INTRODUCTION

Heavy Metal:

Over the past two decades, the term "heavy metals" has been widely used. It is often used as a
group name for metals and semimetals (metalloids) that have been associated with
contamination and potential toxicity or ecotoxicity. At the same time, legal regulations often
specify a list of "heavy metals" to which they apply.

Heavy metals are generally defined as metals with relatively high densities, atomic weights,
or atomic numbers. The criteria used, and whether metalloids are included, vary depending
on the author and context. In metallurgy, for example, a heavy metal may be defined on the
basis of density, whereas in physics the distinguishing criterion might be atomic number,
while a chemist would likely be more concerned with chemical behaviour. More specific
definitions have been published, but none of these have been widely accepted. The
definitions surveyed in this article encompass up to 96 out of the 118 known chemical
elements; only mercury, lead and bismuth meet all of them. Despite this lack of agreement,
the term (plural or singular) is widely used in science. A density of more than 5 g/cm3 is
sometimes quoted as a commonly used criterion and is used in the body of this article.

The earliest known metals—common metals such as iron, copper, and tin, and precious
metals such as silver, gold, and platinum—are heavy metals. From 1809 onwards, light
metals, such as magnesium, aluminium, and titanium, were discovered, as well as less well-
known heavy metals including gallium, thallium, and hafnium.

Some heavy metals are either essential nutrients (typically iron, cobalt, and zinc), or
relatively harmless (such as ruthenium, silver, and indium), but can be toxic in larger
amounts or certain forms. Other heavy metals, such as cadmium, mercury, and lead, are
highly poisonous. Potential sources of heavy metal poisoning include mining, tailings,
industrial wastes, agricultural runoff, occupational exposure, paints and treated timber.

Physical and chemical characterisations of heavy metals need to be treated with caution, as
the metals involved are not always consistently defined. As well as being relatively dense,
heavy metals tend to be less reactive than lighter metals and have much less soluble sulphides
and hydroxides. While it is relatively easy to distinguish a heavy metal such as tungsten from
a lighter metal such as sodium, a few heavy metals, such as zinc, mercury, and lead, have
some of the characteristics of lighter metals, and, lighter metals such as beryllium, scandium,
and titanium, have some of the characteristics of heavier metals.

What is heavy metal?

The availability of good quality water is an indispensablefeature for preventing diseases and
improving quality of life (Oluduro and Aderiye, 2007). Natural water contains some types of
impurities whose nature and amount varywith source of water. Metals for example, are
introducedinto aquatic system through several ways which include,weathering of rocks and
leaching of soils, dissolution of aerosol particles from the atmosphere and from severalhuman
activities, including mining, processing and theuse of metal based materials (Ipinmoroti and
Oshodi,1993; Adeyeye, 1994; Asaolu et al., 1997). Metals afterentering the water many be
taken up by fauna and floraand eventually, accumulated in marine organisms thatare
consumed by human being (Asaolu et al., 1997).

The contamination of aquatic and terrestrial ecosystems with heavy metals is a major
environmental problem. Some of these metals are potentially toxic or carcinogenic at
sufficient concentrations and can cause serious human health hazards if they enter the food
chain. Investigations have been made of the extent of heavy metal pollution of surface water,
groundwater, soils, air and vegetation by mining and associated industrial activities,
particularly thermal power plants and opencast coal mines. Metal pollution by mining and
associated industrial activities is somewhat mitigated today by strict implementation of clean
technology and environmental measures. However, metals released previously by such
activities have been retained in the sediments and soils, and still contaminate surface and
ground water resources.

In this thesis, we examined an area that includes three very large (Mines I, II and III) and few
small lignite mines, associated industries (two pit-head thermal power plants, a urea plant,
and a briquetting and carbonization plant) that are operated by Neyveli Lignite Corporation
Ltd. (NLC), and an independent power plant.
Accumulation of heavy metals:

Accumulation of heavy metals is a process by which highly toxic heavy metals accumulate in
the bodies. These heavy metals accumulating finally enter the food web and create many
hazards.

