Beruflich Dokumente
Kultur Dokumente
Edited by
Sanjay K. Sharma
Department of Chemistry, JECRC University, Jaipur, India
Email: drsanjay1973@gmail.com
11:25:17.
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Preface
Agriculture and industrial developments are not possible without the in-
dispensable element water. All living and non-living things require water for
their existence in one way or another. So, if somebody says that water is the
liquid of life, it is absolutely correct. Nobody can live without water.
The population explosion, increasing urbanization and industrialization
are the major reasons for the depletion of water availability worldwide and
thats why the water crisis has become a global challenge today. Scientists,
policy makers and academicians are continuously trying hard to address this
problem to the best of their knowledge and abilities, but without complete
success.
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
v
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vi Preface
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
Sanjay K. Sharma
Jaipur, India
vii
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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-FP009
This book is for Pratima, my wife, without whose love, support and
cooperation I could not achieve anything in my life.
11:25:25.
11:25:25.
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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
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Contents
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
2.1 Introduction 25
2.2 Advanced Oxidation Processes for Heavy Metal
Removal 27
2.3 Basic Principle of Heterogeneous Photocatalysis 29
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xiv Contents
2.4 Mechanism of Photocatalytic Reactions 29
2.5 Thermodynamics of Photoreduction of Different
Metal Ions 30
2.6 Dependence of Photoreduction Kinetics on Different
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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
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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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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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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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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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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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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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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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
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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
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2 Chapter 1
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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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
metals and extensive use in the leather and tannery industries.21 Hexavalent
chromium is more toxic than trivalent chromium.
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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8 Chapter 1
1.4.2 Phytoremediation
Bioremediation is the technological process whereby biological systems,
plants and animals, including microorganisms, are harnessed to eect the
cleanup of pollutants from environmental matrices.23 During the past few
years, microbe-assisted bioremediations have been widely applied for the
treatment of wastewater contaminated with heavy metals and metalloids.
Here we will address the global problem of heavy metal pollution originating
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whereas all the biomass can be utilized in the form of fertilizer, forage,
mulch or for the production of bio-gas.27 Even though it is well known that
metals are toxic to many plants, they have developed some internal mech-
anisms that allow the uptake, tolerance and accumulation of high concen-
trations of metals that would be toxic to other organisms. Many researchers
have reported that aquatic macrophytes viz. Typha, Phragmites, Eichhornia,
Azolla and Lemna are potential wetland plants for removal of heavy metal
and metalloids due to their morphological change.24,28 Being a cost-eective
and easily applicable technique, phytoremediation can be implemented for
their enhancement to metal accumulations and translocations. In general,
two strategies of phytoextraction have been developed, which are: (1) normal
phytoremediation of heavy metals from aquatic bodies through the plants in
their entire growth cycle2931 and (2) chemically induced phytoextraction
techniques to cleanup contaminated water by using metal-tolerant plants to
remove heavy metals and metalloids.32 The eciency of phytoextraction can
be increased by using more biomass producing plant species and with the
application of suitable chelates. Hyperaccumulators or hyperaccumulating
plants are capable of accumulating large amounts of heavy metals and
metalloids, including Ni, As, Zn, Cd and Pb, in their aboveground tissues
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10 Chapter 1
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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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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12 Chapter 1
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
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been observed that the metal uptake decreased with decreasing pH, indi-
cating competition of protons for binding to acidic sites. Gurgel and Gil131
have described the preparation of two new chelating materials, MMSCB 3
and 5, derived from succinylated twice-mercerized sugarcane bagasse
(MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two
dierent methods. In the first method, MMSCB 1 was activated with 1,3-
diisopropylcarbodiimide and in the second with acetic anhydride, and later
both were reacted with triethylenetetramine in order to obtain MMSCB 3 and
5. The capacity of MMSCB 3 and 5 to adsorb Cu21, Cd21 and Pb21 from
aqueous single metal ion solutions was evaluated at dierent contact times,
pH and initial metal ion concentrations. Adsorption isotherms were well
fitted by a Langmuir model. Maximum adsorption capacities of MMSCB 3
and 5 for Cu21, Cd21 and Pb21 were found to be 59.5 and 69.4, 86.2 and
106.4, 158.7 and 222.2 mg g 1, respectively.
A few biosorbents have been reported for the adsorption of heavy metals
not only in the form of metallic ions but also organometallic compounds.
Saglam et al.132 have prepared the biosorbents from the biomass of
Phanerochaete chrysosporium, which adsorbed inorganic mercury and alkyl-
mercury species with an anity of CH3HgCl 4 C2H5HgCl 4 Hg21, with
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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
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16 Chapter 1
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.
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
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18 Chapter 1
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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108. Q. Tao, B. J. Reddy, H. He, R. L. Frost, P. Yuan and J. Zhu, Mater. Chem.
Phys., 2008, 112, 869.
109. H. J. Spratt, S. J. Palmer and R. L. Frost, Thermochim. Acta, 2008, 479, 1.
110. Y. H. Lin, M. O. Adebajo, R. L. Frost and J. T. Kloprogge, J. Therm. Anal.
Calorim., 2005, 81, 83.
111. J. T. Kloprogge, M. Weier, I. Crespo, M. A. Ulibarri, C. Barriga, V. Rives,
W. M. Martens and R. L. Frost, J. Solid State Chem., 2004, 177, 1382.
112. J. T. Kloprogge, L. Hickey and R. L. Frost, Mater. Chem. Phys., 2005,
89, 99.
113. J. T. Kloprogge, L. Hickey and R. L. Frost, J. Solid State Chem., 2004,
177, 4047.
114. T. E. Johnson, W. Martens, R. L. Frost, Z. Ding and J. T. Kloprogge,
J. Raman Spect., 2002, 33, 604.
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24 Chapter 1
CHAPTER 2
Photocatalytic Processes
for the Removal of Toxic
Metal Ions
PANKAJ CHOWDHURY,*a ALI ELKAMELa AND AJAY K. RAYb
a
University of Waterloo, Department of Chemical Engineering, Waterloo,
ON, Canada; b University of Western Ontario, Department of Chemical
Engineering, London, ON, Canada
*Email: p3chowdh@uwaterloo.ca
11:25:32.
2.1 Introduction
A group of metals and metalloids with high atomic density (46 g cm3) are
referred to as heavy metals. Heavy metals naturally occur in rocks, soils,
sediments and anthropogenic materials.1 Ore minerals such as PbS (galena),
ZnS (sphalerite and wurtzite), CuFeS2 (chalcopyrite), FeCr2O4 (chromite),
etc., are the most common.2 The normal background concentration of these
elements depends on the alliance of metals with waters, soils, sediments and
living organism.1
Metals and metalloids (Fe, Mg, Li, Zn, Cu, Cr, Ni, Co, V, As, Mo, Mn, Se,
etc.) at trace levels play significant roles as microelements in both cells and
tissues of plants and animals. These trace metals serve as enzyme and
protein components and also maintain the ionic balance as well as the
osmotic potential of cells. However, at higher concentration levels the
heavy metals show adverse eects.3 Considering the toxicity and environ-
mental impacts, the term heavy metal generally relates to metals such as
25
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26 Chapter 2
cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead
(Pb), zinc (Zn), and metalloids such as arsenic (As).
Heavy metals are released into the environment from several domestic
(automobile exhaust, smelting processes, burning fossil fuels, incineration
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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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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.
28
Table 2.2 Heavy metal removal technologies.12
Treatment method Significant factors Other details Advantages Disadvantages
Ion exchange: using Functional groups (sulfonic For clinoptilolite resin: bath i) High removal eciency, i) Expensive for large
synthetic or natural acid, carboxylic acid and fixed bed operation; ii) fast kinetics, iii) high amounts of wastewater
cation-exchange resin group); pH, initial metal pH range 47; eciency treatment capacity with low conc. of metal
ion concentration, ionic range 55100% ion, ii) regeneration
charge, contact time requirement of resins
11:25:32.
Adsorption: using activated Surface area; electrostatic Physisorption or i) Design flexibility, i) High cost of activated
carbon, carbon nanotube attraction; sorption chemisorption depending ii) generate high quality carbon, ii) performance is
(CNT), low-cost precipitation; surface on the binding treated euents, adsorbent dependent,
adsorbents from functional group of CNTs iii) regeneration is iii) works better at low
industrial or agricultural possible by proper concentration of heavy
waste desorption process metals in wastewater
Membrane filtration: Membrane pressure, RO4NF4UF (membrane i) High eciency, ii) easy i) High cost, ii) complex
ultrafiltration (UF), pore size. For UF: pressure) operation, iii) space saving process, iii) fouling of
reverse osmosis (RO), concentration of metal, membrane, iv) low
nanofiltration (NF), concentration of permeate flux, v) high
electrodialysis surfactant, solution pH, power consumption for
ionic strength RO process
Chemical precipitation: For hydroxide precipitation: Lime, NaOH (hydroxide i) Simple inexpensive, i) Large volume of relatively
hydroxide and sulfide pH 811, use of precipitation); sulfate ii) sulfide precipitation low density sludge, ii) mix
precipitation coagulants (alum, iron reducing bacteria (sulfide is better than hydroxide metal euent is dicult
salt, organic polymers) precipitation) precipitation to remove, iii) sulfide
precipitation may produce
toxic H2S fumes
Coagulationflocculation pH, formation of Common coagulants: i) Better settling, ii) better i) Complete removal not
hydrophilic colloids, FeSO4, FeCl3, sodium sludge dewatering possible, ii) use of several
electrostatic attraction xanthogenate chemicals, iii) sludge
Flocculent: PAC, PFS, PAM generation
Electrochemical treatment: Current density, initial Optimum pH range: 68 i) Rapid and well controlled i) Large capital investment,
Chapter 2
electrocoagulation, metal ion concentration, method, ii) less sludge ii) expensive electricity
electro flocculation, pH generation, iii) 78100% supply
electrodeposition yield
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reduction reactions and is applicable in all the heavy metal and metalloids
removal/recovery processes.
There are numerous photocatalysts such as TiO2, GaP, WO3, ZnO, ZnS, CdS,
etc., that are well known for their photodegradation and complete mineral-
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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
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
30 Chapter 2
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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
Reaction Scheme
Step 1: Initiation
hJ Ebg
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025
HO + h+ HO (2.2)
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
32 Chapter 2
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025
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).
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
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00025
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.
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
34 Chapter 2
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.
View Online
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
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.
View Online
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
38 Chapter 2
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
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.
References
1. D. W. OConnell, C. Birkinshaw and T. F. ODwyer, Bioresour. Technol.,
2008, 99, 6709.
2. E. Callender, Treatise Geochem., 2003, 9, 67.
3. D. B. Kosolapov, P. Kuschk, M. B. Vainshtein, A. V. Vatsourina,
A. Wiebner, M. Kastner and R. A. Muller, Eng. Life Sci., 2004, 4, 403.
4. D. Sud, G. Mahajan and M. P. Kaur, Bioresour. Technol., 2008, 99, 6017.
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42 Chapter 2
57. X. Wang, S. O. Pehkonen and A. K. Ray, Electrochem. Acta, 2004, 49, 1435.
58. W. R. Cullen and K. J. Reimer, Chem. Rev., 1989, 89, 713.
59. D. Mohan and C. U. Pittman, Jr., J. Hazard. Mater., 2007, 142, 1.
60. V. K. Sharma, P. K. Dutta and A. K. Ray, J. Environ. Sci. Health., Part A,
2007, 42, 997.
61. S.-H. Yoon and J. H. Lee, Environ. Sci. Technol., 2005, 39, 9695.
62. P. K. Dutta, S. O. Pehkonen, V. K. Sharma and A. K. Ray, Environ. Sci.
Technol., 2005, 39, 1827.
63. H. Lee and W. Choi, Environ. Sci. Technol., 2002, 36, 3872.
64. M. A. Ferguson, M. R. Homann and J. Hering, Environ. Sci. Technol.,
2005, 39, 1880.
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
Metals are intrinsically persistent in nature1 and play an integral role in the
life processes of living organisms. Heavy metals are elements having atomic
weights between 63 and 200, and a specific gravity of greater than 5.0.2 Some
metals such as Cr, Cu, Ca, Co, Fe, K, Mg, Mn, Na, Ni and Zn are essential up
to a maximum concentration limit and serve as micronutrients. They are
commonly used in redox-processes to stabilize molecules through electro-
static interactions, as components of various enzymes and for regulation of
osmotic pressure.3,4 Many other metals, such as Cd, Pb and Hg have no
biological role and are non-essential and potentially toxic to living organ-
isms, especially microorganisms.4 At high concentration levels, both es-
sential and non-essential metals could change enzyme specificity, imbalance
cellular functions and destroy cell membranes and the structure of DNA.5
Complexes of heavy metal ions such as Cd and Hg are very harmful to cell
vital activity, so the internal concentration and increase of heavy metal ions
should be controlled.6
44
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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.
46 Chapter 3
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.
3.3.4 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.
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
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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.
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.
50 Chapter 3
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.
excellent capability for removing heavy metals from wastewater. Roane and
11:25:36.
52 Chapter 3
Table 3.3 Improvement of heavy metals removal by genetically modified
microorganisms.
Plasmids
Improvement used and
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Microorganisms
Although using bioremediation is a great idea, quite often the contaminants
are also toxic to the active microbes involved in the bioremediation process.2
This problem can significantly aect the rate of bioremediation. The rate is
reduced with respect to time and after some time the bioremediation
process ceased. A solution to this problem is genetically modified microbes
that are resistant to the extreme conditions of the contaminated site and also
have bioremediation properties. Table 3.3 presents a summary of genetically
modified microorganisms used for the removal of heavy metals.
From the studies discussed here, it is evident that the engineered bacteria
achieve better removal eciency with respect to the natural ones. The im-
provement in removal eciency in all the cases is noticeable.
3.7 Conclusion
Bioremediation using living microbial cells is a feasible alternative to pure
biosorptive removal of metal contaminants from industrial wastewater.
Isolated super-resistant strains from contaminated sites have proved to be
an ecient way to scavenge dierent heavy metals. Genetic engineering may
further enhance the potential of robust environmental strains. Use of mixed
consortia comprising of multiple species has proved advantageous for a
View Online
higher level of metal removal and provided more stability against environ-
mental fluctuations. However, the choice of consortia and carbon/nutrition
source must depend upon the nature of the euents due to the diering
complexing properties of the metals and the nutritional content of the ef-
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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35. S. Raghuvanshi, S. Majumder and S. Gupta, in Bioremediation and Sus-
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65. T. Jong and D. L. Parry, Water Res., 2003, 37, 33793389.
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67. C. Casiot, G. Morin, F. Juillot, O. Bruneel, J.-C. Personne, M. Leblanc,
K. Duquesne, V. Bonnefoy and F. Elbaz-Poulichet, Water Res., 2003, 37,
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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.
4.1 Introduction
Heavy metals pollution is a serious threat to aquatic ecosystems because
some of these metals are potentially toxic, even at very low concentrations.
Contamination of heavy metals in the surroundings has done great harm to
human and other organisms due to the high toxicity and carcinogenicity.16
The United States Environmental Protection Agency (USEPA) has classified
heavy metals as priority pollutants. The presence of heavy metals in aqueous
solutions has become a serious challenge for environmental scientists as
they are non-biodegradable and pose toxicity to biological systems. Lead
(Pb), cadmium (Cd), chromium (Cr), nickel (Ni), cobalt (Co), zinc (Zn) and
copper (Cu) are some examples of the toxic metals that exist in wastewater
euents.79 In addition, heavy metals are not biodegradable and tend to
57
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58 Chapter 4
accumulate in living organisms, and they can cause severe problems to both
human health and wildlife. Natural processes and human activities have
polluted and reduced the quality of water resources all over world.
Groundwater and superficial water have been contaminated in various ways,
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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.
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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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
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forms, which are Cr(0), Cr(III) and Cr(VI). Chromium is discharged into the
environment from natural and anthropogenic sources, with the largest oc-
curring from industrial releases. Chromium is widely used in manufacturing
processes to make various metal alloys such as stainless steel. The anthro-
pogenic sources of chromium are electroplating, leather tanning, textile
production and the manufacture of chromium-based products.27 Burning of
natural gas, oil and coal also releases chromium into the environment.
Lead is a heavy, low melting, bluish-grey metal that occurs naturally in the
earths crust. The major natural ores that contain lead are galena, anglesite
and cerussite. It is usually found combined with two or more other elements
to form lead compounds. Lead is commonly used in pipes, batteries, am-
munition, cable covers and sheets used in shields from radiation. The
largest use for lead is in batteries, which are used in heavy motor vehicles.28
Tetraethyl lead may still be used in gasoline in most of the low-income
countries. It is also still used in a number of developing countries. Anthro-
pogenic activities are the major source of lead in the environment. Lead may
enter the aquatic sources through releases from mining and from industries
that use lead for making various items.
Zinc is mainly found in sulfide deposits. During weathering, zinc is im-
mobilized easily and finds its way into the aquatic systems. Zinc has had
many industrial applications since ancient times, for making bronze and
brass. It is used in galvanizing iron and steel, and zinc sheets are used for
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62 Chapter 4
building purposes. Sulfides and oxides of zinc have been used for making
white paints and ceramics.29
Cobalt occurs naturally in the environment, found in rocks and soils. It is
an essential element for living beings because it is associated with the
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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
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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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.
66
Table 4.2 Materials used for coating of magnetic nanoparticles and their applications.
11:25:40.
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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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.
route. Fe3O4 nanoparticles with uniform size and relatively better mono-
dispersity were synthesized at room temperature. It was reported that the
synthesized product was mainly composed of uniform Fe3O4 nanoparticles
with an average diameter of about 20 nm. The selected area electron dif-
fraction (SAED) pattern indicated the crystalline nature of the synthesized
materials. As a result, the prepared Fe3O4 nanoparticles showed uniform size
and relatively better monodispersity.
Cao et al.74 reported a new reaction route to obtain rice- and cube-shaped
single-crystalline a-Fe2O3 nanostructures via a reaction between
Fe(NO3) 9H2O and NH3 H2O in ethylene glycol at 200 and 280 1C, re-
spectively. The morphology of the products was studied using TEM and
high-resolution TEM. The single-crystalline nature of synthesized a-Fe2O3
was confirmed by the strong spots of the SAED pattern. On the basis of these
results, the authors have indicated that the reaction temperature plays a key
role in varying the morphology of the synthesized a-Fe2O3. The following
equation shows formation of magnetic nanoparticles:
Fe(NO3)3 3NH3 H2O-Fe(OH)3 3NH4NO3
and a-Fe2O3 particles will form through a two-step phase transformation,
according to the equation:
Fe(OH)3-b-FeOOH-a-Fe2O3
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4.5.3 Microemulsions
Magnetic nanoparticles can be obtained using the microemulsion pro-
cess.7579 In an eort to make ultra-small, coated and uniform size magnetic
nanoparticles, Santra et al. performed water-in-oil microemulsion mediated
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best synthesizing method for controlling shape and size of magnetic nano-
particles. It gives scalable and high production yield. However, success in
precise particles size control of Fe3O4 nanoparticle has only been achieved
through thermal decomposition using large amounts of toxic and expensive
precursors and surfactants in an organic solvent.83
70 Chapter 4
water dispersion and dried under ambient conditions revealed the presence
of clearly defined features with an average size of B817 nm, with a narrow
size distribution. They examined their ability to adsorb Cd21 from aqueous
solutions. The adsorption eciency of the particles for Cd21 was of the order
of 0.170.20 mmol Cd per mg Fe3O4(np)-COOH, which was amongst the
highest reported in the literature. As reported by the authors, the adsorption
eciency of the 8 nm particles was a bit higher than that for the 17 nm
analogues. It had been clearly observed that an increase in the acidity of the
media led to desorption of Cd21.
In order to provide long term high quality water or to enable water re-
cycling, Girginova et al.94 recently synthesized silica coated magnetite par-
ticles for magnetic removal of Hg21 from water. Silica coated magnetite
particles derivatized with dithiocarbamate groups were evaluated as mag-
netic nanodrivers to remove trace levels of Hg21 from aqueous solutions
using a simple external NdFeB magnet. The authors reported that the
uptake eciency for Hg21 was significantly higher for the particles bearing
dithiocarbamate groups at the surface (74%), as compared with the non-
derivatized silica coated magnetite (24%). On the basis of this study, one can
suggest that this eciency of nanomaterials is related to the high stability of
the chelates formed between the dithiocarbamate group and Hg21.
To further facilitate the adsorption anity of guest molecules on nano-
materials, surface modification, including inorganic and organic coating,
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and covalent binding, has often been explored to enable specific metal
complexation. Amino coated materials showed high sorption capacity for
Cu(II), Co(II), Ni(II), Zn(II), Pb(II), Cr(VI) and Cd(II) from aqueous solutions.95
The SiO2 coating provides plenty of surface hydroxyl groups, which oers
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particles. The Cr(VI) removal performances were compared and the ad-
sorption capacities followed the order: MnFe2O44MgFe2O44ZnFe2O44
CuFe2O44NiFe2O44CoFe2O4. The points of zero charge pHpzc for various
magnetic nanoparticles were measured to be around 7.08.0. MnFe2O4
showed a very high BET surface area in comparison with other syn-
thesized ferrite nanoparticles. The equilibrium times for Cr uptake by
MnFe2O4, MgFe2O4, ZnFe2O4, CuFe2O4, NiFe2O4 and CoFe2O4 nanomaterials
were 5, 45, 30, 20, 15 and 60 min, respectively. MnFe2O4 showed a strong
adsorption capacity for Cr(VI) ions. A 0.01 M NaOH solution was used as an
elutant for recovery of the metal ions.
Recently, Fe3O4 and g-Fe2O3 nanocages were synthesized by using
the solgel method.98 Figure 4.1(a) and (b) shows the TEM microimage for
the synthesized materials. FeSO4 and KOH were poured together to gen-
erate Fe(OH)2; subsequently KNO3 was added to the mixture for the for-
mation of magnetite of 50100 nm [Figure 4.1(c)]. The HRTEM images
were obtained near the center region of hollow nanocages for observation
of the morphologies and structures of the iron oxide nanocages
(Figure 4.2).
Cheng et al.99 applied maghemite (g-Fe2O3) nanoparticles for the se-
questration of metals from electroplating liquids. They have synthesized
maghemite nanoparticles of 60 nm by a coprecipitation method. The
magnetization with respect to the applied field was recorded at room
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72 Chapter 4
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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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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).
74 Chapter 4
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.
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
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
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.
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.
Chapter 4
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KL Ce
qe qmax
1 KL Ce
78 Chapter 4
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.
4.10 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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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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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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102. H. M. F. Freundlich, J. Phys. Chem., 1906, 57, 385.
103. M. J. Temkin and V. Pyzhev, Acta Phys. Chim. USSR, 1940, 12, 217.
104. O. Redlich and D. L. Peterson, J. Phys. Chem., 1959, 63, 1024.
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S. Ismadji, J. Hazard. Mater., 2009, 162, 616.
106. Y. S. Ho, Water Res., 2006, 40, 119.
107. Y. S. Ho, G. Mckay, D. J. Wase and C. F. Foster, Adsorpt. Sci. Technol.,
2000, 18, 639.
108. Y. S. Ho and G. McKay, Process Biochem., 1999, 34, 451.
109. Y. S. Ho and G. McKay, Chem. Eng. J., 1998, 11, 5.
110. W. J. Weber and J. C. Morris, J. Sanit. Eng. Div.: Am. Soc. Civil Eng., 1963,
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S. Wattanachira and T. F. Marhaba, Bioresour. Technol., 2006, 97, 2321.
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Toxicol. Environ. Chem., 2012, 94(1), 40.
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11:25:40.
CHAPTER 5
Arsenic Contamination:
An Overview
MAURIZIO CAROTENUTO,*a GIUSY LOFRANOb AND
SANJAY K. SHARMAc
a
Department of Chemistry and Biology University of Salerno, via Giovanni
Paolo II, 84084 Fisciano (Sa), Italy; b Department of Environment, Waste
Divison, Salerno Province, via Mauri 61, 84129 Salerno, Italy; c Department
of Chemistry, JECRC University, Jaipur-303905, India
*Email: mcarotenuto@unisa.it
11:25:46.
5.1 Introduction
Arsenic is a ubiquitous trace element with a natural presence, not only in the
environment (rocks, soils, natural waters and groundwater) and in living
organisms but also in some foods (such as rice, vegetables, seafood and
milk). In recent decades, following a series of serious accidents in dierent
parts of the world, the study of arsenic has become of increasing interest due
to its high toxicity.
The word arsenic is derived from the Persian word Zarnikh, meaning
yellow orpiment, which was adopted in ancient Greek in the form arsenikon.
Since its discovery in 1250 by Albertus Magnus, arsenic has been at the
centre of many controversies in the history of mankind for its use as a
powerful and discreet deadly poison. Many arsenic compounds, in fact, are
odourless and tasteless with a high solubility in water, which make it an
element at high risk for humans. Ingesting food or drinking water that
contains more than 0.01 mg L1 of inorganic arsenic can be dangerous,
while a content of inorganic arsenic greater than 60 mg L1 is fatal to living
86
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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
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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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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.
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.
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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94 Chapter 5
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tend to have lower values, reflecting the absence of arsenic in their dominant
minerals, such as quartz and feldspar with a mean value of the toxic element
of about 4 mg kg1. Argillaceous deposits have values of As concentrations
higher than the sandstones (typically about 13 mg kg1) reflecting the
greater proportion of the content of sulfates, oxides, organic matter and clay.
Marine argillaceous deposits have higher concentrations of As (up to 15 mg kg1)
than non-marine deposits reflecting the grain-size distributions and the
higher S concentrations. Arsenic concentrations in coal and bituminous
deposits are very high (100200 mg kg1) while in carbonate rocks they are
low (about 3 mg kg1) reflecting the constituent minerals. High contents of
arsenic, up to 2900 and 400 mg kg1, were found in rocks rich in pyrite and
iron oxides and phosphates, respectively.
With respect to the sediments, the arsenic content varies between 3 and
10 mg kg1 and the baseline world soil concentration is about 7 mg kg1. An
increase in the arsenic content of the sediments and soils is observed in
mining areas where As is found in close association with transition metals
such as Cd, Pb, Ag, Au, Sb, P, W and Mo.12
96 Chapter 5
that about 19% of the soluble forms of soil related arsenic reaches surface
water and groundwater via run-o and leaching.14 The major arsenic content
in unpolluted natural water has been attributed to several natural geo-
chemical processes. An arsenic concentration typically ranging from 0.001 to
0.010 mg L1, rising to 0.1005.000 mg L1, has been detected in waters
which are in contact with ores or tailings, waters near former mining or
smelting sites.15 High levels of arsenic can also occur naturally in geo-
thermal springs such as in New Zealand,13 up to 8.5 mg L1, in Japan16 with
a value between 1.8 and 6.4 mg L1 and at Yellowstone National Park (WY,
USA), where As concentrations often exceed 1.00 mg L1. However, not all
geothermal springs are contaminated with As. The concentrations in
groundwater depend on the arsenic content of the bedrock and the high
tendency in aquifers for the physical and geochemical conditions to be
favourable for As mobilization and accumulation. Unusually high values
have been reported in carbonate spring waters in New Zealand, Romania,
the Russian Federation and the United States (0.41.3 mg L1), artesian wells
in Taiwan, China (up to 1.8 mg L1) and groundwater in Cordoba, Argentina
(up to 3.4 mg L1). Seawater ordinarily contains 0.0010.008 mg L1 of
arsenic.13
The maximum permissible As concentration in drinking water is
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0.050 mg L1, while the recommended value by the EPA and WHO13 is
0.010 mg L1. Drinking water is the significant contributor to oral intake in
regions where the As concentrations in well-water or in mine drainage areas
are very high. More commonly, drinking-water sources generally contain
arsenic at concentrations of less than 0.010 mg L1.
Higher concentrations of arsenic have been found in the porewater ex-
tracted from unconsolidated sediments than in the overlying surface water.
