Environ Monit Assess (2010) 162:123137

DOI 10.1007/s10661-009-0781-4
Groundwater geochemistry and identication
of hydrogeochemical processes in a hard
rock region, Southern India
T. Subramani N. Rajmohan L. Elango
Received: 12 May 2008 / Accepted: 27 January 2009 / Published online: 28 February 2009
Springer Science + Business Media B.V. 2009
Abstract Hydrogeochemical investigations were
carried out in Chithar River basin, Tamil Nadu,
India to identify the major geochemical processes
that regulate groundwater chemistry. For this
study, long-term (19911997) and recent water
quality data (20012002) for 30 groundwater wells
spread over the study area were used to un-
derstand the groundwater geochemistry and hy-
drogeochemical process regulating groundwater
quality. Groundwater quality data obtained from
more than 400 water samples were employed.
Results of electrical conductivity and chloride ex-
press large variation between minimum and max-
T. Subramani
Department of Civil Engineering,
Government College of Engineering,
Salem, 636 011, Tamil Nadu, India
e-mail: geosubramani@yahoo.com
N. Rajmohan
Department of Waste Treatment and Conditioning
Research, Nuclear Energy Division,
Commissariat a lenergie atomique (CEA),
Centre De Valrho/Marcoule, BP 1717F 30207
Bagnols-Sur-Ceze Cedex, France
e-mail: nrmohan_2000@yahoo.com
L. Elango (B)
Department of Geology, Anna University,
Chennai, 600 025, Tamil Nadu, India
e-mail: elango@annauniv.edu
URL: www.geocities.com/elango
imum values and high standard deviation, which
suggests that the water chemistry in the study
region is not homogeneous and inuenced by
complex contamination sources and geochemical
process. Nitrate and depth to water table expose
the inuences of surface contamination sources,
whereas dissolved silica, uoride and alkalinity
strongly suggest the effect of rockwater interac-
tion. In the study region, weathering of carbonate
and silicate minerals and ion exchange reactions
predominantly regulate major ion chemistry. Be-
sides, the concentrations of sulphate, chloride and
nitrate rmly suggest the impact of agricultural
activities such as irrigation return ow, fertiliser
application, etc on water chemistry in the study
region.
Keywords Groundwater Geochemistry
Hydrogeochemical processes Waterrock
interaction Chithar River basin
Tamil Nadu India
Introduction
Chemistry of groundwater is an important factor
determining its use for domestic, irrigation and
industrial purposes. Interaction of groundwater
with aquifer minerals through which it ows
greatly controls the groundwater chemistry. Hy-
drogeochemical processes that are responsible for
124 Environ Monit Assess (2010) 162:123137
altering the chemical composition of groundwater
vary with respect to space and time. In any area,
groundwater has unique chemistry due to several
processes like soil/rockwater interaction during
recharge and groundwater ow, prolonged stor-
age in the aquifer, dissolution of mineral species,
etc. (Hem 1985). Earlier studies reported the im-
portance of hydrogeochemical studies of ground-
water in a particular region (Sikdar et al. 2001;
Apodaca et al. 2002; Elango et al. 2003; Tesoriero
et al. 2004; Devadas et al. 2007; Mller et al. 2007),
and hydrogeochemical studies will help to cre-
ate suitable management plans to protect aquifer
as well as remedial measures for contaminated
groundwater by natural and manmade activities.
Moreover, detailed knowledge about geochem-
ical process regulates groundwater chemistry is
necessary to overcome the groundwater-related
issues.
Some of the previous studies carried out in
Chithar River basin focused on groundwater po-
tential assessment (Balasubramanian and Sastri
1994), groundwater level uctuation and quality
monitoring (Public Works Department (PWD),
Tamil Nadu, India; PWD 2002), groundwater
quality and its suitability for drinking and agri-
cultural purposes (Subramani et al. 2005a) and
study on the occurrence of various rock types and
their mineral composition (including petrographic
studies; Subramani et al. 2005b). Hence, it is ap-
parent that the hydrogeochemical processes that
control the groundwater chemistry of the basin
have not been attempted in the previous studies.
As groundwater is being continuously exploited
in this basin to meet the demand for water supply
and irrigation due to insufciency of surface water
storage in reservoirs and non-perennial River, it is
essential to know the hydrogeochemical processes
that take place in the aquifer system. Thus, the
present work was carried out with the main ob-
jective of identifying the major hydrogeochemical
processes that are responsible for groundwater
chemistry in the study region.
Study area
Chithar River basin is located in the extreme
south of Tamil Nadu state, India, between lati-
tudes 8