Process of accumulation:

Heavy metals accumulate in environment by many ways, industrial activities, spray of

pesticides, improper irrigation, mixing of highly toxic substances in water, mining, improper
waste disposal , e waste etc.,

Due to use of improper water or un healthy water for irrigation the mean concentrations of
Pb, Ni, Cu , Cd content in soil were much above the recommended level. The concentrations
of Pb, Zn, Cd, Cr and Ni in all the examined vegetables were beyond the safe limits. This
shows us that heavy metal-contaminated vegetables grown in wastewater-irrigated areas may
pose public health hazards. (An Assessment of Heavy Metal Contamination in Vegetables
Grown in Wastewater-Irrigated Areas of Titagarh, West Bengal, India)

A study in dakha from bangladesh tells us that the concentrations of Cu, Zn, Pb, Cr, Cd, Fe,
and Ni have been estimated in soils and vegetables grown in and around an industrial area
of Bangladesh. The order of metal contents was found to be Fe > Cu > Zn > Cr > Pb > Ni >
Cd in contaminated irrigation water, and a similar pattern Fe > Zn > Ni > Cr > Pb > Cu >
Cd was also observed in arable soils. Metal levels observed in different sources were
compared with WHO, SEPA, and established permissible levels reported by different
authors. Mean concentration of Cu, Fe, and Cd was higher than the recommended.

(Heavy metal contamination in water, soil, and vegetables of the industrial areas in Dhaka,
Bangladesh)
Heavy metals enter into soil, water and food even by use of pesticides and fertilizer. It is
studied furter with a study done by (Timothy Musa CHIROMA, Bala Isah ABDULKARIM,
Haruna Mavakumba KEFAS ) stating that the impact of Pesticides (DELVAP 1000EC)
application on the levels of Cd, Pb and Cu in two species of Spinach (maroon and green) was
investigated. The results shows highest accumulation in leaves compared to stem and roots
for both species. The levels of Cd, Pb and Cu in leaves of maroon Spinach treated with
pesticides are 6.8, 1.4 and 18.6 times respectively higher than the maximum tolerable levels
of 30µg/g, 300µg/g and100µg/g for Cd, Pb and Cu respectively in plants, while in green
Spinach treated with pesticides the levels of Cd and Cu in leaves are 4.9 and 14.7 times
respectively higher than the maximum tolerable levels. The concentration of Cd, Pb and Cu
in leaves, stem and roots of maroon Spinach treated with pesticides are 163%, 222% and
178%; 364%, 325% and 449%; and 254%, 363%and 224% respectively higher than the
untreated Spinach while their corresponding concentration in green Spinach treated with
pesticides are 1! 56%, 238% and 150%; 163%, 454% and 462%; and 156%, 407% and 346%
respectively higher than the untreated green Spinach.

Mining can be also considered as a major reason for heavy metal exposure (Heavy metal
pollution induced due to coal mining effluent on surrounding aquatic ecosystem and its
management through naturally occurring aquatic macrophytes).
These are some major ways of exposure to heavy metals.

Hazards of accumulation:

Heavy metal toxicity has proven to be a major threat and there are several health risks
associated with it. The toxic effects of these metals, even though they do not have any
biological role, remain present in some or the other form harmful for the human body and its
proper functioning. They sometimes act as a pseudo element of the body while at certain

times they may even interfere with metabolic processes. (Toxicity, mechanism and health

effects of some heavy metals).

The heavy metal cadmium (Cd) is known to be a widespread environmental contaminant

and a potential toxin that may adversely affect human health. Exposure is largely via the
respiratory or gastrointestinal tracts; important non-industrial sources of exposure are
cigarette smoke and food (from contaminated soil and water). The kidney is the main organ
affected by chronic Cd exposure and toxicity. Cd accumulates in the kidney as a result of
its preferential uptake by receptor-mediated endocytosis of freely filtered and
metallothionein bound Cd (Cd-MT) in the renal proximal tubule.( Heavy metal poisoning:
the effects of cadmium on the kidney )

The 21st generation diseases are more generated by heavy metal poisoning.

Heavy metal poisoning:

Heavy metal poisoning is caused by the accumulation of certain metals in the body due to
exposure through food, water, industrial chemicals, or other sources. While our bodies need
small amounts of some heavy metals — such as zinc, copper, chromium, iron, and
manganese — toxic amounts are harmful.
List of heavy metals:

Heavy metal is a dense metal that is (usually) toxic at low concentrations. Some lighter
metals and metalloids are toxic and, thus, are termed heavy metals though some heavy
metals, such as gold, typically are not toxic.

Most heavy metals have a high atomic number, atomic weight and a specific gravitygreater
than 5.0 Heavy metals include some metalloids, transition metals, basic metals,
lanthanides, and actinides. Although some metals meet certain criteria and not others, most
would agree the elements mercury, bismuth, and lead are toxic metals with sufficiently high
density.