Measures of dierent inorganic arsenic species (arsenate, arsenite and total
arsenic) concentrations in the porewaters collected from 18 piezometers
installed in a thick till and clay-rich aquitard sequence located in southern
Saskatchewan (Canada), are in the ranges of from 0.00031 to 0.097, 0.00071
to 0.021 and 0.0032 to 0.098 mg L1, respectively. Arsenic concentrations up
to 100 mg L1 have been found in porewater extracted from sediments af-
fected by mining contamination (tailings, mineral-rich deposit) in the
province of Ontario. High concentrations of As(III) (40.3 mg L1) were de-
tected in sediment porewater in an area contaminated from historic gold
mine operations (Moira watershed, Ontario), while As concentrations in the
surface water of the Moira River and Moira Lake are up to 0.075 and
0.05 mg L1, respectively, with the 98% as As(V)4 possibly being the result of
the reducing conditions below the sedimentwater interface, which pro-
motes the reduction of As(V) to As(III).14 It is known that As(III) and As(V) are
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usually the main soluble species in waters with relative proportions of As(V)
and As(III) varying according to sources, pH and redox conditions, and mi-
crobial activities. Aggett and OBrien5 found stratification of arsenic con-
centrations in some lake waters due to varying redox conditions that can be
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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.
100 Chapter 5
than 0.00030.147 mg g1 (dry weight), with the exception of hair, nails and
teeth and other keratin-rich tissues where inorganic arsenic has a special
anity. The normal amount of arsenic in human hair is about 0.000 08
0.000 25 mg g1 while a concentration of 0.0010 mg g1 is an indication of
poisoning. Nail clippings from a patient with acute arsenic poisoning con-
tained arsenic at 0.00200.130 mg g1, whereas the normal arsenic con-
centration in nail ranged between 0.000 09 and 0.000 59 mg g1. The arsenic
content of urine can normally vary from 0.005 to 0.040 mg per day (total).
Acute and sub-acute poisoning will produce an excess of 0.100 mg per day.
Great daily variation of arsenic exists and depends on the amount of arsenic
in various foodstus. In general, it is found that organic arsenicals are more
rapidly excreted than inorganic forms, where As(V) compounds are cleared
faster than those of As(III).11
Gamberg and Braune15 reported that arsenic residues in the kidney
of male Yukon wolves were 0.51 (o18 months) and 0.21 mg kg1 (dry
weight) (1936 months). Values were slighter higher for females, 0.57 and
0.25 mg kg1, respectively. Arsenic residues in the liver of male wolves were
0.31 (o18 months) and 0.21 mg kg1 (dry weight) (1936 months), whereas
the values were 0.17 and 0.14 mg kg1 for female wolves.
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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
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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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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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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
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are quite simple, but the disadvantage associated with them is the pro-
duction of large amounts of toxic sludge, which needs further treatment
before disposal into the environment. In the following paragraphs an at-
tempt has been made to review and update the recent advances made in the
technological developments in arsenic removal technologies and to explore
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Figure 5.5 Optimal pH ranges for arsenic treatment technologies (reprinted from
Jain and Singh42 with kind permission of Elsevier).
108 Chapter 5
However, there is still insucient data and more experiments are required
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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
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.
between adsorbed molecules and the solid surface are due to chemical
bonding, the adsorption process is called chemisorption.
The factors aecting the adsorption process are: (1) surface area, (2) nature
and initial concentration of adsorbate, (3) solution pH, (4) temperature,
(5) interfering substances and (6) nature and dose of adsorbent. Adsorbents
are characterized first by the surface properties, such as surface area and
polarity.43 Development of ecient adsorbents is thus vital to the successful
application of adsorption in water and wastewater remediation.54 As a
consequence, in recent years a variety of adsorbents have been developed to
improve the performance of the processes.
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).
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
cost of adsorbents
need of their regeneration
special waste production.
114 Chapter 5
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.
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.
116 Chapter 5
118 Chapter 5
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Physicochem. Eng. Aspects, 2011, 379, 116120.
35. D. Mohan and C. U. Pittman Jr., J. Hazard. Mater., 2007, 142, 153.
36. E. Fogarassy, I. Galambos, E. Bekassy-Molnar and G. Vatai, Desalination,
2009, 240, 270273.
37. P. Mondal, C. B. Majumder and B. Mohanty, J. Hazard. Mater., 2008, 153,
136145.
38. J. A. G. Gomes, P. Daida, M. Kesmez, H. Moreno, J. R. Parga, G. Irwin,
H. McWhiney, T. Grady, E. Peterson and D. L. Cocke, J. Hazard. Mater.,
2007, 139, 220231.
39. P. Lakshmipathiraj, S. Prabhakar and G. B. Raju, Sep. Purif. Technol.,
2010, 73, 114121.
40. S. Zodi, J.-N. Louvet, C. Michon, O. Potier, M.-N. Pons, F. Lapicque and
J.-P. Leclerc, Sep. Purif. Technol., 2011, 81, 6268.
41. A. K. Lizama, T. D. Fletcher and G. Sun, Chemosphere, 2011, 84, 1032
1043.
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120 Chapter 5
69. M. Sen, A. Manna and P. Pal, J. Membr. Sci., 2010, 354, 108113.
70. E. Lacasa, P. Canizares, C. Saez, F. J. Fernandez and M. A. Rodrigo, Sep.
Purif. Technol., 2011, 79, 1519.
11:25:46.
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CHAPTER 6
6.1 Introduction
As two of the earths most common transition metals, iron (Fe) and man-
ganese (Mn) often occur together naturally in the aquatic environment as
several dierent forms of dissolved ions. Although these two elements have
widespread uses, including metallurgical applications, such as in iron, steel
and other alloys, manganese dioxide (MnO2) in dry cell batteries and an
octane-enhancing agent (methylcyclopentadienyl manganese tricarbonyl) in
unleaded petrol, the sources of iron and manganese in the aquatic en-
vironment are mostly of natural origins, such as weathering of rocks and
sediments that are composed of iron and manganese minerals, as well as
microbial oxidation and reduction.1,2 In addition, various iron salts, such as
ferric chloride (FeCl3) and ferric sulfate [Fe2(SO4)3], are often used as co-
agulants in water treatment, whereas several manganese products, such as
potassium permanganate (KMnO4) and MnO2, are also used as oxidants in
water treatment. Based on a broad classification, both iron and manganese
122
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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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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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Figure 6.2 Generation of reduced manganese and sulfide in the anoxic hypolimnion
of a thermally stratified reservoir (unpublished data by the authors).
126 Chapter 6
This equation indicates that the oxidation of Fe(II) to Fe(III) with aeration
requires hydroxide ion and may be accelerated at high pH. Theoretically,
1 mg of oxygen will oxidize 7 mg of iron. At neutral pH, complete oxidation of
Fe(II) may take 2040 min by aeration. Some reduced iron is complexed with
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natural organic matter (NOM) and becomes very stable towards oxidation by
dissolved oxygen. Therefore, aeration is sometimes impractical for iron oxi-
dation. Alternative oxidants, such as free chlorine (gaseous chlorine or so-
dium hypochlorite), chlorine dioxide, potassium permanganate and ozone,
may be used to accelerate the reduced iron oxidation.1214 For example, the
oxidation of Fe(II) by chlorine and potassium permanganate can be shown as:
2Fe21 Cl2 6H2O-2Fe(OH)3(s) 2Cl 6H1 (6.2)
Scheme 6.2 Fe(II) oxidation by free chlorine.
Ozone and chlorine dioxide are stronger oxidants than the others and may
be able to destroy and oxidize complexed iron and manganese compounds.
It should be noted that chloramines such as monochloramine and
dichloramine are very weak oxidants and are not generally usable for iron
and manganese oxidation.18 The rate constant for iron oxidation by ozone is
8.2 105 M1 s1 at ambient temperature.21
The oxidation of manganous ion is much slower (440 min at pH 9.5) than
that of ferrous ion and requires more hydroxide.22 The water pH must be
raised to about 9.5 for this to be practical. Thus, manganese removal by
aeration alone is not generally practiced in water treatment and a stronger
oxidant such as chlorine and potassium permanganate is required to achieve
eective Mn(II) ion oxidation:12,23,24
128 Chapter 6
Actually, the direct oxidation of Mn(II) by chlorine is slow with a very small
apparent rate constant of k 6.4 104 M2 s1 at pH 8 and 22 1C.24
However, adsorption of Mn(II) onto the surface of MnO2, which is a product
of initial Mn(II) oxidation, is very fast (apparent k 4 106 M2 s1).
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In this way, soluble Mn(II) in source water becomes part of the solid filter
media and the media increase in their size. In reality, the solid MnO2 may be
better represented as MnOx (where x is between 1.64 and 1.99)6 because of
11:25:49.
constant of 1.5 103 M1 s1.21 According to Jacobsen et al.,27 the Mn(II)
oxidation mechanism by ozone is the formation of manganyl ion (MnO21),
followed by the formation of Mn(III) ions, which disproportionate into Mn(II)
and Mn(IV).
Mn21 O3-MnO21 O2 (6.17)
Mn(IV)-MnO2 (6.20)
Schemes 6.17 to 6.20 Mn(II) oxidation by ozone.
concerns
J presence of other reduced constituents
130 Chapter 6
Other considerations
J oxidation by-products
The basic components for an iron and manganese removal system include
pre-oxidation and media filters. Table 6.1 presents the characteristics of
common oxidants used for iron and manganese removal. Although the use
of air is not generally recommended due to its low oxidizing power and slow
reactions,22 mechanical aeration, such as cascade aerators, followed by sand
filtration may be employed as a low-cost treatment alternative for low-
manganese, high-iron source waters in developing countries, as both iron
and manganese pose minimal threats to public health at levels commonly
found in drinking waters.
Various filtration media may be used, including silica sand, anthracite,
greensand and synthetic MnO2 media, to capture Fe(III) and Mn(IV) precipi-
tates, depending on water flow rates and water quality. Practical implications
of the chemical oxidants and filtration media and their characteristics are
discussed in the following subsections.
131
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132
Table 6.2 Major interfering constituents.
11:25:49.
Chapter 6
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must be paid when the source water to be treated contains elevated levels of
sulfide and manganese because of the slower reactions of manganese oxi-
dation (k 6.4 104 and 1.5 103 M1 s1 with chlorine and ozone,
respectively).21,23
Ammonia also reacts with chlorine very rapidly (k 3.1 106 M1 s1)33 to
form various chloramines (combined chlorine), including monochloramine
and dichloramine. These chloramines are much weaker oxidants than free
chlorine. One milligram of ammoniacal nitrogen may consume up to 7.6 mg
of free chlorine. It is known that the resultant chloramines cannot oxidize
reduced iron and manganese.18 Although no literature can be found
that explored the impact of ammonia and chloramines formation during
iron and manganese removal in the presence of solid MnO2 media, it is
speculated that chloramines have a limited ability to regenerate spent
(i.e., fully reduced) solid media. Use of other oxidants, such as ozone, chlorine
dioxide and permanganate, may be considered if elevated chlorine demand
and incomplete iron and manganese removal due to the presence of ammonia
is becoming an issue. Ozone reacts with ammonia at a much slower rate
(k 20 M1 s1) than with iron and manganese.21 In addition, it is desirable to
use ozone and chlorine dioxide when the majority of iron and manganese
are present as tight complexes with NOM and other chelating agents.
11:25:49.
134 Chapter 6
treating high-NOM water since there may be a high risk of the production of
halogenated disinfection by-products (DBPs), such as trihalomethanes
(THMs) and haloacetic acids (HAAs). Possible remediation methods for the
DBPs formation may include NOM removal by granular activated carbon
(GAC) adsorption or the use of chloramination as a secondary disinfection.
The use of ozone solely for iron and manganese removal from groundwater
is rare,17 although it may be used in conjunction with other treatment goals,
such as colour removal and primary disinfection.
As described in the previous section, raw water must be analysed for
various water constituents and parameters because co-occurrence of other
reduced constituents, including hydrogen sulfide and ammonia, are very
common. Pre-oxidant dosage must be adjusted accordingly, or the oxidative
capacity may be exhausted and incomplete removal of iron and manganese
may occur. Some of the constituents and parameters require on-site meas-
urements, including hydrogen sulfide, pH, DO and ORP. Performance of
bench- and pilot-scale treatment trials is highly recommended as the data
from these smaller scale experiments can be very useful to determine and
optimize the operational parameters, such as oxidant dosage, media re-
quirements and hydraulic loading rate, as well as to identify any unforeseen
issues, such as DBPs formation.
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Figures 6.4 and 6.5 present a simplified process scheme for a basic
groundwater filtration system for iron and manganese removal and an ex-
ample of such filtration system installations. When properly designed,
constructed and operated, this type of system can continuously achieve less
than 0.05 mg L1 of total iron and manganese, respectively, in finished water
(Figure 6.6). The high-capacity, synthetic MnO2 media could remove iron
Figure 6.4 Simple schematic for a groundwater filtration system for iron and
manganese removal.
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Figure 6.5 A 2200 m3 d1 filtration system for iron and manganese removal.
11:25:49.
Figure 6.6 Iron and manganese removal from groundwater using pre-chlorination
with NaOCl and MnO2 media filtration (unpublished data by the
authors).
136 Chapter 6
unit processes is often employed and iron and manganese removal occurs at
several locations. Figure 6.7 shows a simplified process scheme for a typical
surface water treatment system.
In this scheme, iron and manganese removal may occur at several lo-
cations, including pre-oxidation, coagulationflocculationsedimentation,
intermediate ozonation and filtration. Various pre-oxidants may be used,
including gaseous chlorine, NaOCl, ozone, chlorine dioxide and KMnO4,
depending on the cost, availability and other treatment goals and site-
specific considerations (Table 6.1). After the pre-oxidation, oxidized and
precipitated iron and manganese [Fe(OH)3 and MnO2] can be removed by
coagulation, flocculation and sedimentation, although this process is usu-
ally not optimized for iron and manganese removal. In the United States,
intermediate ozonation is often used as a primary disinfection for Crypto-
sporidium and Giardia for taste and odour control.17 Additional iron and
manganese oxidation occurs during the intermediate ozonation. However,
there is a major risk of manganese over-oxidation to permanganate when the
ozone dose has to be increased in order to respond to seasonal water quality
events, such as taste and odour and spring runo. Therefore, the filtration
after ozonation is very important for residual manganese discharge control.
Inert filter media such as silica sand and anthracite may be used if the in-
11:25:49.
Figure 6.8 Removal of particulate and dissolved manganese within a surface water
treatment system (unpublished data by the authors).
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138 Chapter 6
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When inert filter media are used, caution must be paid when replacing old
filter media with fresh media or performing chemical cleaning of the filter
media. These maintenance activities may cause incomplete manganese re-
moval and manganese breakthrough.26
11:25:49.
6.4 Conclusions
Iron and manganese are essential elements to humans and relatively non-
toxic heavy metals commonly found in drinking water sources such as
groundwater and surface water. They typically exist as dissolved ions in their
reduced forms, Fe(II) and Mn(II), in the water. The sources of iron and
manganese in the aquatic environment are mostly of natural origins, such as
weathering rocks and sediments that are composed of iron and manganese
minerals, as well as microbial oxidation and reduction. Although these
metals pose little public health risks, ions of these elements in water often
cause mild to severe aesthetic problems such as discoloured water, pre-
cipitation, scaling, staining and metallic water tastes.
Removal of dissolved Fe(II) and Mn(II) can be achieved by pre-oxidation
using air (oxygen), chlorine, chlorine dioxide, potassium permanganate and
ozone, followed by media filtration. Both inert and reactive filtration media
may be used. Source water quality is an important factor for designing and
operating iron and manganese removal systems. If properly designed, con-
structed and operated, the oxidative pre-treatment followed by a media fil-
tration process described in this chapter can consistently produce treated
water containing iron and manganese well below their current non-health
based limits of 0.3 and 0.05 mg L1, respectively. However, several reduced
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Acknowledgements
The authors would like to thank their co-workers, namely Mr James A.
Matthews, Ms Janet A. Fordunski, Mr Jacob D. Peterson, Mr Brian W. Reid,
Mr Nathan A. Kramer and Mr Nima Maleky at Pacific Advanced Civil En-
gineering, Inc., for providing technical assistance, valuable insight and in-
spiration for preparing this book chapter.
References
1. K. H. Nealson and D. Saarini, Annu. Rev. Microbiol., 1994, 48, 311343.
2. B. Thamdrup, Adv. Mcirob. Ecol., 2000, 16, 4184.
11:25:49.
140 Chapter 6
CHAPTER 7
*Email: kikehata@pacewater.com
7.1 Introduction
Toxic metals (often called heavy metals) constitute one of the groups of
chemicals of major public and environmental health concern due to their
great potency to causing a wide variety of adverse health eects, ranging
from acute toxicity (including mortality) to chronic toxicity such as neuro-
toxicity, developmental toxicity and cancers.1 Despite the fact that many
metals have been used in various industrial applications to improve our
quality of life since the very beginning of civilization, at the same time the
toxicity of metals has been a long-standing issue for human beings.
Metals and metal compounds may be released into the environment
within the lifecycle of metallic products, including: (1) mining, (2) extraction,
smelting and refining, (3) production, (4) use and (5) disposal, recycling and
141
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142 Chapter 7
reuse. They may enter the environment either as a main component of the
metal product or as impurities during any of the stages of the lifecycle, es-
pecially at the beginning (i.e., mining to production) and the end (i.e., dis-
posal) of the cycle.1 The recent rise in the electronics industry has increased
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the public health risk due to some heavy metals, such as cadmium, lead,
mercury and chromium, in the environment as they are all linked to both the
manufacturing and recycling of electronics as well as other industries, such as
chemical production and mining.24 The industry-created pollution of heavy
metals is often through the discharge of partially treated or untreated eu-
ents, and can cause possible dangers to the public by contaminating the local
water sources for drinking water supplies and agricultural irrigation water.
Toxic heavy metals have been a universal pollution issue around the world
whenever and wherever heavy manufacturing industries are on the rise and
dominate a countries economy during their rapid development. The Peo-
ples Republic of China (China) is one such country, along with India and
other developing countries, who are currently enjoying a rapid development
and great economic growth. Unfortunately, China is no exception with respect
to environmental pollution and is indeed facing a variety of serious pollution
problems in water, air and soil that are threatening human beings, domestic
animals and wildlife alike and degrading the urban, rural and natural en-
vironments.5,6 Toxic heavy metals, such as lead, mercury, chromium and
arsenic, are considered to be one of the priority pollutants in China.5,7
The hydrosphere (the aquatic environment) is one of the four compartments
of the earth that interconnects with the other compartments, namely the at-
11:26:06.
mosphere, lithosphere and biosphere.1 Water is essential for life and acts
mostly as a vehicle for constituents and pollutants (including toxic heavy
metals) transport between these environmental compartments. In this chapter,
the current status of heavy metal pollution in the water resources in China, with
respect to relevant water quality standards in dierent types of water, including
drinking water, surface water and wastewater, along with recent data on their
occurrences in the water resources in China, are reported and discussed. Spe-
cial attention is made to addressing human health risks associated with heavy
metals in contaminated drinking water, contamination of sediments in rivers
and lakes and the impacts of industrial euents and wastewater irrigation.
some metalloids may fall into the category of heavy metals. Others consider
heavy metals as toxic metals and metalloids that tend to accumulate in the
food chain.9 According to the World Health Organization (WHO),10 the
common toxic heavy metals that can be of public health concerns include
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beryllium (Be), aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe),
cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se),
molybdenum (Mo), silver (Ag), cadmium (Ca), tin (Sn), antimony (Sb), bar-
ium (Ba), mercury (Hg), thallium (Tl) and lead (Pb). This list includes
beryllium, which is the second lightest metallic element (an alkaline earth
metal) after lithium with an atomic number of four, as well as aluminium,
one of the most widely used industrial light metals with a density of
2.7 g cm3, and arsenic and selenium, which are not even metals, but a
metalloid and a non-metal, respectively.
144 Chapter 7
Table 7.1 Basic properties of priority toxic heavy metals.
Standard
Atomic atomic Specific Major toxic eects
Element number weight gravity Category (oral route)
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cadmium and chromium (Table 7.1) are more relevant in the present-day,
industrially driven economies, and can carry public health and ecological
concerns when found in the environment. Therefore, these five elements
were selected for further discussion in this chapter. They also coincided with
Chinas five priority key heavy metals.
Four of these priority elements (As, Cd, Pb and Hg) are also listed as
chemicals of major public health concern by the WHO, along with six other
chemicals or groups of chemicals, namely air pollution, asbestos, benzene,
dioxins and dioxin-like substances, inadequate or excess fluoride and highly
11:26:06.
7.2.3.1 Chromium
Chromium is a transition metal that is widely distributed in the earths
crust. Chromium has many industrial applications such as in alloys
(e.g., stainless steel) and chrome plating due to its excellent corrosion re-
sistance and hardness. It can exist in valences of 2 to 6, and the majority
is present as chromium(III) or chromium(VI) in the aquatic environment
depending on the redox potential.17 While chromium(III) is an essential
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cinogenicity via the oral route (i.e., consumption of contaminated food and
water) is inconclusive and controversial, especially at low doses.15,18 Because
chromium(VI) is an oxidizing agent, it can be readily reduced to non-toxic
chromium(III) by reducing agents (i.e., sulfides and thiols) in human gastric
juice and rat liver microsomal fraction. Recent studies suggested that a
cytotoxic mode of action would be dominant in the low-dose region where
exposure of humans to chromium(VI) occurred via drinking water con-
sumption instead of a mutagenic mode of action.15
7.2.3.2 Arsenic
Arsenic has had uses as an anti-corrosive in zinc and lead alloys, a dopant for
semiconductors, in pesticides and wood preservatives.19,20 It is also a by-
product of copper smelting. Arsenic can be found in water either as arsenates
(e.g., AsO43) or as arsenites (e.g., AsO33), depending on the redox potential.
Because these arsenic compounds are oxyanions, they become more soluble
at higher pHs. Arsenic compounds are acutely toxic to humans. In general,
arsenites [arsenic(III)] are more toxic than arsenates [arsenic(V)] and organic
arsenic compounds. Inorganic arsenics are considered as carcinogenic to
humans (Group 1) by the International Agency for Research on Cancer (IARC)
11:26:06.
7.2.3.3 Cadmium
Cadmium can be found in the aquatic environment as Cd21. It is closely
related to zinc (a Group 12 element) and they often occur together.
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146 Chapter 7
very long biological half-life of 1030 years, depending on the organ and
tissues.12 It accumulates primarily in the kidney.25 According to the IARC,
cadmium is probably carcinogen (Group 2A) via inhalation, although no
evidence of carcinogenicity or genotoxicity via an oral route (i.e., drinking
water and food consumption) has been found.27 Toxic levels of cadmium
seem to cause brittle bones, and put those aected in extreme pain.12,28,29
It is thought that cadmium mediates damage to bones indirectly by its
interactions with organs in the body, and it can eventually lead to death
through organ shut down, especially renal failure.29 One of the most famous
cases of cadmium pollution occurred in Japan, in the early 20th century.
Mining operations produced cadmium polluted run-o that became the
cause of itai-itai disease, and caused severe damage to the aected local
population.12
7.2.3.4 Lead
Lead is abundant, cheap and has various industrial uses, such as leadacid
batteries, alloys, solder and pigments. Alkyl lead compounds including tet-
raethyl lead (TEL) and tetramethyl lead were used extensively as antiknock
agents in gasoline for motor vehicles in the past,3032 although the use of
11:26:06.
lead has been phased out in most countries, including China. However, the
use of TEL in aviation gasoline for aircrafts using reciprocating engines
still continues. Lead compounds may exist in two oxidation states, namely
2 and 4. Lead(II) is more stable and more common in the aquatic en-
vironment.32 Lead compounds may enter the aquatic environment via sur-
face run-os, dry and wet deposition from the atmosphere. Lead has been
used in pipes and fittings, as well as in soldered connections in water dis-
tribution systems, and in plumbing in residences.32
The problem with lead is that its adverse eects on children are quite
profound as it can hinder development in a childs mental capacity. It has
been shown that the levels of lead leaching from soldered connections in
water pipes could be as high as 210390 mg L1, which would be enough to
intoxicate children.33 By inhibiting haem synthesis through the disruption
of iron inclusion in the complex, lead can cause a state of anaemia.34
Furthermore, lead can function as an analogue of calcium, which is one
way it hinders development. As calcium is a crucial part of nerve network
formation and communication, by binding instead of calcium, lead can
prevent the formation of vital pathways and slow the propagation of action
potentials across synapses.26 This aects children in particular, due to
their sensitive developmental stages, and can leave permanent
mental disabilities in aected youths.35,36 Beyond the disruption of
neuronal pathways, lead, being able to react as calcium, would cause it to
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build up in bones in the body, and thus it is dicult to fully purge through
excretion and even treatment.3,35 According to the IARC, although the
evidence for carcinogenicity of lead in humans is inconclusive, inorganic
lead compounds are probably carcinogenic to humans (Group 2A).27
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7.2.3.5 Mercury
Mercury is the only metallic element that is liquid at standard conditions for
temperature and pressure (273.15 K and 100 kPa). It has a vapour pressure of
0.16 Pa at 20 1C.38 It can readily mix with various metals to form amalgams.
Mercury mostly occurs as cinnabar (mercuric sulfide, HgS) in nature, which
was used as a scarlet pigment called vermilion from ancient times to the
Middle Ages. Its modern uses include thermometric materials for thermo-
meters, barometer liquids, conductive materials for electrical switches and
relays, vapour sources in mercury-vapour lamps and fluorescent lamps,
pesticides, pharmaceuticals and dental amalgams, although these uses of
mercury and mercury compounds are decreasing due their toxicity and en-
vironmental concerns.38
Mercury compounds, especially some inorganic mercuric salts and
11:26:06.
148 Chapter 7
Metals in Water
As with many other industrialized nations worldwide, environmental pol-
lution in China has been realized and actively discussed in the past years. In
particular, Chinas environmental problems were getting much attention in
the late 1980s to early 1990s, which coincided with the beginning of the
major industrial and technological development of the country. The eco-
nomic reform and opening up started by the reformists led by Deng
Xiaoping in 1978 took dramatic eect in the early 1980s and stimulated vast
improvement in many industrial sectors, including agriculture, food,
manufacturing, mining, iron and steel and construction. Increase in foreign
trade further accelerated the rate of economic growth and production of
consumer goods, textiles and various commodities, such as agricultural
goods, steel and petrochemicals. In addition to the major cities such as
Beijing and Shanghai, a number of special economic zones (the most not-
able ones include Shenzhen, Zhuhai, Xiamen and Shantou) in southern
China, which were originally established in the 1980s, became the centres of
the economic growth in the early 1990s, in particular the high-tech indus-
tries such as electronics manufacturing, pharmaceuticals and other
biotechnologies.
11:26:06.
Although China has managed to grow so rapidly during the last few dec-
ades, many of the booming industries that have been sustaining the growth
have, at the same time, caused environmental pollution. Among the notable
pollutants, heavy metals constitute a major class that poses serious threats
to humans and the environment.57 For example, with the booming elec-
tronics industry, cadmium is a very relevant issue in wastewater treatment.
Also, being the largest producer of leadacid batteries, and having diculty
enforcing regulations, China has found large quantities of lead in waste-
water euents that contaminate local water sources. This, coupled with
electronic waste (e-waste) disposal and lead mining, has become a great
public health concern in China.3,26 In this subsection, Chinese heavy metal
standards in water and the sources and pollution status are discussed.
evaluation for categorizing the cross sections of a river, that is, the class of
the section is determined by the highest rating among all the parameters
tested.45 If the number of cross sections for a river is less than five, the
average concentration of each parameter will be assessed. When the number
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of rated cross sections for a river is more than five, each class percentage will
be evaluated and the class of water body will be classified according to
Table 7.2. The class function for each class is summarized in Table 7.3.