48

to 9

14

N and longitudes 77

11

to
77

46

E (Fig. 1). It occupies an area of 1,722 km

2
,
and the regional slope of the basin is towards east.
The plain lands of this basin fall under semi-arid
climatic type, and the areas adjacent to Western
Ghats are of dry to moist sub-humid climatic types
(Rammohan 1984). Hence, the study area experi-
ences mostly dry climatic condition with average
maximum temperature of 39

C during the months

of April and May and average minimum tempera-
ture of 24

C during the months of November and

December. The average annual rainfall recorded
at eight rain gauge stations spread over the basin
is 917.88 mm. Among which, northeast monsoon
from October to December contributes almost
70% of the total rainfall and the rest by southwest
monsoon from June to September. Considerable
amount of rain showers are also received during
the transitional period.
Geology and hydrogeology
The Proterozoic (Post-Archaean) basement of the
area consists of quartzite, calc-granulite, crys-
talline limestone, charnockite and biotite gneiss
with or without garnet (Yoshida 1992; GSI 1995;
Jayananda et al. 1995). Kankar (lime-rich top soil)
observed in few places are of recent to sub-recent
age. Quartzite shows NWSE trend in most of the
places with numerous NS minor joints. In some
places, it is associated with calc-granulite and crys-
talline limestone. Calc-granulite and crystalline
limestone also show the NWSE trend. Calcitic-
and dolomitic-limestones are being quarried in
a few places for cement industries. Charnockite
outcrops as massive hills in the western part of the
basin. Garnetiferous charnockites are also noticed
in a few well cuttings in the eastern part. Most
of the basin is composed of biotite gneiss with
or without garnet. The different lithological units
encountered in the Chithar River basin are illus-
trated in the Fig. 2. A thin layer of topsoil, varying
between 1 to 1.5 m in most of the places, overlies
the basement rocks. Three major soil types were
identied in the study area: black cotton, deep
red and red sandy soils. Lithological cross sections
plotted along XX

, YY

and XZ(see Fig. 2) are

illustrated in the Figs. 3, 4 and 5.
Environ Monit Assess (2010) 162:123137 125
Fig. 1 Chithar River
basin and location
of monitoring wells
Groundwater recharge, transmission and dis-
charge of a basin are controlled by the basin ge-
omorphology, geology and structural patterns of a
region (Salama et al. 1994). It is inferred from the
cross sections that the occurrence of weathered
zone is not uniform in both space and depth.
Weathered zone thickness ranges from 8 to 34 m
below ground level. Groundwater in this basin
occurs under water table conditions in weathered
crystalline formations. In the study area, depth to
water table varies between 2.1 and 16 m during
pre-monsoon while between 0.91 and 16 m during
post-monsoon. Overall view of groundwater level
uctuation and the hydrograph results suggest
that the water table tends to rise during November
and December to reach the peak in January and
starts declining from February onwards to reach
the valley in September or October (Subramani
2005). Aquifer parameters of various geological
formations established by the PWD (PWD 2002)
from 30 bore wells spread over the basin re-
veals that hydraulic conductivity varies from 0.1
to 24 m/day in weathered rock formations.
Materials and methods
Groundwater sampling and analysis
Based on detailed well inventory survey in
Chithar River basin, 30 representative ground-
water wells (Created by PWD, Government of
126 Environ Monit Assess (2010) 162:123137
Fig. 2 Geology of Chithar River basin
Tamil Nadu, India for regular monitoring of water
level (monthly) and water quality (Bi-annual))
were selected for groundwater sampling program
(Fig. 1). Most of these wells are shallow irrigation
wells, and groundwater sampling campaigns were
carried out during July 2001 and 2002. Twenty-
four samples during July 2001 and 18 samples
during July 2002 were collected from the 30 rep-
resentative wells. In overall, 42 samples were
collected for chemical analysis. Field parame-
ters such as electrical conductivity (EC), pH and
temperature were measured in the eld using
portable meters. Groundwater samples collected
from these wells were transported to the labora-
tory in the same day and ltered using 0.45 m
Millipore lter paper. The cations and silica sam-
ples were acidied to pH<2 with several drops of
Fig. 3 Lithological
cross-section along XX

