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Environmental impact assessment and seasonal variation study of the

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Environ Monit Assess
DOI 10.1007/s10661-008-0185-x
Environmental impact assessment and seasonal variation
study of the groundwater in the vicinity of River Adyar,
Chennai, India
T. Venugopal & L. Giridharan &
M. Jayaprakash & P. Periakali
Received: 18 July 2007 / Accepted: 14 January 2008
# Springer Science + Business Media B.V. 2008
Abstract Hydrochemical investigations of the ground-
water and the seasonal effect on the chemical budget of
ions along the course of the polluted river Adyar were
carried out. From the geochemical results, it has been
found that the seasonal effect does not change the order
of abundance of both cations and anions, but it does
change the concentration of various ions present in the
groundwater. Among the chemical budget of ions,
sodium and chloride were found to be the most
predominant ions. The nitrate concentration in the
groundwater ranges from 4.21 to 45.93 mg/l in pre-
monsoon and in post-monsoon it ranges from 1.02 to
75.91 mg/l. The nitrate concentrations in the post-
monsoon are high in some places especially in the upper
stretch of the river. The intense agricultural activities
near the upper stretch of the river may be an important
factor for the higher concentration of nitrates in these
aquifers. In order to determine the geochemical nature
of water, the data was interpreted using the piper
diagram wherein the results show the predominance of
NaCl and CaMgCl types. Equiline diagrams, 1:1, were
applied to evaluate the affinity ion relationship between
various ions present in these waters. The quality of the
T. Venugopal (*) : L. Giridharan
Department of Geology and Mining,
Thiru.Vi.Ka Industrial Estate,
Guindy, Chennai 600 032, India
e-mail: t.venu@yahoo.co.in
M. Jayaprakash : P. Periakali
Department of Applied Geology, University of Madras,
Chennai, India
groundwater was assessed with regard to its suitability
to drinking and irrigation. A comparison of the
groundwater quality in relation to drinking water quality
standards shows that most of the water samples are not
suitable for drinking, especially in post-monsoon
period. US Salinity Laboratory’s, Wilcox’s diagrams,
Kellys ratio and magnesium ratio were used for
evaluating the water quality for irrigation which suggest
that the majority of the groundwater samples are not
good for irrigation in post-monsoon compared to that in
pre-monsoon. Moreover the source of the ions in the
water was examined and classified accordingly using
Gibb’s diagram. The analytical results reveals that the
TDS values of the pre-monsoon samples were found to
be lower than the post-monsoon reflecting that leaching
predominates over that of the dilution factor.
Keywords River Adyar . Geochemistry . Groundwater
Introduction
The environmental impact of human activity on the
groundwater is considered as one of the major hazard
in the modern days. Rapid Urbanization and increased
agricultural activities has resulted in the degradation
of the water quality. Unused fertilizers, pesticides,
effluents discharged from industries and sewage water
are the main contaminants of the groundwater. The
chemical budget of major ions and heavy metals are
important in determining the quality of groundwater.
DO00185; No of Pages