Heavy metals are one of the key pollutant groups in water. In the basic
parameters standards, eight common and toxic heavy metals are included,
as shown in Table 7.4.44 If the surface water body is classified as a drinking
water source, additional heavy metal parameters should be monitored,
which are listed in Table 7.5.
The Class I and II surface water standards, which are applied to drinking
water sources, for hexavalent chromium, arsenic, cadmium, mercury and lead,
are generally in agreement with the WHO Drinking-water Guideline values
Z40%
150 Chapter 7
Table 7.4 Comparison of basic heavy metals standards for surface water and
drinking water (mg L1).
Chinese surface water (GB 3838-2002)44 Drinking water
Class
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Standard
Parameter limit (mg L1)
Supplemental parameter:
Iron (Fe) 0.3
Manganese (Mn) 0.1
Particular parameter:
Molybdenum (Mo) 0.07
Cobalt (Co) 1.0
Beryllium (Be) 0.002
Antimony (Sb) 0.005
Nickel (Ni) 0.02
Barium (Ba) 0.7
Vanadium (V) 0.05
Titanium (Ti) 0.1
Thallium (Tl) 0.0001
and the most recent Chinese Drinking Water Standards (GB 5749-2006)46
(Table 7.4). Thus, if properly enforced, the Chinese surface water standards are
protective to public health. It can be seen that the surface water mercury
standards are a lot more stringent than the WHO guideline value (0.006 mg L1
as inorganic Hg), while arsenic standards are generally less stringent
(0.01 mg L1 in the WHO guideline). Thus, arsenic removal may be required at
drinking water treatment plants in some cases.
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At present, heavy metal occurrence data in Chinese rivers and lakes are
scarce or unavailable. By reviewing the data presented in the Report on the
State of the Environment in China by the MEP,47 one can get a glimpse at the
current state of surface water quality in China. The water quality in seven
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major rivers in China, namely the Yzangtze River, Yellow River, Pearl River,
Huai River, Songhua River, Liao River and Hai River, has been greatly im-
proved over the last ten years (Figure 7.1). Still, a significant portion
(on average 14%) of the sections of these rivers were classified as heavily
polluted (worse than Class V) in 2012. Although the majority of the pollution
problems were reportedly caused by organics (i.e., biochemical and chemical
11:26:06.
Figure 7.1 Change in the proportion of qualitative evaluation of seven major rivers
in China: (a) 2002 and (b) 2012.47,48
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152 Chapter 7
47
oxygen demand), nutrients (e.g., ammonia and phosphorus), those heavily
polluted river sections were aected by heavy metals, which is discussed in
Section 7.4 of this chapter.
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Table 7.8 Key heavy metals discharge quantities in Chinese surface water.53
Parameter (tonnes)
Total
Source Arsenic Lead Cadmium Mercury chromium
Industrial 145.2 150.8 35.1 1.2 290.3
wastewater
Centralized waste 1.4 4.4 0.8 0.2 2.9
control facilitiesa
11:26:06.
a
Wastewater and leachate from domestic waste treatment plants and hazardous waste control
facilities.
are mainly from industrial wastewater discharge.51 The National 12th Five-
Year Plan for Environment Protection identified five key heavy metals,
namely, lead, cadmium, mercury, chromium and arsenic, which should be
under strict control.52 The plan also pointed out major polluting industries,
which consist of non-ferrous heavy metals mining and dressing, the
non-ferrous heavy metals smelting industry, lead batteries manufacturing,
leather manufacturing (including leather tanning process and fur manu-
facturing), chemicals and chemical synthesis products manufacturing (basic
chemicals manufacturing, painting, printing ink, pigment and other com-
parable manufacturing). Non-ferrous heavy metals include copper, lead,
nickel, tin, antimony and mercury. In addition, electroplating industries and
coal-fired power plants should be taken into account.
Based on the most recent statistics presented in the China Statistical
Yearbook on Environment by the MEP,53 the key heavy metals content in
industrial wastewater made up more than 95% of the national discharge in
2011, except for 14% of mercury which came from a centralized treatment
(Table 7.8). Figure 7.2 displays the annual discharge of each key heavy metal
via wastewater from 2000 to 2011.5357 Among these, both arsenic and lead
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154 Chapter 7
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Figure 7.2 Key heavy metals annual discharge in China from 2000 to 2011.5357
70%, even though several major and minor fluctuations occurred in the last
decade. Cadmium displayed a sharp drop in 2004 while chromium(VI) went
the opposite way, and was then followed by gradual decrease. Mercury dis-
charge also decreased rapidly during 20002004 and became stable at
around 1.3 tonnes after 2007.
Figure 7.3 shows the composition of key heavy metals discharge by dif-
ferent industries. From 2007 to 2009, non-ferrous metals mining and
dressing were the primary sources of heavy metals discharge, followed by
non-ferrous metal smelting and rolling processing, the chemical industry
and ferrous metal smelting. In 2010, metal products manufacturing sur-
passed the ferrous metal smelting industry and became the fourth greatest
contributor. The industry composition had an obvious change in 2011, in
terms of both discharge percentages and composition. The heavy metals
discharge from leather, fur and feather manufacturing and shoe manu-
facturing made up almost 20% of the total discharge, while non-ferrous
metals mining and dressing decreased remarkably to 14%. Additionally, the
heavy metals contribution from metal products manufacturing showed an
upward trend. The cause(s) of the major changes that occurred in the 2011
data in Figure 7.3 (i.e., appearance of leather, fur, feather and shoe manu-
facturing, and the disappearance of the chemical industry) are unknown.
This is possibly due to some changes in statistical data collection methods
and possible industrial restructuring.
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Figure 7.3 The composition of heavy metals discharge from industries in China
from 2007 to 2011.5357
Resources
This section reviews and discusses examples of the recent investigations on
heavy metal pollutions in the water resources in China. Five important topics
are covered, including: (1) impacts of industrial wastewater, (2) impacts
of wastewater irrigation, (3) pollutions in Beijing, the nations capital,
(4) human health risk assessment and (5) contamination of sediments.
These study locations were spread across the country, as shown in Figure 7.4.
Many of the papers reviewed here were written in Chinese.
156 Chapter 7
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Figure 7.4 Locations of the sites covered in the reviewed articles (the original map
was downloaded at http://d-maps.com/carte.php?num_car 27749&
lang en).
11:26:06.
Table 7.9 Aqueous-phase heavy metals monitoring data at the Xiawan wastewater
discharge outlet (mg L1) (adapted from Qi59).
Total
Sampling date Lead Cadmium chromium Chromium(VI) Mercury Arsenic
8/26/2010 0.132 0.104 0.137 0.079 0.006 0.131
8/27/2010 0.144 0.092 0.105 0.046 0.023 0.051
8/28/2010 0.111 0.028 0.081 0.034 0.008 0.057
mercury and arsenic in the Xiawan drainage area were all rated as Class V.59
Monitoring data are summarized in Table 7.9.
The pollution control for wastewater discharged into the Xiang River at
Xiawan was desired because two major cities of Hunan Province, Changsha
and Xiangtan, are located downstream of Xiawan, which are ecologically
sensitive. The recommendations for improving the water quality included
upgrading the wastewater treatment facilities and separating stormwater
and sewage systems to enable treatment equipment downsizing and low-
ering of the capital costs. In addition, averaged lead contents in the river
sediments downstream of Xiawan were ten times higher than those in other
main rivers or comparable rivers in China, indicating serious lead
pollution.58
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to 2.5, 0.123 and 0.592 mg L1, respectively) in the aqueous phase, which
were well above the WHO and Chinese Drinking Water Guidelines
(Table 7.4), as well as those in the river sediment (12.367, 334, 1.392 and
37.178 mg kg1, respectively).
The impacts of acid mine drainage on groundwater quality have been
studied in the northern Guangdong Province.61 The Guangdong Dabaoshan
Mining Corporation is a state-run mining company that mines and refines
iron and copper. The acid mine drainage was first collected through mud-
retaining impoundment and it then flowed through a stream towards the
Shangba floodplain, which is located about 11 km south of the mine. The pH
of the groundwater in the Shangba floodplain was lower at the monitoring
sites, close to the mine (as low as 4.6) showing the impact of acidic stream
water (pH 2.9) originating from the mine and being used for agricultural
irrigation. Elevated levels of heavy metals were detected in both groundwater
and stream water. For example, high levels of cadmium, copper and zinc
(as high as 0.03, 1.93 and 4.03 mg L1, respectively) were detected in
groundwater samples. Although lead was found in the stream water (up to
1.2 mg L1), this heavy metal was not detected in the groundwater samples.
Based on the results of the Daphnia carinata toxicity test, the groundwater
was found to be very toxic, probably due to the high levels of heavy metals.
11:26:06.
158 Chapter 7
Water Quality Standard (Class V for agricultural water; Tables 7.3 and 7.4).
Contamination of paddy soils and rice samples was also confirmed in this
study and a potential health risk to the local residents was suggested. Hang
et al.65 also reported a deterioration of surface water quality by the euent
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public health risk due to mercury and total phosphorus in the Miyun Res-
ervoir watershed in Beijing during the period of from 1980 to 2003. However,
other heavy metals including lead and chromium did not exceed the Chinese
Surface Water Standards during the study period. Gao et al.78 performed a
preliminary health risk assessment of heavy metals (Cu, Hg, Cd and As) in
drinking waters using the health assessment model of the United States
Environmental Protection Agency (US EPA) throughout the Beijing area
about the same time. The concentrations of four heavy metals ranged from
0.81 to 6.96 mg L1 for copper, 0.34 to 0.82 mg L1 for cadmium, 0.10 to
0.74 mg 1L for mercury and 0.19 to 3.02 mg L1 for arsenic. The major cancer
risks were associated with arsenic in Tongzhou County (2 105 probability)
and with cadmium in Changping County (2.3 106 probability). These
levels of cancer risk are not considered to be excessive as compared with
background levels (i.e., 1 105 probability).79 The reported highest non-
carcinogenic risk in drinking water in Beijing at that time was associated
with mercury, followed by copper.
160 Chapter 7
Table 7.10 Summary of recent health risk assessments of water in China.
Locations
(water source) Carcinogenic risk Non-carcinogenic risk Reference
Beijing Ingestion: As Hg and Cu (108 Gao et al.78
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water in dierent parts of China. Table 7.10 summarizes the findings of such
recent research works. In addition to the preliminary health risk assess-
ment in Beijing performed by Gao et al.78 discussed earlier, Zhang et al.80
11:26:06.
it is well known that these metals have a tendency to accumulate in the bot-
tom sediments of rivers, estuaries and lakes.8385 For example, the significant
accumulation of heavy metals such as lead, copper, nickel and zinc were re-
ported in the Pearl River Delta in Guangdong Province and Hong Kong.85 The
urban rivers in the City of Hangzhou, Zhejiang Province, have been receiving
both industrial and domestic wastewaters, and the pollutants, including heavy
metals, have been found to accumulate in the sediments of the rivers.86 Both
water and sediments were sampled in six targeted rivers. Four heavy metals
were analysed, namely, lead, cadmium, copper and zinc. Based on the in-
vestigation results, water quality of all sampled cross sections were Class V due
to ammonia nitrogen and total phosphorus as the main pollutants. The
aqueous-phase concentrations of four heavy metals were within the range of
Class I to Class II, but sediments contained elevated levels of lead, zinc and
copper compared with the background levels and indicated a slight degree of
hazard according to an ecological risk assessment. Cadmium reached a severe
pollution level. The key pollution sources were identified as machine manu-
facturing, dyeing, papermaking and chemical industries along the rivers.
Lake sediments tend to accumulate more heavy metals than those in rivers
because of the longer hydraulic retention time. Huang et al.87,88 studied the
distribution and accumulation of several heavy metals including lead, cad-
11:26:06.
mium, arsenic, copper and zinc in Baihua Lake, which is one of the source
water reservoirs for Guiyang City in Guizhou Province. The surface area and
capacity of the lake are 14.5 km2 and 190 million m3, respectively. There were
seven headwater streams and most of them were seriously aected by the
development of industrial and agricultural activities, as well as domestic
sewage. The highest concentrations of heavy metals, including lead, cad-
mium, arsenic, copper and zinc, in ten sediments samples from Baihua Lake
were 29.7, 1.23, 74.1, 116.0 and 449.6 mg kg1, respectively. Among the heavy
metals evaluated, the loadings of cadmium and arsenic represented critical
factors in ecological hazards in the lake.
Recently, a significant increase in heavy metal content of surface sedi-
ments over the last 30 years (from 1980 to 2010) has been recognized in
Chaohu Lake in Anhui Province.89 Chaohu Lake is the largest lake in the
province and the fifth largest freshwater lake in China. Besides the heavy
metal pollution, serious water quality issues including algal bloom have
been reported around this lake.90 The sediment samples collected from the
lake showed elevated levels of manganese (44% of the area), zinc (20%), iron
(16%), arsenic (14%), chromium (6%) and nickel (6%). Chromium, copper,
zinc and arsenic concentrations in the lake sediments had increased by
200% as compared with the data from the 1980s in the western lake, where
major urban development in Hefei and agricultural activities had aected
the deteriorating water quality.
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162 Chapter 7
Acknowledgements
The authors would like to thank Mr Kun Li at the Chinese Academy of Sci-
ences in Beijing for providing help with data collection. The editorial help of
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References
1. S. E. Manahan, Environmental Chemistry, CRC Press, Boca Raton, FL,
2004.
2. A. S. Sheoran and V. Sheoran, Miner. Eng., 2006, 19, 105116.
3. X. Huo, L. Peng, X. Xu, L. Zheng, B. Qiu, Z. Qi, B. Zhang, D. Han and
Z. Piao, Environ. Health Perspect., 2007, 115, 11131117.
4. J. Cui and E. Forssberg, J. Hazard. Mater., 2003, 99, 243263.
5. S. P. Cheng, Environ. Sci. Pollut. Res., 2003, 10, 192198.
6. K. M. Zhang and Z. G. Wen, J. Environ. Manage., 2008, 88, 12491261.
7. B. Wei and L. Yang, Microchem. J., 2010, 94, 99107.
8. J. H. Duus, Pure Appl. Chem., 2002, 74, 793807.
9. US EPA, EPAs Terms of Environment, U.S. Environmental Protection
Agency, Washington, DC, 2000.
10. WHO, Adverse Health Eects of Heavy Metals in Children, World Health
Organization, Geneva, Switzerland, 2011, http://www.who.int/ceh/
capacity/heavy_metals.pdf.
11. WHO, Guidelines for Drinking-water Quality, World Health Organization,
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164 Chapter 7
42. J. W. Vonk and A. K. Sijpesteijn, Antonie Van Leeuwenhoek, 1973, 39, 505513.
43. M. Ranchou-Peyruse, M. Monperrus, R. Bridou, R. Duran, D. Amouroux,
J. C. Salvado and R. Guyoneaud, Geomicrobiol. J., 2009, 26, 18.
44. and (General Bureau of
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66. M. Liu, B. Huang, X. Bi, Z. Ren, G. Sheng and J. Fu, Environ. Sci. Process.
Impacts, 2013, 15, 919929.
67. Y. Guo, C. J. Huang, H. Zhang and Q. X. Dong, J. Environ. Qual., 2009, 38,
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68. J. Zheng, K. H. Chen, X. Yan, S. J. Chen, G. C. Hu, X. W. Peng, J. G. Yuan,
B. X. Mai and Z. Y. Yang, Ecotoxicol. Environ. Saf., 2013, 96, 205212.
69. K. Ikehata, in Wastewater Reuse and Management, ed. S. K. Sharma and
R. Sanghi, Springer, New York, NY, 2013, pp. 165191.
70. WHO, WHO Guidelines for the Safe Use of Wastewater, Excreta and Gray-
water, Vol. 1, Policy and Regulatory Aspects, World Health Organization,
Geneva, Switzerland, 2006.
71. M. Qiao, C. Cai, Y. Huang, Y. Liu, A. Lin and Y. Zheng, Environ. Monit.
Assess., 2011, 172, 353365.
72. S. Khan, Q. Cao, Y. M. Zheng, Y. Z. Huang and Y. G. Zhu, Environ. Pollut.,
2008, 152, 686692.
73. P. J. Li, X. Wang, G. Allinson, X. J. Li and X. Z. Xiong, J. Hazard. Mater.,
2009, 161, 516521.
74. J. Tang, X. Bai and W. Zhang, Soil Sediment Contam., 2011, 20, 722732.
75. G. H. Wu and S. S. Cao, Bull. Environ. Contam. Toxicol., 2010, 84, 336341.
76. S. Pan, Environmental Assessment on Surface Water Quality of Beijing City,
China ( ), China Agricultural Uni-
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78. J. J. Gao, L. P. Zhang, S. B. Huang, M. Ma and Z. J. Wang, Huan Jing Ke
Xue, 2004, 25, 4750.
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CHAPTER 8
8.1 Introduction
Taihu Lake is the third largest freshwater lake in China. The entire area of
the Taihu Lake basin is approximately 36 500 km2, and the actual lake region
is about 2338 km2, with a mean water volume of around 44.297 108 m3.1
The run-o sources of the lake are mostly from the mountainous west and
southwest, and outflows are located throughout East Taihu Lake.24 Taihu
Lake is a large sedimentary shallow lake with a mean depth of 1.9 m, and
there are 172 rivers or channels connected to it.5 As a densely-populated and
highly-industrialized area, the Taihu Lake basin plays an important role in
both the economical and social development of China.68 Taihu Lake is the
most important water supply source and is an attractive site for tourism,
shipping and recreation for Shanghai, Wuxi, Suzhou and other nearby
cities. However, owing to rapid development and industrial and agricultural
production in this region, the lake has been polluted from a range of
168
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Heavy Metals Distribution in Surface Water Samples of Taihu Lake, China 169
8.2 Methods
8.2.1 Sample Collection
Forty-nine surface water samples were collected in February 2010 from
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various locations around Lake Taihu (Figure 8.1 and Table 8.1). All the
samples were stored at 4 1C until the analyses.
Figure 8.1 Map of Taihu Lake showing the distribution of the sampling sites.
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170 Chapter 8
Table 8.1 Details of sampling sites.
Region No. Longitude Latitude No. Longitude Latitude
0 00 0 00 0 00
East Taihu Lake 1 120121 09 31107 30 12 120125 37 31111 0 3400
2 120121 0 5400 31108 0 1800 13 120123 0 5300 31111 0 1100
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8.3 Results
8.3.1 Chromium (Cr)
The Cr concentrations for all samples taken from Taihu Lake were low
(o0.01 mg L1), which were better than Grade I surface water standards of
China.17
Heavy Metals Distribution in Surface Water Samples of Taihu Lake, China 171
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11:26:23.
0.05 mg L1 (water quality level, Grade V), which is above the fishery
water quality standards of China (Pb r 0.05 mg L1).17,18 The other samples
had Pb concentrations below 0.01 mg L1, which qualify for Grade I water
quality.17 In West Taihu Lake, the Pb concentrations of all samples ex-
ceeded 0.01 mg L1, except for two, which were higher than 0.05 mg L1
(Figure 8.2).
172 Chapter 8
meets the drinking water standard limits for China (Zn r 1.0 mg L1) and
this level satisfies Grade I water quality17,19 (Figure 8.3).
Heavy Metals Distribution in Surface Water Samples of Taihu Lake, China 173
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11:26:23.
174 Chapter 8
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11:26:23.
Heavy Metals Distribution in Surface Water Samples of Taihu Lake, China 175
176 Chapter 8
References
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CHAPTER 9
9.1 Introduction
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177
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178 Chapter 9
metals in drinking water. The new standards inevitably require many water
utilities to upgrade their current treatment systems or to consider new
purification technologies. During the past decades, much eort has been
spent on developing high-eciency and cost-eective adsorbents for heavy
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metal removal, such as metal oxides, modified activated carbons, resins and
gels.810 With the pressures of climate change, population growth and in-
dustrialization of developing countries, the demand for clean drinking water
is increasing. Therefore, ecient treatment of the wastewater is more im-
portant than ever.
In recent years, nanotechnology has successfully introduced dierent
types of nanomaterials for water treatment. Some benefits include increased
eciency for contamination removal, reduced consumption of raw materials
and substitution of more abundant and less toxic materials than ones cur-
rently used.11,12 As absorbents, nanomaterials have been shown to work
eectively against heavy metal contaminants in aqueous systems.1315
9.2 Nanoclays
Clays, or hydrous aluminosilicates, can be broadly defined as the minerals
that make up the colloid fraction (o2 mm) of soils, sediments, rocks and
water. Individual natural clay particles are less than 0.004 mm in diameter;
to be considered nanosized, the clay must be o100 nm in diameter. Most of
the nanoclay for industrial use is extracted from the natural deposits.16
Natural nanoclay, such as montmorillonite, bentonite, kaolinite, hectorite
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9.2.1 Nano-Kaolinite
Kaolinite has a plate sheet structure with a diameter of approximately 0.2
10 mm and a thickness of 0.7 nm. The 1 : 1 sheet structure of kaolinite is
made up of an [Si2O5]2 sheet and an [Al2(OH)4]2 sheet. The sheets are so
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tightly stacked that water molecules are unable to pass between them.
Though kaolinite is the least reactive of the clays, its metal adsorption ability
is highly pH dependent. Kaolinite is a common sorbent for heavy metals.18
This adsorption process is usually accompanied by the release of hydrogen
cations from the edge sites of kaolinite. When cations, i.e., Pb21, Zn21 or
Cd21, are adsorbed, the displacement of H1 ions could create swelling,
flocculation or compressibility.19 The substitution of H1 cations for heavy
metal cations could influence the van der Waals forces within the kaolinite
structure.20 Adsorption may also take place on the flat exposed planes of the
silica and the alumina sheets.
9.2.2 Nano-Montmorillonite
Montmorillonite is a member of the 2 : 1 smectite family; it has two tetra-
hedral sheets with an octahedral sheet between them. The silica
aluminasilica units cause a very weak bond and an excellent cleavage
between these units. Owing to the unique structure of montmorillonite,
water and other polar molecules can enter between the layers, causing ex-
pansion. The layers are separated by a regular van der Waals gap due to the
negative charges. The layer thickness is around 1 nm and the other di-
mensions may vary from 300 to several microns. Montmorillonite clay has
excellent sorption and possesses sorption sites that are available within its
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180 Chapter 9
21
interlayer space as well as on the outer surface and edges. Naturally oc-
curring montmorillonite clay has a CEC of between 60 and 100 meq per
100g. The nanocomposites prepared by montmorillonite should have a CEC
of 70150 meq per 100g.22 Compared with kaolinite, montmorillonite has a
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very large adsorption capacity; the values may be three times higher.23
sible for metal removal, based on modern analytical techniques (XAS, ATR-
FT-IR, NMR, etc.) or mathematical models, and develop metal oxide based
materials of better applicability for practical use (such as granular oxides or
composite materials).29
TiO2 nanoparticles, which were synthesized using TiCl4, were found to have
an adsorption capacity of 96 mg g1 at pH 9.36 FeTi binary oxide nano-
particles were recently produced to remove As from the water with a high
adsorption capability of 33 mg g1 at pH 7.37 In addition to As, nano-TiO2 has
been used to treat other heavy metals in water such as Cd38 and Pt.39
182 Chapter 9
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Figure 9.3 Arsenic adsorption isotherms in a 1.0 M TiO2 and 0.04 M NaCl suspen-
sion at equilibrium pH 7.0 0.1, equilibrium time 22 h. The lines are
model calculations.32
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Figure 9.4 Arsenic adsorption isotherms in a 1.0 M TiO2 and challenge water at
equilibrium pH 7.0 0.1, equilibrium time 22 h. The lines are model
calculations.32
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184 Chapter 9
As(V) and As(III) adsorption capacity than conventional Fe oxide due to its
large surface area; this may serve as a promising adsorbent for As in water.
The removal of heavy metals from water has also been explored using
nanomaterials made of various metals, such as Zn,57 Mg,58 Sn,59 Ni,60 Zr60
and Mn.61
9.4.2 Graphene
Graphene, a rising star among 2D carbon materials, led scientists to being
awarded the Nobel Prize in 2010. It is a one atom thick material made up of
sp2-bonded carbon atoms. Owing to the high conductivity, large surface area,
low mass and excellent mechanical and thermal properties,7072 graphene-
based materials have shown excellent potential for various applications.7375
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186 Chapter 9
The mechanisms of heavy metal ions absorbed onto graphene are pretty
similar to those of heavy metal ions absorbed onto CNTs. The high disper-
sion property of graphene oxide nanosheets in aqueous solution is favorable
for the surface oxygen-functional groups to freely form strong complexes
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products like cosmetics, ICT, food and feed, environmental health and
agriculture.82,83 A high surface area to volume ratio provides nanosized
materials with specific physico-chemical characteristics and high reactivity;
however, its applications also pose potential negative environmental
impacts.
One of the most famous examples is nano-silver used in nanoformula-
tions. Owing to the properties of silver at the nanoscale, such as biological
properties and unique optical and physical properties, nano-silver has been
used in an increasing number of consumer and medical products. Of the
more than 800 consumer products that contain nanomaterials, roughly 30%
are claimed to contain silver particles.81 Examples are food packaging ma-
terials and food supplements, odour-resistant textiles, electronics and
household appliances, cosmetics and medical devices, water disinfectants
and room sprays. Some of the applications of nano-silver have resulted in
concern amongst government agencies and the public. A recent study re-
vealed that the silver can easily leak into wastewater during washing and, as
a result, could disrupt helpful bacteria used in wastewater treatment facil-
ities or endanger aquatic organisms in lakes and streams.84 Nano-silver not
only has physical and surface properties that could pose a threat to human
and environmental health,85 but could also serve as a reservoir for toxic
silver ions. Recent research with zebra fish showed that single silver 12 nm
nanoparticles aected early development of fish embryos.85 In addition,
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188 Chapter 9
in vitro and in vivo toxicity studies with mammalian species have shown that
silver nanoparticles have the capability to enter cells and cause cellular
damage.86
Concerns about the safety of emerging nanotechnology have been on the
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rise for the past few years. Consequently, more research is urgently needed
to investigate whether nanoparticles present a threat to environmental
health in general, as the direct and indirect exposure to nanomaterials in-
creases. The risk assessments of the engineered nanomaterials prior to their
application in the market and society are critical to ensuring a sustainable
nanotechnology industry.87
9.6 Conclusions
In this chapter, we provide a review of the removal of heavy metal con-
taminants using nanomaterials, including clays, metal oxides and carbon
materials. The chapter briefly addresses important material properties of the
nanomaterials that contribute to heavy metal removal from water, followed
by a critical explanation of the adsorption of heavy metal contaminants on
nanomaterial based on the literature currently available. Finally, potential
negative environmental impacts of nanotechnology are presented.
To date, nanomaterials are widely explored as highly ecient adsorbents
for heavy metal removal from water/wastewater. They exhibit various ad-
vantages such as fast kinetics, high capacity and preferable sorption
towards heavy metals in water and wastewater. Nevertheless, to further
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19. K. G. Bhattacharyya and S. Sen Gupta, Adv. Colloid Interf. Sci., 2008, 140,
114131.
20. P. W. Schindler, P. Liechti and J. C. Westall, Neth. J. Agric. Sci., 1987, 35,
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21. O. Abollino, M. Aceto, M. Malandrino, C. Sarzanini and E. Mentasti,
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22. A. Okada and A. Usuki, Mater. Sci. Eng. C-Biomimetic Mater. Sens. Syst.,
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23. F. Coppin, G. Berger, A. Bauer, S. Castet and M. Loubet, Chem. Geol.,
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2011, 2011, 26242630.
25. T. Wen, X. L. Wu, X. L. Tan, X. K. Wang and A. W. Xu, ACS Appl. Mater.
Interf., 2013, 5, 33043311.
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27. J. Gaume, S. Therias, F. Leroux, A. Rivaton and J. L. Gardette, J. Appl.
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7175.