Environ Monit Assess (2010) 162:123137 127

Fig. 4 Lithological cross-section along YY

ultra-pure HCl in the laboratory and then refrig-

erated at 4

C until analysis.
Samples were analysed for major ions, nutri-
ents, silica and minor ions in the laboratory using
the standard methods (APHA 1995). Samples
were analysed for sulphate, nitrate, phosphate,
uoride and silica using UV/visible spectropho-
tometer; sodium, potassium using ame pho-
tometer and calcium, magnesium, chloride and
alkalinity (HCO
3
+ CO
3
) by the titration tech-
nique. Overall, measurement reproducibility and
precision for each analysis were less than 2%. The
analytical precision for the total measurements of
ions was checked again by calculating the ionic
balance errors and was generally within 5%.
Rock sampling and analysis
Detailed geological eld survey was also carried
out in the basin to relate the groundwater chem-
istry with lithology. Thirty-nine rock samples were
collected fromoutcrops, quarries and well cuttings
in the eld. Similar rock types were grouped to-
gether in the laboratory after megascopic studies.
Among them, 25 samples were chosen for thin
section preparation (microscopic studies) to un-
derstand the petrographic nature of various rocks.
Data collection and analysis
Long-term groundwater quality data (from 1991
to 1997, pre-monsoon (July) and post-monsoon
(January) periods, 361 samples) for the same
PWD wells (30 wells used for 2001 and 2002
groundwater sampling) were collected from PWD
to understand the long-term variation in ground-
water chemistry and hydrogeochemical process
(PWD 2004). This long-term water quality data
are considered as secondary data (SD).
Fig. 5 Lithological cross-section along XZ
128 Environ Monit Assess (2010) 162:123137
Results and discussion
Groundwater geochemistry
Groundwater samples of this basin are alkaline,
with a pH ranging between 6.9 and 9.2, showing
an average value of 8.3 (Table 1). Electrical con-
ductivity ranges from 79 to 9,300 S/cm with an
average of 1,595 S/cm. The statistical summary
of water quality parameters is given in Table 1.
Table 1 illustrates that ECand chloride showlarge
variation between minimum and maximum value
and also express high standard deviation. This
inference not only suggests that the water chem-
istry in the study region is not homogeneous but
also reveal the inuences of complex contamina-
tion sources and geochemical process. Moreover,
nitrate and depth to water table expose the inu-
ences of surface contamination sources, whereas
dissolved silica, uoride and alkalinity strongly
suggest the effect of rockwater interaction
(Table 1). Table 1 also shows a variation in the
mean values of chemical parameters between pri-
mary and secondary data. The mean and median
values of EC and major ions are higher in primary
data compared to the secondary data, which ap-
parently suggests the enhancement of solute load
in the aquifer.
Hydrogeochemical processes
Reactions between groundwater and aquifer min-
erals have a signicant role on water quality,
which are also useful to understand the genesis
of groundwater (Cederstorm1946). As mentioned
earlier, groundwater chemistry in the study region
is regulated by diverse processes and mechanisms.
Since the study region experiences dry and semi-
arid climatic condition, evaporation may also con-
tribute in water chemistry in the study region.
Hence, Gibbs plot is employed in this study to un-
derstand and differentiate the inuences of rock
water interaction, evaporation and precipitation
on water chemistry (Gibbs 1970). Figure 6 illus-
trates that most of the groundwater samples of
the Chithar River basin fall in the waterrock
interaction eld and few samples plotted on evap-
oration zone, which suggests that the weathering
of rocks primarily controls the major ion chem-
istry of groundwater in this region. Therefore,
the concentrations of major ions in groundwater
and the mineralogy of different rocks have been
used to determine the source of these major ions
to the groundwater and their relation to regional
geology and weathering processes.
Carbonate weathering and dissolution
Calcium and magnesium are the dominant cations
present in groundwater next to sodium in this
region. Similarly, bicarbonate is also present in
considerable amounts. Carbonate-rich rocks such
as crystalline limestone, dolomitic limestone, calc-
granulite and kankar (lime-rich weathered mantle
overlies carbonate rocks) are the major sources
for carbonate weathering. The available carbon-
ates in these rocks might have been dissolved and
added to the groundwater system during irriga-
tion, rainfall inltration and groundwater move-
ment. InCa
2+
+Mg
2+
vs alkalinity + SO
4
2
scatter
diagram (Fig. 7a), the points falling along the
equiline (Ca
2+
+Mg
2+
= alkalinity + SO
4
2
) sug-
gest that these ions have resulted fromweathering
of carbonates and sulphate minerals (gypsum or
anhydrite; Datta and Tyagi 1996). Moreover, if the
Ca
2+
and Mg
2+
solely originated from carbonate
and silicate weathering, these should be balanced
by the alkalinity alone. However, most of the
points are placed in the Ca
2+
+ Mg
2+
side, which
indicates excess calcium and magnesium derived
from other process such as reverse ion exchange
reactions.
In silicate terrain, if the calcium and bicar-
bonate in groundwater are solely originated from
calcite, the equivalent ratio of dissolved Ca
2+
and
HCO
3

