Gautam

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

Edited by Sanjay K. Sharma
r The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org
1
2 Chapter 1
nature of heavy metals has been recognized because of their bioaccumula-

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

Heavy metals differ widely in their chemical properties, and are used ex-
tensively in electronics, machines and the artifacts of everyday life, as well as
in high-tech applications. As a result they are able to enter into the aquatic
and food chains of humans and animals from a variety of anthropogenic
sources as well as from the natural geochemical weathering of soil and
rocks. The main sources of contamination include mining wastes, landfill
leaches, municipal wastewater, urban runoff and industrial wastewaters,
particularly from the electroplating, electronic and metal-finishing indus-
tries. With increasing generation of metals from technologies activities, the
problem of waste disposal has become one of paramount importance. Many
aquatic environments face metal concentrations that exceed water quality
criteria designed to protect the environment, animals and humans. The
problems are exacerbated because metals have a tendency to be transported
with sediments, are persistent in the environment and can bioaccumulate in
the food chain. Some of the oldest cases of environmental pollution in the
world are due to heavy metal use, for example, Cu, Hg and Pb mining,
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 nickel–cadmium
compounds are also sources of cadmium.3–5 Cadmium exposure causes
renal dysfunction, bone degeneration, liver and blood damage. It has
been reported that there is sufficient 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 effects 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
Contamination of Heavy Metals in Aquatic Media 3
concentrations. Mining, metallurgy and industrial applications are the

major sources of copper exposure in the environment.
Zinc is also an essential element in our diet. Too much zinc, however, can
also be damaging to health. Zinc toxicity in large amounts causes nausea
and vomiting in children. A higher concentration of zinc may cause anemia
and cholesterol problems in human beings. Mining and metallurgical pro-
cessing of zinc ores and its industrial application are the major sources of

zinc in the air, soil and water. It also comes from the burning of coal.
Nickel occurs naturally in soils and volcanic rocks. Nickel and its salts are
used in several industrial applications such as in electroplating, automobile
and aircraft parts, batteries, coins, spark plugs, cosmetics and stainless
steel, and is used extensively in the production of nickel–cadmium batteries
on an industrial scale. It enters into the water bodies naturally by weathering
of rocks and soils and through the leaching of the minerals.4 The water
soluble salts of nickel are the major problems of contamination in aquatic
systems.5 Paint formulation and enameling industries discharges nickel
containing effluents to the nearby bodies of water.6 Nickel is also found in
cigarettes, as a volatile compound commonly known as nickel carbonyl.7
Arsenic is found naturally in the deposits of earth’s crust worldwide. The
word arsenic is taken from Zarnikh in Persian literature, which means yellow
orpiment.8 It was first isolated as an element by Albert Magnus in 1250 AD.
Arsenic exists in powdery amorphous and crystalline forms in the ores. In
certain areas the concentration of arsenic may be higher than its normal
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.9–12 Ad-
sorption and solution pH commonly controls the mobility of arsenic in the
aqueous environment.13–17 Metal oxides of Fe, Al and Mn play a role in the
adsorption of arsenic in aquatic bodies.18–20 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 effects 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
4 Chapter 1
and anthropogenic sources. Volcanic eruptions, geological weathering of