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192 Chapter 9
CHAPTER 10
10.1 Introduction
In last few decades, metallic items or metal-based substances have been in
high demand and their uses are expected to increase day by day. Water
contamination from heavy metals such as Cr, Cd, Hg, Cu, Ni, As, Pb, Zn, etc.,
is a big environmental concern, which is continuing to require significant
attention.1 The major sources of heavy metal pollution are municipal waste,
metal plating facilities, mining operations, fertilizer industries, tanneries,
batteries, paper industries and pesticides, etc.2 Heavy metals are non-
biodegradable and they can be accumulated by living organisms/tissue. If
the metals are ingested beyond the permitted limit, they can cause serious
diseases and disorders.3,4 Therefore, it is necessary to treat metal-
contaminated wastewater prior to its discharge into the environment. Heavy
metal removal from aquatic euent can be achieved using numerous
existing procedures, such as chemical precipitation, ion-exchange and
electrochemical removal. These processes have significant disadvantages,
193
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194 Chapter 10
metals found in drinking water sources has raised concern in many parts of the
world. These heavy metals have deleterious cytotoxic eects on the biota that
exist there and, consequently, on human health.11 Heavy metals generally enter
the human body through water, in the aquatic food chain. Aquatic species such
as fish or aquatic species based products are the major source of heavy metal
transfer into the human body. Exposure to these toxic metals is associated with
many serious diseases including Alzheimers,12 Parkinsons,13,14 digestive,15
heart disorders16 and liver, kidney, stomach and lung cancers.17,18
In past decades, several studies have been carried out to investigate the
mechanism of toxicity induced by heavy metals and oxidative stress, inter-
ference with essential metals and enzymes, and interactions with cellular
macromolecules, etc., and mechanisms have been described.19 Oxidative
stress is one of the major mechanisms behind metal toxicity.20 The for-
mation of large amounts of reactive oxygen species, such as superoxide
anion (O2), hydrogen peroxide (H2O2), hydroxyl radical ( HO) and singlet
oxygen (1O2), has been reported to promote the induction of oxidative
stress.21 In fact, various studies connect heavy metals with oxidative DNA
damage since these metals may reduce the level of the main antioxidant
compounds in several animal tissues by inactivating enzymes and other anti-
oxidant molecules.22 In humans, oxidative stress is responsible for various
diseases, including cancer, Parkinsons disease, Alzheimers disease, ath-
erosclerosis, heart failure and myocardial infarction.19,23
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 195
Table 10.1 Source, permissible limits and health eects of various toxic heavy
metals.
WHO,
permissible
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limit for
portable
Heavy water
metals Sources (mg L1) Potential health eects
As Electronics, metallurgical 0.01 Skin manifestations,
industries, manures visceral cancers,
sewage vascular disease
Cd Metalliferous mining, 0.003 Kidney damage, renal
agricultural materials, disorder, human
fertilizers, waste disposal, carcinogen
landfill leachate,
electronics, metallurgical
industries, manures
sewage
Cr Metal finishing industry, 0.05 Headache, diarrhea,
electroplating nausea, vomiting,
carcinogenic
Cu Metal finishing industry, 2 Liver damage, Wilson
electroplating, disease, insomnia
metalliferous mining
Ni Metalliferous mining, 0.02 Dermatitis, nausea,
metal finishing industry, chronic asthma,
electroplating, manures coughing, human
sewage, sludge, alloys carcinogen
11:26:32.
and steels
Zn Metal finishing industry, 3.0 Depression, lethargy,
electroplating, neurological signs and
metalliferous mining, increased thirst
agricultural materials,
fertilizers, manures
sewage sludge
Pb Electronics, metallurgical 0.01 Damage the fetal brain,
industries, specialist diseases of the kidneys,
alloys and steels, waste circulatory system and
disposal, landfill leachate nervous system
Hg Electronics, waste disposal, 0.001 Rheumatoid arthritis,
landfill leachate and diseases of the
kidneys, circulatory
system and nervous
system
Various agencies have recommended safe levels for heavy metals for the
protection of drinking water and aquatic life, which are given in Table 10.1.
Although, awareness of metal poisoning has been rising in recent years,
removal of metal ions from wastewater in an eective manner has become
an important issue today. Owing to strict regulation and increased concern
about heavy metals, abundant amounts of research have been carried out
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196 Chapter 10
Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 197
32
Kolodynska prepared polyacrylate anion exchangers and chelating anion
exchangers for the removal of Cu(II), Zn(II), Ni(II) and Cd(II) complexes with
HEDP (1-hydroxyethylene-1,1-diphosphonic acid) from aqueous solution. The
result reported by Kolodynska shows that modified ion exchangers are more
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ecient than the parent one. Despite the several advantages, ion exchangers
have some limitations, such as they cannot handle concentrated metal solu-
tions as the matrix becomes easily fouled by organics and other solids in the
wastewater. Moreover, ion exchange is non-selective and is highly sensitive to
the pH of the solution and the capital and operational costs are high.30
Membrane filtration systems, including ultrafiltration, reverse osmosis,
nanofiltration and electrodialysis, show great potential for the scavenging of
heavy metals from wastewater. The major advantages of these technologies
are high eciency, easy operation and space saving, and membrane fouling
and high operating costs are the major disadvantages of the membrane
process.33 Although there are several methods used for the removal of heavy
metals from wastewater, each method has some advantages and disadvan-
tages, as summarized in Table 10.2. Of the many techniques that can be
Table 10.2 Current treatment technologies for heavy metals removal involving
physical and/or chemical processes.54
Method Advantage Disadvantage
Oxidation Rapid process for toxic High energy costs and formation
pollutants removal of by-products
Ion exchange Good removal of a wide Absorbent requires regeneration
11:26:32.
198 Chapter 10
Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 199
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Figure 10.1 SEM image of carbonized coconut fiber (left) and carbonized coconut
fiber containing zeolite Y (adapted from reference 40).
200 Chapter 10
Table 10.3 Adsorption capacities of modified natural materials for heavy metals.
Adsorption capacity (mg g1)
Adsorbent Pb21 Zn21 Cu21 Ni21 Cr61 Reference
Modified zeolite 123 44
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 201
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Figure 10.2 Schematic of synthetic routes from blast furnace slag (BFS) to various
mineral compounds (adapted from reference 56).
5.2 to 8.5 [for Pb(II)] were optimized. The iron slag had a much higher
sorption capacity for metals than the steel slag due to its higher surface area,
higher porosity and higher ion-exchange ability.
Fly ash from industries also showed good potential for the removal of
heavy metals from industrial wastewaters. Gupta et al.59 explored bagasse fly
ash, a solid waste from the sugar industry, for Cd(II) and Ni(II) removal from
synthetic solutions at pH ranging from 6.0 to 6.5. Mohan and Gandhimathi
used fly ash for the removal of heavy metals in a batch process.60 The uptake
behaviour of fly ash for heavy metal ions follows the order
Pb214Cd214Zn214Cu214Mn21, and the Freundlich isotherm fitted well
for the adsorption of heavy metals on the fly ash. The fly ash contains oxi-
dized functional groups as SiO2 and Al2O3 and above pH 6.9 these groups
acquire negative charge. The negative charges at an active site on the surface
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202 Chapter 10
21
of the fly ash, which allow cationic metals (M ) and metal hydroxides
[M(OH)2] to be complexed at the surface, are as follows:
SiOH OH-SiO H2O (10.2)
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 203
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Figure 10.3 Adsorption mechanism of heavy metals on yuzu and lemon cellulose
matrix gels (adapted from reference 65).
heavy metal and the carboxylic acid of pectic acid in the lemon and yuzu
11:26:32.
gels, improving the amounts of Pb(II), Cu(II), Cd(II) and Zn(II) adsorbed onto
the lemon and yuzu gels by approximately 5- and 6-fold, respectively. The
binding mechanism for the adsorption of heavy metals onto the biosorbent
surface is shown in Figure 10.3.
Surface modifications of coconut shell charcoal (CSC) and commercial
activated carbon (CAC) with chitosan and/or oxidizing agents, such as sul-
furic acid and nitric acid, respectively, are also carried out to improve
Cr(VI) removal performance.3 CSC and CAC chemically modified with nitric
acid showed higher Cr(VI) adsorption capacities (CSC 10.88 and CAC
15.47 mg g1) than those oxidized with sulfuric acid (CSC 4.05 and CAC
8.94 mg g1) and non-treated CSC coated with chitosan (CSCCC 3.65 mg g1),
respectively, suggesting that surface modification of a carbon adsorbent with
a strong oxidizing agent generates more adsorption sites on their solid surface
for metal adsorption.
Cu(II) and Zn(II) removal from real wastewater were studied using pecan
shells activated carbon.66 Bishnoi et al.67 conducted a study on Cr(VI) re-
moval by rice husk activated carbon from aqueous solution. They found that
the maximum metal removal by rice husk took place at pH 2.0. Rice hull,
containing cellulose, lignin, carbohydrate and silica, was investigated for
Cr(VI) removal from a simulated solution.68 To enhance its metal removal,
the adsorbent was modified with ethylenediamine. The maximum Cr(VI)
adsorption of 23.4 mg g1 was reported to take place at pH 2.
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204 Chapter 10
Three dierent cortex fruit wastes, including banana, lemon and orange
peel treated with NaOH, were evaluated as biosorbents by Vargas et al.69 It
was found that for Pb and Cu removal, lemon and orange cortex showed
better biosorption capabilities when compared with banana cortex (up to
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00193
15% less for Pb and 48% less for Cu). For Cd, banana cortex showed better
biosorption capability of 57% (67.2 mg g1 of cortex) more than orange
(28.8 mg g1 of cortex) and 82% more than lemon (12 mg g1 of cortex).
Baki and Shemirani70 used sodium dodecyl sulfate (SDS) coated micro-
particles of walnut sawdust modified with dimethylglyoxim for the de-
termination and preconcentration of Ni(II) from real samples. The eects of
solution pH and initial metal ion concentration, contact time, etc., were
investigated, as shown in Figure 10.4. The equilibrium time was found to be
30 min and maximum adsorption was at pH 7.5. The maximum monolayer
adsorption capacity was 22 mg g1.
In recent years, biological materials such as bacteria, algae, yeasts and
fungi have received increasing attention for heavy metal removal and re-
covery due to their good performance, low cost and the large available
quantities.7175 The biosorbent contains a variety of functional sites, in-
cluding carboxyl, imidazole, sulfhydryl, amino, phosphate, sulfate, thio-
ether, phenol, carbonyl, amide and hydroxyl moieties.76 Several algal
biomass such as Spirogyra species,71 Ecklonia maxima,72 Ulva lactuca,73
Oedogonium sp. and Nostoc sp.74 and brown alga Fucus serratus75 have
been utilized as adsorbents for the removal of heavy metals. The adsorption
capacities of these biosorbent are reported in Table 10.5. The mechanism for
11:26:32.
Figure 10.4 Eect of solution pH (a) and adsorption isotherm of nickel ions on
modified walnut sawdust (b) (adapted from reference 70).
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 205
Table 10.5 Adsorption capacities of some agriculture and biological wastes for
heavy metals.
Adsorption capacity (mg g1)
Adsorbent Pb21 Cd21 Zn21 Cu21 Ni21 Cr61 Reference
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uptake capacities were 10.36 and 15.33 mg g1, respectively, for intact and
disrupted biomass at an initial concentration of 100 ppm, pH 5, biosorbent
dosage 0.3 g, biomass drying temperature 180 1C and contact time 120 min.
FTIR analysis revealed that disulfides (SS) and ester (SOR) bonds con-
tribute to Cu(II) removal in addition to the carboxyl and hydroxyl functional
groups, which play important roles in metal removal.
206 Chapter 10
Table 10.6 Adsorption capacities of modified biopolymers for heavy metals.
Adsorption
Adsorbent Metal capacity (mg g1) Reference
Modified cellulose Cu21 153.5 83
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Cd21 250
Pb21 500
Oxidized cellulose Cu21 268.2 85
Cs1 133.8
Magnetic cellulosechitosan Cu21 44.7 5 89
Fe21 94.1 7
Pb2 28.1 3
Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 207
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208 Chapter 10
heavy metals. For given initial metal ions concentration and a finite liquid
volume, in order to achieve the desirable removal of heavy metals on a large
scale, the amount of adsorbent to be used and the residence time of the
liquid in the batch need to be determined. For a given equilibrium con-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00193
centration, Ce, the amount of metal ions adsorbed onto the adsorbent at
equilibrium, qe, can be estimated from the Langmuir isotherm model. The
required amount of adsorbent, mD, to treat a volume of liquid, VD, can then
be calculated as follows:
mD (Ci Ce)VD/qe (10.7)
where Ci is the initial metal ion concentration in the liquid. In practice, there
would be a trade-o between the maximized utilization of the adsorbent and
the adsorption time since the adsorption rate is very low when the equi-
librium is approached. The adsorption system would thus usually be de-
signed at less than 100% saturation of the adsorbent, such as 9095%
saturation.90,91 The residence time (cycle time) of the liquid in the batch
could then be estimated using pseudo-second order kinetics. The design
amount of heavy metals removal qt, can be estimated as:
qt (Ci Ct)VD/mD (10.8)
where Ct is the specified (or design) heavy metals concentration remaining
in the liquid at the end of the adsorption cycle.
10.6 Summary
11:26:32.
Although all the heavy metal wastewater treatment techniques can be em-
ployed for the detoxification of water containing heavy metals, adsorption
technology is receiving the greatest attention because of its easy operation
and it is eco-friendly and low cost. It is important to note here that the
maximum adsorptive removal of heavy metals mainly depends on the ex-
perimental conditions, nature of adsorbent and metal ions. The use of agro-
industrial waste materials as low-cost adsorbents for removing metallic
pollutants from water and wastewater presents many attractive features,
especially their contribution in the reduction of costs for waste disposal.
However, dierent types of modified materials have been summarized in
this chapter, which show great potential for the scavenging of heavy metals
from industrial wastewaters. However, there is still a need to investigate
more materials with better adsorption capacity and fast separation.
References
1. R. Apak, K. Guclu and M. H. Turgut, J. Colloid Interf. Sci., 1998, 203, 122.
2. S. ay, A. Uyank and A. Ozask, Sep. Purif. Technol., 2004, 38, 273.
3. S. Babel and T. A. Kurniawan, Chemosphere, 2004, 54, 951.
4. W. S. W. Ngah and M. A. K. M. Hanafiah, Bioresourource Technol., 2008,
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Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 209
210 Chapter 10
Modified and New Adsorbents for Removal of Heavy Metals from Wastewater 211
59. V. K. Gupta, C. K. Jain, I. Ali, M. Sharma and S. K. Saini, Water Res., 2003,
37, 4038.
60. S. Mohan and R. Gandhimathi, J. Hazard. Mater., 2009, 169, 351.
61. A. Bhatnagar and M. Sillanpaa, Chem. Eng. J., 2010, 157, 277.
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62. R. Kumar and M. A. Barakat, Chem. Eng. J., 2013, 226, 377.
63. J. C. Igwe, D. N. Ogunewe and A. A. Abia, African J. Biotechnol., 2005,
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65. M. Minamisawa, H. Minamisawa, S. Yoshida and N. Takai, Green Chem.,
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66. P. R. Bansode, J. N. Losso, W. E. Marshall, R. M. Rao and R. J. Portier,
Bioresource Technol., 2003, 89, 115.
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68. P. Tang, C. K. Lee, K. S. Low and Z. Zainal, Environ. Technol., 2003,
24, 1243.
69. K. K. Vargas, M. C. Lopez, S. R. Tellez, E. R. Bandala and J. L. S. Salas,
Phys. Chem. Earth, Parts A/B/C, 2012, 3739, 26.
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71. V. K. Gupta, A. Rastogi, V. K. Saini and N. Jain, J. Colloid Interface Sci.,
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73. A. El-Sikaily, A. El Nemr, A. Khaled and O. Abdelwehab, J. Hazard. Mater.,
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88. H. Tang, C. Chang and L. Zhang, Chem. Eng. J., 2011, 173, 689.
89. Z. Liu, H. Wang, C. Liu, Y. Jiang, G. Yu, X. Mu and X. Wang, Chem.
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90. J. D. Seader and E. J. Henley, Separation Process Principles, John Wiley &
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CHAPTER 11
11.1 Introduction
The worlds supply of clean and safe waters for human consumption and
needs is becoming more and more scarce due to various anthropogenic and
industrial activities. Such activities have inevitably released substantial
amounts of wastewater containing toxic substances, thus accounting for
great environmental concerns for many years. Heavy metals are broadly
defined as those metals and metalloids of relatively high specific gravity (at
least five times that of water) or of high relative atomic weight, which are
considered to be of sucient dissemination and prevalence as to be in some
way environmentally or biologically significant as poisonous elements. Such
a substance is highly life-threatening towards living organisms due to its
high toxicity even at a very low concentration, non-biodegradability and
persistent nature and it is bio-accumulative (passed up the food chains to
humans).1 Heavy metal poisoning of humans via inhalation, ingestion and
skin absorption can result in reduced mental and central nervous functions,
changes in numerous metabolic body processes and damage to blood
213
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214 Chapter 11
composition, kidneys, lungs, liver and other vital organs. Long-term ex-
posure may result in degeneration of physical, muscular and neurological
functions that mimics Parkinsons disease, Alzheimers diseases, muscular
dystrophy and multiple sclerosis.24 Heavy metals rich euents are dis-
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come a frequently used technique and a viable option for controlling the
fate, transport and bioavailability of heavy metals in terrestrial and aquatic
environments due to its simple design and operation, cost-eectiveness,
wide adaptability and high removal eciency, which produces high-quality
euents. Nowadays, special attention has been focused on the pursuit of
Table 11.1 Maximum acceptable limits of several toxic heavy metal ions in the
surface waters based on WHO and US EPA regulations.
Heavy metal Toxicity rank WHO (mg L1) US EPA (mg l1)
As 1 10 10
Pb 2 10 15
Hg 3 1 2
Cd 8 3 5
Cr, hexavalent 17 50 100
Co 52 NRa 100
Ni 57 70 100
Zn 75 NGLb 5000
Cu 125 2000 1300
Mn 140 400 50
Fe 300
a
NR, not recorded.
b
NGL, no guideline.
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Table 11.2 The advantages and disadvantages of several conventional technologies for the treatment of heavy metal contaminated
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal
euents.
Working
Technology Advantages Disadvantages concentration
Chemical Ready availability of equipment Large volumes of sludge are generated, incurring 410 mg L1
precipitation and many chemicals additional waste-disposal costs
Convenient, self-operating and Extra coagulationflocculation is compulsory for
11:26:35.
215
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216
Working
Technology Advantages Disadvantages concentration
Reverse osmosis High eectiveness (over 99% of High procurement and operating cost of the 410 mg L1
all dissolved minerals can be membranes
removed) The use of elevated pressures makes this
The capability to reduce the technique costly and sensitive to operating
11:26:35.
Chapter 11
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 217
natural adsorbents that possess high loading capacity, fast kinetics, a large
availability and are renewable and economically viable.
Numerous kinds of natural adsorbents ranging from industrial by-
products to agricultural waste have been explored for the remediation of
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aquatic environments that are polluted by heavy metals and they may be an
alternative to more costly materials such as commercial activated carbons
or synthetic ion-exchange resins.1025 Despite their abundant availability
and cheapness, most of these solids show unimpressive results, associated
with poor removal capacity. Of particular interest are clays and clay min-
erals, which are highly valued for their ion sorption/exchange capacity, low
permeability, swelling ability, chemical and mechanical stability, large
specific surface area and ubiquitous presence on earth in the geological
deposits, terrestrial weathering environments and marine sediments.26 In
the terrestrial environments, clay deposits may act as a natural scavenger
by taking up pollutants from water passing through the soil by ion ex-
change and/or adsorption mechanisms. Many types of clay materials have
been tested for the removal of heavy metal ions from waters and waste-
waters, including diatomite, illite, sepiolite, bentonite, kaolinite, clin-
optilolite, halloysite and palygorskite.2741 These clays and clay minerals
possess important surface reactivity, which stems from the permanent
negative charge within the layers. Furthermore, the natural exchangeable
alkali and alkali earth metal cations, such as Na1, K1, Ca21 and Mg21
located between two adjacent layers, can be replaced with larger molecular
mass cations, expanding the interlayer space and consequently the
11:26:35.
218 Chapter 11
Table 11.3 Several well-known classes of clay minerals and their structural
properties (adapted from reference 47).
Layer
CEC charge
Clay Layer (meq/ per unit
mineral Chemical formula type 100 g) cell
Kaolinite [Si4]Al4O10(OH)8 nH2O (n 0 or 4) 1:1 315 o0.01
Illite Mx[Si6.8Al1.2]Al3Fe0.25Mg0.75O20(OH)4 2:1 1040 1.42.0
Smectite Mx[Si8]Al3.2Fe0.2Mg0.6O20(OH)4 2:1 70120 0.51.2
Vermiculite Mx[Si7Al]AlFe1.5Mg1.5O20(OH)4 2:1 100150 1.21.8
Chlorite Mx[Si6.8Al1.2]Al3.4Mg0.6O20(OH)4 2 : 1 : 1 1040 Varied
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 219
(e.g., Al31 - Si41).54 Among the soft base 2 : 1 silicate clay minerals are
montmorillonite, hectorite, glauconite and celadonite, while among the
hard base are vermiculite, saponite, beidellite and illite. Brigatti et al. have
proven that the layer charge location at a 2 : 1 layer type clay mineral aects
the hydration of the layers and, more importantly, the sorption process of
the cationic species.55 In general, hard acids (e.g., metal cations) complex
with hard bases and soft acids (e.g., organic cations) complex with soft bases.
The SiOSi bonds of silica tetrahedrons form a reactive surface called a
siloxane, while the OAlOH bonds of alumina octahedrons form an oxy-
hydroxy surface. The siloxane surface, typical of 2 : 1 silicate clay minerals,
can be classified as inner-sphere or outer-sphere in terms of cation ad-
sorption complexes.50 In the inner-sphere surface complex, water molecules
will not be able to penetrate siloxane ditrigonal cavities (each being nearly
0.26 nm in diameter), whereas the adsorption of cations may be still feasible
due to their smaller sizes than the cavity size. Meanwhile, the outer-sphere
surface complex has at least one water molecule interposed between the
surface functional group and the bound ion or molecule,50 in other words, a
hydrated adsorbed cation is accommodated. The reactivity of the siloxane
surface towards cationic species (e.g., heavy metal ions) may stem from the
negative charge-bearing patches arising from isomorphic substitution of an
aluminium atom in place of a silicon atom. In this regard, the molecular
interaction between metal cation and inner-sphere surface complex can be
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220 Chapter 11
monodentate (the ion is bonded to one oxygen atom), bidentate (the ion is
bonded to two oxygen atoms), mononuclear or multinuclear.56
The oxyhydroxy surface is characterized by a plane of exposed hydroxyl
sites underlying Mg, Al or Fe atoms in the centre of the octahedrons. Clays
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with a 1 : 1 layer type structure such as kaolinite and rectorite usually consist
of a siloxane surface on one basal plane and an oxyhydroxy surface on an-
other basal plane. The exposed basal hydroxyl groups are subject to dis-
sociation, therefore they are reactive toward positively charged ions.
Considering those properties, it can be implied that the sorption of cationic
species onto siloxane and oxyhydroxy surfaces takes place through surface
complexation phenomena.
The location of cation complexation (i.e., inner-sphere or outer-sphere)
and its modes are the major area that is still continuously studied to date
due to the lack of theoretical understanding and incoherent data in the
literature. Therefore, a number of molecular-scale investigations and com-
putational studies have sought to investigate the adsorption mechanisms of
heavy metal ions onto the surfaces of siloxane and oxyhydroxy groups and
the modes of cation-surface complexes using various in situ molecular-scale
spectroscopy techniques, such as X-ray absorption fine-structure spec-
troscopy, neutron scattering spectroscopy, nuclear magnetic resonance
spectroscopy and Fourier transform infrared spectroscopy.50,56 The study
of Sposito and coworkers reported that excess negative charge density in
the siloxane surface makes it possible for this surface to create strong ad-
sorption complexes with cations and water molecules.50 Electron spin
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 221
64
per kg of clay. Based on previous studies, one can conclude for conveni-
ence that alkali and alkali earth metal cations primarily bound to the surface
complexes by forming outer-sphere complexes or through an ion-exchange
process (categorized as non-specific adsorption), while trace and heavy metal
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222 Chapter 11
edge sites, which provide negatively charged ligands for the binding of
metal cations.
The cation-exchange capacity (CEC), expressed in milliequivalents per
100 g of clays/clay minerals, or centimoles of charge per kilogram [cmol()
per kg], is defined as the maximum holding capacity to which a clay/clay
mineral can adsorb and exchange cations from the clay suspensions at a
specific pH,55 therefore it directly determines the eectiveness of clay/clay
mineral sorbents in removing metal cations. Each clay/clay mineral has a
specific range of exchange capacities, as shown in Table 11.3, because of
structural dierences and the variation of chemical compositions. The
higher this number, the higher the negative charge and the more cations the
clays and clay minerals can hold through electrical attraction. Generally
speaking, the exchange capacities of clays and clay minerals can be en-
hanced by either adding organic matter or increasing the suspension pH.
The latter is preferred and adopted in most sorption studies for eective
removal of heavy metal ions from aqueous solutions. Increasing the pH
would provide negatively charged surface sites for the binding of heavy metal
ions, resulting from deprotonation of structural hydroxyl groups, mainly
silanol and aluminol groups. Thus, one can infer that the acting uptake
mechanism, in connection with cation-exchange capacity, is a reversible
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 223
loading capacity and (2) alter the mineralogy, adsorptive and electrokinetic
properties of the minerals so that they become widely applicable. In their
native state, clays and clay minerals are potential sorbents for removing
cationic species (e.g., heavy metal ions) because they readily sorb onto un-
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and Hg(II) cations has been studied by Ghassabzadeh et al.70 They observed
excellent performance of expanded perlite in removing Ag(I) and Cu(II) ions
at near-neutral pH with a removal percentage that reached 92% for Cu(II) and
100% for Ag(I), while for Hg(II) it was 35%. Natural clinoptilolite and ben-
tonite clays have also been utilized as a low-cost material for fast uptake of
bivalent lead ions from aqueous solutions in a batch mode.71 It was found
that bentonite clays were able to sorb higher amounts of Pb21 ions with a
removal percentage that reached 100% at ambient temperature with mild
agitation. Under the same conditions, the removal percentage of clin-
optilolite with particle sizes ranging between 2.5 and 5 mm and in a dust
form were about 42 and 55%, respectively. This dierence is due to the
higher specific surface area of clinoptilolite dust than that of granular
clinoptilolite, which facilitates the mobilization of transport with respect to
the incoming lead ions.
The adsorption potential of two volcanic rock grains, namely Scoria (VSco)
and Pumice (VPum), towards Ni(II) ions has been tested by Alemayehu and
Lennartz.72 The maximum uptake capacity of Ni(II) ions was 980 mg kg1 for
VSco and 1187 mg kg1 for VPum at room temperature under weak acidic
conditions (pH of 5). The potential application of Turkish illitic clay for re-
moving Cd21 and Pb21 ions has been evaluated by Ozdes et al.73 A removal
eciency of nearly 100% for Pb(II) ions and 78% for Cd(II) ions was obtained
in their study.
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224 Chapter 11
Table 11.4 The removal capacity of various natural clays and clay minerals towards
various heavy metal ions.
Heavy Maximum sorption
Clays/clay minerals metals capacity (mg g1)a Reference
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 225
29.17 wt% bentonite and 4.16 wt% kaolin, displayed a maximum sorption
capacity of 140.9 mg g1. Natural clays and clay minerals are also acquiring
prominence for nuclear waste management. In the study of Zhao et al.,
laboratory-grade MX-80 bentonite was used to treat tetravalent thorium ions
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the clay particles. The resulting material, termed calcined or sintered clay,
possesses a lower degree of crystallinity, which is cluster-shaped or
amorphous with coarse-shaped pores, poor dispersibility in aqueous solu-
tions (e.g., water) and a generally lower sorption capacity in conjunction with
a reduced specific surface area.