Groundwater with low pH values can cause gastroin-
testinal disorder and this water cannot be used for the
drinking purposes. Contamination of groundwater by
heavy metals has been given much attention due to
their low biodegradability and toxic effects (Numberg
1982; Ramesh et al. 1995; Howari et al. 2005; Samuel
Obiri 2007). TDS values are considered important in
determining the usage of water and groundwater with
high TDS values are not suitable for both irrigation
and drinking purposes (Davis and DeWiest 1966;
Fetters 1990; Freeze and Cherry 1979). Study of
chemical budget of the major ions gains importance
since it explains the origin of the ions in groundwater
and the level of the contamination by natural as well
as anthropogenic sources (Woo et al. 2000; Gowd
2005; Jalali 2005; Subba Rao 2006).
Presence of Fluoride ion in the groundwater above
1.5 ppm can cause fluorosis and the monitoring of the
fluoride levels in the groundwater gains significance
(Woo et al. 2000; Subba Rao and Nevada 2003). The
surface run-off from the agricultural field is the main
source of nutrients in the groundwater. The presence
of nitrate, nitrite and phosphate in the groundwater
above the permissible limit is not conducive for the
drinking purpose (Julia Pacheco et al. 2001; Lee et al.
2003; Rajmohan and Elango 2005). Ratios and
diagrams like Kellys ratio, magnesium ratio, Wilcox
diagram and US Salanity Laboratory diagrams are
used to find out the nature of the water and its
suitability to irrigation. Many authors have used these
diagrams to check whether the water is useful for
irrigation (Gowd 2005; Abhay Kumar Singh et al.
2005; Subramani et al. 2005).
This study of the groundwater near the River Adyar
aims in analyzing the effect of the river water on the
near by groundwater and also the seasonal effect. In
this study, major ions are determined so as to draw a
conclusion on the source of origin of these ions
whether it is natural or anthropogenic. The nutrients
and heavy metals in these water are determined to
check the quality of the water. Ratios and diagrams are
drawn in order to determine whether the groundwater
can be utilized for the irrigation purpose.
Study area
In this study, the groundwater in the proximity of river
Adyar is taken for geochemical analysis (Fig. 1). River
Environ Monit Assess
Adyar starts from Malaipattu tank (80.00° latitude and
12.93° longitude) near Manimangalam village, Sriper-
umbathur taluk, at about 15 km west of Tambaram
near Chennai. Though it originates from the above
point, appears as a stream only after it receives surplus
water from the Chembarambakkam tank. It flows
through Kancheepuram, Tiruvallur and Chennai dis-
tricts for a distance of about 50 km and enters into the
Bay of Bengal near Adyar. The river receives a
sizeable quantity of sewage from its neighborhood
after it reaches Nandambakkam near Chennai. This
river is almost stagnant and do not carry enough water
except during rainy season (NW-monsoon). Rapid
industrialization and urbanization along the river
course during 80s and 90s of last century has increased
the pollution of the river watershed, which leads to the
present day deteriorated condition of water level.
It has been observed that in the upper part of the river
(Fig. 1), there is no settlement along the bank of the
river and hence, this part is not polluted by domestic
effluents. But the chance of pollution due to agricultural
activities is still there. Now-a days, fertilizers play a
vital part in the crop growth. In the chosen area, nitrate
and phosphate fertilizers are found to be in use in the
upper part of the river. The bulk use of these fertilizers
leaves behind unused wastes that are driven off by rain
and enters into the river, which causes excess nitrates
and phosphates pollution. Several studies have reported
that the release of nitrates from agricultural activities
contaminated the groundwaters (Mukherjee and Pandey
1994; Chandu et al. 1995; Prasad 1998 and Pacheco et
al. 2001). Groundwater near the midstream is found to
be contaminated by the domestic sewage water directed
into the river course and the groundwater in the
proximity of the lower part of the river is observed to
be polluted by saline water intrusion.
The major part of the river basin of Adyar is covered
by alluvium soil with tertiary and Gondwana rocks at
depth. The alluvium soil varies from 10 to 20 m thickness
and is mostly granular. In the down stream area of the
river Basin coastal sand predominates while the middle
part and upper parts are dominated by sand and silt.
Charnockites are also found in some part of the basins.
Methodology
Twenty-five groundwater samples were collected during
September 2005 and February 2006 representing pre-
Environ Monit Assess
Fig. 1 Base map of Adyar river
and post-monsoon seasons to evaluate the seasonal
variations in chemical compositions. The water samples
were collected from wells adjacent to the river at a depth
of 10 to 20 ft. The samples were collected in new 1-
l HDPE bottles pre-washed with dilute hydrochloric
acid and rinsed three to four times with the water sample
before filling it to capacity and then labeled accordingly.
The samples were stored at a temperature below 4°C
prior to analysis in the laboratory. For collection,
preservation and analysis of the samples, the standard
methods (Rainwater and Thatcher 1960; Brown et al.
1970; AWWA 1971; APHA 1995) were followed. EC
and pH of water samples were measured in the field
immediately after the collection of the samples using
pH and electrical conductivity meters. Before each
measurement, the pH meter was calibrated with
reference buffer solution of pH=4. Na+ and K+ were
measured by using a flame photometer (Model:
Systronics Flame Photometer 128). Silica content was
determined by Molybdate Blue method using UV–
visible spectrophotometer. Total dissolved solids (TDS)
were measured by evaporation and calculation methods
(Hem 1991). Ca2+ and Mg2+ were determined titri-
metrically using standard EDTA. Chloride was esti-
mated by AgNO3 titration. Sulphate was analysed
using the turbidimetric method (Clesceri et al. 1998).
Nitrate, nitrite, phosphate, fluoride were analysed using
UV–visible spectrophotometer (Rowell 1994). Stan-
dard solutions for the above analysis were prepared
from the respective salts of Analytical Reagent grade.
Trace metals were determined by Graphite Furnace
Atomic Absorption Spectrophotometer (Perkin-Elmer
AAnalyst 700). Multi element Perkin-Elmer standard
solutions were used for the estimation of Trace metals.
Results and discussion
Chemistry of groundwater
The analytical results of the chemical analysis and the
statistical parameters such as minimum, maximum,
mean, standard deviation and t test of groundwater are
presented in Table 1 for both pre-monsoon and post-
 Environ Monit Assess