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

1.3 Environmental and Health Risks
Cadmium is the most toxic element, even at its low concentration in the food
chain and has been found to cause of itai-itai disease in Japan. Unlike other
heavy metals, cadmium is not essential for biological systems. Hence it has
no benefit to the ecosystem and only harmful effects have been reported. It is
used in the manufacturing of nickel–cadmium batteries, plastics and pig-
ments. Phosphate fertilizers and waste dumping are both routes for cad-
mium transference into the environment. Concern regarding the role and
toxicity of cadmium in the environment is on the increase, because it can be
highly toxic to human beings and animals at very low concentrations. Cad-
mium toxicity causes renal dysfunction and lung cancer, and also osteo-
malacia in the human population and animals, in addition to increasing
blood pressure. Smoking of cigarettes is one of the sources of cadmium
poisoning in humans.
Chromium is commonly used in the leather and tanning industries, paper
and pulp and rubber manufacturing applications. High levels of exposure
cause liver and kidney damage, skin ulceration and also affects the central
nervous system. With plant species it reduces the rate of photosynthesis. It is
also associated with the toxic effects on hematological problems and im-
mune response in freshwater fish. Chromium(VI) causes greater toxicity than
chromium(III) in animal and human health.
Copper has been used by man since prehistoric times. It is used in the
production of utensils, electrical wires, pipes and in the manufacture of
brass and bronze. It has a role as an essential element in human and animal
bodies. However, at a higher dose it shows toxic effects, such as kidney and
stomach damage, vomiting, diarrhea and loss of strength.
Human exposure to lead causes severe toxicity. Higher doses may damage
the fetus and be toxic to the central nervous system. Newborn babies are
more sensitive than the adults. Lead toxicity may harm hemoglobin syn-
thesis, the kidneys and reproductive systems. Exposure to higher doses of
lead may disrupt the function of the central nervous system and gastro-
intestinal tract. Airborne lead may cause the poisoning of agricultural food
by the deposition on fruits, soils and water.7
Mercury is a very toxic element in its organic form and has been the cause
of Minamata disease in Japan. It shows toxicity to the physiology of animals
and human beings. Mercury toxicity has been found to be associated with
physiological stress, abortion and tremors. Methyl mercury is highly toxic
and causes toxic effects on the central nervous system in the human
population. Mercury can result from volcanic eruptions and degassing. The
exposure to mercury causes toxicity to the brain, blindness, mental retar-
dation and kidney damage.
Nickel plays an essential role in the synthesis of red blood cells; however,
it becomes toxic when taken in higher doses. Trace amounts of nickel do not
damage biological cells, but exposure to a high dose for a longer time may
damage cells, decrease body weight and damage the liver and heart. Nickel

poisoning may cause reduction in cell growth, cancer and nervous system
damage.5–7
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 effects 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,
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 effects.
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 suffering 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 effects and poisoning by heavy metal ions worldwide and
strict discharge regulations for wastewater effluents to aquatic bodies
requires better treatment techniques. Environmental scientists have de-
veloped several procedures such as coprecipitation, membrane filtration,
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Table 1.1 The standard metal concentration in drinking water and the health
effects.
Metal Effects Drinking water standards
Lead Toxic to humans, aquatic By the Environmental
fauna and livestock Protection Agency
High doses cause maximum concentration:
metabolic poison 0.1 mg L 1
Tiredness, irritability anemia By European Community:

and behavioral changes of 0.5 mg L 1
children Regulation of water quality
Hypertension and (India) 0.1 mg L 1
brain damage
Phytotoxic
Nickel High conc. can cause By the Environmental
DNA damage Protection Agency
Eczema of hands maximum concentration:
High phytotoxicity 0.1 mg L 1
Damaging fauna By European Community:
0.1 mg L 1
Regulation of water quality
(India) 0.1 mg L 1
Chromium Necrosis nephritis and death By the Environmental
in man (10 mg kg 1 of body Protection Agency
weight as hexavalent maximum concentration:
chromium) (hexavalent and trivalent)
Irritation of gastrointestinal total 0.1 mg L 1
mucosa By European Community:
0.5 mg L 1
(India) 0.1 mg L 1
Copper Causes damage in a variety By the Environmental
of aquatic fauna Protection Agency
Phytotoxic maximum concentration:
Mucosal irritation and 1.0 mg L 1
corrosion By European Community:
Central nervous system 3 mg L 1
irritation followed by Regulation of water quality
depression (India) 0.01 mg L 1
Zinc Phytotoxic By the Environmental
Anemia Protection Agency
Lack of muscular maximum concentration:
coordination 5 mg L 1
Abdominal pain etc. By European Community:
5 mg L 1
(India) 0.1 mg L 1
Cadmium Cause serious damage to By the Environmental
kidneys and bones in humans Protection Agency
Bronchitis, emphysema, maximum concentration:
anemia 0.005 mg L 1
Acute effects in children By European Community:
0.2 mg L 1
(India) 0.001 mg L 1
Table 1.1 (Continued)
Metal Effects Drinking water standards
Mercury Poisonous By the Environmental
Causes mutagenic effects Protection Agency
Disturbs the cholesterol maximum concentration:
0.002 mg L 1
By European Community:
0.001 mg L 1

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

of wastewater effluents containing heavy metals.
1.4 Remediation Technologies

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

Ion exchange
Membrane filtration
Bioremediation
Heterogeneous photocatalysts
Adsorption
1.4.1 Membrane Filtration