Talaat et al. studied the performance of Egyptian kaolin and bentonite
clays and their heat-treated forms for the removal of five heavy metal ions,
namely chromium, cadmium, nickel, zinc, copper and lead.87 The experi-
mental results showed that all modified kaolinite clays displayed lower re-
moval capacities towards Cr(III) and Cd(II) ions, although Na-bentonite
exhibited the highest adsorptivity towards Cd(II), Cu(II), Zn(II), Pb(II) and Ni(II)
cations. The calcination of Turkish bentonite clay to remove the radio-
nuclide U(VI) ions from synthetic euent has been conducted by Aytas
et al.88 They observed a strong correlation between calcination temperatures
and U(VI) removal capacity in which the adsorptivity of uranyl ions (UO221)
onto thermally treated bentonite (TAB) surfaces gradually fell at extreme
calcination temperatures, typically above 400 1C, due to the distortion of the
internal structure of clay. In this regard, a calcination temperature of 400 1C
was selected as the optimum point that gave the highest adsorption capacity
of uranyl (UO221) ions.
Similar attempts were made by by Alkan and colleagues to investigate the
sorption performance of calcined kaolin for preconcentrating copper ions
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226 Chapter 11
89
from aqueous solutions. They found that the phase transition from kao-
linite to the metakaolinite phase took place by calcinating clay at 600 1C.
Another useful finding in their study is that the extent of copper sorption
onto the clay surface decreased with increasing activation temperature due
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 227
mass loss and those associated with phase transformation in many solids.
The distinctive characteristics of endothermic and/or exothermic peak
temperatures that appear at a certain temperature region represent any
thermal reaction or phase transition in the solid phase and the corres-
ponding percentage of mass loss. In the study by Alkan et al.,89 the structural
distortion of silica tetrahedral and alumina octahedral of kaolinite clay
could be identified at four temperature points: (1) removal of physically
bound water in pores and on the surfaces at 100 1C; (2) mass loss associated
with dehydration of a surface hydroxyl group in the alumina octahedral
sheet at about 400 1C; (3) dehydroxylation of kaolinite and formation of a
metakaolinite phase between 400 and 650 1C; and (4) decomposition of a
metakaolinite phase at 950 1C to form an AlSi spinel phase.
228 Chapter 11
found to increase after acid leaching, which is beneficial for removal pur-
poses. Sulfuric acid-activated Tunisian green (RGC) and red (RRC) clays have
been tested for the adsorption of lead metal from aqueous solution in a
batch system.94 The surface properties of acid-treated RGC and RRC clays,
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00213
including specific surface area, total pore volume, internal porosity and
pore size, increased and they showed maximum retention capacities of
27.15 mg g1 for H2SO4 treated RRC and 40.75 mg g1 for H2SO4 activated
RGC, as predicted with the Langmuir adsorption model.
Jiang et al. also obtained Al2(SO4)3 modified kaolin with excellent ad-
sorption capacity and high selectivity to remove Pb(II) ions from synthetic
and plating factory wastewater.95 Compared with the parent clay, the sorp-
tion capacity of Al2(SO4)3 modified kaolin is almost 5-fold higher with a
Langmuir monolayer adsorption capacity of 32.2 mg g1. It could be that
modification of kaolin clay by aluminium sulfate octadecahydrate in this
study revealed that the modifying chemical did not impregnate the clay in-
terior, but might exist on the outer surface and provide more available ex-
change sites for enhanced adsorption. During activation of clays/clay
minerals with inorganic acids, the exchangeable cations are substituted by
protons and part of the octahedral cations (mainly Al31) dissolve, creating
new acid centres in the solid structure and making them amorphous, more
porous and acidic. Furthermore, the acid treatment method is eective for
minimizing the possible decomposition of the crystalline structure, thus
generating the desired features for further thermal activation of clay ma-
terials to prepare an eective adsorbent towards heavy metals.
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 229
also has value for the elimination of lead ions from water in the study by
Mana et al.98 The SBE, after being thermally treated at a mild temperature
(100 1C) following NaOH impregnation treatment to form SBTE material,
exhibited a significantly higher sorption capacity than those of virgin
bleaching earth and pristine SBE, as well as faster kinetics uptake at the same
metal concentration. Modification of bentonite using phosphate and sulfate
anion salts has been carried out by Olu-Owolabi and Unuabonah.99 Although
the modification process causes the specific surface area of bentonite clays to
decrease due to blockading of the pores, the CEC, as well as adsorption
capacity towards bivalent zinc and copper ions, increased due to the presence
of more binding sites introduced from the physisorbed sulfate and chemi-
sorbed phosphate anions, in which the latter were preferentially adsorbed
onto the AlOH and AlH2O surface functional groups of bentonite clay.
Another ecient pathway to chemically tailoring the surface chemical
nature of clays and clay minerals is through chemical conditioning. Chem-
ical conditioning is a technique with the aim of removing certain ex-
changeable cations from the clay layers and locating more easily removable
ones that are more willing to undergo ion-exchange processes. Lihareva et al.
studied the behaviour of natural and sodium-loaded clinoptilolite as a cation
exchanger of monovalent silver ions.100 The Na form of clinoptilolite showed
11:26:35.
an improved ability for cation exchange of Ag1 ions due to the more
monoionic character of modified clay from the replacement of K1, Ca21 and
Mg21 interlayer cations. The introduced exchangeable Na1 cations from the
conditioning treatment help to increase the exchange performance to
remove Ag1 ions.
Similar work dealing with chemical conditioning of clinoptilolite using
NaCl and HCl solutions has been conducted by Coruh for the removal of zinc
ions.101 They found that the conditioned clays, irrespective of the types of
chemicals, exhibit higher eective ion-exchange capacity due to lower Si to Al
ratios. Chemical conditioning with saturated NaCl solution resulted in the
exchange of tightly bound K1 and Ca21 cations from the zeolitic lattice and
removal of fine dust particles, making the channel apertures more easily
accessible for incoming metal cations. Pretreatment of clinoptilolite with four
dierent chemicals, namely NaCl, KCl, HCl and CaCl2 has been carried out by
Gedik and Imamoglu.102 The results of this study reveal that pretreatment
with NaCl can be adopted as an ecient way to obtain the monoionic form of
clinoptilolite, which shows more than 2-fold enhancement in the metal re-
moval capacity compared with that of the as-received form.
Alkaline Ca-bentonite (ACB) was utilized in the study by Zhang et al. by
treating raw bentonite clay with calcium hydroxide as a cheap sorbent to
remove zinc(II) ions.103 The ACB sorbent displayed a monolayer sorption
capacity 2-times greater than raw bentonite and a more eective
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230 Chapter 11
The adsorbed Zn21 ions were found to intercalate between the clay layers,
causing structural changes and generation of micropores in the sorbent wall.
In another work, Dimirkou conditioned natural clinoptilolite using an
Fe(NO3)3 solution under strong basic conditions to prepare a fully iron ex-
changed form of clinoptilolite, designated as a Clin-Fe-oxide system.104 The
hardness as well as the concentrations of alkali and alkali earth metal cat-
ions of the Clin-Fe-oxide system dramatically dropped after Fe conditioning,
nevertheless the Si to Al ratio of the clay system remained intact compared
with the respective ratio of the parent clay. The synthesized Clin-Fe-oxide
system contains high iron concentrations, exceeding the practical and the-
oretical cation-exchange capacity of the parent clay, characterizing the over-
exchanged feature. The non-crystalline iron clusters (as FeOH) deposited
in the zeolite channels and on the external sites give rise to the Clin-Fe
system higher specific surface area as well as extra-framework positions for
Zn(II)-exchange through outer-sphere complexation.
Abu-Eishah synthesized a chemically modified local clay (termed Sarooj
clay) by saturating the solid phase with 0.01 M NaNO3 solution.105 The Na-
saturated clay was employed to sorb three heavy metal ions, namely Zn21,
Cd21 and Pb21, and showed an eective performance due to its higher
surface properties, including BET surface area, specific micropore surface
11:26:35.
area, external surface area and total pore volume. During chemical treat-
ment, more than half of the interlayer Ca21 cations were exchanged with
Na1 ions, while other metal cations (in the oxide forms) such as Al2O3,
Fe2O3, MgO and K2O were increased. From several of the previous studies
discussed earlier, it can be concluded that the final monoionic and near-
monoionic nature of the clays was found to enhance their eective exchange
capacity and performance in ion-exchange applications, including heavy
metals sorption. Recently, surface modification processes of clays and clay
minerals have been switched to pillaring, grafting or intercalation techni-
ques because they are simpler, and provide cost and energy savings.
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 231
bromide (CTAB), lauryl alkyl sulfate (LAS), sodium dodecyl sulfate (SDS),
cetylpyridinium bromide (CPBr), tetramethylammonium bromide (TMAB),
phenyl trimethylammonium bromide (PTMAB) and hexadecyltrimethyl
ammonium (HDTMA)], metal salts that are Lewis acids (e.g., FeSO4, NaNO3,
NaCl and ZnCl2), amino acids or polypeptides, chelating agents (e.g., chit-
osan, chitin, citric acid, succinic acid and organosilanes) and metallic/
composite oxides (e.g., Al2O3, Fe2O3, Fe3O4, TiO2, ZnO, MnO2, SiO2 and
MnFe2O4).
Nowadays, pillared clays (PILCs) have become a well-known class of por-
ous materials with properties exceeding those of zeolitic clays. The pillaring
of clays and clay minerals involves intercalation of bulky inorganic and or-
ganic clusters, such as polynuclear complex inorganic ligands (e.g., hydroxo
and chloro ligands), large metal complex ions with organic ligands and
polyhydroxy cations (e.g., AlCl3 6H2O, ZrOCl2 8H2O and hydroxyl zir-
conium) to exchange interlayer cations. Upon high-temperature treatment
(calcination), the intercalated polyoxycations convert into their metal oxide
forms, which expand the internal pores and create a solid with a stable two-
dimensional microporous structure and large surface area. Some important
factors in the clay pillarings include the size and amount of pillars and their
configuration in the interlayer space, which are highly sensitive to the clay
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characteristics (e.g., the layer charge and its location) and hydrolysis con-
ditions under which the polyoxycations are formed.108,109 The resulting
pillared clays also inherit properties specific to the chemical nature of the
pillaring species, in addition to their improved permanent porosity.
Karamanis et al. studied the application of Al-pillared montmorillonite for
the fast uptake of strontium and caesium ions from aqueous solutions.110 In
the study of Bhattacharyya and Gupta,111 kaolinite and montmorillonite
pillared with polyoxo-Zr ions were used for the removal of Fe(III), Co(II) and
Ni(II) ions in single batch systems. After the pillaring and calcination pro-
cesses, the exchange capacity of clays substantially fell due to dehydroxyla-
tion and interlayering of positively charged cations. Accordingly, the
sorption capacity of pillared clays was lower compared with the parent clays,
possibly due to the blockade of negatively charged adsorption sites and
probably some pore networks by bulky polyoxycations.
The surface modification of clays and clay minerals with cationic sur-
factants involves both a cation-exchange process and the bonding of a
hydrophobic moiety in the clay layers. In this regard, the concentration of
the loaded surfactant crucially determines the types of adsorptive layer
formed. Cationic surfactants can form two types of adsorptive layers:
monolayers and bilayer/patchy bilayers.112,113 At low loading levels, sur-
factant cations eventually create an adsorptive monolayer, while at higher
loading levels, the formation of a bilayer, patchy bilayer or bilayer with a
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232 Chapter 11
parts of the surface pores and negatively charged sites by bulky ammonium
cations. The intercalation of Algerian halloysites with saturated sodium
acetate solution has been conducted by Mellouk et al.118 In their study, the
intercalation process causes the basal spacing of halloysite to increase from
7.6 to 10.1 and the specific surface area from 58 to 884 m2 g1, of which the
increase in basal spacing was found to be unaected with an increase in
contact time during the modification process. The CH3COONa intercalated
halloysite was used thereafter for removing Cu21 ions and shows a max-
imum uptake capacity of 52.3 mg g1.
Silane coupling agents are a family of organosilicon monomers with the
general structure of RSiX3 where R and X refer to the organo-functional
group attached to silicon and hydrolysable alkoxy groups are typically
methoxy (OCH3) or ethoxy (OC2H5), respectively.119 This coupling agent
has found many applications related to uses involving site-specific inter-
actions because of its capability of providing chemical bonding between an
organic and an inorganic material. In the case of surface modification of
clays/clay minerals, the organosilanes (e.g., organosiloxanes and organo-
chlorosilanes) are attached to the clay edge sites through condensation re-
actions between surface hydroxyl groups (SiOH or AlOH) and the
chloro or alkoxy groups of the organosilane.120122 Dogan et al. functiona-
lized sepiolite with [3-(2-aminoethylamino)propyl]trimethoxysilane for the
preconcentration of six metal ions from aqueous solutions namely Co21,
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 233
21 21 21 31 21 123
Cu , Mn , Zn , Fe and Cd . The functionalized material was
characterized using FT-IR, XRD and zeta potential measurements to investi-
gate its surface and electrokinetic properties. It was revealed from their study
that the anchored pendant chains contain basic nitrogen active sites that
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facilitate the uptake of metal ions. The intercalated clays exhibit dierent
sorption characteristics, including higher selectivity and sorption capacity.
A low cost chemical sensor for detecting various toxic heavy metals
was prepared from sepiolite grafted with 3-aminopropyltriethoxysilane
(3-APT).106 The grafted sepiolite clays acquire basic amino centres that are
favourable for retaining more metal cations. The specific adsorption of
metal cations onto the grafted sepiolite imparts more positive charges and
shifts the isoelectric point (iep) of the modified clay to higher pH. The fol-
lowing sequence of metal adsorptivity onto the grafted sepiolite surface
(Fe4Mn4Co4Cd4Zn4Cu4Ni) may reflect that basic amino centres
preferentially sorb hard cations such as iron and manganese.
Three dierent intercalation methods of montmorillonite with aluminium
hydroxypolycation and cetyltrimethylammonium bromide (CTAB) have been
performed by Hu and Luo.124 Based on the combined characterization
analyses, including X-ray diraction analysis, Fourier transform infrared and
zeta potential measurements, it was found that the modifying agent had
either entered the interlayer spaces or sorbed onto the external surface of the
clay. Furthermore, they also studied the intercalation orders of surfactant
agents for batch adsorption process of hexavalent chromium. Modification
of various clay minerals such as zeolite, bentonite, exfoliated vermiculite and
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234 Chapter 11
and 2.38 : 1, respectively. Modified bentonites have also proved their worth
for the remediation of water polluted by antimony ions from aqueous so-
lutions. Polyvinyl alcohol (PVA) modified kaolinite was also employed to
remove Pb21 ions in a two-stage counter-current batch adsorber design.128
Although PVA-modified kaolinite had lower specific surface area and ex-
change capacity, it showed higher adsorptivity toward Pb21 ions due to more
active sorption sites donated from the deprotonation of hydroxyl group of
PVA species. In another study, the functionalizing of 2 : 1 clay minerals (i.e.,
vermiculite and montmorillonite) with an amino acid [e.g., cysteine,
H2NCH(CH2SH)CO2H] has been undertaken by Malferrari et al.129 They de-
scribed the modification to the structure of clay minerals addressing the
sorption behaviour of Cd(II) ions onto both untreated and treated clays.
Chelating agents or natural polysaccharide materials have also now been
widely used to modify surface characteristics of clays, with the aim of ren-
dering the clay surface to be more hydrophobic or hydrophilic, at will, de-
pending on the chelating functionalities and, more importantly, to improve
the selectivity and sorption capacity of the sorbents towards specific metal
ions. Moreover, the incorporation of clays/clay minerals into polymeric
networks can strengthen the swelling properties, gel strength and reduce the
production costs of the corresponding adsorbents. Some common func-
11:26:35.
tionality inserted into the clays/clay minerals platelets are amine (NH2) and
hydroxyl (OH) groups. Natural polymer materials with high amino or hy-
droxyl contents have been found to possess good sorption capacity for many
heavy metal ions through surface complexation with these active surface
groups. Chitosan, a hydrophilic and cationic polymer product of chitin has
been used as a chelating agent of zeolite to prepare a chitosanzeolite
composite adsorbent with a weak basic nature.130 The optimum pH for Cu(II)
sorption using a chitosanzeolite composite was 3, when electrostatic ions
were sorbed onto the solid surface by forming electrostatic attractions.
Similar work employing chitosan to prepare a magnetically separable
composite adsorbent was taken by Chen et al.131 The composite adsorbent,
termed chitosanmontmorilloniteFe3O4 microspheres, showed a notable
maximum sorption capacity of 74.2 mg g1 towards Cr(VI) at low pH. In this
study, the separation of composite microspheres from metal solution after
the adsorption process was easily performed with the aid of an external
magnetic force. Natural Wyoming montmorillonite embedded with dierent
chelating functional groups (e.g., NH2, COOH, SH and CS2) from
ammonium organic derivatives was tested for the removal of Pb21, Cd21 and
Zn21 ions from aqueous solutions by Sathi et al.132 When compared with the
unmodified montmorillonite, the resulting organoclays showed considerable
improvement in terms of sorbing selectivity and metal loading capacity. The
insertion of four guest organic functionalities into the lamellar space of clay
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Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 235
chelating agent to remove copper ions from spiked natural water and granite
samples.133 The intercalated clay possessed good chemical tolerance in acids,
bases and common ionic species such as Na1, K1, Ca21, Cl or SO42 as well
as good removal eciency towards Cu(II) ions (119 meq per 100 g) at pH 6.
They also found that the grafted MMT-clay also found potential application
for the treatment of real contaminated euent.
The possibility to use natural chitinbentonite biocomposites for re-
moving toxic chromium(VI) ions in batch mode was conducted by Saravanan
et al.134 The results showed that the prepared biocomposite materials were
able to sorb more than 80% Cr(VI) ions at pH 4 with fast uptake in the initial
30 min and the sorption tends to slow after 45 min. From this study, one can
conclude that the negatively charged nitrogen or oxygen ligands of chitin
macromolecules serve as ancillary sites that are responsible for chelating
higher amounts of metal ions.
The preparations of clays/clay minerals modified with metallic/composite
oxides have gained increasing awareness because they are specifically
functional for sorbing dierent heavy metal ions. The following are several
reasons for employing metal/composite oxides to modify clays/clay minerals:
(1) the surface groups of metal/composite are amphoteric in nature and can
function as an acid or a base, depending on the suspension pH; (2) metal/
11:26:35.
composite oxides have relatively high surface energy and reaction activity
stemming from the large specific surface area; and (3) favourable physical
and chemical properties such as swelling ability, stiness, catalytic, optical,
electronic and magnetic properties. Despite these advantages, most metallic/
composite oxides possess low durability and mechanical strength so they
often aggregate due to lack of dispersibility, which reduces the specific
surface area and eectiveness to sorb pollutants in aqueous suspensions.
The aggregated metal oxides also possess diculties in the separation
process after the metal sorption. To address this challenging issue, various
immobilization techniques are being developed for improving stability and
dispersibility of metal/composite oxides and one of the convenient, cost-
eective methods is by loading with clays and clay minerals as a support
material. Among the metal oxides, iron (Fe) oxides and manganese oxide are
the two most widely used because they have high anity towards metal ions,
large surface area and microporous structure. Clays/clay minerals pillared
with metal oxides exhibit superior structural and chemical properties, such
as high thermal stability, large surface area, intrinsic catalytic activity and
significant sorption capacity over a wide pH range. For example, kaolin
loaded nanoscale zero-valent iron, nZVI (sizeo100 nm), was synthesized
and tested in the removal process of Pb(II) ions from aqueous solution.135
Kaolin-loaded nZVI showed higher specific surface area than untreated
kaolin (26.11 m2 g1 versus 3.67 m2 g1), which may be ascribed to the kaolin
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236 Chapter 11
observation is in good agreement with the study by Uzum et al. for Cu(II) and
Co(II) removal using Turkey kaolinite-supported nZVI.136
According to the study carried out by Sari and Tuzen, the surface area of
MnO2-modified vermiculite increased about 10-fold from 0.84 to 8.42 m2 g1
after the modification process.137 The MnO2-modified vermiculite also
demonstrated higher sorption capacity than the parent vermiculite (46.2
versus 69.2 mg g1). The optimum concentration of MnO2 deposited onto
the clay surface ranged between 0.2 and 0.3 g g1 while at higher loading
concentrations, the adsorption eciency levels o due to obstructed
micropores, which reduced the number of active adsorption sites.
Manganese oxide coated zeolite has been tested for the removal of Mn21
ions in a batch adsorption system.138 The coating of manganese oxide on the
surface of zeolitic clay provides more available sites for the sorption of Mn(II)
ions at suspension pHs higher than the point of zero charge of the sorbent.
The MnO2 species bound on the zeolite surface (mainly as vernadite) are also
responsible for higher adsorption capacity compared to untreated zeolite for
removing metal ions, which might be ascribed to the increased anity of
MnO2 particles toward Mn21 ions in solution arising from specific equi-
librium reaction Mn21 MnO2 2 H2O22 MnOOH 2 H1. The interfacial
reactions of surface hydroxyl groups are also responsible for the enhanced
11:26:35.
sorption process of metal cations. Similar results were obtained by Eren for
the removal of copper ions using MnO2-modified bentonite.139 After modi-
fication, the maximum sorption capacity of raw bentonite was enhanced
significantly from 42.41 to 105.38 mg g1. Incorporation of manganese oxide
was evidence of increasing the specific surface area and the resultant surface
charge of raw bentonite giving rise to eective removal of Cu(II) ions.
In another study, the preparation of low-cost ceramisite consisting of three
raw materials, namely sintering bentonite, hematite powder (Fe2O3) and ac-
tivated carbon, and its adsorption performance towards zinc and lead metals,
has been tested by Yuan and Liu.140 The presence of fine hematite particles
on the outer surface of the ceramisite composite were found to react and
enhance the removal percentage while the increase of activated carbon dos-
age led to decreasing bulk density. The maximum removal capacity of cer-
amisite was found to be 17.5 mg g1 for Pb21 ions and 7.4 mg g1 for Zn21
ions at pH 5. Additionally, the chemical reaction between the hydroxyl group
and heavy metal ions occurred during metals removal, forming new pris-
matic and spherical crystalline grains containing Pb(II) and Zn(II), respect-
ively, that accumulated and piled up onto the surface of the adsorbent.
Therefore, it can be concluded that the incorporation of metal/composite
oxides enhances removal eciency due to the increase in the surface area
and negative surface charge associated with the formation of deprotonated
oxides on the sorbent surface.
View Online
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 237
Considering the sorption process of heavy metal ions onto the surface of
clays and clay minerals, some crucial information such as adsorption
equilibria, kinetics and thermodynamics are of great importance for reliable
prediction of adsorption parameters and behaviour, eective design of the
sorption system and optimization of the sorption mechanism pathways.
Given this, adsorption isotherms are invaluable for the adsorption studies
because they describe the equilibrium relationship of adsorbate concen-
tration in the bulk liquid phase (i.e., aqueous solution) and in the solid
phase (i.e., adsorbent surface) at a constant temperature and pH. Adsorption
equilibrium is established when an adsorbate-containing phase has been in
contact with the adsorbent for sucient time, with both the adsorption and
desorption rates being equal.141 This knowledge is not only indispensable
for the process design and optimization, but also in understanding the
adsorption kinetics and thermodynamics of single and multicomponent
systems. Typically, the mathematical models describing such phenomenon
are usually depicted by graphically expressing the solute concentration in
the solid phase (qe, mg g1 or mmol g1) against its residual concentration
in the liquid phase (Ce, mg L1 or mmol L1).
Over the years, a wide variety of empirical and semi-empirical adsorption
equations have been widely used to correlate experimental isotherm data of
11:26:35.
238 Chapter 11
1 1
sorption capacity for a given solid (qmax, mg g or mmol g ) or characterizes
the monolayer surface coverage. The essential characteristic of a Langmuir
equation can be characterized with a dimensionless equilibrium constant
called the separation factor (RL), as defined by Weber and Chakravorti:144
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00213
RL (1 KL C0)1 (11.5)
Various RL values indicate the types of adsorption to be unfavourable
(RL41), linear (RL 1), favourable (0oRLo1) or irreversible (RL 0). The
applications of this isotherm model have found reasonable success for
correlating various heavy metalclay sorption systems15,16,18,8998 with
favourable adsorption nature and can be implied as the platform and most
useful isotherm model for describing physical and chemical adsorption
phenomena, both in gas and liquid phases.
The Freundlich equation is another adsorption isotherm model that has
been frequently used to describe non-ideal and reversible adsorption phe-
nomena,145 specifically for complex solids with non-uniform distribution in
terms of adsorption energy and anity, such as activated carbons or mo-
lecular sieves. In this isotherm perspective, the amount of adsorbate re-
tained in the solid phase continually rises with increasing concentration in
the bulk solution, which means that infinite adsorption can take place
on the solid surface. Generally, a Freundlich isotherm gives accurate pre-
dictions in the intermediate range of adsorption equilibrium data, typically
at moderate solute concentrations. In some cases, the favourability of the
adsorption process can also be evaluated from the Freundlich empirical
11:26:35.
constant, called the intensity factor (nF), in which the characteristic of the
adsorption process is poor (nFo1), moderately dicult (1onFo2), feasible
(2onFo10) and approaching a rectangular or non-reversible isotherm when
nF value is larger than 10, respectively.143 However, this model is criticized
due to the lack of a fundamental thermodynamic basis and not approaching
Henrys law at the vanishing concentration and saturation adsorption limit at
high-end concentrations. The same as for the Langmuir isotherm model, the
successful applications of Freundlich isotherms have been reported in many
sorption studies involving heavy metal ions and clays/clay minerals, apart
from the limitation and lack of fundamental thermodynamics in this model.
In the past few years, much eort has been paid to formulating various
empirical or semi-empirical adsorption equations, either to overcome some
drawbacks in the predecessor equations (e.g., Langmuir and Freundlich
equations) or to propose new adsorption models featuring adequate fun-
damental kinetics and thermodynamics as well as satisfactory agreement
over a wide range of concentrations. Some examples are Hill, Temkin, Flory
Huggins, DubininRadushkevich, LangmuirFreundlich or Sips, Toth,
RedlichPeterson and BrunauerEmmettTeller adsorption equations.146
Table 11.5 presents several studies with successful applications of the two-
parameter or three-parameter adsorption equations mentioned here for
describing liquid phase adsorption behaviour for heavy metalclays/clay
mineral systems.
Published on 16 September 2014 on http://pubs.rsc.org |
Table 11.5 Several two-parameter and three-parameter isotherm models used for liquid phase heavy metals adsorption equilibria
correlation.
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal
Isotherm models Mathematical form Adsorption parameters Systems References
Langmuir KL Ce qm maximum adsorption Sarooj clay Zn(II) 105
qe qm
1 KL Ce capacity (mg g1 or Sarooj clay Cd(II)
mmol g1) Sarooj clay Pb(II)
KL Langmuir adsorption VSco Ni(II) 72
anity (L mg1 or VPum Ni(II)
L mmol1)
11:26:35.
Kaolinite Cu(II) 89
CPBr/bentonite Cr(VI) 114
CPBr/bentonite Mo(VI)
TBA/kaolinite Co(II) 117
TBA/montmorillonite
Co(II)
Smectite Pb(II) 97
Clinoptilolite Zn(II) 101
Functionalized sepiolite 123
Co(II)
Functionalized sepiolite
Mn(II)
Tunisian clay Pb(II) 94
Na-exchanged 100
clinoptilolite Ag(I)
Spent bleaching earth 98
Pb(II)
Halloysite Cu(II) 118
Attalpugite Cr(VI) 125
Diatomite Th(IV) 91
Chitosan/zeolite Cu(II) 130
MnO2-coated zeolite 138
Mn(II)
Chitosan/montmorillonite 131
Cr(VI)
239
Organo montmorillonite 126
Cr(VI)
Published on 16 September 2014 on http://pubs.rsc.org |
240
Isotherm models Mathematical form Adsorption parameters Systems References
Alkaline Ca-bentonite Zn(II) 103
Polyvinyl-modified kaolin 128
Pb(II)
Expanded perlite Hg(II) 70
Palygorskite Pb(II) 69
Organobentonite Cr(VI) 127
11:26:35.