N
N

N
N
N

N
N
N
N
R

S
S

S
S

S
monsoon. The seasonal variation of the various
chemical parameters in the groundwater of the study

1.66
1.66
3.09
2.98
1.59
0.67
0.20
4.91
3.12
1.12
0.49
1.98
1.05
3.40
27.51
area is shown in Fig. 2.
t

The salient features of the hydrochemistry of the

groundwater are as follows:
0.16

0.04

1.06
1.06
14.62
109,651
309
219,540

815,701

491
13,095
20,300

4,660
9,189,451
3,763,999 The pH values of groundwater are acidic ranging
from 5.95 to 6.73 with an average value of 6.30 during
Var

pre-monsoon. However during the post-monsoon, the

17.60 pH of groundwater was found to be alkaline ranging

68.27

22.15
3,031.41
1,940.10

0.20

1.03
0.03
3.82
142.48
331.14

148.17

903.16
114.43

from 7.15 to 8.96. In both the pre- and post-monsoon,

0.4

the TDS values of the stations 24 and 25 are found to

σ

be very high viz., 34,355, 34,970 and 30,170,

30,874 ppm respectively. At these stations, it is found
3,558.15
2,277.22

21.07

26.47
8.29

0.50

0.06
197.70
134.17
391.25

368.86
176.74
956.96
11.31

0.7 that the concentration of all ions are high especially the
Mean

values of Na and Cl are found to be very high. Since

these groundwaters are very near to the estuary, the
penetration/percolation of the saline water into the
Maximum

8.96

8,806.00

1,120.00

3,470.00
0.91

3.61
0.13
424.00
686.00

732.00
272.00
13,759.38

64.80

75.91

28.3

t Stands for t test, critical two-tail 2.07, σ standard deviation, Var variance, S significant, N non-significant, R result
adjacent aquifers is high and hence only the saline
water dominates the geochemistry of these waters.
Post-monsoon

Hence in the present discussion of the groundwater

geochemistry, these two stations are not taken into
Minimum

7.48

0.00

0.15
1.02
0.09
656.25
420.00

170.80

150.00
48.00
12.00
31.82

32.42

account. Concentration of salinity (TDS) ranges from

9.2
0

1,075 to 3,277 mg/l with a mean of 1,733.13 mg/l in

pre-monsoon and 420 to 8,806 mg/l with a mean of
0.05

0.05
1.22
4.20

2,277.22 mg/l in post-monsoon. There is a consider-

519,780

189

915

814
128
37,432

44,288

72,249
1,281
1,040
1,268,996

able increase in the concentration of ions during the

post-monsoon and the increase in the ionic concentra-
Var

tion may be due to the leaching of salts from the soil

and also by anthropogenic activities. During post-
0.023

35.80
32.25

13.78

30.26

0.39

0.22

2.05
1,126.50

11.32
720.96

193.47

210.45

268.79

1.11

monsoon the water table in the study area is nearer to

the surface and active leaching and subsequent
σ

infiltration would have changed the chemical compo-

sition of groundwater. Higher concentration of TDS is
2,708.02
1,733.13
6.31

1.18

0.25
1.09
124.96

375.48
238.58
435.39
55.60

12.90

18.67

29.44
311.94

observed in the groundwater near the lower part of the

Mean

river basin, which is near to the Bay of Bengal ocean.

