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Introduction
Natural waters having a contact with different chemical variations of the rocks, inevitably
gain a specific composition. Anthropogenic activities can alter the relative contributions of the
natural causes of variations and also introduce the effects of pollution. The interaction of all
factors leads to various river water types. The Geochemical study of river water gives significant
information on chemical weathering of rock as well as sediment, chemical and isotopic
compositions of drainage and even of the upper continental crust. The hydro-chemical
characteristics of river water determine its usefulness for agricultural, municipal, industrial and
domestic water supplies. The suitability of water for each of its various uses depends on the type
and concentration of the dissolved minerals. River pollution has become a major environmental
problem that is becoming critical in developing countries of the world because of inadequacy of
surface water quality protection measures and proper management.
Environmental geochemistry focuses on the processes involved in the distribution and
transport of chemical substances, as well as the identification of element sources. The studies of
river water are important due to the need to understand the weathering, hydrological, seasonal,
and various anthropogenic factors which influence the water quality. The chemical properties of
rivers are reflections of complex natural and interdependent relationships involving the
chemistry of precipitation, the weathering of minerals, and the evolution or history of its water.
Chemical weathering is an extremely important component of many basic geochemical processes
on the surface of the earth by which simpler dissolved ions and secondary clay minerals are
released from primary minerals and ultimately transported to ocean by rivers. Minerals present in
the rocks completely or partially dissolve in water according to the resistance of chemical
weathering and make the chemical composition of the river water. The solute concentration of
the river water system is proportional to the reactivity of the bedrock minerals constituting the
catchment. Moreover, the changes in river water chemistry can reflect the influence of
anthropogenic activities on water environment to some extent. Urbanization also affects the
processes that control stream flow of the river channels and water quality. Climatic influence on
chemical weathering might also be the reason for the differences in the thermodynamic
interactions between minerals and solutions. Geochemical processes, occurring within the river
water and their reactions with the sediment materials are responsible for changes in the river
water chemistry and a number of studies of river water chemistry and geochemistry focused on

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identifying the various contributions of the different sources to the water solutes, and estimating
weathering rates of continental crust.
The dissolved ions in river water are derived from various sources and compositional
relations among them can reveal the origin of solutes and the processes that generated the
observed water compositions. Chemistry of rivers is also dependent upon their watershed
features namely vegetation, geology, temporal and spatial variation in climate and topographical
features. The interaction of all factors leads to various water types. In the recent years, the
growth of industrial technologies, population, and water usage has increased the stress upon the
river water resources. Rivers play an important role in the progress of human civilization and are
important natural potential sources of different uses. Agriculture is a major source of several
nonpoint source pollutants, including nutrients, sediment, pesticides, and salts. The impact of
point source pollution in rivers can be localized and well-defined, whereas the influence of non-
point pollution is less obvious because of the poorly defined origins, volume, and frequency of
loading. Regardless of origin, both the source loads typically find their way to rivers and streams
and potentially lead to substantive pollution.
Heavy metals in drinking water represent a variety of health concerns among them some
are known or suspected carcinogens, such as lead and cadmium. Some metals are essential to
human nutrition at low doses, yet demonstrate adverse health effect at higher doses. Heavy metal
contamination is a major problem of riverine environment due to their non-degradable nature and
often accumulates through trophic level causing deleterious biological effects. Therefore,
monitoring of heavy metals is important for safety assessment of the environment in general and
human health in particular. Industrial wastewater contain appreciable amounts of metals, and
their long term, continuous discharge into the water body results elevated metal concentrations in
water and sediments. Even though the metals are present in the dilute, undetectable quantities,
their recalcitrance and consequent persistence in water bodies imply that through natural
processes, concentrations may become elevated to such an extent that they begin to exhibit toxic
characteristics.

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Damodar river basin

The river Damodar is one of the prominent tributaries of our holy river the Ganga. The river
originating from the Khamarpet hill, Palamou district of Chotonagpur Plateue of Jharkhand
travels about 541 km in the eastern part of India and ends to the river Hooghly at lower Ganga
near Syampur at 55 kms downstream of Howrah. During its course the river flows through the
large cities like Ramgarh, Bokaro, Dhanbad, Asansol, Durgapur, Burdwan and Howrah.
Industrial discharges from coke oven plants, sponge iron industries and several coal washeries
discharge their thick effluents directly / indirectly into the river at different points in its course.
The River basin area extends from 22°45’N to 24°30’N and 84°45’E to 88°00’E and
circumscribes parts of Jharkhand and West Bengal. Basin geology is mainly characterised by
rocks consisting of granites and granitic gneisses of Archean age, sandstones and shales of the
Gondwana age and the recent alluvials. Seasonal rainfall occurs due to the South-Western
monsoon every year and floods occur depending on the intensity of the storms. The Damodar
being a peninsular Indian river, its tributaries are used to serve a variety of purposes including
drinking, recreation, agriculture, and industry. Such an indispensable vital water course is
affected by the changing land use pattern, together with the discharge of excessively huge
volume of industrial effluents and silt load from sand and coal mining activities.