Freundlich 1=n
qe KF Ce KF Freundlich adsorption Bentonite U(VI) 27
anity (mg g1)(L mg1)1/n Clinoptilolite Zn(II) 101
or (mmol g1)(L mmol1)1/n Na-exchanged 100
clinoptilolite Ag(I)
n dimensionless intensity Spent bleaching earth Pb(II) 98
factor characterizing the Halloysite Cu(II) 118
surface heterogeneity degree Attalpugite Cr(VI) 125
Diatomite Th(IV) 91
Chitosan/zeolite Cu(II) 130
MnO2-coated zeolite Mn(II) 138
Chitosan/montmorillonite 131
Cr(VI)
Organo montmorillonite 126
Cr(VI)
Alkaline Ca-bentonite Zn(II) 103
Chitin/bentonite Cr(VI) 134
Palygorskite Cd(II) 90
Boron-containing clay Ni(II) 84
Kaolinite Cu(II) 89
Dubinin qe qm exp(be2) qm the maximum Organo montmorillonite 126
Radushkevich (DR) adsorption capacity Cr(VI)
(mg g1 or mmol g1) Diatomite Th(IV) 91
Chapter 11
b the Dubinin Attalpugite Cr(VI) 125
Radushkevich constant of Sepiolite U(VI) 96
adsorption energy (mol2 Perlite Pb (II)
kJ2) Dolomite Pb(II)
Published on 16 September 2014 on http://pubs.rsc.org |
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal
e the Dubinin Unye clay Cu(II) 67
Radushkevich constant of 139
the Polanyi potential, with
e equal to RTln[1/(1 Ce)]
RedlichPeterson (RP) K1 Ce K1, K2 RedlichPeterson Chitosan/zeolite Cu(II) 130
qe
1 K2 Ceb isotherm constants, in Halloysite Cu(II) 118
(mg g1) or (mmol g1) and Organo montmorillonite 126
(mg g1)b or (mmol g1)b Cr(VI)
11:26:35.
b RedlichPeterson
isotherm exponent which
lies between 0 and 1
Temkin RT RT A Temkin isotherm constant Organo montmorillonite 126
qe ln A ln Ce
b b of adsorption anity Cr(VI)
(L mg1 or L mmol1) Diatomite Th(IV) 91
b Temkin isotherm constant
of heat of sorption
(kJ mol1)
FloryHuggins (FH) Y KFH FloryHuggins Diatomite Th(IV) 91
log ln KFH adsorption equilibrium
Ci
constant
nFH log1 Y nFH the FloryHuggins
model exponent
Y the degree of surface
coverage, expresses as
1 Ce/Ci
Elovich qe qe KE Elovich adsorption Organo montmorillonite 126
ln lnKe qm equilibrium constant Cr(VI)
Ce qm
(L mg1 or L mmol1)
qm the maximum
adsorption capacity
(mg g1 or mmol g1)
241
View Online
242 Chapter 11
the liquid contained in the pores of the solid particles and along the pore
walls (intraparticle diusion); and (4) adsorption and desorption of solute on/
from the solid surface. In this context, some extensively used mathematical
models for describing the kinetics of sorption for a particular system are
pseudo-first order (Lagergren), pseudo-second order, intraparticle diusion
and the Elovich equations. These formulae have usually been associated with
surface reaction kinetics as the rate-controlling step and oer some advan-
tages, such as compactness and simplicity with few computer resources re-
quired to solve the rate equations. The common procedure used to verify
whether the best kinetic models are suitable to fit experimental data is
through best-fit either using linear or non-linear regression techniques.
11.5 Conclusions
Clays and clay minerals are promising low-cost materials for the cost-eec-
tive and ecient remediation of synthetic and real waste euents con-
taminated by toxic heavy metal ions. Considering several previous studies
dealing with the adsorption of heavy metal ions using clays and clay min-
erals, the following conclusions can be deduced:
a. The layer characteristics with structural negative charge and the sur-
face chemical nature of natural clays and clay minerals are both
View Online
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 243
References
1. M. A. M. Abdallah, Bull. Environ. Contam. Toxicol., 2013, 90, 552.
2. N. Calace, D. A. Nardi, E. Petronio and M. B. Pictroletti, Ind. Eng. Chem.
Res., 2002, 41, 5491.
3. J. W. Patterson and R. Passino, Metals Speciation Separation and Re-
covery, Lewis Publishers, Chelsea, MA, USA, 1987.
4. B. M. W. P. K. Amarasinghe and R. A. Williams, Chem. Eng. J., 2007,
32, 299.
5. Agency for Toxic Substances & Disease Registry (ATSDR), Priority List
of Hazardous Substances, http://www.atsdr.cdc.gov/SPL/index.html
(accessed 16 June 2013).
6. US Environmental Protection Agency, The Comprehensive Environmental
Response, Compensation, and Liability Act (CERCLA), USEPA, Washing-
ton, 2011, http://www.epa.gov/superfund/policy/cercla.htm (accessed
20 May 2013).
7. O. B. Akpor and M. Muchie, Int. J. Phys. Sci., 2010, 5, 1807.
8. G. Rich and K. Cherry, Hazardous Waste Treatment Technologies, Pudvan
Publishers, New York, 1987.
9. K. Kadirvelu and J. Goel, Eco-Friendly Technologies for Removal of
Hazardous Heavy Metal from Water and Industrial Wastewater, in
Hazardous Materials and Wastewater: Treatment, Removal and Analysis,
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244 Chapter 11
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 245
36. K. S. Low, C. K. Lee and T. S. Lee, Environ. Technol., 2003, 24, 197.
37. O. Abollino, M. Aceto, M. Malandrino, C. Sarzanini and E. Mentasti,
Water Res., 2003, 37, 1619.
38. N. Y. Dho and S. R. Lee, Environ. Monit. Assess., 2003, 83, 177.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00213
246 Chapter 11
Natural Clays/Clay Minerals and Modified Forms for Heavy Metals Removal 247
91. S. Yusan, C. Gok, S. Erenturk and S. Aytas, Appl. Clay Sci., 2012,
6768, 106.
92. G. A. Mills, J. Holmes and E. B. Cornelius, J. Phys. Chem., 1950, 54, 1170.
93. A. K. Panda, B. G. Mishra, D. K. Mishra and R. K. Singh, Colloids Surf. A,
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00213
248 Chapter 11
CHAPTER 12
12.1 Introduction
The tanning process aims to transform skins into stable and imputrescible
products, namely leather.1 Production of leather can be performed by both
vegetable and chrome tanning. The vast majority of leather production relies
on chromium(III) based tanning processes, nevertheless leather production
based on vegetable tanning (VT) is utilized extensively by traditional tan-
neries in developing countries.2 Chrome-tanned leather tends to be softer
and more pliable than vegetable-tanned, has higher thermal stability, is very
stable in water and takes less time to produce than vegetable-tanned leather.
Almost all leather made from lighter-weight cattle hides and from the skin of
249
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250 Chapter 12
sheep, lambs, goats and pigs is chrome tanned. The first steps of the process
(soaking, fleshing, liming/dehairing, deliming, bating and pickling) and the
drying/finishing steps are essentially the same as in vegetable tanning.
However, in chrome tanning, the additional processes of re-tanning, dyeing
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00249
and fat liquoring are usually performed to produce usable leathers, and a
preliminary degreasing step may be necessary when using animal skins,
such as sheepskin. A re-tanning bath procedure applied for production of
clothes in one of main industrial Italian leather districts is shown in
Figure 12.1.
When the chromium salts are used as tannage, only 60% of the total
chromium reacts with the hides and about 40% of the chromium remains in
the solid waste and spent tanning solutions. The tanning wastewaters con-
tain the highest concentration of total chromium (up to 4950 mg L1). Al-
though the leather tanning industry is known to be one of the leading
economic sectors in many countries, there has been an increasing en-
vironmental concern regarding the release of various recalcitrant pollutants
and metals in tannery wastewater and sludge.1 Now, as ever, its future de-
pends on the challenge of making the process environmentally friendly and
recovering primary resources.
Figure 12.1 A re-tanning bath procedure applied for production of clothes; percent-
ages are for 100 g of leather product, which proceeds in the tumbler (6 l
of water are used for production of 12 kg raw pre-pickled leather (600%
of water for 100% of leather) (reprinted from Lofrano et al.3 with kind
permission of Taylor and Francis).
252
Table 12.1 Characteristics of tannery wastewater (mg L1)a (reprinted from Lofrano et al.1 with kind permission of Elsevier; data has been
compiled from references6,19,3955).
pH COD BOD5 TSS TS SS TDS Alk. Chloride Sulfate Sulfide NH4-N Phosph. Cr Iron
11:26:38.
Chapter 12
total dissolved solids; Phosph., phosphorus.
View Online
12.2.2.1 Wastewater
Removal of metals from tannery wastewater is achieved by the application of
several processes, such as chemically assisted sedimentation,8,9 coagulation/
flocculation,10 electrochemical processes,11,12 ion exchange,13 ad-
sorption,1417 filtration and membrane processes7 and their combinations.18
The coagulationflocculation (CF) process, generally using inorganic co-
agulants such as aluminium sulfate (alum), ferric chloride (FeCl3) or ferrous
sulfate (FeSO4), has been applied to leather tanning wastewater to reduce the
organic load and suspended solids in addition to removing chromium be-
fore biological treatment. Ates et al.19 investigated the eectiveness of alum
and FeCl3 based CF for the treatment of a homogenized inlet of a central
treatment plant in a leather tanneries district. All experiments resulted in
470% of COD removal. Total chromium was also eectively (o5 mg L1)
removed by the alum, while it was almost completely removed using FeCl3,
as seen in Figure 12.2.
Kabdasli et al.20 also reported 4070% removal of COD and 499% of total
chromium from leather tanning wastewater using FeSO4, FeCl3 and alum.
According to Song et al.10 7499% removal of chromium with an initial
concentration of 12 mg L1 can be achieved by using the optimum coagulant
11:26:38.
dosage (FeCl3 800 mg L1) in the optimum pH range (around 7.5). The initial
chromium concentrations and pH values of the wastewater have a great ef-
fect on the chromium removal eciency. Low chromium concentrations and
high pH produce a more eective result for chromium removal than high
chromium concentrations and low pH. Higher dosages do not significantly
increase pollutant removal and are not economical.
Among the various adsorbents, bentonite clay has been found to be
eective in the removal of chromium from tannery wastewater by Tahir and
Naseem.16 Natural materials that are available in large quantities or certain
10000 1000
[mg L-1]
[mg L-1]
5000 10
0 0.1
A B C D A B C D
COD in Cr in
Figure 12.2 The chemical settling of a homogenized raw wastewater from a central-
ized leather tanning district: A, alum polyelectrolyte (600 2) mg L1;
B, alum polyelectrolyte (400 2) mg L1; C, FeCl3 polyelectrolyte
(1000 2) mg L1; D, FeCl3 polyelectrolyte (750 2) mg L1 (data
from Ates et al.19).
View Online
254 Chapter 12
et al.17
The selection of the best treatment options needs to take into account
discharge limits. To this eect, Table 12.2 provides a comparison between
the legal discharge limits for Cr(III) adopted in several countries.
Chromium recovery from tanning exhausted baths represents a significant
economic advantage for the leather industry in terms of its reuse and for the
simplification of the polishing process of global wastewaters. The exhausted
baths from chromium tanning contains about 30% of the initial salt and it is
normally sent to a clean-up plant. The traditional method for chromium
recovery is based on the precipitation of the chromium salt with NaOH
followed by the dissolution of Cr(OH)3 in sulfuric acid. However, the quality
of the recovered solutions is not always optimal with respect to the presence
of metals, lipidic substances and other impurities. Therefore in recent years
membrane technology has become increasingly attractive for chrome re-
covery and recycling. The main advantage of a membrane process is that
concentration and separation are achieved without changing the physical
state or the need to use chemical products. Crossflow microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and supported
liquid membranes (SLMs) can be applied in the leather industry for the
recovery of chromium from spent liquors. The application of these mem-
11:26:38.
brane systems (MF, NF, UF and RO) and dual schemes MFUF, UFNF and
NFRO for the treatment of tannery wastes and for the recovery of chromium
and other chemicals has been experimentally investigated by several
12.2.2.2 Sludge
The management of mixed physico-chemical and biological tannery slud-
ges pose a serious environmental concern and a health risk for humans.
Thermal incineration is considered as the cheapest alternative and the
most attractive method because of its simultaneous energy production and
volume reduction of the sludge. However, special attention is required with
respect to issues such as release of toxic chromium(VI), halogenated organic
compounds, polyaromatic hydrocarbons, etc., into the environment. The
high concentration of heavy metals (Cu, Cr, Zn and Pb) causes chronic air
pollution.23 The major species formed from Cr(III) during thermal in-
cineration of solid waste are Cr2(SO4)3(s), CrOCl2(g) and Cr2O3(s), which
subsequently account for a path to the formation of Cr(VI). Sludge com-
position and oxygen concentration in the incinerator determine the extent
of conversion of Cr31 to Cr61. Attempts have been made to inhibit the
formation of these species under a supply of a reduced oxygen atmos-
phere.24 However, in this case bottom-ash containing toxic heavy metals
and partially burnt carbon, which need to be carefully managed, are also
produced. An eective solidification and stabilization of bottom-ash has
been resorted to in order to change potentially hazardous solid wastes into
11:26:38.
256 Chapter 12
Figure 12.3 Populations estimates are preliminary and based on an on-going global
assessment of known polluted sites.33
Estimated
Number of sites in impacted
Country Blacksmith database33 population
South Asia 62 1 147 400
Central America 3 310 500
South America 11 205 000
Africa 9 143 000
12.3.2 Phytotoxicity
When present in small amounts, the metals that accumulate in tannery
sludge, Cr, Cd, Cu, Pb and Zn, may be essential for plant growth; however, in
higher concentrations they are likely to have a detrimental eect. The ac-
cumulation of heavy metals in vegetables resulting from irrigation with
contaminated water obtained from industrial euents may create a poten-
tial public health risk.
Chromium (Cr) naturally occurs in rocks, soils and plants. Owing to its low
solubility, only a little chromium is bioavailable. As a consequence crops
grown on soils treated with sludge relatively high in Cr rarely show any
phytotoxicity eect. Zinc (Zn) is essential for plants and animals. A Zn tissue
concentration of less than 15 mg kg1 (dry weight) leaves a plant deficient,
whereas a concentration over 400 mg kg1 (dry weight) is potentially
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258 Chapter 12
34
phytotoxic. The tolerance of animals to Zn strictly depends by the presence
of Cu, Mn, Fe, Pb and Cd. Zinc can be accumulated in plants tissues, which
can be used for human consumption. However, its toxicity in plants occurs
before reaching the level that is harmful to humans who ingest the plant.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00249
References
1. G. Lofrano, S. Meri, G. E. Zengin and D. Orhon, Sci. Total Environ., 2013,
461462, 265281.
View Online
260 Chapter 12
http://www.docstoc.com/docs/118305556/pollution-report-2011-top-ten-
wwpp (accessed 21 May 2014).
34. E. Epstein, The Science of Composting, Technomic Publishing Company,
Lancaster, PA, 1997.
35. M. Ahmed, A. Idris and S. R. S. Omer, Malaysian J. Anal. Sci., 2007, 11,
340350.
36. G. Lofrano, S. Meri, V. Belgiorno and R. M. A. Napoli, Desalination,
2007, 211, 1021.
37. A. Cassano, R. Molinari and E. Drioli, Water Sci. Technol., 1999, 40, 443450.
38. A. Cassano, J. Adzet, R. Molinari, M. G. Buonomenna, J. Roig and
E. Drioli, Water Res., 2003, 37, 24262434.
39. B. Ram, P. K. Bajpai and H. K. Parwana, Process Biochem., 1999, 35, 255265.
40. D. Orhon, E. Ates and S. Sozen, Water SA, 2000, 26, 4345.
41. Z. Song, C. J. Williams and G. J. Edyvean, Water Res., 2000, 34, 2171
2176.
42. T. L. P. Dantas, H. J. Jose and R. F. P. M. Moreira, Acta Sci. Technol., 2003,
25, 9195.
43. Y. N. Koteswari and R. Ramanibai, Turk. J. Biol., 2003, 27, 163170.
44. M. Cotman, Z. Koncan and A. Gotvajn, Water Sci. Technol., 2004, 49, 3946.
45. M. Thanigavel, Biodegradation of tannery euent in fluidized bed
11:26:38.
CHAPTER 13
*Email: cchrist@chem.auth.gr
261
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262 Chapter 13
deep bedrock groundwater of South Korea and reported that the median
fluoride concentration in groundwater is related to the mineral composition
of granitoids, metamorphic and complex rocks, where the basic minerals are
biotites and the granite intrudes into deeper parts of the aquifer.4,5 Sedi-
mentary rocks have a fluorine concentration of 200 mg L1 (limestone) up to
1000 mg L1 (shales). In carbonate sedimentary rocks the fluorine is present
as fluorite. Clastic sediments have higher fluorine concentrations as the
fluorine is concentrated in micas and illites in the clay fractions. High
concentrations may also be found in sedimentary phosphate beds (shark
teeth) or volcanic ash layers.
In general, groundwater contains higher fluoride concentrations than
surface water due to higher contact times with fluoride-bearing minerals
in rockwater interactions.2,5 These types of groundwater formations are
usually associated with deep aquifer systems and a slow groundwater
movement. Shallow aquifers, which contain recently infiltrated rainwater,
usually have low fluoride concentrations. Exceptions can occur in shallow
aquifers situated in active volcanic areas aected by hydrothermal
alteration.
Volcanic activity constitutes the second and most persistent source of
fluorides. Volcanic aerosols and ash, emitted during eruptions, are crucial
factors for the enrichment of the fluoride content in drinking waters.
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Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 263
264 Chapter 13
Table 13.1 Manufactured chemicals containing fluoride, their use and sources.
Chemical Use Source
Hydrogen fluoride Synthetic cryolite Calcium fluoride
(HF) Aluminium fluoride (AlF3) (CaF2)
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 265
The use of fluorides for dental health reasons has been a controversial
issue. Fluoridation of drinking water was introduced after early studies on
the link between caries and low fluoride water content. Today around 10%
of the population in Britain is supplied with fluorinated water.5 As of
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
Acute Toxicity. Acute oral exposure to fluoride may produce eects in-
cluding nausea, vomiting, abdominal pain, diarrhoea, fatigue, drowsiness,
coma, convulsions, cardiac arrest and death. Also, it has been reported
that exposure through dermal contact to hydrofluoric acid can cause
Published on 16 September 2014 on http://pubs.rsc.org |
266
Table 13.2 Major compounds chemical composition in mg L1 of dierent types of waters.
Reference ID pH F HCO3 Cl SO42 Na NH41 Mg Ca Al As
72 Drinking water 6.59.5 1.5 250 250 200 0.5 0.2 0.01
maximum
permissible levels
bdla
11:26:40.
49, 50 Far from the 5.7 bdl 0.33 1.12 1.08 0.27 0.14 1.18 0.003 bdl
Nyamuragira volcano
area
Near the Nyamuragira 4.2 8.3 25.3 15.8 6.6 3.4 3.3 12.6 2.66 0.0019
volcano area
20, 41 Geothermal waters 1.67.52 3.3648.6 bdl232 2.86802 21.63490 310576 bdl86.6 bdl9.12 0.86736.8 0.1681.6 0.003714.6
47 Kolar District (drinking 6.297.91 0.363.34 156634 26462 15153 18369 10.783 30254
water)
Tumkur District 6.678.33 0.785.35 157869 18582 15206 26350 4.894 15.2248
(drinking water)
73 Natural spring water, 5.68.2 0.0060.9 0.1540 135.9 0.0430 bdl 0.01217.4 0.4897.1 bdl0.38 bdl0.01
Turkey
Natural mineral water, 5.37.9 0.031.52 7.3760 bdl702 1.611770 bdl0.44 9.24447 46420 bdl2.5 bdl0.01
Turkey
Drinking water, Turkey 6.08.2 bdl1.0 10.773.8 2.431 7.350 bdl 0.98.5 625 bdl0.05 bdl0.001
Processed drinking 5.88.0 bdl0.7 2.914 2.315.2 bdl 0.0486 0.98.2
water, Turkey
39 Na-HCO3 water sample 8.29.1 0.88.2 337484 3.512.6 13213 109298 0.52.1 0.82.4 4.07.5 bdl0.0015
type
Ca-Na-Mg-SO4-HCO3 6.77.6 0.42.9 173571 4.174.4 144512 44.1173 bdl3.1 9.482.1 6.6217 bdl0.00006
water sample type
Ca-HCO3 water sample 7.07.7 0.20.4 261462 2.616.4 37.0129 9.780.6 bdl0.6 9.222 79.0153 bdl0.0013
type
55 Groundwater 7.318.85 0.512.0 460913 28.6369 35.4602 235687 3.962.9 3.250.4 bdl0.25
74 Nanital District 5.98.1 0.010.66 2.213 2.5140 1.214 7.750 17120
Chapter 13
(drinking water)
a
bdl: below detection limit.
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Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 267
severe tissue damage, respiratory eects, cardiac arrest and death. In-
gestion of toxic amounts of fluoride may result in gastrointestinal eects
due to the corrosive action of the HF produced within the acidic environ-
ment of the stomach.21,22 Toxicity levels dier according to the fluoride
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
1.5 mg L1 for fluorides in drinking water. The limit must be lowered to
1 mg L1 for fluorides in areas with a warm climate due to higher water
consumption.
The US Environmental Protection Agency (USEPA)23 has set the primary
standard (enforceable limit) at 4 mg L1 for fluoride in drinking water,
although the secondary standard (non-enforceable) for the United States
drinking water is 2 mg L1. In countries with special fluoride problems
and high occurrence in the drinking water supply, higher standards have
been implemented (8 mg L1) reflecting the problems and diculties to
eectively remove the higher fluoride content, complying with WHO
guidelines. It is estimated (not accurately) that more than 200 million
people consume water with fluoride content higher than the established
WHO guidelines.2
268 Chapter 13
Algae and Aquatic Plants. According to Camargo,14 fluoride can aect ei-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
also on ionic fluoride species. It was additionally found that the soil type
can have a great eect on the uptake rates and the toxicity potential of
fluorides.
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 269
3436
epithelium. It has been reported also that high fluoride concentrations
can delay the hatching of fertilized fish eggs.37,38
vertebrates varies greatly among dierent species. Some species are not af-
fected living in or feeding on a fluoride-rich environment, while others are
aected in various ways, such as excessive egg production, growth and co-
coon building inhibition. Herbivorous animals accumulate fluorine in the
form of fluoroapatite to their skeleton either through direct ingestion par-
ticulates (e.g., volcanic ash) deposited over grass or by feeding on fluoride
rich vegetation. Thus, carnivores will not accumulate fluoride through
their feed.11 Another fluoride source for animals is contaminated water.
Symptoms of toxicity include emaciation, stiness of joints, abnormal
teeth and bones, decreased milk production and detrimental eects on
the reproductive capacity of animals.2
present such as certain clay minerals, illite, chlorite, smectite and also or-
ganic matter. For this reason, igneous (such as granites, gneisses and bas-
alts), volcanic rocks and sedimentary rocks (such as shales, limestone and
sandstone) are mainly associated with high fluoride contents.39,40
Drinking water is also aected by the presence of hydrothermal water
systems in the nearby area. Hydrothermal waters are generally alkali chlor-
ide solutions with high temperatures of from 50 to 90 1C and neutral pH
values, thus leading to easy fluoride dissolution from minerals in ground-
water. Deng et al.41 studied the correlation between the fluoride content
and the hydrothermal water samples from Yellowstone National Park, USA.
It was proven that high fluoride concentrations are found consistently
in waters with field pH values higher than 6 and temperatures higher
than 50 1C.
Among all its fluoride forms, fluorite (CaF2) seems to be the main mineral
that controls the geochemistry of fluoride in most environments42 and the
amount of fluoride ions released into the groundwater is dependent on the
degree of saturation of fluorite and calcite (CaCO3). Fluoride concentration
is inversely related to calcium and directly related to bicarbonate concen-
tration in groundwater.4345 Fluorite dissolution in groundwater seems to
be increased in sodium bicarbonate waters, whereas it appears to be in-
hibited in calcium rich water,46 especially when the calcium concentration is
above the limit for fluorite solubility owing to a common ion eect.42,46,47
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270 Chapter 13
48
Rosborg et al. also proved that the highest fluoride values were associated
with low Ca : Al ratios and HCO32 values and were related to acid soils.
Cuoco and coworkers49,50 proved that the eruption of Mount Nyamuragira
during January 2010 had a significantly negative impact on the drinking
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water quality of the Virunga Volcanic Province, since rain water is the essential
drinking water resource for most inhabitants in this region. The results indi-
cated that the Nyiragongo Volcano severely aected the chemistry of the sur-
rounding atmosphere. The pH of the drinking water was significantly aected
due to the production of several volcanic acids, among them HF. The content
of fluoride anions was enormously increased and was linearly correlated
with the content of Cl and SO42 anions. The team found that the ratios of
Cl : F, SO42 : F and SO42 : Cl could be indicative of the contaminated and
non-contaminated toxic rains and directly related to the quality of the drinking
water. By measuring these parameters they divided the rainwater samples
into two main categories: (1) uncontaminated, with higher values of 20, 40
and 5, respectively, and (2) contaminated acid rain showing values as low as
1.5, 5.0 and 0.5, respectively. They also concluded that the relative enrichment
factor of high field strength elements such as Al, Fe, Hf and Th is also
correlated with the sum of the fluoride and chloride anions concentration.
Similar results were achieved also by Ruggieri et al.51 who investigated the
environmental geochemical behaviour of the rhyolitic ashes from the 2008
eruption of the Chaiten volcano, Southern Chile. They concluded, after
conducting leaching experiments, that fluoride anion concentrations was
extremely high.51
11:26:40.
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 271
Figure 13.1 Fluoride speciation in water varies with pH in the absence of Al.41
272 Chapter 13
The presence of ion-exchange media in the aquifer often also leads to high
fluoride contents. For example, reduction in calcium ions due to precipi-
tation of calcite may increase the sodium to calcium ratio, which in turn
increases the soluble fluoride concentration in the groundwater. Waters that
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
are sodium (Na)-, potassium (K)- and chloride (Cl)-rich but calcium (Ca)
poor, tend to contain high fluoride concentrations. In the geothermal waters
from Thailand,20 the mean fluoride concentration of 18.5 mg L1 was in-
fluenced by the salinity and sodium concentration in particular, as for the
same samples, sodium (Na) concentration was the highest and ranged from
49.0 to 95.8 mg L1. For the same water types the conductivity was also in-
creased ranging from 250 to 553 mS cm1 while the Ca21 concentration was
estimated at approximately 3.5 mg L1.
It was therefore observed that solubility of fluoride was increased at a
high concentration of sodium in groundwater. This process has been stud-
ied in the sedimentary basin of the Aigion area, Greece, where during the
1980s several fluorosis incidents had been detected due to consumption of
groundwater with fluoride content exceeding 8 mg L1.39 The researchers
showed that the groundwaters from the broader area can be identified as
belonging to three main hydrochemical types (Ca-HCO3, Na-HCO3 and
Ca-Na-Mg-HCO3-SO4). Concerning their quality, it is shown that elevated
fluoride concentrations are related to the second water type (Table 13.2).
They concluded that the water uprising through fractures, due to hydrostatic
pressure, deposits a significant quantity of fluoride in lignite lenses hosted
in the Plio-Pleistocene sediments of the area. The process that follows is the
11:26:40.
