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Heavy Metals in Water


Presence, Removal and Safety
11:25:17.
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Heavy Metals In Water


Presence, Removal and Safety
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP001

Edited by

Sanjay K. Sharma
Department of Chemistry, JECRC University, Jaipur, India
Email: drsanjay1973@gmail.com
11:25:17.
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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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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP005

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.
11:25:20.

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
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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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP005

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
11:25:20.

Jaipur, India
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP007

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
11:25:24.

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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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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11:25:25.
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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP011

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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

xi
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xii About the Editor

Chemistry, Green Chemistry Letters & Reviews, Ultrasonics and Ultrasonics


Sonochemistry, etc.
His recently published books are:
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 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

Heavy Metals in Water: Presence, Removal and Safety


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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
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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
3.3.5 Membrane Filtration 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
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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
5.4.3 Membrane Filtration 113
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
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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
11:25:28.

Keisuke Ikehata, Yao Jin, Nima Maleky and Aijun Lin

7.1 Introduction 141


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
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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

8.1 Introduction 168


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

9.1 Introduction 177


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
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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

10.1 Introduction 193


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
10.4.3 Adsorption of Heavy Metals on Modified
Agriculture and Biological Wastes
(Biosorption) 202
10.4.4 Adsorption of Heavy Metals on Modified
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

11.1 Introduction 213


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
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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

12.1 Introduction 249


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
13.4 Conclusions 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
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14.1 Introduction 281


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
14.6 Conclusions 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

15.1 Introduction 296


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
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15.5 New Perspectives 309


15.6 Conclusions 309
References 310

Chapter 16 Chromium in Tannery Wastewater 315


Mariliz Gutterres and Bianca Mella

16.1 Introduction 315


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
16.5 Conclusions 339
References 340

Subject Index 345


11:25:28.
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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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
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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.
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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
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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
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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
11:25:29.

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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Contamination of Heavy Metals in Aquatic Media 5

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,
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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
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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
 Regulation of water quality
(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
 Regulation of water quality
(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
 Regulation of water quality
(India) 0.001 mg L 1
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Contamination of Heavy Metals in Aquatic Media 7


Table 1.1 (Continued)
Metal Eects Drinking water standards
Mercury  Poisonous  By the Environmental
 Causes mutagenic eects Protection Agency
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 Disturbs the cholesterol maximum concentration:


0.002 mg L 1
 By European Community:
0.001 mg L 1
 Regulation of water quality
(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.
11:25:29.

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
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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
11:25:29.

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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Contamination of Heavy Metals in Aquatic Media 9

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,
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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
11:25:29.

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
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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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Contamination of Heavy Metals in Aquatic Media 11


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
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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
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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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Contamination of Heavy Metals in Aquatic Media 13

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.
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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
11:25:29.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001

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
11:25:29.

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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Contamination of Heavy Metals in Aquatic Media 15

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001

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
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Contamination of Heavy Metals in Aquatic Media 17

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00001

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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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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
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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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Photocatalytic Processes for the Removal of Toxic Metal Ions 29

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-
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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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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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Photocatalytic Processes for the Removal of Toxic Metal Ions 31

Reaction Scheme

Step 1: Initiation
hJ Ebg
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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
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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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Photocatalytic Processes for the Removal of Toxic Metal Ions 33

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
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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-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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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Photocatalytic Processes for the Removal of Toxic Metal Ions 35

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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
Published on 16 September 2014 on http://pubs.rsc.org |

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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Photocatalytic Processes for the Removal of Toxic Metal Ions 37

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).
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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.
11:25:32.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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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Photocatalytic Processes for the Removal of Toxic Metal Ions 39

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
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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
11:25:32.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025

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
11:25:32.

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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65. T. Xu, P. V. Kamat and K. E. OShea, J. Phys. Chem. A, 2005, 109, 9070.
66. S.-H. Yoon, S.-E. Oh, J. E. Yang, J. H. Lee, M. Lee, S. Yu and D. Pak,
Environ. Sci. Technol., 2009, 43, 864.
67. H. Fei, W. Leng, X. Li, X. Cheng, Y. Xu, J. Zhang and C. Cao, Environ. Sci.
Technol., 2011, 45, 4532.
11:25:32.
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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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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
11:25:36.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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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Removal of Dissolved Metals by Bioremediation 47

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-
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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
11:25:36.