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

Partitioning water and dissolved salts between the membrane and the bulk
solution, and transport of water and salts across the membrane, depend on
the chemical properties of the membrane as well as the physical structures
on nano- to microscales. The nanometer length scale is defined as between
the scale of macroscopic particles suspended in water and dissolved atomic
and molecular species. From a filtration perspective, this intermediate range

contains, for example, colloidal solids, large organic and biological mol-
ecules, polymers and viruses. It also corresponds to the dimensions at which
that we recognize distinct modes of material transport across a membrane.
For a larger dimension of porous membranes, transport is described in
terms of convective flow through pores. On the other hand, transport in a
dense reverse osmosis membrane is typically described in terms of diffusive
flow through a homogeneous material.
1.4.2 Phytoremediation
Bioremediation is the technological process whereby biological systems,
plants and animals, including microorganisms, are harnessed to effect 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
from increased industrialization and urbanization and its amelioration by
using plants from various environmental conditions. Conventional tech-
nologies are not cost effective and may produce adverse impacts on aquatic
ecosystems. Microbe-assisted bioremediation and phytoremediation of
heavy metals are cost-effective technologies and metal ion accumulating
plants have been successfully used for the treatment of wastewater.24
Aquatic plants, especially ‘‘wetland ecosystems’’, have unique properties to
sequester heavy metals and metalloids.
Wetland ecosystems are much superior in comparison with other con-
ventional methods, for example because of the low cost, frequent growth of
microorganisms, easy handling and low maintenance cost. The rhizospheres
in wetlands provide an enhanced nutrients supply to the microbial eco-
systems of plants, which actively transform and sequester heavy metals
in their biological functions. Constructed wetlands have been actively used
for the treatment of heavy metals from agricultural runoff, mine drainage
and municipal wastes. Many aquatic plants such as Phragmites, Lemna,
Eichchornia, Azolla and Typha have been used for the treatment of wastewater
containing heavy metals.
Phytoremediation is a low-cost, low-tech and emerging cleanup technol-
ogy for contaminated soils, groundwater and wastewater.25 Plants are very
sensitive to metals but in phytoremediation wild and genetically modified
plants, including grasses, herbs, forbs and woody species, are mainly used.
The plants take up heavy metals and metalloids through the process of
phytostabilization, phytoextraction, phytofiltration or rhizoremediation.

However, in contrast to organic compounds the heavy metals and metalloids
cannot be metabolized but accumulate in the plant biomass.26 The biomass
generated by phytoremediation remains very limited in amount and persists,
whereas all the biomass can be utilized in the form of fertilizer, forage,
mulch or for the production of bio-gas.27 Even though it is well known that
metals are toxic to many plants, they have developed some internal mech-

anisms that allow the uptake, tolerance and accumulation of high concen-
trations of metals that would be toxic to other organisms. Many researchers
have reported that aquatic macrophytes viz. Typha, Phragmites, Eichhornia,
Azolla and Lemna are potential wetland plants for removal of heavy metal
and metalloids due to their morphological change.24,28 Being a cost-effective
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 cycle29–31 and (2) chemically induced phytoextraction
techniques to cleanup contaminated water by using metal-tolerant plants to
remove heavy metals and metalloids.32 The efficiency 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
without any toxic symptoms.33
Metals uptake in relation to the external concentration of the toxic heavy
metals may differ due to the different genotypes of plants. Those plants that
have low uptake of metals at quite high metal concentrations are called
excluders. These plants have some kind of barrier to avoid uptake of heavy
metals, however, when metal concentrations are at a high level this barrier
losses its function, probably due to the toxic action of the metals. Some
plants have certain detoxification mechanism within their tissue, which
allow the plant to accumulate high amounts of metals.34 Several reports are
available in the literature on the hyperaccumulator plants: Pteris vittata L.
and Thlaspi caerulescens were found to hyperaccumulate As, Minuartia verna
for Pb, Aellanthus biformifolius for Co and Cu, Berkheya coddi for Ni,
Macadamia neurophylla for Mn and Thlaspi caerulescens for Zn.34,35 However,
phytoremediation on a commercial scale is limited because of its low bio-
mass production, limited growth rate and time consumption.35 In order to
compensate for the low metal accumulation, much research has been con-
ducted using synthetic chelators or ligands such as ethylenediaminetet-
raacetic acid (EDTA); S,S-ethylenediaminedisuccinic acid (S,S-EDDS);
nitrilotriacetate (NTA) and naturally occurring low molecular weight organic
acids to enhance the availability of heavy metals and increase phytoextr-
action efficiency.36,37
Phytoextraction is a publically appealing ‘‘green’’ remediation technique.
However, phytoextraction can be effectively applied only for soils and
10 Chapter 1
wetlands contaminated with specific potentially toxic metals and metalloids.