Objectives of the research:

• Spatio-temporal variation of solute load and elemental chemistry, hydrogeochemical

• Assessment of spatio-temporal distribution of heavy metals in river bottom sediment and

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• Metal pollution assessment and thematic zonation of the Damodar river on the basis of
various pollution indices in GIS environment.

Methodology Adopted
This chapter includes the various techniques and methods involved in the study of the
river water and sediment characteristics along with detailed description of the materials required
and equipments used for analytical tools. In order to obtain the research objective, samples were
collected from twenty seven locations from the river Damodar on seasonal basis (premonsoon,
monsoon and postmonsoon season) with the duration of three years (2007-2009). Analysis of
physicochemical parameters like pH, electrical conductivity (EC), total dissolved solids (TDS),
bicarbonate (HCO3−), sulphate (SO42−), chloride (Cl−), dissolved silica (H4SiO4), calcium (Ca2+),
magnesium (Mg2+), sodium (Na+) potassium (K+) phosphate (PO43−), nitrate (NO3−) along with
heavy metals like lead (Pb), cadmium (Cd), manganese (Mn) and iron (Fe), was carried out as
per standard method APHA (1998).
Quality control measures were taken to assess contamination and reliability of the
analyzed data. Double distilled deionized water was used throughout the experiment. E-mark
(AR grade) standards were used for the preparation of standard curve during analysis of samples.
For FTIR analysis KBr (spectroscopic grade) was used for the preparation of pellets. Metal
fractions were estimated by sequential extraction process as per BCR (Community Bureau of
Referance) optimized three step sequential extraction procedure (modified by Rauret et al, 1990).
Metal concentrations in extract and digests were determined by atomic absorption
spectrophotometer (GBC – Avanta). For supervised classification- IRS-P6 LISS-IV satellite
image of January 7, 2011 was taken as a base image for the classification. A standard technique
is adopted for georeferencing the image using PCI Geomatica V10.1 software. Then
georeferenced image was reprojected to UTM projection. UTM projection was done to minimize
the map distortion and to activate the grid option. Post Classification Analysis is done by
merging classes and by masking and unmasking methods after each field survey. The obtained
matrix of hydrogeochemical data was subjected to multivariate analytical technique. DEM is
generated by using VEDIMINT algorithm in the Geomatica V.10.1 software. The output DEM is
represented as a zonation map of the said parameter.

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Results and Discussion
The measured values of pH in the Damodar river water ranged from 7.00 to 8.94
indicating the river water is neutral to alkaline in nature. Small local differences were observed
with no clear seasonal variations at all the sites of the study area. The increase of pH in the
agriculture dominated downstream area may be due to the contribution from agricultural run-off.
Electrical conductivity of the water samples is ranged from (100 –710 µS/cm), depicting a wide
range of fluctuations at different locations and can be explained by high concentrations of
dissolved solids and ions in it. The higher values for EC and TDS at some discharge points in the
Damodar river water reveal its ionic strength/concentrations. Spatial distribution of TDS follows
the same trend like EC. The average total dissolved solid (TDS) of the present study (176.37
mg/l) is comparable to the Indian average (159 mg/l) and higher to global average values (115
mg/l) for an aquatic system. This large variation in TDS values may be attributed to the variation
in geological formations, hydrological processes and prevailing mining and industrial conditions
in the region.
Calcium and magnesium in the studied river ranged from 7.452 to 48.942 mg/l and 3.233
to 28.513mg/l respectively. The average concentration of calcium (19.620 mg/l) is lower than the
Indian average (30 mg/l) and comparable to global average values (16 mg/l) for an aquatic
system. Sodium and potassium in the studied river ranged from 4.28 to 50.46 mg/l and 1.21 to
24.882 mg/l respectively. The average sodium concentration (15.585 mg/l) is comparable to the
Indian average (12 mg/l) and higher to global average values (4.4 mg/l) for an aquatic system.
Nitrate and phosphate in the studied river ranged from BDL to 4.119 mg/l and 0.010 to 1.382
mg/l respectively. The nitrate concentration in the river water reached their maximum value
during monsoon season (0.845±0.087 mg/l), minimum during the postmonsoon season
(0.720±0.067mg/l) while the premonsoon season is characterised by intermediate values
(0.771±0.108 mg/l). Seasonal distribution of phosphate follows the same trend like nitrate i.e. the
concentration in the river water reached their maximum value during monsoon season
(0.261±0.043 mg/l), minimum during the postmonsoon season (0.141±0.010 mg/l) while the
premonsoon season is characterised by intermediate values (0.168±0.066 mg/l).