List:

Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Gallium,
Germanium, Arsenic, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium,
Rhodium, Palladium, Silver, Cadmium, Indium, Tin, Tellurium, Lutetium, Hafnium,
Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Thallium, Lead,
Bismuth, Polonium, Astatine, Lanthanum, Cerium, Praseodymium, Neodymium,
Promethium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium,
Thulium, Ytterbium, Actinium, Thorium, Protactinium, Uranium, Neptunium, Plutonium,
Americium, Curium, Berkelium, Californium, Einsteinium, Fermium, Nobelium, Radium,
Lawrencium, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium,
Darmstadtium, Roentgenium, Copernicium, Elements 113-118.

Indentification of heavy metals:

Presently there are huge number of ways of ways to find the presence of heavy metals. Our
concerned technique is voltametry . Some other techniques and the presence of heavy metals.

1. Multivariate statistical techniques

Arable layer of pastureland in Galicia (NW Spain) was monitored for total content of heavy
metals, and analysed by multivariate statistical techniques, in order to investigate the different
origin that metals may have in pasture soils. Principal component analysis (PCA), cluster
analysis (CA) and correlation matrix (CM) were applied to 65 samples in which the total
concentrations of Mn, Fe, Zn, Cu, Cr, Co, Ni, Cd and Pb were measured. Four significant
components were extracted by PCA, explaining 78.830% of total variance. Mn, Co and Ni
(and partially Cu), and Fe and Cr, were associated in two lithogenic components,
respectively, while an anthropogenic origin was identified for Cd, Pb and Zn. Zn (and Cu)
were mainly associated with soil fertilisation by cattle slurry or with other activities regarding
cattle management. Although the origin of Cd and Pb was also attributed to slurry
application, other sources like commercial fertilisers, vehicle exhaust or aerial deposition
were not discarded as possible contributors.( Source identification of heavy metals in
pastureland by multivariate analysis in NW Spain)

Volatametry:

Voltammetry is a category of electroanalytical methods used in analytical chemistry and

various industrial processes. In voltammetry, information about an analyte is obtained by
measuring the current as the potential is varied. The analytical data for a voltammetric
experiment comes in the form of a voltammagram which plots the current produced by the
analyte versus the potential of the working electrode.

Types of volametry:

1. Linear sweep voltammetry

2. Staircase voltammetry
3. Squarewave voltammetry
4. Cyclic voltammetry
5. Anodic stripping voltammetry
6. Cathodic stripping voltammetry
7. Adsorptive stripping voltammetry

8. Alternating current voltammetry

9. Polarography
10. Rotated electrode voltammetry
 11. Normal pulse voltammetry
12. Differential pulse voltammetry
13. Chronoamperometry

Study Area:

Materials and Methods

Twenty-eight representative surface-water samples were collected from mine sumps and
effluents power-plant reservoirs and effluents, fly-ash ponds, natural ponds and the river in
the vicinity of the Neyevli mine industrial complex. Sampling was carried out in Feb. 2003
using standard techniques (APHA 1995). Sampling stations are shown in Figure 5. Water
samples were collected in sterile 1 L polyethylene bottles and after being filtered (pore
size=0.45µm), each sample was treated with 10 ml HNO3 to prevent possible precipitation of
heavy metals.

The water samples were analyzed for heavy metals according to international standard
methods (APHA 1995). The analyses of Cu, Fe, Cr, Mn, Ni and Co were performed in the
Dept of Geology, A.M.U., Aligarh, using Atomic Absorption Spectrophotometer (AAS)
(Perkin-Elmer, Aanalyst 800). The Pb, Hg, and Cd analyses were done in the Toxicology and
Environmental Lab, Dept. of Medical Elementology and Toxicology, Hamdard University,
New Delhi, using AAS (Analytic Xena Zeenit 65). In the heavy metal analysis by AAS,
quality control was monitored using 10% sample blanks and 10% sample replicates in each
set of sample analyses.
What are the components of heavy metal?

Where are they present?

Why we need to anyasis the heavy metals?

What are the methods used?

Reasons of location selections.