Table 1 Summary statistics of the analytical data

As per the TDS classification (Fetters 1990) most of

the groundwater samples collected during the
Maximum

5,120.31
3,277.00

1,037.00

1,210.00
6.73

2.03

1.07
4.67
44.17

45.93

32.50
208.00
120.60
795.00

292.00

pre-monsoon and post-monsoon periods belong to

brackish type (TDS>1,000 mg/l). The groundwater
classifications of Freeze and Cherry 1979 and Davis
Pre-monsoon

and DeWiest 1966 are presented in Tables 2 and 3.

Minimum

1,679.69
1,075.00

110.00
5.95

0.00

0.48
4.21
0.01
0.24
56.00
16.40

26.60
136.30

224.80
204.00

During pre-monsoon, the concentration of cations

Ca2+, Mg2+, Na+, K+ ions ranged from 56 to 208;
16.4 to 120.60; 136.3 to 795; 0 to 44.17 mg/l with a
Parameters (mg/l)

mean of 124.96, 55.60, 311.94 and 12.90 mg/l respec-

tively. The ionic concentrations (based on mmol/l) are
EC (μS/cm)

16.19, 11.86, 70.27 and 1.71%. The order of

HCO

abundance is Na+ > Ca2+ > Mg2+ > K+. But during
3
SO2

3

Mg2+

NO

NO

3
2

SiO2
Ca2+
TDS

PO4
Na+

Cl−
pH

K+

post-monsoon the concentration of cations Ca2+,

F−
Environ Monit Assess
Mg2+, Na+, K+ ions ranged from 48 to 424; 12 to 686;
31.82 to 1120; 0 to 64.8 mg/l with a mean of 197.7,
134.17, 391.25 and 11.31 mg/l respectively. The ionic
concentrations (based on mmol/l) are 17.80, 19.89,
61.28 and 1.04%. The order of abundance is Na+ >
Mg2+ > Ca2+ > K+. The seasonal effect changes both
the order of abundance of cations and also changes
the concentration of various ions and it is found that
there is a considerable change in the case of all major
ions. Similarly in the case of anions during pre-
−
monsoon, HCO
2


3 , SO4 , Cl , NO3 ranged from
224.8 to 1037, 204 to 292, 110 to 1210 and 4.21 to
45.93 mg/l with a mean of 375.48, 238.58, 435.39
and 18.41 mg/l respectively. The ionic concentrations
(based on mmol/l) are 29.01, 11.71, 57.88 and 1.42%.
The order of abundance is Cl
> HCO
3 > SO4 >
2

NO3 . During post-monsoon, HCO3 , SO4 , Cl−,


2

NO
3 ranged from 170.8 to 732, 32.42 to 272, 150 to
3470, 1.02 to 75.91 mg/l with a mean of 368.86,
176.74, 956.96 and 21.07 mg/l respectively. The ionic
concentrations (based on mmol/l) are 17.17, 5.23,
76.65 and 0.96%. The order of abundance is
Cl
> HCO


3 > SO4 > NO3 . As far as anions are
2

concerned, the seasonal effect on the concentration
of ions is significant except that of nitrates.
Fluorides varied from 0.48 to 2.03 mg/l with a mean
of 1.18 mg/l in pre-monsoon and during post-monsoon
it varied from 0.15 to 0.91 with a mean of 0.50 mg/l.
Hence the demonstration of monsoon over the dilution
of the concentration of fluorides is obvious. The
variation in the range of silica concentration during
both the seasons is only narrow. During pre-monsoon,
it varied from 26.6 to 32.5 mg/l with a mean of
29.54 mg/l and in post-monsoon, it ranges from 9.2 to
28.3 with a mean of 26.47 mg/l. A t test was performed
to determine the effect of monsoon on the chemical
constituents/variables present in the groundwater. The
results show that Na+, K+, Cl−, HCO
−