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 273
respectively). They also defined that the higher contents of As and F are
related to the presence of NaHCO3 water type, in which amorphous silica
(e.g., volcanic glass) dissolves, together with the dissolution of calcite. In
non-bicarbonate water, there is no dissolution of glass, therefore when cal-
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00261
274 Chapter 13
is of great importance although the exact eects on human health are yet
unknown. As summarized in Chouhan and Floras review62 there is no
conclusive experimental evidence as to whether the combined exposure will
lead to synergistic or antagonistic eects in humans and animals. For ex-
ample, there are some studies showing that co-exposure can lead to distinct
damage on the nerve system of osprings, leading to decreased learning
ability, and some others have reported altered histology of the cerebral
hemisphere following combined arsenicfluoride exposure.63,64 On the other
hand, fluoride may be able to minimize the toxic eects of arsenic either
through strong bonding or perhaps decrease its anity for active cell
components.62
Table 13.4 Popular removal methods for fluoride from drinking water.5
Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals
Relative
Removal method Capacity/dose Working pH Interferences Advantages Disadvantages cost
Precipitation:
Alum (aluminium 150 mg per mg F Non-specific Established process Sludge produced, treated water in Medhigh
Sulfate) acidic residual Al present
Lime 30 mg per mg F Non-specific Established process Sludge produced, treated water in Medhigh
alkaline
11:26:40.
Alum lime 150 mg alum 7 mg Non-specific Low-tech, Sludge produced, high chemical Medhigh
(Nalgonda) lime per mg F established dose, residual Al present
process
Gypsum fluorite 5 mg gypsum Non-specific Simple Requires trained operators. Low Lowmed
o2 mg fluorite eciency, high residual Ca21,
per mg F SO42
Calcium chloride 3 mg CaCl2 per mg F 6.58.0 Simple Requires trained flocculent Medhigh
(e.g., FeCl3)
Adsorption exchange:
Activated carbon Variable o3.0 Many Large pH changes before and after High
treatment
Plant carbon 300 mg F per kg 7.0 Locally available Requires soaking in potassium Lowmed
hydroxide
Zeolites 100 mg F per kg Non-specific Poor capacity High
Defluoron 2 360 g F per m3 Non-specific Alkalinity Disposal of chemicals used in resin Medium
regeneration
Clay pots 80 mg F per kg Non-specific Locally available Low capacity, slow Low
Activated alumina 1200 g F per m3 5.5 Alkalinity Eective, well- Needs trained operators, chemicals Medium
established not always available
Bone 900 g F per m3 47.0 Arsenic Locally available May give taste, degenerates not Low
universally accepted
Bone char 1000 g F per m3 47.0 Arsenic Locally available Not universally accepted. May give Low
high capacity adverse colour, taste
Other:
Electrodialysis High Non-specific Turbidity Can remove other Skilled operators, high cost. Not used Very high
ions. Used for much
high salinity
Reverse osmosis/ High Non-specific Turbidity Can remove other Skilled operators, high cost Very high
275
nanofiltration ions. Used for
high salinity
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276 Chapter 13
easier accessibility and the lower cost of the materials used. Researchers are
still trying to develop new more eective adsorbents, improve the ones
currently used and lower the treatment costs.68,69
In theory, fluoride adsorbs onto solid particles in three main steps:70
(1) F ions are diused or transported to the external surface of the adsorbent
from bulk solution, crossing the boundary layer surrounding the adsorbent
particle (called external mass transfer); (2) F ions adsorb onto particle sur-
faces; and (3) the adsorbed F ions probably replace some of the structural
elements inside the adsorbents particles, if the chemistry of the solids allow
it, or the adsorbed F ions are transferred through the porous material to the
internal surfaces of the particles (intra-particle diusion).
In order for an adsorbent to be eligible for practical use, one must take
into consideration the adsorption capacity in dilute solutions, pH, time for
fluoride removal, stability of adsorbent, regeneration and loading capacity in
the presence of other anions and cations and, finally, the overall cost for
fluoride removal. Until now a wide variety of adsorbents have been used for
F removal from water. Some of these are activated and impregnated alu-
mina, rare earth oxides, activated clay, impregnated silica, carbonaceous
materials, solid industrial wastes like red mud, spent catalysts and fly ash,
zeolites and related ion exchangers, biosorbents, alum, alum sludge and
11:26:40.
modified chitosan.57 Many adsorbents have been studied so far, but only a
few can lower the fluoride concentration in water below the established
WHO limits for drinking water or for euent water that might find its way
into drinking water sources.71 Nevertheless, higher limits for euents that
are not discharged in sensitive areas are easily reached.
Industrial euents with high fluoride content are usually treated with a
calciummagnesiumbarium hydroxide slurry, in order for the fluorides to
precipitate in the form of CaF2, MgF2 or BaF. By this method fluoride con-
centration is brought down to about 30 mg L1.57
13.4 Conclusions
Fluorides can be found in the environment through various anthropogenic
and natural sources. Volcanic activity and underground mineral weathering
are the most common natural sources of pollution. Their presence in
surface- and groundwater is dependent on various factors, such as the
prevailing physico-chemical properties, the minerals present, the contact
time and depth of aquifer. Heavy metal industries, aluminium and
steel production, phosphate fertilizer production and glue/adhesive pro-
duction are among the most widespread anthropogenic sources. Depending
on the pollution source and its proximity to the examined water, samples
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Fluorides in Dierent Types of Aquatic Systems and their Correlation with Metals 277
been reported to promote fluorosis and bone deterioration. Fluoride can act
as an inhibitory factor for the growth of algae and microorganisms, while it
can be a decisive factor for plant toxicity, depending on the available calcium
and magnesium concentrations.
Studies have explicitly shown the correlation between the presence of
fluorides and various physico-chemical parameters. As far as hydro-
geological and geochemical processes are concerned, the temperature and
pH values are the main factors controlling the dilution of fluoride in
groundwater. Fluoride is mainly released by fluorite dissolution in ground-
water, which is controlled by the presence of calcium and bicarbonate ions.
A linear correlation has been observed between fluoride content and Cl and
SO42 concentrations. Moreover, the ratios of Cl : F, SO42 : F and SO42 :
Cl could be indicative of water quality and are directly related to fluoride
concentrations. Fluoride concentrations can be aected by the formation of
strong complexes with polyvalent cations such as Al31, Mg21, Fe31 and Ca21
or other components such as B, Si, Be, Li and V. There is also a direct cor-
relation between fluoride and aluminium content, under various pH values.
The interaction leads to complex formations and changes in fluoride
solubility.
The presence of ion-exchange media can also aect the presence of
11:26:40.
fluorides, since those media retain other ionic species, which in turn aect
fluoride dissolution. Fluoride presence is strongly positively related to so-
dium concentrations and negatively related to calcium and magnesium
concentrations, due to the formation of compounds with varying solubility.
Finally a significant correlation between arsenic and fluoride concentrations
has been proven in numerous studies, and in various groundwater types,
due to the common source of these pollutants and their positive relation to
the presence of sodium.
The main removal techniques, such as adsorption and membrane meth-
ods are presented, highlighting their advantages and technical aspects.
References
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in the Environment, Series: Advances in Industrial and Hazardous Wastes
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2. World Health Organization, Fluorides, in Environmental Health Criteria,
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3. CEPA, Priority Substances List Supporting Document for Inorganic
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17. CDC Centers for Disease Control and Prevention, The Benefits of
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18. S. A. Zabin, M. A. Foaad and A. Y. Al-Ghamdi, Hum. Ecol. Risk Assess.,
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21. W. Augenstein, D. Spoerke, K. Kulig, A. Hall, P. Hall, B. Riggs, M. Saadi
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30. J. C. Pushnik and G. W. Miller, Fluoride Q. Rep., 1990, 23(1), 5.
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36. M. Sands, S. Nicol and A. McMinn, Mar. Biol., 1998, 132, 591.
37. M. M. Ellis, B. A. Westfall and M. D. Ellis, Determination of Water Quality,
Research Report 9, Fish and Wildlife Service, Department of Interior,
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38. K. S. Pillai and U. H. Mane, Toxicol. Lett., 1984, 22, 139.
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42. W. B. Apambire, D. R. Boyle and F. A. Michel, Environ. Geol., 1997, 33, 13.
43. B. K. Handa, Ground Water, 1975, 13, 275.
44. D. K. Nordstrom and E. A. Jenne, Geochim. Cosmochim. Acta, 1977,
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45. S. J. Gaciri and T. C. Davies, J. Hydrol., 1993, 143, 395.
46. D. L. Ozsvath, Rev. Environ. Sci. Biotechnol., 2009, 8, 59.
47. P. Mamatha and S. M. Rao, Environ. Earth Sci., 2010, 61, 131.
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142, 261.
49. E. Cuoco, A. Spagnuolo, Ch. Balagizi, S. De Francesco, F. Tassi, O. Vaselli
and D. Tedesco, J. Geochem. Explor., 2013, 125, 69.
50. E. Cuoco, D. Tedesco, R. J. Poreda, J. C. Williams, S. De Francesco,
Ch. Balagizi and T. H. Darrah, J. Hazard. Mater., 2013, 244245, 570.
51. F. Ruggieri, J. L. Fernandez-Turiel, J. Saavedra, D. Gimeno, E. Polanco,
A. Amigo, G. Galindo and A. Caselli, Sci. Total Environ., 2012, 425, 75.
52. G. T. Chae, S. T. Yun, M. J. Kwon, S. Y. Kim and B. Mayer, Geochemistry,
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54. D. Sujatha, Environ. Geol., 2003, 44(5), 587.
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Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00281
CHAPTER 14
14.1 Introduction
Heavy metal contamination of water is a major concern throughout the
world due to the ecological and health risks it poses. Heavy metals com-
monly released into water include lead, arsenic, mercury, cadmium, chro-
mium, copper and nickel. These metals are discharged into water bodies by
industries such as mining operations, tanneries, paper mills, electronics,
batteries, textile mills and electroplating.1,2 Even though maximum allow-
able concentrations for these contaminants have been established by several
agencies (with those of the EPA listed in Table 14.13), these concentrations
are often exceeded as a result of industrial activity. Table 14.2 shows the
metal concentrations of two rivers contaminated with mine tailings
281
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282 Chapter 14
Table 14.1 EPA established maximum concentration
limits for heavy metals.3
Maximum
concentration
limit (mg L1)
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00281
Heavy metal
Arsenic (As) 0.01
Lead (Pb) 0.015
Mercury (Hg) 0.002
Cadmium (Cd) 0.005
Chromium [Cr(VI)] 0.01
Zinc (Zn) 5.0
Manganese (Mn) 0.05
Copper (Cu) 1.3
Table 14.2 Heavy metal concentrations (ppm) for two mine waste contaminated
rivers (Pilcamayo and Tarapaya) and an uncontaminated river (Cachi
Mayu).4
Area Lead (Pb) Cadmium (Cd) Zinc (Zn) Copper (Cu)
Pilcomayo, 0.0022 0.00015 0.028 0.0006
Poituco reach (0.0006 (0.00008 (0.011 (0.0001
0.0042) 0.00028) 0.058) 0.0016)
Pilcomayo, 1.399 (0.911 0.0592 6.021 0.304
Potosi reach 2.111) (0.0199 (1.490 (0.098
0.101) 10.557) 0.463)
11:26:43.
Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 283
eciency, produce less toxic waste products as an end product and have the
potential to recover metals for reuse. Some common waste products include
bagasse, sawdust, fruit peels, nutshells, shellfish, yeast and fly ash.8 These
products may be used as is, or can be physically and chemically modified
(such as heat or acid treatment) to improve their adsorption eciency.
Biosorption using waste products is not yet used on a commercial scale, but
the studies conducted so far prove it is a promising method for heavy metal
removal from aqueous solutions. This chapter describes the mechanism
behind adsorption and summarizes select studies that have been conducted
so far on the use of industrial and agricultural waste products as adsorbents
for heavy metals.
284 Chapter 14
constant.
The Langmuir model is defined by Equation (14.3):
X KL QCe
(14:3)
M 1 KL Ce
where KL is the Langmuir bonding term and Q is the Langmuir maximum
capacity.19
Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 285
14.4.1 Physical
Physical modification of waste materials includes heating and grinding to
increase the surface area. One of the most popular methods for the physical
modification of biomass is pyrolysis. Pyrolysis is the process of heating
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00281
Figure 14.1 BET surface areas of the chars pyrolysed at 400900 1C for various
retention times.24
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286 Chapter 14
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00281
Figure 14.2 SEM images of (a) raw oil palm stones, (b) oil palm stone char produced
at 600 1C, (c) oil palm stone biochar produced at 800 1C and (d) oil palm
11:26:43.
adsorption capacities for Cu(II) than grape seed activated carbon due to
chestnut shell having a greater surface area than grapeseed.28
14.4.2 Chemical
Many chemical solutions can be used to modify raw waste materials in order
to improve adsorption capacities for heavy metals. They may be basic solu-
tions, mineral and organic acid solutions, organic compounds or oxidizing
agents.12 Figure 14.3 shows the dierence between the surface structures of
raw and various chemically modified soybean straws.29 Passion fruit skin
also displays a dierence between raw and modified forms,30 as shown in
Figure 14.4. Modified materials can also be pyrolysed to create chemically
activated charcoals. Chemical activation is preferred to physical activation
because it is more time and energy ecient.31
Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 287
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11:26:43.
Figure 14.3 FESEM micrographs of soybean straw before and after citric acid (CA)
modification: (a) raw, (b) milled, (c) water washed, (d) base (NaOH)
washed, (e) water washed, CA modified and (f) base washed, CA
modified.29
method is listed. Experimental conditions are also listed when given by the
original study.
288
11:26:43.
Figure 14.4 From left to right: micrographs of raw passion fruit skin, passion fruit skin modified with NaOH and passion fruit skin
modified with NaOH and citric acid.30
Chapter 14
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Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 289
Table 14.3 Summary of sorption capacity of various waste materials to heavy
metals.
Adsorptive
Temperature capacity
(mg g1)
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carbon
Activated Cr(III) 6 25 29.47
carbon
Activated Cr(VI) 1 25 34.70
carbon
Banana peel Raw Cr(VI) 2 40 131.56 38
Canna indica Raw As(V) 7 1.717 39
pulp
Carrot Raw Cr(III) 4 25 45.09 40
residues Raw Cu(II) 5 25 32.74
Raw Zn(II) 5 25 29.61
Chestnut shell Activated Cu(II) 2 25 38.76 28
carbon
Activated Cu(II) 5 25 98.04
carbon
Activated Cu(II) 2 35 59.88
carbon
Activated Cu(II) 5 35 100
carbon
Coconut Activated Pb(II) 6 30 94.35 41
buttons carbon
Activated Hg(II) 7 30 82.09
carbon
Activated Cu(II) 6 30 75.78
carbon
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290 Chapter 14
Table 14.3 (Continued)
Adsorptive
Temperature capacity
Feedstock Raw or modified Metal pH (1C) (mg g1) Reference
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pulp
Honeycomb HNO3 Pb(II) 5 50 74.17 1
HNO3 Cd(II) 5 50 61.16
HNO3 Cu(II) 5 50 56.52
HNO3 Ni(II) 5 50 52.71
Maple sawdust Raw Cu(II) 7 23 1.79 43
Mosambi peel Raw Cr(VI) 2 40 250 36
Orange peel Raw Cu(II) 6 30 44.28 20
Methyl acrylate Cu(II) 6 30 289
Parkia speciosa Raw Cd(II) 7 25.64 10
pods
Passion fruit Raw Pb(II) 4 85.68 30
skin NaOH Pb(II) 4 112.99
NaOH and citric Pb(II) 4 204.08
acid
Peanut hull Hydrochar Pb(II) Room 1.04 44
temperature
Hydrochar, Pb(II) Room 22.82
modified with temperature
H2O2
Pistachio hull Raw Cr(VI) 2 40 116.3 45
Psidium Raw Cd(II) 7 39.68 10
guajava peel
Red mud H2O2, activated Pb(II) 4 30 88.20 46
H2O2, activated Cr(VI) 2 30 75.00
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Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 291
Table 14.3 (Continued)
Adsorptive
Temperature capacity
Feedstock Raw or modified Metal pH (1C) (mg g1) Reference
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while most eective at sorbing Cr(VI) with sorption capacities of 22.85 and
34.7 mg g1, respectively.33 Walnut sawdust shows highest adsorption for
Pb(II) and agave bagasse for Zn(II).34
292 Chapter 14
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Figure 14.5 The eect of equilibrium pH on the adsorption of Cu(II). Conditions: C0,
50 mg L1; contact time, 3 h; temperature, 30 1C; adsorbent concen-
tration, 2 g L1.20
apricot stone activated carbon also increased. However, they found that the
opposite occurred for Cr(VI), as the removal rate was highest at a pH of 1 and
decreased as pH increased. This is because the predominant form of Cr(VI) at
low pH levels is HCrO4, which is the active form of Cr(VI). At higher pH
levels, Cr(VI) is shifted towards the CrO4 and Cr2O7 forms, which do not sorb
11:26:43.
as well.33 Saha et al. also observed this phenomenon when they tested Cr(VI)
removal using mosambi peel as the adsorbent. They found that adsorption
was most eective at a pH of 2.36
Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 293
14.6 Conclusions
The sorption of heavy metals onto industrial and agricultural waste ma-
terials is a complex process, as sorption capacity varies according to a
combination of the types of sorbents and sorbates, whether or not the sor-
bents are raw or modified, modification methods and sorption conditions
such as pH and temperature. Chemically modified materials are shown to be
much more eective at enhancing heavy metal sorption than the raw or
physically modified ones. In order to determine the best way to use or to
modify an adsorbent, it is important to identify the functional groups on its
surface that are responsible for the binding of heavy metals. This is further
emphasized by the fact that some chemical treatment methods may actually
decrease the adsorption capacity of a material because they alter the surface
functional groups. Overall, waste materials prove to be eective at heavy
metal removal in most cases. With more comprehensive research conducted
on these waste materials and more experimentation with dierent types of
modification procedures to pinpoint the best production method, creating
low-cost and eective sorbents to use on a commercial basis will become
more convenient.
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294 Chapter 14
References
1. D. H. K. Reddy, S.-M. Lee and K. Seshaiah, Water, Air, Soil Pollut., 2012,
223, 59675982.
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Use of Industrial and Agricultural Waste in Removal of Heavy Metals Present in Water 295
CHAPTER 15
15.1 Introduction
Increasing awareness of environmental pollution with heavy metals and its
long-term and xenobiotic eects has instigated growing research and de-
velopment eorts towards pollution abatement. The application of dierent
biological materials in the removal and recovery of metals from wastewater
has been reported in numerous studies.15 Usually, the mechanisms of
biosorption are defined as being metabolic independent, but some authors2
have defined biosorption as the ability of biological materials to accumulate
heavy metals from waste streams by either metabolic mediation or by purely
physico-chemical uptake pathways. These dierent perspectives will be
presented. It is important to identify and evaluate extensively the factors that
aect the performance of biosorption systems in order to optimize their
practical application. The main operational conditions that significantly
influence the biosorption of heavy metals are the solution pH, the biomass
and the metal concentrations, the temperature, age of the cells, contact time
and the competitive presence of other metals in solution. All these points
296
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Biosorption of Metals From the Basics to High Value Catalysts Production 297
Metals are widespread in the environment and results from both natural and
anthropogenic sources (Table 15.1). Certain metals are essential elements
for plant growth and for animal and human health. However, if present
in excessive concentrations they may become toxic and even xenobiotic.
According to Roberts et al.,6 metals are usually classified into categories such
as light, heavy, semimetal (i.e., metalloids), toxic and trace, depending on
several physical and chemical criteria such as density, atomic weight, atomic
number and degree of toxicity. Sparks7 suggested that there are 13 trace
metals and metalloids that should be considered as priority pollutants
(Ag, As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Tl and Zn) and they can be derived
from both natural and anthropogenic sources. Natural sources may include
parent rocks and metallic ores and, on the other hand, agriculture (fertil-
izers, animal manures, pesticides), metallurgy (mining, smelting, metal
finishing), energy production (leaded gasoline, battery manufacture, power
plants), microelectronics, sewage sludge and scrap disposal may be included
in the anthropogenic sources.8
Metals such as arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu),
lead (Pb), mercury (Hg), nickel (Ni) and zinc (Zn) are commonly found at
contaminated sites and in aqueous systems. A brief description of the
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15.2.1 Arsenic
Arsenic is the 20th most abundant element of the earths crust and con-
tamination of aqueous sources is known to occur naturally, although human
activity also contributes to the release of this metal into the environment.9,10
298 Chapter 15
15.2.2 Cadmium
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Biosorption of Metals From the Basics to High Value Catalysts Production 299
37
contaminated euents. According to Mudhoo et al., most of these tech-
niques are ineective or extremely expensive in terms of energy and reagent
consumption, especially when concentrations of dissolved metals are in the
order of 1100 mg L1. An alternative, using the biomass of microorganisms,
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15.2.3 Chromium
Chromium is the sixth most abundant element of the earths crust40 and its
deposition results from its widespread use in various activities, such as
electroplating, leather tanning, cement, mining, dyeing, fertilizers and
photography industries.37 Owing to these industrial processes, large quan-
tities of Cr compounds are discharged in liquid, solid and gaseous wastes
into the environment and can ultimately have significant adverse biological
and ecological eects.
Chromium exists in a series of oxidation states from 2 to 6 valence, the
most important stable states being 0 (element metal), 3 (trivalent) and 6
(hexavalent). Cr(VI) is the dominant and toxic form of Cr in shallow aquifers.
Chromate CrO42 and dichromate Cr2O72 are major Cr(VI) species but Cr(III)
is the dominant form of Cr at pH lower than 4. Under anaerobic conditions,
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Cr(VI) can be reduced to Cr(III) by soil organic matter, S2 and Fe21 ions.
Chromium is very toxic when in the hexavalent state. Metallic Cr does not
present significant toxicity while Cr31 is an essential trace element for living
beings. In humans, it assists the metabolism of glucose and cholesterol.41
Cr61 forms oxyanion compounds in aqueous media. These species are
highly soluble and mobile in both aquifers and soils, which renders Cr61
compounds very accessible to life forms.41
The conventional methods for chromium removal from industrial waste-
water are similar to known methods for removing other metals in general
and include coagulation, precipitation, ion exchange, cementation, electro-
winning, electrodialysis, electrocoagulation and reverse osmosis.42 These
technologies are often inecient and/or expensive, mainly when applied to
dilute solutions, and they usually generate huge volumes of sludge con-
taining high levels of heavy metals. Owing to these limitations, new pro-
cesses and technologies are necessary and biosorption is gaining relevance
as one such process.4345
15.2.4 Copper
Copper has been known since ancient times. The early use of copper prob-
ably resulted from its natural occurrence in native form. Copper is mainly
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300 Chapter 15
37
employed in electrical and electroplating industries, smelting, metal pro-
cessing, machine manufacturing, organic synthesis and tanning industries.
Cu occurs in 0, 1 and 2 oxidation states. In aerobic alkaline systems,
CuCO3 is the dominant soluble species and, in the presence of sulfur, CuS(s)
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15.2.5 Mercury
Mercury, the seventh most abundant toxic element is released into the
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Biosorption of Metals From the Basics to High Value Catalysts Production 301
15.2.6 Lead
Lead is one of the most dangerous contaminants, which is released into the
environment by various anthropogenic activities. Process industries such as
battery manufacturing and metal plating and finishing are prime sources of
Pb(II) pollution.57 In recent years lead contamination has decreased because
some anthropogenic sources of lead, most notably leaded gasoline, lead-
based paint, lead solder in food cans, leadarsenate pesticides, shot and
sinkers, have been eliminated or strictly regulated due to leads persistence
and toxicity.37
Pb occurs in 0 and 2 oxidation states and this last one is the most
common and reactive form of Pb. Low solubility compounds are formed by
complexation with inorganic (Cl, CO32, SO42, PO43) and organic ligands
(humic and fulvic acids, EDTA, amino acids).58
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15.2.7 Nickel
Nickel occurs naturally in various mineral forms. Nickel contamination of
the environment occurs locally from emissions of metal mining, smelting
and refining operations, from combustion of fossil fuels, from industrial
activities, such as nickel plating and alloy manufacturing, mordents for
dying and textile printing and battery manufacturing industries, from land
disposal of sludge, solids and slags and from disposal of euents.37
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302 Chapter 15
15.2.8 Zinc
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Zinc and its compounds are found in the earths crust and are present in
most rocks, certain minerals and some carbonate sediments. As a result of
weathering of these materials, soluble compounds of zinc are formed and
may be released into water.64 Zinc is one of the metals found in euents
discharged from industries involved in galvanization, electroplating,
manufacture of batteries and other metallurgical industries.
Zn occurs in 0 and 2 oxidation states and it forms complexes with anions,
amino acids and organic acids. Zn is bioavailable at high pH and it hydrolyses
at pH 7.07.5, forming Zn(OH)2. Under reducing conditions Zn readily pre-
cipitates and may coprecipitate with hydrous oxides of Fe or manganese.65
Zinc in its metallic form has limited bioavailability and poses no eco-
logical risk. However, zinc can react with other chemicals such as acids and
oxygen to form compounds, which can be potentially toxic and can cause
serious damage to biological systems.65,66 Zn is an essential and beneficial
element for humans and plants. Complete exclusion of Zn is not possible
due to its dual role, an essential microelement on the one hand and a toxic
environmental factor on the other.37
The removal of Zn21 from euents is a major problem due to the diculty
in treating such wastewaters by conventional treatment methods.37,67,68
Biosorption could be the appropriate alternative and several studies re-
ported in the literature for the removal of this metal support the feasibility of
this removal technique.67,68
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Biosorption of Metals From the Basics to High Value Catalysts Production 303
15.3.1 Assimilation
Assimilation of metals by microorganisms or other biosorbents involves the
11:26:47.
uptake of these elements and their incorporation into the structure of the
Biosorption Mechanisms
Physical Adsorption
Complexation
Precipitation
Co-ordination
Reduction
Ion exchange
304 Chapter 15
15.3.2 Adsorption
The adsorption phenomena include physical adsorption, complexation,
precipitation, ion exchange, reduction and co-ordination, as the main
reaction steps.
15.3.2.2 Complexation
Complexation plays an important role in the fixation of heavy metals by
microbial aggregates. This process can take place by complex formation on
the cell surface after the interaction between the metal and the active surface
groups. Many functional groups in the extracellular polymeric substances
(EPS), such as carboxyl, phosphoric, sulfhydryl, phenolic and hydroxyl
groups, can complex with heavy metals.71 The complexation as a biosorption
step was investigated by Schiewer77 who modeled the complexation and
electrostatic attraction in heavy metal biosorption by Sargassum biomass and
by Allaboun and Al-Rub78 who reported the dynamics, mechanistic
and equilibrium studies for the biosorption of nickel on palm tree leaves.
15.3.2.3 Precipitation
Metal precipitation is usually involved in biosorption and it may be either
dependent on the cellular metabolism or not. The precipitates may be
formed and remain in contact with or inside the microbial cells but they also
may be independent of the solid phase of the microbial cell. Precipitation
may be a consequence of the chemical interaction between the metal and the
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Biosorption of Metals From the Basics to High Value Catalysts Production 305
70
cell surface when there is no dependence on the cellular metabolism. The
presence of the solid phase microbial cell or biofilm also enhances
precipitation.
Precipitation usually refers to the formation of insoluble inorganic metal
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15.3.2.4 Co-ordination
Tsezos et al.80 arm that metal atoms have preferences for specific donor
atoms (hardhard/softsoft) and for the stereochemical arrangements that
play an important role in the binding with the available ligands on the
microbial cell. It is suggested that there is limited information on surface
complexation models to describe metal biosorption, based on the theory of
surface co-ordination chemistry. Nevertheless, metal biosorption capacities
and biosorption mechanisms may be explained by the preferences of the
metal species.