Many researchers have reported that common crop plants with a high bio-
mass can be triggered to accumulate large amounts of low bioavailability
metals when applied the phytochelates.38,39 In such chemically enhanced
phytoextractions, chelating agents are used almost exclusively as the mo-
bilizing agents.40 However, EDTA was the most efficient chelate to increase
metal uptake by plants of Pb, but the slow degradation of chelating com-
pounds in the root zone limits its application on an industrial scale.41

Nevertheless, more biodegradable chelates, such as NTA, (S,S-EDDS) and
other chelates are also recognized for metals removal. Application of these
chelating agents with plants for the uptake of metal ions is gaining more
popularity and has become an interesting field of research. Several studies
have been carried out using EDTA as a metal chelator for sequestration of
metals.42 The full-scale application for treating wastewater on an industrial
scale should be based on optimization of several parameters such as solu-
bilization of metals, chelates stability, plant roots and the capacity of metal
transport through the shoots of plants.43
1.4.3 Heterogeneous Catalysts and Catalysis

In 1972 Fujishima and Honda discovered the photocatalytic splitting of
water on titanium dioxide (TiO2) electrodes.44,45 Their discovery provided the
foundation stone for photocatalysis. Since this remarkable discovery much
research has been carried out on the efficiency of TiO2 as a photo-
catalyst.46–48 During the past few years, the applications of TiO2 for en-
vironmental cleanups have been performed by several laboratories for the
treatment of industrial effluents.49,50
During the photocatalysis system, photo-induced reactions take place at
the surface of a catalyst. Depending on where the initial excitation occurs,
photocatalysis can be generally divided into two classes of processes. When
the initial photo-excitation occurs in an adsorbate molecule, which then
interacts with the ground state catalyst substrate, the process is referred to as
a catalyzed photoreaction. When the initial photo-excitation takes place in
the catalyst substrate and the photo-excited catalyst then transfers an elec-
tron or energy into a ground state molecule, the process is referred to as a
sensitized photoreaction. The initial excitation of the system is followed by
subsequent electron transfer and/or energy transfer. It is the subsequent de-
excitation process that leads to chemical reactions in the heterogeneous
photocatalysis process.
1.4.4 Photocatalysts
Reduction of Cr(VI) using semiconductor heterogeneous photocatalysts
has been carried out as an economical and simple method of wastewater
treatment.51,52 Surface-catalyzed Cr(VI) reduction is a very slow reaction and
has been described as a feasible process in the presence of oxide surfaces
53
such as TiO2. Furthermore, organic donors have a chelation capacity for
the TiO2 surface, which accelerates the reduction of Cr(VI).54–57
Testa et al.58 carried out the reduction of Cr(VI) over TiO2 under near-UV
radiation. At pH 2, the addition of oxalate facilitated Cr(VI) reduction. It has
been found that the oxalic acid accelerates the reduction of Cr(VI) over TiO2
particles. Guo et al.59 have synthesized a plasmonic photocatalyst of Ag–
AgCl@TiO2 by deposition–precipitation and photoreduction. This photo-

catalyst exhibited efficient 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-
coagulation of heavy metals offers a cost-effective and easy-handling
technique on an industrial scale.63 This technique has been used for the
treatment of dyes, heavy metals, nitrates, fluorides and phenolic compounds
from wastewater.64–74 Recently, various workers have investigated electro-
coagulation for the removal of heavy metals from wastewater.75–77
Removal of Cr31 from aqueous solution by electrocoagulation using iron
electrodes is a feasible process. Golder et al.78 investigated the removal of
Cr31 from water by electrocoagulation methods. It was found that the co-
agulation and adsorption play very important roles in the removal of Cr31
during electrocoagulation. The removal of Cr31 from aqueous solution was
highest at a higher current density. A multiple electrode was used in the
electrocoagulation system for the removal of Cr31 from aqueous solution
with both bipolar and monopolar configurations.79 This technique can be
used for the treatment of pollutants down to the ppb level, but the high cost
of resin makes the process costly for industrial scale applications.80,81 Gao
et al.82 used a combined electrocoagulation and electroflotation system for
the removal of Cr61 from aqueous solutions. The performance of an elec-
trocoagulation system with aluminium electrodes for removing heavy metal
ions on a laboratory scale was studied systematically by Heidmann and
Calmano.83
Removal of heavy metal ions from wastewater by electrocoagulation with
iron and aluminium electrodes with monopolar configurations was in-
vestigated by Akbal and Camcı.84 They explored the influence of electrode
12 Chapter 1
material, current density, wastewater pH and conductivity on removal per-

