption, 48
(chromium), 3537 chemical precipitation,
group 15 metalloid 4647
(arsenic), 3940 coagulationflocculation,
group 10 metals (nickel 47
and platinum), 37 electrochemical
group 12 metals (zinc, precipitation, 47
cadmium and ion exchange, 46
mercury), 3739 membrane filtration,
basic principle of 4748
heterogeneous, 29 phytoremediation technology, for
11:26:52.
dependence of photoreduction heavy metals, 810

kinetics, 3133 phytotoxicity, tannery wastewater
eect of electronhole and sludge treatment, 257258
scavenger, 33 pickling, in leather processing, 322
eect of initial metal ion pillaring, and clays/clay minerals,
concentration, 3132 230236
eect of light intensity, 33 plants
eect of photocatalyst arsenic contamination in, 98100
mass, 3233 health eects, and fluorides,
and photcatalyst 267269
development, 35 platinum, and photocatalytic
and photoreactor process, 37
development, 34 prefinishing, in leather processing,
reaction mechanisms of, 2930 323
thermodynamics of pre-fleshing, in leather processing,
photoreduction, 3031 322
photocatalysts preliminary treatment, and tannery
development, and euents, 327, 339
photocatalytic process, 35 presoaking, in leather processing,
and heavy metals, 1011 322
mass eect, and photocatalytic primary treatment, and tannery
process, 3233 euents, 339
View Online
Subject Index 355
pseudo-first order kinetic and phytotoxicity, 257258

modeling, 74 removal and recovery, 253256
pseudo-second order kinetic soaking, in leather processing, 322
modeling, 74 softening, in leather processing, 323
soil, arsenic contamination in, 9698

quality control, in leather sorption, and heavy metal removal,
processing, 323 283, 286293
biomass sorbents, 283
raw vs. modified materials, and dierences between materials,
heavy metal removal, 292293 287291
regulatory limits, of heavy metals, 45 eect of pH on adsorption,
remediation technologies, heavy 291292
metals inorganic sorbents, 283
biomass and biosorption of raw vs. modified materials,
metal ions, 1315 292293
clays/layered double temperature eect on
hydroxides, 1213 adsorption, 293
electrocoagulation, 1112 splitting, in leather processing, 322
heterogeneous catalysts and structural features, of clays/clay
catalysis, 10 minerals, 218222
and magnetic nanoparticles as surface modification techniques, of
nanosorbents, 15 clays/clay minerals, 222236
membrane filtration, 78 chemical activation/
and photocatalysts, 1011 conditioning, 227230
11:26:52.
phytoremediation, 810 description, 222225

removal techniques, fluorides, pillaring, grafting and
274276 intercalation, 230236
adsorption, 276 thermal activation, 225227
membrane methods, 274 surface water treatment, for iron and
retanning, in leather processing, manganese removal, 136138
323 synthesis, of magnetic nanoparticles
reverse osmosis (RO). See membrane (MNPs), 6469
filtration coprecipitation, 6568
hydrothermal syntheses, 68
salt shake-o, in leather processing, microemulsions, 69
322 thermal decomposition, 69
samming, in leather processing, 322
secondary treatment, and tannery Taihu Lake surface water, and heavy
euents, 329330 metals. See also Chinese water
shaving, in leather processing, 322 resources, heavy metals in
sludge treatment, tannery description, 168169
characteristics, 250253 methods, 169170
description, 249250 sample collection, 169170
euents, 330 sample processing and
future challenges of, 258 analytical procedures,
and health eects, 256257 170
View Online
356 Subject Index
Taihu Lake surface water, and heavy salts, 323327

metals. (continued) in water, 319320
results, 170175 description, 315316
arsenic, 173 temperature eect, and heavy metal
cadmium, 171 removal, 293

chromium, 170 terrestrial invertebrates and
cobalt, 173 fluorides, 269
copper, 172 terrestrial plants, and fluorides, 268
lead, 170171 tertiary treatment, and tannery
manganese, 175 euents, 330
nickel, 174 TGA (thermogravimetric analysis),
tin, 174 227
zinc, 172 thermal activation, and clays/clay
tannery euents treatment, 327339 minerals, 225227
chromium recovery thermal decomposition, and
and adsorption, 338 magnetic nanoparticles, 69
by chemical thermodynamic analysis, and MNPs,
precipitation, 332335 7778
electrocoagulation of, thermodynamics evaluation, and
335338 clays/clay minerals, 237242
and flotation, 339 thermogravimetric analysis (TGA),
and ion exchange, 338 227
and membrane filtration, tin, in Taihu Lake surface water, 174
338339 titanium oxides, nanosized, 181
11:26:52.
and reverse osmosis, toxicity, of heavy metals