in the groundwater is 1:2, whereas from

dolomite weathering, it is 1:4 (Garrels and
Mackenzie 1971; Holland 1978). Similarly, if the
calcium and sulphate in groundwater derived
from dissolution of gypsum or anhydrite, then
the Ca
2+
/SO
4
2
ratio is almost 1:1 (Das and
Kaur 2001). In Ca
2+
vs Alkalinity scatter diagram
(Fig. 7b), some groundwater samples follow the
1:2 and 1:4 lines and indicate the contribution of
both calcite and dolomite weathering on ground-
water chemistry in this basin. Moreover, in Ca
2+
E
n
v
i
r
o
n
M
o
n
i
t
A
s
s
e
s
s
(
2
0
1
0
)
1
6
2
:
1
2
3

1
3
7
1
2
9
Table 1 Summary of water quality parameters
Parameter EC pH Wl Na K Ca Mg Cl Alk SO
4
NO
3
SiO
2
F PO
4
(S/cm) (mbgl) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (meq/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)
Primary Minimum 80.0 6.9 2.60 4.00 2.00 10.0 2.00 7.00 0.30 BDL BDL 20.9 0.17 BDL
(2001 and 2002) Maximum 9,040 9.2 17.2 897 86.0 880 485 2,482 8.70 576 56.0 112 1.30 0.89
Mean 1,838 8.0 8.28 133 13.6 120 78.1 391 4.15 94.5 17.9 70.8 0.59 0.06
Med 1,225 8.0 7.14 106 10.5 66.0 54.0 213 3.39 60.0 10.0 71.2 0.60 0.00
Standard deviation 1,661 0.5 4.10 140 14.7 167 85.1 466 2.22 119 17.2 19.3 0.28 0.18
n 42 42 34 42 42 42 42 42 42 42 42 42 42 42
Secondary Minimum 79.0 7.0 0.91 4.00 BDL 4.00 2.00 6.50 0.10 BDL NA NA NA NA
(199197) Maximum 9,300 9.2 16.4 840 297 620 462 2,552 14.8 624 NA NA NA NA
Mean 1,566 8.4 7.10 146 21.4 78.2 67.6 336 3.56 75.4 NA NA NA NA
Med 1,150 8.4 6.65 92.0 9.00 46.0 49.0 209 3.11 46.0 NA NA NA NA
Standard deviation 1,354 0.3 4.09 134 35.7 93.7 60.4 361 2.06 83.9 NA NA NA NA
n 361 258 160 361 361 361 361 361 361 361 NA NA NA NA
Total Minimum 79.0 6.9 0.91 4.00 BDL 4.00 2.00 6.50 0.10 BDL BDL 20.9 0.17 BDL
Maximum 9,300 9.2 17.2 897 297 880 485 2,552 14.8 624 56.0 112 1.30 0.89
Mean 1,595 8.3 7.30 145 20.6 82.6 68.7 342 3.62 77.4 17.9 70.8 0.59 0.06
Med 1,160 8.4 6.80 92.0 9.00 48.0 50.0 209 3.20 48.0 10.0 71.2 0.60 0.00
Standard deviation 1,389 0.4 4.10 134 34.2 104 63.4 373 2.08 88.2 17.2 19.3 0.28 0.18
n 403 300 194 403 403 403 403 403 403 403 42 42 42 42
n number of samples analysed, Wl groundwater level, Med median, NA not analysed, BDL below detection limit
130 Environ Monit Assess (2010) 162:123137
Fig. 6 Gibbs plots
explain groundwater
chemistry and
geochemical process
in the study region
Secondary data Primary data
1
10
100
1000
10000
100000
0.0 0.2 0.4 0.6 0.8 1.0
(Na+K)/(Na+K+Ca)
T
D
S
(
m
g
/
l
)
1
10
100
1000
10000
100000
0.0 0.2 0.4 0.6 0.8 1.0
Cl/(Cl+Alk)
T
D
S
(
m
g
/
l
)
P
r
e
c
ip
it
a
t
io
n
Rock water interaction
E
v
a
p
o
r
a
t
i
o
n
P
r
e
c
ip
it
a
t
io
n
E
v
a
p
o
r
a
t
i
o
n
Rock water interaction
Fig. 7 Relation between
Ca, Mg, SO
4
and
alkalinity in the
groundwater
0
5
10
15
20
25
0 20 40 60 80 100
Ca+Mg (meq/l)
A
l
k
a
l
i
n
i
t
y
+
S
O
(
m
e
q
/
l
)
4
1
:
1
l
i
n
e
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50
Ca (meq/l)
A
l
k
a
l
i
n
i
t
y
(
m
e
q
/
l
)
1
:
2
l
i
n
e
1
:
4
l
i
n
e
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50
Ca (meq/l)
S
O
(
m
e
q
/
l
)
4
1
:
2
l
i
n
e
1
:
1
l
i
n
e
Primary data Secondary data
a) b)
c)
Environ Monit Assess (2010) 162:123137 131
vs SO
4
2
scatter diagram (Fig. 7c), few samples
fall along the 1:1 equiline