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The chloride value in the studied river ranged from 1.298 to 72.643 mg/l. Higher concentration
of chloride was observed at S16 (Shyampur) and S17 (Majher mana). The average chloride
concentration (13.709 mg/l) is comparable to the Indian average (15 mg/l) and higher to global
average values (4 mg/l) for an aquatic system. The average concentration of dissolved silica
(12.00 mg/l) is higher than the Indian average (7 mg/l) and comparable to global average values
(12.00 mg/l) for an aquatic system. The cation chemistry of the river water is dominated by Ca2+
and Mg2+ comprising 38.672% and 30.024% of total cation balance in their equivalent weight.
Na+ and K+ concentrations represent on an average to 26.060%, and 5.244% of the total
cations (TZ+), respectively, and the order of abundance is Ca2+>Mg2+> Na+>K+. On an
equivalent basis, HCO3– accounts for 67.759% of the total anions. HCO3– is followed by SO42–,
and Cl– which accounts for 17.903% and 14.518% of the total anions respectively. The high
concentration of HCO3– in river water indicates that intense chemical weathering takes place in
the catchment area.
The mean value of lead (Pb) in the river water reached their maximum value during the
premonsoon season (133.73±589.54 µg/l), minimum during the monsoon season (0.999±1.36
µg/l) while the postmonsoon season is characterised by intermediate values (22.312±101.226
µg/l). High concentration of Pb was found at S16 (Shyampur) and S17 (Majher mana) site. The
cadmium (Cd) in the river water reached their maximum value during premonsoon season
(0.800±0.998 µg/l), minimum during the monsoon season (0.157±0.217 µg/l) while the
postmonsoon season is characterised by intermediate values (0.337±0.432 µg/l). The iron and
manganese in the studied river ranged from 7.452 to 48.942 mg/l and 3.233 to 28.513 mg/l
respectively. The results of the present study indicate a remarkable increase in pollution along
with heavy metals concentration at Shyampur, Majher mana, Dihika and Chinakuri of river
Damodar due to the increased loading of the indiscriminate and long term disposal of effluents
from thermal power plant and mining discharge. Sampling covered both monsoon and non-
monsoon seasons and it was observed that generally the water quality in monsoon season was
slightly better than that in non-monsoon seasons due to flushing effect. The mean values of metal
concentrations can be arranged in the order Fe > Mn > Pb > Cd. The values for most of the
metals in the river water of the downstream region were found to be much lower than those of
the upstream region. However, heavy metal concentrations in surface water which are not very

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high, dilute and undetectable quantities, their recalcitrance and consequent persistence in water
bodies exhibiting toxic characteristics (Atkinson et al. 1998).

From the factor analysis it was observed that the geogenic sources, industrial discharges and
natural factors strongly influence the water quality of the study area. Taken together the data of
two types of ternary diagram [(Na++K+), (Ca2++Mg2+) and SiO2 and (SO42–+ Cl–), HCO3– and
SiO2)] indicate that the stretches of the Damodar river is a chemically active river with a
dominance of continental weathering and secondary inputs of anthropogenic sources. The
geochemical nature and relationship between dissolved ions in water may also be evaluated by
plotting the analytical value on Piper trilinear diagram. The trilinear diagram reveals that Ca2+–
Mg2+– HCO3– is the dominant hydrogeochemical facies in the river water samples. There is no
significant change in the hydrochemical facies noticed during the study period, which indicates
that most of the major ions are natural in origin. Present investigation shows that rock weathering
as major process for liberating ions in the river and also responsible for controlling water
chemistry. The Gibbs diagram suggests that rock weathering as major process for liberating ions
in the river and also responsible for controlling water chemistry.
To assess the suitability for drinking and public health purposes, the hydro-
chemical parameters of the river water of the study area were compared with the prescribed
limit of WHO (2006). Concentration of NO3– is found to be lower than the recommended level
of 50 mg/l in all the river water samples. High value of nitrate in some of the study area is
attributed to decaying organic matter and sewage water in the urban region. The study in
general reveals that the Cd concentration in the entire study area was found to be well
below the WHO norms (0.003 mg/l) for drinking water (WHO 2006). Water quality parameters
were compared with the prevalent water quality standards indicates that, with few exceptions, the
Damodar river water in the study area is fit for drinking and livestock uses. The suitability of the
river water for irrigation depends upon the effects of its mineral constituents. Excessive amount
of dissolved ions such as sodium, bicarbonate, and carbonate in irrigation water affects plants
and agricultural soil physically and chemically, thus reducing the plant development, disrupt
plant metabolism which ultimately affects the productivity. All the samples in the study area
(except some areas) have RSC values much less than 1.25 meq/l (safe for irrigation), which
revealed that all samples are of safe quality categories for irrigation. The analyzed water samples