formance. The results indicated that an electrocoagulation system with an
Fe–Al electrode was useful and 100% of the Cu, Cr and Ni were observed
within 20 min with a current density of 10 mA cm 2 and a pH of 3.0. The
performance of electrocoagulation, with an aluminium sacrificial anode, in
the treatment of wastewater containing metal ions has been investigated by
Adhoum et al.85 Cu, Zn and Cr were removed successfully by using this

technique. The method was found to be highly efficient and relatively fast
compared with conventional existing techniques. Direct electrochemical
reduction of Cr61 can be carried out at the cathode.86 The hydroxyl ions
produced at the cathode induce the coprecipitation of Cu, Zn and Cr.87–89
1.4.6 Clays/Layered Double Hydroxides (LDHs)

Clays have been widely used for the removal of heavy metals from aqueous
solutions due to their outstanding properties.90,91 Heavy metals can be re-
moved by ion exchange or a complexation reaction at the surface of clays.
During the past few years, surface modifications of natural clays with re-
agents containing metal binding groups have been explored.91–93 Several
modification techniques such as intercalation of organic molecules into the
interlayer space and grafting of organic moieties have been applied.94,95
Organic-modified clays based on montmorillonite were prepared by em-
bedding ammonium organic derivatives with different chelating function-
alities for heavy metal removal.96 Montmorillonite intercalated with poly-
hydroxyl Fe(III) complexes was used for the sorption of Cd(II).97 Sodium
dodecyl sulfate modified iron pillared montmorillonite has been success-
fully applied for the removal of aqueous Cu(II) and Co(II).98 Smectite inter-
calated with a non-ionic surfactant shows a good performance for the
removal of heavy metals.99 Through the grafting of inorganic and organic
components, natural clay can be functionalized to obtain a better sorption
capacity.100,101 Heavy metals have been removed through the grafting of
amino or mercapto by reaction with the silanol groups onto the surface of
clays.102,103 Synthesis of layered magnesium organosilicates for the removal
of heavy metals has been carried out with different organosiloxanes.104
Sepiolite can be grafted with organic moieties due to its high content of
silanol groups. Liang et al.90 have functionalized the sepiolite by nano-
texturization in aqueous sepiolite gel and surface grafting in toluene with
mercaptopropyltrimethoxysilane. The sorption of Pb(II) and Cd(II) were
studied and it was found that the surface modification can obviously in-
crease the sorption capacities for Pb(II) and Cd(II).
LDH materials appear in nature and can be easily synthesized in the la-
boratory. In nature they are formed from the weathering of basalts or pre-
cipitation in saline solution. All natural LDH minerals have a structure
similar to hydrotalcite, which has the formula [Mg6Al2(OH)16]CO3 4H2O.
LDHs have been prepared using many combinations of divalent to trivalent
cations including Mg, Al, Zn, Ni, Cr, Fe, Cu, Ga and Ca.105–118 A number of
synthetic techniques has been successfully employed in the preparation of

LDHs. There are a number of methods used to synthesize LDHs including
coprecipitation methods, hydrothermal synthesis, urea hydrolysis methods,
sol–gel methods, ion-exchange methods and rehydration methods.
LDHs have been investigated intensively for anion-exchange properties
due to recent interest in developing the use of anionic clays for environ-
mental remediation. The main characteristic that has been studied is to

clearly characterize the adsorption properties of the materials under vigor-
ous solid–liquid interface conditions. The effect of sorbent composition,
surface and bulk adsorption and concentration of adsorption site have been
assessed. The adsorption capacity is significantly affected by the nature of
the counter anion of the LDHs layer. LDHs can be used as precipitating
agents of heavy metal cations for the decontamination of wastewater. Mn21,
Fe21 and Cu21 cations have been removed by synthetic hydrotalcite-like
compounds, with zaccagnaite and hydrotalcite thin films being used for the
remediation of aqueous wastes containing hazardous metal ions.119
1.4.7 Biomass and Biosorption of Metal Ions