Ca
2+
= SO
4
2

, and
most of them show excess calcium over sulphate.
Groundwater samples following the 1:1 equiline
seem to be derived from gypsum or anhydrite
dissolution, whereas excess calcium highlights ad-
ditional geochemical process. Similarly, excess
sulphate over calcium in few samples expresses
the removal of calcium from the system likely by
calcite precipitation.
Mayo and Loucks (1995) explained that if Ca
2+
/
Mg
2+
molar ratio is equal to one, dissolution of
dolomite should occur, whereas a higher ratio
is indicative of greater calcite contribution. Katz
et al. (1998) also explained that the higher Ca
2+
/
Mg
2+
molar ratio (>2) is indicative of dissolution
of silicate minerals. The molal ratio is generally
less than or equal to 1 in Chithar River basin, and
some of them have this ratio more than 1, which
indicates that the dissolution of dolomite and
calcite are the dominant geochemical processes
followed by the dissolution of silicate minerals.
Effect of silicate weathering on water chemistry
Dissolved silica data apparently show the inu-
ences of silicate weathering on water chemistry in
the study region (Table 1). Participation of silicate
minerals in the chemical reactions plays a vital
role in groundwater geochemistry. Quantication
of the products of silicate weathering are more
difcult because the degradation of silicates is
incongruent, generating a variety of solid phases
(mostly clays) along with dissolved species (Das
and Kaur 2001). However, silicate weathering can
be understood by estimating the ratio between
Na + K and total cations (TZ+). The relationship
between Na + K and total cations (TZ+) of the
area (Fig. 8a) indicate that the majority of the
samples are plotted near the Na + K = 0.5TZ +
line. This observation shows the involvement of
silicate weathering in the geochemical processes,
which contributes mainly sodium and potassium
ions to the groundwater (Stallard and Edmond
1983; Sarin et al. 1989). However, some samples
Fig. 8 Relation between
total cation, Na + K
and Ca + Mg in the
study region
Secondary data Primary data
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80 90 100
Ca+Mg (meq/l)
T
o
t
a
l
c
a
t
i
o
n
(
m
e
q
/
l
)
1
:1
lin
e
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80 90 100
Na+K (meq/l)
T
o
t
a
l
c
a
t
i
o
n
(
m
e
q
/
l
)
N
a
+
K
=
0
.
5
T
Z
1
:1
lin
e
132 Environ Monit Assess (2010) 162:123137
deviated from the line and show lower Na + K
concentration, which seems to be Ca/Na exchange
reactions.
Weathering of soda feldspar (albite) and potash
feldspars (orthoclase and microcline), which are
common in biotite gneiss occurring in this area,
is greatly responsible for the contribution of Na
+
and K
+
ions to groundwater. Feldspars are more
susceptible for weathering and alteration than
quartz in silicate rocks. The average