Literature survey:

Indian locations:

Abida Begum et al. analysed the heavy metals in water, sediments and fish samples of
Madivayalakesh of Bangalore, Karnataka [1]. The river Ganges has been one of the major
recipients of industrial effluents in India. Aradhna Gupta et al. [6] studied the occurrence and
bioaccumulation of heavy metals (Cu, Cr, Cd, Pb, Zn) in the riverine water, sediment, and the
muscles of two cat fish species, Channa punctatus and Aorichthysaorprocured from the river
Ganges atAllahabad. For their studies, they used Atomicabsorption spectrophotometer
method for the heavy metals detections. They concluded that the heavy metals accumulation
in fish muscles was found to be similar to thatobserved in sediment and water such as
Zn>Pb>Cu>Cr>Cd.Kamala-Kannan et al. [13] studied the concentrations of three heavy
metals chromium (Cr), cadmium (Cd) and lead (Pb) in water, sediment and green algae (Ulva
lactuca). They collected the samples from six different stations at Pulicat Lake, which
receives effluents from industries located in North Chennai Coastal region. Concentrations of
Cd (64.21 μg g−1) and Cr (28.51 μg g−1) were found to be high in sediment, whereas in green
algae concentration of Pb (8.32 μg g−1) was higher than water and sediment samples.Suthar et
al. [16] took the studied of heavy metals (Cd, Cr, Cu, Fe, Mn, Zn and Pb) in water and
sediments of Hindon River in industrialized city Ghaziabad, India. A total of 6 stations,
covering the upstream and downstream sites of Hindon, were selected for their study. They
found that the metal concentration (mg kg−1) ranged in the following: Cd, 1.15–3.47; Cu,
9.42–195.1; Cr, 42.9–250.4; Fe, 221.2–237.9; Mn, 61.0–201.7; Zn, 3.98–85.0; and Pb, 5.07–
59.1 in river sediments.
In order to achieve a better understanding of the nature of the factors influencing
ground water composition as well as to specify them quantitatively, multivariate statistical
analysis (factor analysis) were performed on the hydrochemical data of Neyveli area. R-mode
factor analysis was carried out in [21]. On the geochemical results of the 79-groundwater
samples and the factor scores were transferred to areal maps. In [21], Jayaprakash et al.
fundamental chemical parameters of the groundwater have been compounded together for
characterizing and interpreting a few empirical hydrogeochemical factors controlling the
chemical nature of water. R-mode factor analysis reveals that the groundwater chemistry of
the study area Neyveli reflects the influence of anthropogenic activities, silicate weathering
reactions, precipitation, dissolution and subsequent percolation into the groundwater.

Athimoolam and Ramachandran [22] collected water samples from various places in Neyveli.
The data were processed with computer for statistical interpretation and presented in mean
values (ppm) with Standard Error; significance was calculated with use of student’s ‘t’ test
and ANOVA.

Bably Prasad et al. [23] studied the concentrations of 7 heavy metals have been evaluated at
20important ground water sampling stations at Dhanbad township situated very near to Jharia
coalfields. The detection limit of AAS was well with in the range for all elements analysed.

A long mining history and unscientific exploitation of Jharia coalfield caused many
environmental problems including water resource depletion and contamination. In [24], Singh
et al. considered a geochemical study of mine water in the Jharia coalfield to assess its quality
and suitability for domestic, industrial and irrigation uses. For this purpose, they collected 92
mine water samples collected from different mining areas of Jharia coalfield and analysed for
pH, electrical conductivity (EC), major cations (Ca2+, Mg2+, Na+, K+), anions (F−, Cl−,
HCO3−, SO42−, NO3−), dissolved silica (H4SiO4) and trace metals. The pH of the analysed
mine water samples varied from 6.2 to 8.6, indicating mildly acidic to alkaline nature.

In [25], India Shankar, Aravindan and Rajendran, studied GIS based Groundwater Quality
Mapping in Paravanar River Sub Basin, Tamil Nadu. This study area Paravanar basin lies in
the Cuddalore District of Tamil Nadu, which is near to Neyveli. A GIS based groundwater
quality mapping has been carried out in the region with the help of data generated from
chemical analysis of water samples collected from the basin. They tried to attempted to study
on the quality of ground water for the Villages falling in the Paravanar Sub Basin to
interpolate major ions concentration in groundwater by using ARC/view GIS software. They
concluded that the study area sulphates were found to be within prescribed limit for drinking
purpose.
Groundwater chemistry of mining region of East Singhbhum district, Jharkhand, India
having complex contaminant sources were investigated by Umesh Kumar Singh et al. [26].
Their studies based on heavy metals loads and other hydrochemical constituents. In their
studies they identify the degree of heavy metals exposure and their potential health risk to
local population. The results of hydrochemical analysis showed that Na+, K+, and Ca2+ ions
are the dominant cations in the groundwater, while HCO3−, F− and Cl− ions dominate the
anionic part of the groundwater.