During the last few years numerous new processes have been tested suc-
cessfully, many of which have gone into operation and a great number of
papers have been published on biosorption. In this section we will discuss
‘‘Biomass based biosorbents and biosorption of heavy metals’’. Biosorption
has been defined as the ‘‘property of certain bio-molecules to sequester
metal ions or other molecules from aqueous solutions’’.120,121 It differs from
bioaccumulation, where active metabolic transport takes place, as biosorp-
tion involves a passive process in which interaction between sorbent and
sorbate occurs. Biosorption of heavy metals has become a popular and active
field of research in environmental science.122–126
Rao et al.127 have studied the removal of Cr(VI) and Ni(II) from aqueous
solution using bagasse based biosorbents. The bagasse was chemically
treated with 0.1 N NaOH followed by 0.1 N CH3COOH. The materials ad-
sorption capacity in order of selectivity for Cr(VI) and Ni(II) was powdered
activated carbon 4 bagasse 4 fly ash and powdered activated carbon 4 fly
ash 4 bagasse, respectively. Values for Langmuir and Freundlich isotherm
constants for sorption of Cr(VI) ions onto powdered activated carbon,
bagasse and fly ash were 0.03, 0.0005 and 0.001, and 0.12, 0.03 and 0.01,
respectively. A lower pH of 6.0 favors the uptake of Cr(VI) and pH 8.0 was
suitable for Ni(II) ions removal. However, an increase in pH values of the
solution reduces the Cr(VI) adsorption because of the abundance of OH
ions, causing hindrance to the diffusion of dichromate.128,129 However, the
adsorption capacity was very low and their application for industrial effluent
treatment cannot be justified.
Recently, pectin-rich fruit wastes have been investigated as biosorbents
for heavy metal ion removal.130 It has been observed that biosorption of
cadmium by pectin-rich fruit materials and citrus peels were found to be
14 Chapter 1
most suitable. Equilibrium kinetics were achieved within 30–90 min, de-
pending upon particle size. A pseudo-second order model was found to be
more suitable than a first-order model to describe the kinetics. Isotherm
studies show that the data were well fitted to a Langmuir model. It has also
been observed that the metal uptake decreased with decreasing pH, indi-
cating competition of protons for binding to acidic sites. Gurgel and Gil131
have described the preparation of two new chelating materials, MMSCB 3

and 5, derived from succinylated twice-mercerized sugarcane bagasse
(MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two
different 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 different 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 affinity of CH3HgCl 4 C2H5HgCl 4 Hg21, with
maximum sorption capacities of 79, 67 and 61 mg g 1, respectively.
The efficiency of Parthenium hysterophorous weed for the removal and re-
covery of Cd(II) ions from wastewater has been studied by Ajmal et al.133
These workers reported that the kinetics data for the adsorption process
obeyed the second-order rate equation. The adsorption process was found
to be endothermic and spontaneous in nature. The maximum adsorption
capacity of Cd(II) ions was 99.7% in the pH range 3–4. The desorption studies
confirm 82% recovery of Cd(II) when 0.1 M HCl solution was used as the
effluent. Coconut copra meal, a waste product of the coconut industry, was
used for the removal of cadmium from water.134 The biosorption process
was a spontaneous and exothermic process in nature.
Rao et al.135 tested the biosorption potential of fennel biomass (Foenicu-
lum vulgari) for the removal of Cd(II) from water. It was found that the bio-
sorption of Cd(II) was a chemically controlled process. Removal of Cd(II) was
concentration dependent and increased with an increase in metal ion con-
centration, which showed that the multilayer adsorption takes place at the
surface of the biosorbent and it was best described by a Freundlich isotherm
model and pseudo-second order rate kinetics. El-Said et al.136 utilized rice
husk ash for the removal of Zn(II) and Se(IV) from water. A higher removal
capacity of Zn(II) was found than for Se(IV). The removal capacity increases
with an increase in biosorbent dose from 1 to 10 g L 1.
Recently, Schiewer and Iqbal137 investigated the role of pectin for the
removal of cadmium from water. The carboxyl group plays an important role
in the surface charge and was responsible for the binding of cadmium onto
the biosorbent surface. Typically, metal binding experiments were carried
out at an optimized pH of 5. A Langmuir isotherm model provided the best
fit. Metal binding kinetics were better described by the first-order model
than by the second-order model.
Removal of mercury from water was carried out using Carica papaya as a
biosorbent.138 Sulfuric acid treated almond husk based activated carbon was
prepared and used for the sorption of Ni(II) ions from water.139 The ad-

sorption capacity was very high and 97.8% Ni(II) ions were removed by an
adsorbent dose of 5 g L 1.
1.4.8 Magnetic Nanoparticles as Nanosorbents