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15.3.2.5 Reduction
Reduction is a well-known path for biosorption. A typical example is the
removal of toxic hexavalent chromium from aqueous solution using dier-
ent types of biomass. This removal is often associated with the simultaneous
reduction of Cr(VI) to Cr(III), and then incorporation of Cr(III) in the biomass,
Figure 15.2. Quintelas et al.83 investigated the biosorption of Cr(VI) by dif-
ferent bacteria and asserted that some bacteria can detoxify chromium
wastewater, by either chemical reduction of the ion or by surface adsorption
and accumulation inside the cells. Once inside a cell, Cr(VI) can be reduced
to Cr(V/IV/III) by dierent nonspecific reductants such as glutathione, glu-
tathione reductase, cysteine, carbohydrates, NADH, NADPH, nucleotides
and ascorbic acid. The reactive oxygen species (ROS) by-products of the Cr(VI)
reduction process, can attack and damage DNA and proteins. Considering
the composition of the bacterial cell wall (teichoic acids, polycarbohydrates
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306 Chapter 15
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Figure 15.2 New method of chromium removal from wastewater and catalytic
reutilization in VOCs oxidation.
and other diol-containing substances that possess reducing ability) and the
activity of dierent specific and nonspecific membrane associated reduc-
tases, the authors suggested that Cr(VI) can be partly reduced on the bacterial
cell wall.
15.3.3 Biodegradation
Although biodegradation it is not applied to metals but only to organic
compounds, it was decided to make a reference to this process in this
chapter because usually the euents are a cocktail of metals, organic
compounds and other pollutants. Some of the processes to remove metals
originate as metalcomplexes and these can be removed by biodegradation.
Biodegradation is the capability of microorganisms to degrade hazardous
compounds, producing less toxic substances. In some cases complete deg-
radation of compounds is achieved. Thomas et al.86 investigated the
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Biosorption of Metals From the Basics to High Value Catalysts Production 307
15.4.1 Solution pH
This pH is one of the most important environmental factors aecting bio-
sorption processes. The pH value of a solution strongly influences not only
the site dissociation of the biomass surface, but also the solution chemistry
of the heavy metals. It determines possible hydrolysis, complexation by or-
ganic and/or inorganic ligands, redox reactions, precipitation, the speciation
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Initial pH
Factors Temperature
Cell Age Affecting
Biosorption
Contact Time
Competing
Ions
308 Chapter 15
Biosorption of Metals From the Basics to High Value Catalysts Production 309
available for sorption become fewer compared with the number of moles of
solute present; hence, the removal of solute is strongly dependent upon the
initial solute concentration.
According to Das,96 the dosage of a biosorbent strongly influences the
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15.6 Conclusions
Biosorption of heavy metals has proved to be a competitive alternative to
conventional technologies to concentrate metals from wastewater. It is easy
to implement, demands low investment and may be considered as a green
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310 Chapter 15
while: the application of living biomass, where molecular biology may im-
plement the biosorptive characteristics of the cells to be used, and the use of
inactive biomaterials that demand a deeper optimization of supports,
operational parameters and modeling tools. A broad array of microorgan-
isms have been tested up till now as biosorbent materials and the present
tendency is focused on the biosorption application for detoxifying high
volumes of low concentrations of complex euents. Furthermore, other
approaches are also under investigation, including food enrichment with
complementary elements or purification and enrichment of high-value
pharmaceuticals.
References
1. D. Brady, A. Stoll and J. R. Duncan, Environ. Technol., 1994, 15, 429.
2. J. T. Matheickal, Q. Yu and G. M. Woodburn, Water Res., 1999, 33, 335.
3. F. Pagnanelli, M. Petrangeli Papini, M. Trifoni and F. Veglio, Environ.
Sci. Technol., 2000, 34, 2773.
4. M. X. Loukidou, A. I. Zouboulis, T. D. Karapantsios and K. A. Matis,
Colloids Surf. A: Physicochem. Eng. Aspects, 2004, 242, 93.
5. L. C. Hsu, S. L. Wang, Y. C. Lin, M. K. Wang, P. N. Chiang, J. C. Liu,
11:26:47.
Biosorption of Metals From the Basics to High Value Catalysts Production 311
312 Chapter 15
Biosorption of Metals From the Basics to High Value Catalysts Production 313
72. Y. Suzuki, T. Kametani and T. Maruyama, Water Res., 2005, 39, 1803.
73. M. P. de Souza, I. J. Pickering, M. Walla and N. Terry, Plant Physiol.,
2002, 128, 625.
74. S. V. Yadla, V. Sridevi and M. V. V. C. Lakshmi, J. Chem. Biol. Phy. Sci.,
2012, 2, 1585.
75. M. I. Din, M. L. Mirza, S. Ata, M. Athar and I. U. Mohsin, J. Chem., 2013,
2013, 1.
76. K. Chojnacka, Pol. J. Environ. Stud., 2006, 15, 845.
77. S. Schiewer, J. Appl. Phycol., 1999, 11, 79.
78. H. Allaboun and F. A. A. Al-Rub, Jordan J. Civ. Eng., 2008, 2, 124.
79. E. Remoudaki, A. Hatzikioseyian, P. Kousi and M. Tsezos, Water Res.,
2003, 37, 3843.
80. M. Tsezos, E. Remoudaki and V. Angelatou, Int. Biodeter. Biodegr., 1995,
35, 129.
81. M. H. Al-Qunaibit, Bioinorg. Chem. Appl., 2009, 2009, 1.
82. J. Garca, J. C. Gonzalez, M. I. Frascaroli, S. Garca, P. Blanes, I. Correia,
J. C. Pessoa and L. F. Sala, Can. J. Chem., 2013, 91, 86.
83. C. Quintelas, B. Fonseca, B. Silva, H. Figueiredo and T. Tavares, Bior-
esour. Technol., 2009, 100, 220.
84. C. J. Williams and R. G. J. Edyvean, Biotechnol. Prog., 1997, 13, 424.
11:26:47.
314 Chapter 15
CHAPTER 16
Chromium in Tannery
Wastewater
MARILIZ GUTTERRES* AND BIANCA MELLA
16.1 Introduction
The tanning process in Brazil, and worldwide, is of great economic im-
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315
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316 Chapter 16
required to oxidize the trivalent form to the hexavalent one. The reduction
of Cr(VI) occurs spontaneously, unless the species is in the insoluble
form.6,9
Under normal conditions, Cr(III) and metallic chromium are relatively
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non-reactive in the atmosphere, but Cr(VI) in the air can react with particu-
late materials or gaseous pollutants to form Cr(III).6 The conversion between
trivalent and hexavalent chromium states is an important feature. The Cr(III)
is the less mobile, less toxic form and is found mainly bound to organic
matter in soil and in aquatic environments.10 In contrast to the low mobility
observed for Cr(III) in soils, plants, animals and natural waters, Cr(VI) is more
soluble, mobile bioavailable and toxic than Cr(III).11,12
Cr(III) acts as an essential micronutrient for carbohydrate and lipid me-
tabolism in humans. Trivalent chromium is an essential element for human
nutrition. This nutrient plays an important role in the metabolism of glu-
cose, fats and proteins. It is believed that the biologically active form of
organic Cr(III) complex facilitates the interaction of insulin with its cellular
receptors. Also, cases of atherosclerosis and aorta injuries related to chro-
mium deficiency in rats and rabbits have previously been identified.5
However, the beneficial eects of this element should be considered with
caution. Doses above the adequate level can cause intoxication and a
number of diseases.
Cr(III), once absorbed, combines with plasma proteins, being distributed
in the tissues depending on its quantity.13 Absorption of Cr(VI) is influenced
by the acidity of the gastric juices, which can favour its reduction to Cr(III),
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and the presence of other food components, which can act as reductors
(ascorbic acid, sulfhydric compounds) or blockers. Once inside the cell,
Cr(VI) is rapidly reduced to Cr(III), for example, by hemoglobin and the
endoplasmic reticulum.14 Cr(III) is an active component of the glucose tol-
erance factor and thus enhances the insulininsulin receptor interaction
with consequent biologic response.13 A deficiency of chromium in man15
can cause a glucose intolerance (the most sensitive indicator), an inability to
use glucose for energy, neuropathies with normal insulin levels, increase of
free fatty acids and serum cholesterol in the blood, low respiratory quotient,
abnormalities in nitrogen metabolism, with the consequent reduction in
growth and longevity.16
Cr(III) is considered an essential nutrient and relatively non-toxic to
humans and mammals, however, it can be oxidized in nature, thus be-
coming its most toxic form Cr(VI).5
Cr(VI) is considered to be the most toxic chromium type and commonly
occurs in association with oxygen in the form of chromate (CrO42) or
dichromate (Cr2O72). Cr(VI) acts as a carcinogen and genotoxic agent.17,18 In
man, acute exposure to Cr(VI) produces nausea, diarrhea, liver and kidney
damage, internal bleeding, dermatitis and respiratory problems, while acute
exposure to Cr(III) is rarely reflected in toxic eects. For man, Cr(VI) is
considered a carcinogen substance. Several studies have confirmed the
appearance of lung cancer due to exposure of workers to Cr(VI).
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318 Chapter 16
ultramafic rocks and from 30 to 590 ppm in shale and clay.19 In most soils,
chromium is found in low concentrations (260 mg kg1) and only a fraction
of that chrome is available to plants. In areas where significant deposits of
chromium occur, water sources may present concentrations greater than
50.0 mg L1, values that exceed the national and international standards for
drinking water of 0.05 mg L1. In atmospheric air, the chromium concen-
trations found are lower than 0.1 mg m3 , and uncontaminated water
values are in the region of 1.0 mg L1. In seawater, concentrations are in a
range of between 1 and 10 mg kg1, and the permitted level in drinking
water is 50 mg kg1.6
The concentration of chromium in the soil depends on specific factors
such as the type of industrial process present in the region and the in-
adequate disposal of residues containing heavy metals on the site. The most
common route to chromium contamination in soil is a consequence of the
inadequate method of disposal of the residues containing this metal. The
factors intervening in the transport of substances in soils are: (a) charac-
teristics of the contaminant (solubility, density, concentration, pH, BOD,
COD, etc.); (b) soil characteristics by which it percolates (granulometry, clay
fraction mineralogy, permeability, organic matter, etc.); and (c) character-
istics of the environment (time of soil exposure to the contaminant, presence
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320 Chapter 16
Salty hides
Presoaking Prefleshing
Soaking
Dehairing/Liming
Washing
(Drum) II
Fleshing/Splitting
Weighing II
Deliming/Bating
Pickling
Tanning
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(Drum III)
Samming
Shaving
Weighing III
Deacidification
Retanning
Dyeing
Fatliquoring
(Drum IV)
Mechanical
Treatments/Drying
Operations
Finishing Operations
Classification
Leather Expedition
322 Chapter 16
(a) Salt shake-o. This is performed on hides conserved with salt (so-
dium chloride), with the objectives of removing the salt that is de-
posited (free) in the hide and decreasing the salinity of the euents
from the soaking step. It is performed in an open drum designed
especially for this situation.
(b) Presoaking. This is the step in the process where the hide is placed on
a drum with water to take away any dirt and salt as well as being
subjected to the first hydration.
(c) Pre-fleshing. This is performed in a fleshing machine with the aim of
eliminating the material adhered to the carnal, the subcutaneous
tissue and adipose material.
(d) Soaking. This cleans and re-hydrates the hides in order to eectively
interrupt the salt conservation eects and replenish skin moisture for
its processing. It is done in the soaking drum with the addition of
water, tensoactive, alkali and other chemical products.
(e) Dehairing and liming. This step has finally to take away the hair from
the skin, remove the epidermis, open the fibrous structure for
cleaning through the swelling of the hide, continue the degreasing
which started during soaking and facilitate the stripping through
11:26:49.
hide swelling. This is done in a drum with the addition of water, lime,
sodium sulfide and other chemical agents.
(f) Fleshing. This takes away the residues from subcutaneous material
(hypodermis). If well conducted, the prefleshing is enough and
fleshing is not necessary;
(g) Splitting. The hide is divided into two layers, where the top layer is called
grain or top split (considered to be the noblest part, which contains
the grain or thermostatic layer and part of the reticular layer) and the
bottom layer is called flesh or bottom split (only the reticular layer).
(h) Deliming. Removes alkaline substances introduced into the hide in
the liming by means of delimer chemical products and it reverses the
swelling of the hide.
(i) Bating. Enzymes are added to remove residues of epidermis, hair and
fat leaving the hide clean and the grain thin and smooth.
(j) Pickling. This is the stage that interrupts the action of deliming and
bating and the collagen fibers are prepared for easy penetration of
tanning agents by acidification of the skin in a saline solution.
(k) Tanning. This is the main stage of leather processing, where the hide is
modified by reaction with tanning agents for leather transformation.
(l) Samming and shaving. The leather is dried out in the drying machine
(samming) and after that adjustment is made to the uniformity of its
thickness on a shaving machine.
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ture and surface characteristics of the leather are defined through the
use of retanning substances.
(o) Dyeing. Gives colour to the leather through the use of dyes.
(p) Fatliquouring. The fibers are lubricated with oils to give softness to
the leather.
(q) Mechanical and drying operations. The mechanical treatments of
leather after drumwork in the float are samming, stretching and
setting out followed by the operations of air drying, vacuum drying,
paste drying and wet toggling.
(r) Softening and prefinishing. Leather is made soft by feeding to staking
machines or by milling in rotating drums. The prefinishing oper-
ations are conditioning, toggling, sanding, stucco application, dust
removal, trimming and grain impregnation.
(s) Leather finishing. Surface treatments give the leather presentation
and definitive aspects by means of application of covering and top
layers with film-forming chemical products (polymer resins), pig-
ments and auxiliary agents in water base or solvent base.
(t) Quality control, classification, measurement and leather expedition.
After the beamhouse operations, the hide is ready to receive the tanning
agent. During the tanning the actual transformation of the skin collagen
structure into leather occurs. This modification is achieved by chemical
bonds and transverse links of the collagen chains with the tanning agents.
The tanning provides stability of the hide to putrefaction (microbial and
enzymatic), chemical stability and hydrothermal stability as well as pro-
viding porosity to the material. The eects of the chemical modifications
performed in the hide eliminate its shrinkage through the action of hot
water (or boiling in the case of tanning with chromium), eliminate its ability
to swelling by water absorption, improve its mechanical resistances and the
leather acquires flexibility.
Most classic tannings are those that employ chromium or vegetable tan-
nin. The vegetable tanning provides, in general, a less flexible material and
with brown coloration that is characteristic of vegetable tannin and is aimed
at specific markets, while chromium tanning is more versatile in terms of
properties of the articles produced.
It is also common practice for the association of tanning substances, the
so-called combined tannings. The proportion of the products employed
varies with their function and with the process as a whole. Vegetable tanning
is usually preceded by treatment with phenolic synthetic tannins. There are
tanning systems that combine vegetable tannins with mineral tanning
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324 Chapter 16
of chromium(III) throughout the depth of the hide thickness, fibers and fi-
brils. If the hide has too much anity with chromium, at the very beginning
of the tanning the fixation only occurs in the outer layers, blocking the
chromium penetration to the whole skin depth.28
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00315
between 50 and 60% is reached. The most common basifying agents are
sodium bicarbonate and magnesium oxides. The increase in basicity of the
tanning agent decreases the diusion of the salt, but increases the fixation of
it to the hide, enhancing the tanning power.
The chromecollagen anity depends on the factors: electric charge, di-
mensions of tanning molecules, pH and temperature of the bath, as well as
the characteristics of hide pH and its treatment in the beamhouse
operations.
The chromium salt employed in the tanning is anionic, moving to cationic
over time. As the compound is anionic, it has no tanning action and a
higher diusion rate. The charge change of the complex from anionic to
cationic increases its fixation. This change is a function of time, of alkalinity
(pH) and temperature. The cationization occurs with the basification. The
compound formed by chromium reaction with protein is represented by
Figure 16.2.
According to the ABNT NBR 11054 specification, leather must have a
minimum of 3.5% of Cr2O3 on a dry basis. In leather it can be fixed close to
6% of chromium oxide, which varies according to the supply of salt, the
kinetic conditions of the process and mechanical action.
The excess tanning substances remain in the residual bath or are present
in the structure, but they are not chemically bound to collagen (soluble
chromium in leather).25 The residual liquid euents in the tanning bath
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326 Chapter 16
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328
11:26:49.
Chapter 16
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take away the chromium in the form of a precipitate for reuse or to be dis-
charged to industrial dangerous residues landfill. To accomplish the pre-
cipitation of chromium the following alkaline agents are used: calcium
hydroxide [Ca(OH)2], sodium hydroxide (NaOH), ammonium hydroxide
(NH4OH), magnesium oxide (MgO) or sodium bicarbonate (NaHCO3).
330 Chapter 16
In order to meet the new standards set by environmental legislations, the use
of advanced treatments after secondary treatment has been studied. The
choice of a treatment method depends on a general balance, which involves
the cost of the process, the concentration of the pollutant to be removed and
the flow rate of the euent.
Tertiary treatment incorporates some operations aimed at the removal of
specific pollutants that have not met the euent emission standards and/or
the increase of the eciency of the processes used in the treatment of the
euents. This treatment has been employed in tanneries for the removal of
nitrogen, as the destination of this component in the receiving bodies involves
the risk of eutrophication, and also to reduce the toxicity of the euents.
Generally, the techniques of advanced treatment are not employed too
often in tanneries. Some individual initiatives for these treatment levels in
tanneries have been found, such as physico-chemical post-treatment, sta-
bilization ponds, subsequent filtration, constructed wetlands and ad-
sorption with activated carbon, among others.
being implemented to reduce water consumption and the high costs of water
treatment. The implementation of reuse requires the establishment of
quality guidelines, criteria and standards and procedures that regulate the
practice of wastewater reuse. Wastewater reuse is the process of reusing
treated or non-treated water for the same or another purpose. This reuse can
be direct or indirect, planned or unplanned, according to the following
classification:34
Direct reuse: Occurs when the water used for a given purpose can be reused
without previous treatment to be applied in a less noble purpose. Some
examples include wastewater use in industries or in irrigation.
Indirect wastewater reuse: Occurs when wastewater used for domestic or
industrial purposes is treated in order to be available for another use.
Water recycling: Involves reusing water for the same application for which it
was originally used. In this case, the water is treated (regenerated).
The types of wastewater reuse are classified into four main categories:
urban, industrial, agricultural and groundwater recharge, as is described.
In tanneries, the stages of conditioning and preparation of the hide for
tanning, as well as the transportation and fixation of tanning substances, are
all carried out in aqueous media. Most of the steps of these processes are
carried out with fresh water, which is used as a vehicle for the diusion of
11:26:49.
332 Chapter 16
integration. The combination of more contaminants did not aect the water
saving result.
The recycling of wastewater from dehairing and liming consists of the
recovery of the residual bath used for hide processing and in its use in the
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00315
dehairing process of the next batch, replacing the amount of water and
chemical inputs needed to complete the formulation. In general, the fil-
tering is performed for the removal of hair and solids and the sedimentation
process is performed to remove precipitates and lime. The separation of fat
is carried out in retention tanks, where the floated material is retained. This
material and fat removal, besides reducing the volume and organic load of
the euents, generates a saving of chemical products, as well as enables the
reuse of these baths.
The recycling of baths of dehairing and liming can be total or partial,
according to the demands of the depilation process. To reuse these baths,
the concentration of dissolved salts is controlled, analytically or by meas-
urement of the Baume degree, which is directly related to the saline
solution density (g cm3 ). After measurement, addition of new water is
made to replenish the baths and when it is needed, an entire replacement
is done. The advantages of this practice are: savings in chemical inputs
consumption, reduction in the quantity of oxygen required to oxidize the
residual sulfides or thiosulfates and decreasing the toxic load on the total
euent.
It is possible to recycle the tanning wastewater, passing them through a
sieve, do a chromium solution analysis and replenish the amount of chro-
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mium salt and chemical inputs required for the process. Tests were con-
ducted on an industrial scale for reuse of tanning wastewaters in a tannery in
Brazil.25,41 Before the baths were recycled the pH value, the concentration of
Cr2O3 and the content of oils and greases were measured. It was possible to
reduce the supply of salt (sodium chloride) in tests through recycling. As the
recycled wastewaters already contained a certain amount of salt (necessary to
avoid the swelling of the hide) 3.04.5% of sodium chloride was added in
relation to the mass of hides, while usually 5.5% of sodium chloride is added
to a new bath. In the recycling of tanning wastewater the supply of chro-
mium, from 5.5 to 4.0%, was achieved.
334 Chapter 16
for this function, while at tanneries I, II and III aluminum sulfate was em-
ployed as coagulant. The sludge sedimentation tank of the tanning waste-
water from tannery II, as well as the drying bed used for sludge drying, is
shown in Figure 16.3.
In chemical precipitation assays of chromium with sodium hydroxide
(NaOH), at a concentration of 12 M, in tanning residual baths, chromium
removals above 98% were reached and the best result was 99.74%, with a
final concentration of 5.3 mg L1 of Cr2O3 in the clarified euent at pH 9.98
(Figure 16.4).54
Besides the aforementioned tanneries of the State of Rio Grande do Sul
(Brazil) that segregate and treat the euents from tanning separately, other
tanneries also do this, such as a tannery in the state of Mato Grosso do Sul,
Figure 16.3 (a) Drying bed sludge with chromium; (b) precipitation of the chro-
mium in the form of hydroxide.
100%
90%
80%
Efficiency of removal
70%
60%
50%
40%
30%
20%
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10%
0%
1 2 3 4 5 6 7 8 9 10 11 12
pH
Figure 16.4 Influence of pH on the removal of Cr2O3 from the residual tanning bath
for chemical precipitation.55
which has reported the recovery and reuse all the chrome in the process of
leather tanning55 and another tannery in the State of Goias that employs
good practices in its leather processing, where about 90% of chromium used
in the process is recycled.56
336 Chapter 16
Fe 2H2O-Fe(OH)2 H2 (16.9)
Because electrocoagulation is an alternative treatment without the add-
ition of chemical products it has been shown to be very promising in the
treatment of euents from various industrial sectors. In tannery euents
electrocoagulation was studied60 at low currents (less than 1 A) with electrodes
of steel and aluminium. For the removal of sulfides, steel electrodes led to
removal above 90%, compared with those of aluminium, which had an e-
ciency below 12%. For removal of chemical oxygen demand (COD), ammonia,
total organic carbon (TOC), sulfide and colour, a system was tested where the
euent was first treated with steel electrodes, followed by the filter and, fi-
nally, with aluminium electrodes, resulting in 68.0, 43.1, 55.1, 96.7 and 84.3%,
respectively. Recovery of 99% of residual chromium was reached61 from a
residual tanning wastewater after 2 h of electrolysis of 1.0 V, at pH 5.0 and an
agitation speed of 500 rpm using lead as the cathode and copper as the anode.
Electrodes made of dierent materials,54 aluminium, copper and iron,
were used to assess the influence of these and the extent of the chromium
removal from residual tanning wastewater. The best removal eciencies
were obtained with aluminium electrodes at 3.0 V of 97.76%, with copper
electrodes at 2.0 V of 69.91% and with the iron electrodes at 2.5 V of 90.27%.
All hide had good chromium crossing during the tanning and adequate pH
values and ash contents; hide tanned with chromium recovered by chemical
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338 Chapter 16
The use of the electrolytic process for euent treatment points to some
advantages, such as: it does not generate odours, uses a small area for its in-
stallation, is easy to operate, requires less time for treatment and disinfection
of the euent from the perspective of reusing some compounds recovered
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00315
16.5 Conclusions
There is concern from society regarding the use and provision of the metal
chromium therefore there is an eort by tanneries in order to implement
clean technologies and treat the euents and residues generated in the
industrial process. In Brazil it is now usual practice to recycle liming baths,91
water reuse in other stages of beamhouse has been proposed and tested41
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340 Chapter 16
References
1. Brazilian Association of Chemists and Technicians Leather Industry,
Brazilian Leather Guide, 2013.
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00315
342 Chapter 16
341348.
52. U. Wingenfelder, C. Hansen, G. Furrer and R. Schulin, Environ. Sci.
Technol., 2005, 39, 46064613.
53. Anon, Leather, 1996, 8388.
54. B. Mella, Remoao de cromo de banhos residuais de curtimento atraves
de precipitaao qumica e eletrocoagulaao, Dissertaao de Mestrado,
Universidade Federal do Rio Grande do Sul, RS, 2013.
55. JBS Consolidate Tanneries, Leather International, 2011, October, 36.
56. Tannery of the Year: Coming Industria e Comercio de Couros, Trindade,
World Leather, 2011, August/September, 4150.
57. K. Bensadok, S. Benammar, F. Lapicque and G. Nezzal, J. Hazard. Mater.,
2007, 152(1), 423430.
58. A. Sava Koparal and U. B. Outveren, J. Hazard. Mater., 2002, 89(1),
8394.
59. A. C. S. Wimmer, Aplicaao do processo eletroltico no tratamento de
efluentes de uma industria petroqumica, Dissertaao Mestrado, PUC,
Rio de Janeiro, RJ, Brasil, 2007.
60. J. Feng, Y. Sun, Z. Zheng, J. Zhang, S. Li and Y. Tian, J. Environ. Sci., 2007,
19, 14091415.
61. Sirajuddin, L. Kakakhel, G. Lutfullah, M. I. Bhanger, A. Shah and A. Niaz,
J. Hazard. Mater., 2007, 148, 560565.
62. Chen, G. Sep. Purif. Technol., 2004, 38(1), 1141.
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85. M. Liu, Y. Sanchuan, J. Tao and C. Gao, J. Membr. Sci., 2008, 325-
(December), 947956.
86. L. K. Wang, E. M. Fahey and Z. C. Wu, Dissolved air flotation, in Physi-
cochemical Treatment Processes, ed. L. K. Wang, Y. T. Hung,
Published on 16 September 2014 on http://pubs.rsc.org | doi:10.1039/9781782620174-00315
Subject Index
acid washing, in leather processing, pseudo-second order, 74
323 WeberMorris, 7475
activated carbons, and iron removal, and metal biosorption, 304306
1617 complexation, 304
acute toxicity, 265, 267 co-ordination, 305
adsorption. See also biosorption; ion exchange, 306
metal biosorption physical, 304
and arsenic contamination, precipitation, 304305
110113 reduction, 305306
and batch equilibrium studies, and physico-chemical
207208 treatments of heavy
equilibrium isotherm metals, 48
modeling, 7577 and sorption
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on modified agriculture
genetically modified and biological wastes,
microorganisms, and heavy metal 202205
removal, 52 on modified biopolymers
grafting, and clays/clay minerals, and hydrogels, 205207
230236 on modified natural
graphene, 185187 materials, 198200
groundwater advanced oxidation processes
arsenic contamination, 105 for, 2729
treatment, for iron and application of photocatalytic
manganese removal, process for, 3540
133135 group 6 metal
group 6 metal (chromium), and (chromium), 3537
photocatalytic process, 3537 group 15 metalloid
group 15 metalloid (arsenic), and (arsenic), 3940
photocatalytic process, 3940 group 10 metals (nickel
group 10 metals (nickel and and platinum), 37
platinum), and photocatalytic group 12 metals (zinc,
process, 37 cadmium and
group 12 metals (zinc, cadmium and mercury), 3739
mercury), and photocatalytic and batch equilibrium studies,
process, 3739 207208
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electrocoagulation, 114116
116117 electrocoagulation,
membrane filtration, 116117
113114 membrane filtration,
photochemical and 113114
photocatalytic photochemical and
oxidation, 117 photocatalytic
heavy metals in, 4445 oxidation, 117
industrial, 194196 chromium in, 319320
and toxicity, 194196 iron removal from, 1517
irrigation and Chinese water activated carbons, 1617
resources, 158 ion exchange, 16
reuse, and tannery euents, manganese removal from, 1517
331332 WeberMorris kinetic modeling,
treatment, tannery (See tannery 7475
wastewater and sludge wetlands, constructed, and arsenic
treatment) contamination, 114116
water World Health Organization (WHO),
arsenic contamination in, 123
9698
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