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indicate that most of the river water samples are not exceeding the magnesium ratio of 50. The
high RSC content and Na% were recorded at Shyampur due an industrially polluted water
stream which joins into the river and influence this zone as a result of which the water is not
suitable for irrigation use. The plot of data on the US salinity diagram, in which the EC is taken
as salinity hazard and SAR as alkalinity hazard revealed that maximum number of the water
samples fall into C1S1 (low salinity with low sodium) category. The overall study of salinity
hazard revealed that these river water samples can be used to irrigate all soils for semi-tolerant
and tolerant as well as sensitive crops. Therefore, all river water samples are suitable for
irrigation and can be used for all soil types. Sodium percentage calculated for Damodar river
water in the study area is plotted against electrical conductance in Wilcox diagram shows that
all of river water samples are excellent to good for irrigation.
The relatively higher Kd values observed for Fe, Pb and Cd indicate their preferential
association and enrichment in sediments and suggest that they are characterized by a low
geochemical mobility in water. Relatively lower Kd values for Mn indicate that they are less
likely to be associated with sediments. The overall percentage of metal content in different BCR
fractions is in the sequence of residual > reducible > oxidisable > exchangeable and the order of
metals in each fractions are as follows Exchangeable: Fe > Mn > Pb > Cd, Oxidisable: Pb > Cd
> Mn > Fe, Reducible: Mn > Fe > Pb > Cd, Residual: Cd > Pb > Fe > Mn. The risk assessment
code as applied to the present study reveals that 12.312% of iron, 11.119% of manganese,
3.364% of lead and 3.164% of cadmium exist in exchangeable fraction and therefore, comes
under low to medium risk category and may enter into food chain. The association of these
metals with exchangeable fraction may cause deleterious effects to aquatic life.
Recalcitrant Factor (RF) value of monitored metals in the river sediments ranged from
55.601 (Mn) to 73.672 (Cd) indicating variability in effective retention of individual metals. The
recalcitrant factor (RF) value of Pb and Fe is 71.112 and 58.488 respectively in the monitored
river sediments The ranking of metals with respect to RF value is in the order of Cd > Pb > Fe >
Mn. Higher RF value of Cd and Pb can be explained because of chalcophilic and lithophilic
nature of these elements, therefore indicating poor possibility of mobilization into the aqueous
system. The result of the various indices of the sediment analysis reveals that except some
discharge points the EF, Igeo and PLI of typical pollutants from all sites were far lower than the
limit values, which indicated that the area was overall in good condition.

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The study reveals that the Igeo values for Cd, Pb, Fe, and Mn in the river sediment fall in
class “0” in indicating that there is no pollution from these metals in the downstream riverine
sediment. The negative Igeo value of Mn and Fe in the river suggested that there is no pollution
from these metals in the sediments of the study area. The overall low PLI values were observed
in the river sediments, though relatively higher values were observed at the sites Majher mana
(1.224) which indicates that the site is moderately polluted. Spatial interpolation reveals that
except some portion of the stretch between Shyampur - Majher Mana – Dhobighat (1<PLI>2)
remaining portion of the study area stretch of river Damodar falls under the no pollution (PLI<1)
category. According to areal coverage out of 663.10 sq.km studied stretch of river Damodar only
10.88 sq.km falls under the moderate pollution category.
Comparing the heavy metal concentrations with the consensus-based TEC and PEC
values, revealed that over 26.667% of Pb and 17.037% of Cd concentration of the river bottom
sediment samples exceeded the TEC, with most sample concentrations falling below the PEC
(except 4.450% of Pb and 0.741% of Cd). The site Majher mana receives industrial waste water
from various steel plants, thermal power plants, chloralkalies, sponge iron and chemical
industries and high PEC of Cd and Pb may exerts harmful effects on sediment-dwelling
organisms.

__________________________ _______________________
Signature of the Candidate Signature of the Supervisor
UDAY SANKAR BANERJEE Dr SRIMANTA GUPTA

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