3 , F , NO2 and

2

NO3 and PO4 are found to be non-significant with
respect to seasonal changes. A t value for pH is found
to be very high since the monsoon changes the pH
value of these groundwater from acidic to alkaline.
Standard deviation results show that the TDS values
exhibit high variability in both pre- and post-monsoon
periods. The cause of this variability may be due to the
difference in the chemical constituents of the ground-
water near the fresh water river (upper) course and the
groundwater near the saline estuarine water (lower
course). The above fact is substantiated by the high
standard deviation values of the sodium and chloride
values. During post-monsoon, nitrate values at three
stations (station 11, 12 and 13) are found to be high
crossing the WHO prescribed limit of 50 ppm. All
these three stations are found to be in the groundwater
near the upper course of the river where many
agricultural activities are being carried out. The
precipitation followed by dissolution of the fertilizer
remains, which is known to be highly soluble and
mobile (Freeze and Cherry 1979; Walter et al. 1975)
may be the cause of high concentration of nitrates at
these stations.
Chemical characteristics of major ions
The plot of equilines (Fig. 3) for both the seasons
show a marked difference. In pre-monsoon, the plot
of Na + K vs Cl show that most of the values fall
above and on the equiline and suggest that the alkali
is balanced by the Chloride ions and also the ratio
between the Na + K and total cation is 0.56 and the
ratio between the Cl and total anion is also found to
be 0.52 indicating that most of the alkali ions are
balanced by the chlorides. Among the alkalis, Na is
dominant and the concentration of potassium is
apparently low. The natural source of potassium in
water usually originates from the chemical weathering
and subsequent dissolution of minerals of local
igneous rocks such as feldspars (orthoclase and
microcline), mica and sedimentary rocks as well as
silicate and clay minerals (Howari and Banat 2002).
Since these minerals are not abundant in the study
area, potassium concentration in these waters is only
one tenth of the concentration of sodium and also the
low contribution of K may be due to the greater
resistance of K to weathering and its fixation in the
formation of clay minerals (Sarin et al. 1989). The
high ratio of Na + K vs Z+ suggest that silicate
weathering may to some extent contribute to the total
cation (Sarin et al. 1989). And also it is seen that the
Na + K and Cl values increases gradually from west
to east in which the river flows.
In post-monsoon, the plot of Na + K vs Cl shows that
most of the points are below 1:1 lines suggesting that
there is excess of Cl over Na + K. And also the plot of
Ca + Mg vs HCO3 + SO4 shows that most of the points
lie well above the 1:1 equiline indicating that the
excess chloride ions are balanced by the alkaline earth
metal ions. The ratio of Na + K with TC is 0.45 and
 Environ Monit Assess

Fig. 2 Seasonal variation of the chemical parameters

Environ Monit Assess

Fig. 2 (continued)

Table 2 Groundwater
classification (Freeze and Sl. no. Type of water TDS (range) %
Cherry 1979)
Pre-monsoon Post-monsoon

1 Fresh water type 0–1,000 0 13

2 Brackish water type 1,000–10,000 100 87
3 Saline water type 10,000–100,000 0 0
4 Brine water type >100,000 0 0
 Environ Monit Assess

Table 3 Groundwater
classification (Davis and Sl. no. TDS (range) Suitability of water %
DeWiest 1966)
Pre-monsoon Post-monsoon

1 Up to 500 Desirable for drinking 0 4.3

2 500–1,000 Permissible for drinking 0 8.7
3 Up to 3,000 Useful for irrigation 87 70
4 Above 3,000 Unfit for drinking and irrigation 13 17

Fig. 3 Equiline diagrams

Environ Monit Assess
that of Ca + Mg with TC is 0.55 which indicates that
there is an inversion of ratio during post-monsoon
clearly showing the dominance of alkaline earth metal
ions over the alkalis. As in pre-monsoon, the concen-
tration of sodium predominates over that of potassium.
The ratio of HCO3 + SO4 with TA is 0.26 and that of
Cl with TA is 0.73 indicating that there is an increase
in the concentration of chloride ions in post-monsoon.
Cl− ion concentration in groundwater normally arises
Fig. 3 (continued)
from three sources viz., ancient seawater entrapped
sediments, solution of halite and related minerals in
evaporate deposits and solution of dry fallout from the
atmosphere especially in the arid region (Walker et al.
1991). The high concentration of chloride in the study
area does not seem to arise from the above factors but
it may be caused by anthropogenic activities and due to
the percolation of the saline water near estuary where
the stagnant backwater facilitates the seepage thereby
 Environ Monit Assess
Fig. 4 Diagrams depicting
reverse ion exchange
chemistry