Magnetic nanomaterials are one of the recently highlighted branches of
materials science and technology that have been utilized in the removal of
pollutants from aqueous solutions. Owing to their magnetic properties, high
chemical stability, low toxicity, ease of synthesis and excellent recycling
capability, magnetic nanoparticles have been studied to remove toxic metal
ions from water.
Magnetic nanoparticles are of great interest for researchers from a wide
range of disciplines, including magnetic fluids, catalysis, biomedicine,
drug delivery, magnetic resonance imaging, data storage and environ-
mental remediation.140,141 Although several suitable methods have been
developed for the synthesis of magnetic nanoparticles for a variety of dif-
ferent compositions, successful application of such magnetic nano-
particles in the areas listed here is particularly dependent on the stability of
the particles under a range of different conditions. In the majority of the
envisaged applications, the particles perform best when the size of the
nanoparticles is below a critical value, which is dependent on the source
material but is typically around 10–20 nm.142 The design and fabrication of
nanoparticle-based adsorbents has generated great interest in a variety of
scientific communities ranging from chemical, biological and environ-
mental science to engineering. Magnetic nanoparticle-based adsorbents
can be used in the separation and purification of biologically as well
as environmentally relevant target species with high precision and
accuracy.143,144
1.4.9 Removal of Iron and Manganese from Water

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

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

taneous addition of polyphosphate and chlorine were both fairly successful
at removing the iron.
1.4.9.1 Ion Exchange

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

Omri and Benzina152 achieved the removal of Mn(II) ions from aqueous so-
lutions by adsorption on activated carbons derived from Ziziphus spina-
christi seeds. The effects of process parameters such as solution pH, initial
metal ion concentration and temperature on the adsorption performance of
activated carbons for Mn(II) ions removal were tested to optimize the system.
Maximum adsorption was obtained at pH 4. Freundlich isotherms followed
the adsorption system and the higher adsorption capacity for a Langmuir
isotherm was 172 mg g 1. Adsorption of iron and manganese ions from
aqueous solution by low-cost adsorbents of palm fruit bunch and maize cobs
was carried out.153 Adsorption of iron ions on palm fruit bunch and maize
cobs was in the range of 80–57%, for initial concentrations ranging between
1 and 10 ppm.
Recently, Mengistie et al.154 performed the adsorption of Mn(II) by
using activated carbons of Militia ferruginea leaves from aqueous solutions
in the batch mode. Adsorption equilibrium was achieved within 2 h. It had
been found that pH 4 was appropriate for Mn(II) removal and 95.8% metal
ions were removed. The adsorption isotherms were best fitted to a Freun-

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

The effect of various organic acids, such as acetic, formic, citric, ascorbic,
succinic, tartaric and oxalic acids, on the removal of iron has been studied by
Ambikadevi and Lalithambika.156 It was found that the oxalic acid gives the
best results, both at room temperature as well as at high temperatures, be-
cause of its high acid strength, good complexing capacity and reducing
power. The effects of several parameters such as time, temperature and re-
agent concentration were studied for the optimization process. The removal
of iron was found to be B80% by the authors.
Ganesan et al.157 used an electrocoagulation process for removal of Mn(II)
from aqueous solutions using magnesium as the anode and galvanized iron
as the cathode. Several removal parameters such as solution pH, current
density, electrode configuration, inter-electrode distance, effects of coexist-
ing ions and temperature were studied. The results obtained suggested that
the highest removal of 97.2% at a pH of 7.0 was for a current density
0.05 A dm 2 with an energy consumption of 1.151 kWh m 3. Thermodynamic
parameters indicated that the Mn(II) removal was feasible, spontaneous and
endothermic in nature. A Langmuir adsorption isotherm well fitted to the
adsorption system. The kinetic model was best described by a pseudo-second
order rate at the various current densities. Taffarel and Rubio158 applied
Chilean zeolite as an adsorbent for removal of Mn(II) ions from aqueous
solutions. The solution pH significantly influenced the adsorption of Mn(II)
removal and the best results were been found at pH 6–6.8. The removal
kinetics was best fitted with a pseudo-second order model. The equilibrium
isotherm data were best fitted to a Langmuir isotherm model. It was found
that the Chilean zeolite treated with NaCl, NaOH, Na2CO3 and NH4Cl in-
creased its uptake ability in comparison with natural Chilean zeolite.
18 Chapter 1
1.5 Concluding Notes