Ammaiyappan Selvam and Ayyamperumal Mahadevan [27], gave a survey on Presence of

arbuscular mycorrhizal (AM) species in an abandoned lignite fly ash pond, overburden
dumps and reclaimed overburden dumps in Neyveli region.

MunirathinamVelan and Majeti N V.Prasad [28] were studied Neyveli Lignite Mine Waste
Rehabilitation for Sustainable Development.

Locations outside India:

The distribution of some heavy metals in water and fish from Fayoum Governorate (Egypt)
was studied in [2]. Analysis of Heavy Metals in Water and Surface Sediment in Five Rift
Valley Lakes in Kenya for Assessment of Recent Increase in Anthropogenic Activities was
studied by Ochieng et al. [3].RADULESCU Radulescu et al. [4] studied heavy metals levels
(Pb, Cd, Cr, Ni, Mn, Zn and Fe), in different samples like, surface water, depth water and
therapeutic mud, collected from seven salt lakes from Romania. They used atomic absorption
spectrometry for their studied.The same atomic absorption spectrometry was used for
measuring the heavy metals (Cd, Co, Cu, Fe, Hg, Mn, Mo, Ni, Pb and Zn) in the water by
Karadede, and Ünlü [5]. They took sediment and fish species (Acanthobramamarmid,
Chalcalburnusmossulensis, Chondrostomaregium, Carasobarbusluteus, Capoettatrutta and
Cyprinuscarpio) from the Atatürk Dam Lake, Turkey. They concluded that the heavy metals
Cd, Co, Hg, Mo and Pb were not detected in water, sediments and fish samples, while Ni was
undetectable levels in fish samples. Levels of Cu, Fe, Mn and Zn varied depending on
different tissues.Öztürk et al. [7] studied some heavy metals (Cd, Cr, Cu, Fe, Ni and Pb)
presents in water, sediment and some tissues of Cyprinuscarpiofrom Avsar Dam Lake, which
is an important water source for irrigation and drinking in Turkey. Heavy metal levels in
water, sediment and fish samples were analyzed by inductively coupled plasma spectroscopy
(ICP/AES).Farghaly [8] took tap water samples in Assiut city, Egypt in eight sampling sites
of different locations. The samples were analyzed to determine the total content of cadmium,
copper, lead and zinc by differential pulse anodic stripping voltammetry (DPASV) while
nickel and cobalt were determined by a new simple differential pulse adsorptive stripping
voltammetry (DPAdSV), using dimethylglyoxime (DMG) as the complexing agent.

Bolormaa et al. [9] studied chemical analysis of the Boroo River water samples collected in
mining area of Mongolia focusing the determination of heavy metal contents by particle
induced X-ray emission (PIXE) technique. Bruns [10] conducted experiments under
laboratory conditions to investigate induced sulphur-rich compounds in the presence of heavy
metals using HPLC including on-line derivatization. They took water moss
Fontinalisantipyretica to investigate the heavy metal pollution in the river Elbe, Germany.
The Lerma is one of the most important rivers of Mexico, where it drains highly populated
and industrialized regions. Zarazua et al. [11] took the heavy metal studies in the locality of
the Upper Course of the Lerma River (UCLR). They determined the heavy metal
concentration of Cr, Mn, Fe, Cu and Pb in dissolved and total phases of the UCLR by means
of Total Reflection X-ray Fluorescence Spectrometry (TXRF). For a period of one year, they
collected the surface water samples at 8 sites distributed following the stream flow direction
of the river. They observed that total heavy metal average concentration decrease was in the
following order: Fe (2566 μg/L) > Mn (300 μg/L) > Cu (66 μg/L) > Cr (21 μg/L) > Pb
(15 μg/L).Adefemi and Awokunmi [12] studied the physico-chemical parameters and heavy
metals in hand-dug wells and Ona River in Itaogbolu area of Akure, Nigeria. The
distributions of heavy metals in the Langat River were studied by Sukiman B. Sarmani [14]
for a period of six months between September 1984 and February 1985. Heavy metals such
as arsenic, cadmium, cerium, cobalt, chromium, caesium, lanthanum, rubidium, antimony,
scandium, thorium and zinc were determined in water, suspended materials and sediment
samples from the Langat River by neutron activation and atomic absorption spectrometry.