increasing the chloride content in the groundwater near
the downstream. The leaching of saline residues of the
soil by the action of rainwater during post-monsoon
may also contribute to the chemical composition of the
water.
Reverse ion exchange study
The plot of Ca + Mg vs HCO
3 þ SO4 is expected to
fall close to the 1:1 equiline if the dissolution
reactions of calcite, dolomite, gypsum are dominant
in the system. Ion exchange tends to shift the points to
the right of the equiline due to an excess of SO4 +
HCO3 (Cerling et al. 1989; Fisher and Mulican 1997).
If there is a large excess of Ca + Mg due to the
reverse ion exchange process over SO4 + HCO3 then
the points will shift to the left side of the equiline. In
pre-monsoon, the plot of Ca + Mg vs HCO
3 þ SO4
shows that some of the values falls above the equiline
suggesting that the reverse ion exchange process has
occurred. The plot of Na–Cl versus (Ca + Mg)–
(HCO3 + SO4) (Fig. 4) for the pre-monsoon shows a
slope of −0.33 reflecting that reverse ion exchange
has taken place to some extent. Chloro alkaline
indices (CAI 1 and CAI 2; Table 4) are also positive
confirms the above fact. In post-monsoon the plot of
Ca + Mg versus HCO3 + SO4 shows most of the
value are to the left and well above the equiline which
suggest that reverse ion exchange process has taken
place to a greater extent in all the stations. The plot of
Na–Cl versus (Ca + Mg)–(HCO3 + SO4) in Fig. 4
shows a slope of −0.97 which is nearly equal to −1.0
indicating that Ca, Mg and Na concentrations are
interrelated through reverse ion exchange and also the
ratio of Ca + Mg vs Tc for post-monsoon is 0.55. The
CAI 1 and CAI 2 (Table 4) for the post-monsoon
season shows very high value. Comparing pre- and
post-monsoon the reverse ion exchange is increased
to considerable extent in the post-monsoon indicated
by the high negative slope and high positive chloro
alkaline indices. In post-monsoon season the water
table is generally high and near to the ground surface,
which increases the contact surface area of the water,
so there is an exchange of sodium in groundwater
with calcium and magnesium in the alluvium soils.
Hydrochemical facies
The evolution of hydrochemical parameters of
groundwater can be understood by plotting the

Table 4 Seasonal variation of chemical parameters

Pre-monsoon Post-monsoon t R

Min Max Mean SD Min Max Mean SD

CA1 1.19 33.09 11.15 7.67 3.90 97.37 26.35 25.91 3.21 S
CA2 −10.67 20.51 2.51 6.48 −2.09 82.01 16.12 22.79 2.83 S
Gibbs ratio1 0.51 0.86 0.65 0.12 0.37 0.88 0.58 0.14 2.28 S
Gibbs ratio2 0.38 0.87 0.64 0.12 0.49 0.94 0.76 0.12 3.15 S
%Na 6.77 84.93 45.19 21.94 17.04 70.79 42.82 12.69 0.44 N
SAR 2.18 9.84 4.57 2.37 0.65 9.81 4.17 2.60 0.88 N
Kelly ratio 0.65 2.15 1.21 0.48 0.21 2.49 0.86 0.50 2.79 S
Magnesium ratio 13.21 70.61 40.49 15.89 17.49 74.79 47.03 16.14 1.91 N
Permeability Index 18.48 40.80 24.53 6.56 15.48 51.83 26.49 11.20 1.14 N
Environ Monit Assess
concentration of major cations and anions in the piper
diagram. Figure 5 shows that most of the groundwater
samples analysed during the pre-monsoon and post-
monsoon fall in the field of NaCl, mixed CaMgCl
types and mixed CaMgCl, NaCl and CaCl types of
water respectively. From the plot, it is observed that
alkalis (Na+ and K+) exceed the alkaline earths (Ca2+
and Mg2+) and Cl− exceeds the other anions.
Trace metals in groundwater
The variation in the concentration of trace metals (Cu,
Co, Zn, Fe, Pb and Cr) in both pre-monsoon and post-
monsoon in the groundwater of the study area was
evaluated (Fig. 6). The Cu values ranges from 0.012 to
0.098 mg/l with an average value of 0.064 mg/l during
pre-monsoon. However, during the post-monsoon, the
values range from 0.011 to 0.088 with a mean of
0.051. Both in pre- and post-monsoon, the concentra-
tion of Cu is well within the WHO allowed limit of
2 mg/l. The concentration of cobalt during pre-
monsoon ranges from 0.002 to 0.074 mg/l with a
mean of 0.034 and the post-monsoon shows 0.003 to
0.068 with a mean of 0.028 mg/l. Zinc ranges from
0.006 to 0.066 with a mean of 0.024 mg/l during pre-
monsoon and post-monsoon demonstrates 0.005 to
Fig. 5 Piper diagram repre-
senting hydrochemical
facies
0.25 with a mean of 0.035 mg/l. The concentration of
Zinc in these waters during both the seasons has not
crossed the prescribed limit of 3 mg/l. In the case of
iron, the concentration of Fe in many of the stations is
higher than the WHO permitted limit of 0.3 mg/l and
the values ranges from 0.065 to 4.618 mg/l with a
mean of 0.791 mg/l during pre-monsoon and post-
monsoon demonstrates 0.065 to 3.985 with a mean of
0.598 mg/l. Out of 23 stations, Fe value crosses the
WHO limit in 11 stations during both the monsoon
periods. Though there is a seasonal variation in
the concentration of Fe values, the groundwater near
the upper part of the river shows higher values and the
highest value is recorded in station no. 4 in both the
seasons. Since in this region, except agricultural
activity no other anthropogenic activities were being
carried out and hence the high Fe concentration in
these waters could not be assigned to the anthropo-
genic activities but rather the soil–water interaction
should be the reason for the higher value of Fe
observed in these region. Pb values during pre-
monsoon are ranging from 0.012 to 0.618 with a mean
of 0.186 mg/l and the values of post-monsoon ranges
from 0.008 to 0.548 with a mean of 0.139. Lead is
usually found in low concentration in natural waters
because Pb containing minerals are less soluble in