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.

3.3.5 Membrane Filtration


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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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
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Removal of Dissolved Metals by Bioremediation 49

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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
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Removal of Dissolved Metals by Bioremediation 51


Table 3.2 Microorganisms and mixed consortia having heavy metal removal
capacity.
Microorganisms Toxic heavy metals removed Reference
Bacterial species:
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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
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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
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Removal of Dissolved Metals by Bioremediation 53

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-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00044

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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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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
Environmental Chemistry Research Laboratory, Department of
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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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,
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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
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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
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60
Table 4.1 (Continued)
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
11:25:40.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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
11:25:40.

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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-
11:25:40.

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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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 63

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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
11:25:40.

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.
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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-
11:25:40.

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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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 65

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
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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
11:25:40.

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
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66
Table 4.2 Materials used for coating of magnetic nanoparticles and their applications.
11:25:40.

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
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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
11:25:40.

(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
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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
11:25:40.

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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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 69

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
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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
11:25:40.

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.
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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
11:25:40.

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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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 71

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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-
11:25:40.

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
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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.
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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 73


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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


Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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.
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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 75

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00057

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),
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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
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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 77

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.
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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
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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
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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
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Functionalized Magnetic Nanoparticles for Heavy Metals Removal 79

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
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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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3. Z. Lin, Y. Zhang, Y. Chen and H. Qian, Chem. Eng. J., 2012, 200, 104.
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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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00086

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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00086

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
11:25:46.

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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Arsenic Contamination: An Overview 89

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,
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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
11:25:46.

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
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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
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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
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92
Table 5.2 (Continued)
Mineral Composition Occurrence Location
Orpiment As2S3 In low-temperature hydrothermal veins, USA, Slovakia, Bosnia-Herzegovina,
11:25:46.

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
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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,
11:25:46.

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
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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)
11:25:46.

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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Arsenic Contamination: An Overview 95

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
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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
11:25:46.

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
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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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Arsenic Contamination: An Overview 97

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
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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
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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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Arsenic Contamination: An Overview 99


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,
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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.
11:25:46.

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
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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.
11:25:46.

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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Arsenic Contamination: An Overview 101


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
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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
11:25:46.

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
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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
11:25:46.

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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Arsenic Contamination: An Overview 103


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
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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,
11:25:46.

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
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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
11:25:46.

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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Arsenic Contamination: An Overview 105

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
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(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


11:25:46.

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
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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
11:25:46.

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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Arsenic Contamination: An Overview 107


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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
11:25:46.

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
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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
11:25:46.

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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Arsenic Contamination: An Overview 109


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
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 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
11:25:46.

 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-
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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.
11:25:46.

5.4.2 Adsorption
5.4.2.1 Process Description
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.

5.4.2.2 Mechanisms of Removal


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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Arsenic Contamination: An Overview 111

between adsorbed molecules and the solid surface are due to chemical
bonding, the adsorption process is called chemisorption.

5.4.2.3 Factors Aecting Eciency


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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
11:25:46.

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
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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
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Arsenic Contamination: An Overview 113

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-
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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

5.4.2.4 Drawbacks and Advantages


The main disadvantages of adsorption processes are:

 cost of adsorbents
 need of their regeneration
 special waste production.

5.4.3 Membrane Filtration


5.4.3.1 Process Description
Membrane separation is addressed as a pressure driven process, commonly
11:25:46.

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

5.4.3.2 Mechanisms of Removal


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

5.4.3.3 Factors Aecting Eciency


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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00086

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)
11:25:46.

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.

5.4.3.4 Drawbacks and Advantages


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
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Arsenic Contamination: An Overview 115

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-
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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.

5.4.4.2 Mechanisms of Removal


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.
11:25:46.

5.4.4.3 Factors Aecting Eciency


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

5.4.4.4 Drawbacks and Advantages


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
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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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Arsenic Contamination: An Overview 117


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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00086

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
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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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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

Heavy Metals in Water: Presence, Removal and Safety


Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org

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
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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.
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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
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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.
11:25:49.

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
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Removal of Iron and Manganese from Water 125


Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00122

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