338339 acute, 265, 267
preliminary treatment, 327, of arsenic, 102105
339 to human health, 6264
primary treatment, 339 and industrial wastewater,
secondary treatment, 329330 194196
sludge treatment, 330 toxic metals. See heavy metals
tertiary/advanced treatment,
330 United States Environmental
wastewater reuse, 331332 Protection Agency (USEPA), 57,
tannery wastewater and sludge 123, 159
treatment
characteristics, 250253 volcanic activity, 262263
description, 249250
future challenges of, 258 wastewater
and health eects, 256257 arsenic contamination removal
and phytotoxicity, 257258 from, 105117
removal and recovery, 253256 adsorption, 110113
tanning. See also leather processing advanced and integrated
and chromium technologies, 116117
in environment, 318319 coagulation and
forms in nature, 316320 flocculation, 107110
View Online
Subject Index 357
combined processes, coagulation and

117 flocculation, 107110
constructed wetlands, combined processes, 117
114116 constructed wetlands,
electrocoagulation, 114116
116117 electrocoagulation,
membrane filtration, 116117
113114 membrane filtration,
photochemical and 113114
photocatalytic photochemical and
oxidation, 117 photocatalytic
heavy metals in, 4445 oxidation, 117
industrial, 194196 chromium in, 319320
and toxicity, 194196 iron removal from, 1517
irrigation and Chinese water activated carbons, 1617
resources, 158 ion exchange, 16
reuse, and tannery euents, manganese removal from, 1517
331332 WeberMorris kinetic modeling,
treatment, tannery (See tannery 7475
wastewater and sludge wetlands, constructed, and arsenic
treatment) contamination, 114116
water World Health Organization (WHO),
arsenic contamination in, 123
9698
11:26:52.
arsenic contamination removal zinc, 302

from, 105117 and photocatalytic process,
adsorption, 110113 3739
advanced and integrated in Taihu Lake surface water,
technologies, 116117 172
11:26:52.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00345 View Online

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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP001

Heavy Metals in Water

Heavy Metals In Water

Print ISBN: 978-1-84973-885-9

r The Royal Society of Chemistry 2015

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Published by The Royal Society of Chemistry,

Registered Charity Number 207890

Visit our website at www.rsc.org/books

Heavy Metals in Water: Presence, Removal and Safety

ores and, on the other hand, agriculture (fertilizers, animal manures,

This is the opportunity to express my thanks and gratitude to my friends,

never-ending encouragement, moral support and patience during the course

Heavy Metals in Water: Presence, Removal and Safety

About the Editor

Prof. (Dr) Sanjay K. Sharma is a very well known

Heavy Metals in Water: Presence, Removal and Safety

xii About the Editor

Chemistry, Green Chemistry Letters & Reviews, Ultrasonics and Ultrasonics

 Biosurfactants: Research Trends and Applications (CRC Taylor & Francis,

Chapter 1 Contamination of Heavy Metals in Aquatic Media:

Chapter 2 Photocatalytic Processes for the Removal of Toxic

Heavy Metals in Water: Presence, Removal and Safety

Chapter 3 Removal of Dissolved Metals by Bioremediation 44

Subhajit Majumder, Suresh Gupta and Smita Raghuvanshi

3.1 Heavy Metals in Wastewater 44

Chapter 4 Functionalized Magnetic Nanoparticles for Heavy Metals

Chapter 5 Arsenic Contamination: An Overview 86

6.1 Introduction 122

Chapter 7 Heavy Metal Pollution in Water Resources in

Keisuke Ikehata, Yao Jin, Nima Maleky and Aijun Lin

7.1 Introduction 141

7.4.4 Human Health Risk Assessment of Heavy

Chapter 8 Heavy Metals Distribution in Surface Water Samples

8.1 Introduction 168

8.3.1 Chromium (Cr) 170

Chapter 9 Use of Nanotechnology against Heavy Metals Present

9.1 Introduction 177

9.3.4 Other Nanosized Metal Oxides 184

Chapter 10 Modified and New Adsorbents for Removal of Heavy

10.1 Introduction 193

Natural Materials 198

Chapter 11 Natural Clays/Clay Minerals and Modified Forms for

11.1 Introduction 213

Evaluation of Heavy Metals Sorption onto Clays and

Chapter 12 Heavy Metals in Tannery Wastewater and Sludge:

12.1 Introduction 249

12.4 Future Challenges 258

Chapter 13 Fluorides in Different Types of Aquatic Systems and their

13.1 HeavyMetals and Fluorides in the Environment 261

14.1 Introduction 281

Chapter 15 Biosorption of Metals From the Basics to High Value

Catalysts Production 296

15.1 Introduction 296

15.5 New Perspectives 309

Chapter 16 Chromium in Tannery Wastewater 315

16.1 Introduction 315

16.4.6 Wastewater Reuse 331

Subject Index 345

Chemistry & Sustainability Research Group, Department of Chemistry,

Heavy Metals in Water: Presence, Removal and Safety

nature of heavy metals has been recognized because of their bioaccumula-

Biosurfactants: Research Trends and Applications (CRC Taylor & Francis,

mucosa By European Community:

Disturbs the cholesterol maximum concentration:

Precipitation and coagulation