water. Concentration of lead in natural water increases
mainly through anthropogenic activities. Fifteen sta-
tions during pre-monsoon and seven stations during
post-monsoon crosses the WHO limit of 0.01 mg/l.
During both the seasons, the higher value of Pb is
observed at stations 9,10 and 11 with the highest value
recorded at station no. 10. The lithology of the area
does not support the higher concentration of the
observed lead values. The concentration of various
industries along the course of the river and their
activities impart slight colour to the river water in these
Fig. 6 Seasonal variation of trace metals
Environ Monit Assess
area, which would have percolated into the nearby
groundwater. The value of Cr ranges from 0.012 to
0.457 with an average value of 0.103 during pre-
monsoon and 0.012 to 0.65 with an average value of
0.113 during post-monsoon. Sixteen stations during the
pre-monsoon and 11 stations during post-monsoon
crosses the WHO allowed limit of 0.05 mg/l. The
higher value of Cr is attributed to the anthropogenic
activities such as leather tanning industries around the
river course, which enhance the concentration of Cr in
these water bodies.
Environ Monit Assess
Groundwater quality
Gibbs ratio
The source of the dissolved ions in the groundwater
can be understood by Gibbs diagram (Gibbs 1970). It
is a plot of (Na+ + K+)/(Na+ + K+ + Ca2+) vs TDS and
Cl−/(Cl− + HCO
3 ) vs TDS. Figure 7 shows that
almost all the samples of pre-monsoon and post-
monsoon seasons falls in the rock dominance and
evaporation crystallization dominance area. The
Gibbs’s diagrams suggest that chemical weathering
of the rock forming minerals and evaporation are the
main processes which contribute the ions to the water.
It is interesting to note that during post-monsoon,
precipitation has no dominating effect and no points
falls on the precipitation dominating area. Anthropo-
genic activities may also increase the TDS value
(Hem 1991; Karanth 1997) and the samples tend to
fall on evaporation dominance area in the post-
monsoon. The variation of Gibb’s ratio with pre-
monsoon and post-monsoon was given in Table 4.
Kelley’s ratio
Kelley’s ratio is used to find whether the groundwater
is suitable for irrigation or not. Sodium measured
against calcium and magnesium was considered by
Kelley (1951) for calculating Kelley’s ratio. Ground-
water having Kelley’s ratio more than one is generally
considered as unfit for irrigation. Kelley’s ratio for
Fig. 7 Mechanism control-
ling groundwater quality
pre-monsoon varies form 0.65 to 2.15 with mean of
1.21 and for post-monsoon from 0.21 to 2.49 with a
mean of 0.86 (Table 4). According to Kelley’s ratio,
56.5% of the pre-monsoon samples and 26.1% of the
post-monsoon samples are found to be unfit for
irrigation. A t test performed on the pre- and post-
monsoon Kelley’s ratio showed that there is a definite
contribution of monsoon on the quality of water.
Magnesium ratio
Magnesium present in water would adversely affect the
soil quality rendering it unfit for cultivation. Magnesium
ratio with more than 50% can poison the water. Table 4
reveals that 30.4% of pre-monsoon samples showed
magnesium ratio more than 50% and 47.8% of post-
monsoon samples had magnesium ratio more than 50%.
Wilcox diagram
Wilcox (1948) used % sodium and specific conduc-
tance in evaluating the suitability of groundwater to
irrigation. Sodium-percentage determines the ratio of
sodium to the total cations viz., sodium, potassium,
calcium and magnesium. All concentration values are
expressed in equivalents per million in Fig. 8.
Percent sodium is calculated as follows:
Na
Na % ¼
Na þ K þ Ca þ Mg
 Environ Monit Assess
Fig. 8 Specific conductance
and percent sodium relation
for rating irrigation water
(Wilcox 1948)