The presence of heavy metals and their toxicity to the environment and to
human beings is posing a serious challenge to environmental engineers with
respect to the treatment of wastewater effluents prior to discharge into the
nearby water bodies. Several removal techniques have been developed and
applied for the treatment of these wastes to remove the toxic metal ions.
Technologies such as microbe-assisted phytoremediation, ion exchange,

membrane filtration, photocatalytic oxidation and reduction and adsorption
have their own advantages and disadvantages over metal ion sequestrations
from environmental matrices. During recent years the developments in ad-
sorption of heavy metals from aqueous solutions have gained tremendous
popularity among the scientific community as methods to treat industrial
wastewater. Several adsorbents such as clays, LDHs, zeolites, carbon nano-
tubes and their composites, activated carbons, biomass derived biosorbents,
inorganic nanomaterials, inorganic organic hybrid nanocomposites and
magnetic nanomaterials have been synthesized and investigated for their
ability to sequester metal ions from water.
Functionalized magnetic nanoparticles are very promising for appli-
cations in catalysis, biolabelling and bioseparation. In liquid-phase ex-
traction of heavy metals and dyes in particular, such small and magnetically
separable particles may be useful as they combine the advantages of high
dispersion, high reactivity, high stability under acidic conditions and easy
separation. In this chapter we focused mainly on recent developments in the
synthesis of active adsorbents and nanoparticles. Further, functionalization
and application of magnetic nanoparticles and their nanosorbents for the
separation and purification of hazardous metal ions from the environment
are discussed in detail in a separate chapter in this book.
Acknowledgements
R.K. Gautam thanks the University Grants Commission for the award of a
Junior Research Fellowship (JRF). Suresh Mahiya is grateful to the President,
JECRC University, for the award of Scholarship for his PhD. The authors
equally acknowledge the support and provision of the necessary facilities by
the University of Allahabad, Allahabad, India and JECRC University, Jaipur,
India. The support and encouragement of Prof. V.S. Tripathi from the De-
partment of Chemistry, University of Allahabad, is also appreciated. We also
thank the anonymous editors and reviewers for giving their kind criticisms
and comments, which fuelled the zeal for the manuscript.
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CHAPTER 1

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Heavy Metals in Water: Presence, Removal and Safety

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

1.2 Sources of Heavy Metals

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concentrations. Mining, metallurgy and industrial applications are the

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and anthropogenic sources. Volcanic eruptions, geological weathering of

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ion-exchange resins, photocatalytic reduction and adsorption for treatment

1.4 Remediation Technologies

 Precipitation and coagulation

1.4.1 Membrane Filtration

homogeneous polymer thin films supported by a porous support structure.

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phytostabilization, phytoextraction, phytofiltration or rhizoremediation.

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wetlands contaminated with specific potentially toxic metals and metalloids.

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1.4.3 Heterogeneous Catalysts and Catalysis

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material, current density, wastewater pH and conductivity on removal per-

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1.4.6 Clays/Layered Double Hydroxides (LDHs)

synthetic techniques has been successfully employed in the preparation of

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1.4.7 Biomass and Biosorption of Metal Ions

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1.4.8 Magnetic Nanoparticles as Nanosorbents

1.4.9 Removal of Iron and Manganese from Water

the addition of oxidants such as chlorine and potassium permanganate.

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1.4.9.1 Ion Exchange

1.4.9.2 Activated Carbons

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1.4.9.3 Other Treatment Methods

1.5 Concluding Notes

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3. Agency for Toxic Substances and Disease Registry, Toxicological Profile

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89. U. B. Ogutveren, N. Gonen and A. S. Koparal, Int. J. Environ. Stud., 1994,

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115. L. M. Grand, S. J. Palmer and R. L. Frost, J. Therm. Anal. Calorim., 2010,

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143. F. M. Koehler, M. Rossier, M. Waelle, E. K. Athanassiou, L. K. Limbach,

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