The results (Table 4) show that the groundwater post-monsoon which may be due to the action of
near the upstream is good for irrigation and the leaching and surface runoff of the rainwater.
contamination is found to be high near the down-
stream. This may be due to the increased anthropo-
Sodium absorption ratio (SAR)
genic activities near the downstream owing to intense
settlements along the bank of the river and various
Sodium absorption ratio is also used to determine the
industries located near the river. At many places
suitability of groundwater to irrigation as it gives a
starting from the midstream to the confluence point
measure of alkali/sodium hazard to crops.
of the river, the effluents from the industries as well as
Sodium absorption ratio (SAR) which is given by
the domestic sewages are directed into the river. The
the relation (Karanth 1997)
near stagnancy of the water in this river facilitates long
residence time of the pollutants, which leads to the
Naþ
enhanced percolation of ions into the nearby ground- SAR ¼

water. Seasonal effect is apparent in the stations 10, 11 Ca2þ þ Mg2þ 1=2 =2
and 13 wherein the groundwater quality changes from
good to permissible in pre-monsoon to unsuitable in where concentrations are reported in meq/l.
Environ Monit Assess
Fig. 9 Rating of water sam-
ples in relation to salinity
and sodium hazard
The SAR concentration ranges from 1.96 to 8.28
with a mean of 4.01 for pre-monsoon and from 0.53 to
7.92 with a mean of 3.59 in post-monsoon. Figure 9
shows that only four samples in pre-monsoon and post-
monsoon shows SAR ratio more than 6. The t test
results indicate that the seasonal effect was non-
significant with regard to sodium absorption ratio
(Table 4). The rating of water samples in relation to
salinity and sodium hazard reflects that the high
sodium ion concentration in the water at some of the
stations may produce harmful levels of exchangeable
sodium in the soil. Figure 9 represent the classification
of the groundwater using USSL diagram.
Conclusion
The hydro geochemical study of the groundwater near
River Adyar provides the following conclusion:
– The seasonal variation of the chemical parameters
were evaluated and the order of abundance of the
ions were determined. TDS values in both pre-
monsoon and post-monsoon (except in some
places) were found to be higher than the
permissible limit. The concentration of the major
ions are found to be high in the case of post-
monsoon indicating leaching and anthropogenic
activities predominates over dilution of the
groundwater.
– The Gibb’s diagram shows that the composition
of water during pre-monsoon as well as in the
post-monsoon is dominated by evaporation-
crystallization.
– Equiline diagrams, 1:1, represent the unique
characteristic of the bonding affinity of ions.
The diagram depicts that the Chloride ions are
found to balance the alkali in the pre-monsoon
but during post-monsoon, excess Chloride ion
over alkali is observed indicating pollution due to
anthropogenic activities.
– Piper diagram characterizes the water types of
both the monsoons. Pre-monsoon was found to be
of NaCl and mixed CaMgCl type whereas in the
post-monsoon there is a shift to CaMgCl, NaCl,
CaCl type.

– Trace metal study reveals that during both pre-
monsoon and post-monsoon, concentration of Fe is
high in many stations. Pb and Cr are found to be high
in certain stations due to anthropogenic activities.
– Kelly’s ratio, magnesium ratio, Wilcox and USIS
diagrams suggests that the suitability of the water
to irrigation is high in the case of post-monsoon
than that of pre-monsoon in the groundwater near
the upper stretch of the river.
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