Ca
2+
+
Mg
2+

/HCO
3

equivalent ratio of 3.23 and the

Ca
2+
+ Mg
2+

/TZ+ equivalent ratio of 0.59 sug-

gest that silicate weathering occurs in this region
in addition to the carbonate dissolution. Further,
Ca
2+
+ Mg
2+
vs total cations (TZ+) plot of
groundwater samples (Fig. 8b) have a linear
spread along 0.6:1

Ca
2+
+ Mg
2+
= 0.6TZ+

line,
indicating that some of these ions

Ca
2+
+ Mg
2+

are resulted fromthe weathering of silicate miner-

als. The regional geology also implies that the al-
kali earth silicates occur everywhere in the basin.
Petrographic studies (Subramani et al. 2005b)
indicate that calcic-plagioclase feldspars, pyrox-
enes and amphiboles are the common calcium-
and magnesium-bearing minerals in silicate rocks,
which contribute Ca
2+
and Mg
2+
ions to ground-
water by weathering (Eqs. 1 and 2; Sami 1992).
For pyroxene
CaMg (Si
2
O
6
) +4CO
2
+6H
2
O
= Ca
2+
+Mg
2+
+4HCO
3

+2Si (OH)
4
(1)
For amphibole
Ca
2
Mg
5
Si
8
O
22
(OH)
2
+14CO
2
+22H
2
O
= 2Ca
2+
+5Mg
2+
+14HCO
3

+8Si (OH)
4
(2)
Labradorite and hypersthene are the essential
minerals, and hornblende is the common acces-
sory mineral in charnockite. Potash feldspars and
albite are the major minerals in gneissic rocks, and
biotite is the accessory mineral. In the groundwa-
ter of the basin, K
+
is, however, not as abundant
as that of Na
+
due to its xation in the formation
of clay minerals (Mohan et al. 2000).
Ion exchange
Ion exchange is one of the important processes re-
sponsible for the concentration of ions in ground-
water. Chloro-alkaline indices 1 and 2 (CAI 1 and
CAI 2) calculated for the groundwater samples of
the basin strongly suggest the occurrence of ion
exchange process.
CAI 1 = C1

Na
+
+K
+

C1

(3)
CAI 2 = C1

Na
+
+K
+

SO
4
2
+HCO
3

+CO
3
2
+NO
3

All values are expressedinmeq

(4)
When there is an exchange between Ca or Mg
in the groundwater with Na and K in the aquifer
material, both the above indices are negative, and
if there is a reverse ion exchange, then both these
indices will be positive (Schoeller 1965, 1967).
CAI 1 and CAI 2 values of the study area vary
with respect to time, but they are positive most
of the time, and very few wells show negative
values (Fig. 9). This observation indicates that re-
verse ion exchange is the dominant process in the
groundwater, whereas normal ion exchange is also
noticed in a very fewwells during the study period.
Further, when reverse ion exchange is a signicant
geochemical process for controlling the compo-
sition of groundwater, the relationship between
Na
+
Cl

and Ca
2+
+ Mg
2+
HCO
3

SO
4
2
should be linear with a slope of 1.0 (Fisher and
Mullican 1997). Figure 10 apparently shows that
all the groundwater samples of the study area
dene a straight line (R
2
= 0.99) with a slope of
1.03, which indicates the occurrence of reverse
ion exchange in the study area.
Evaporation
Evaporation process is not only a common phe-
nomenon in surface water but also in groundwater
system. Na/Cl ratio can be used to identify the
evaporation process in groundwater. Evaporation
will increase the concentration of total dissolved
solids in groundwater, and the Na/Cl ratio remains
the same, and it is one of the good indicative fac-
tors of evaporation. If evaporation is the dominant
Environ Monit Assess (2010) 162:123137 133
Fig. 9 Chloro-alkaline indices 1 and 2 (CAI 1 and CAI 2) indicating ion exchange process. PD primary data, SD secondary
data
134 Environ Monit Assess (2010) 162:123137
Fig. 10 NaCl vs Ca +
MgalkalinitySO
4
scatter diagram illustrates
reverse ion exchange
(PD) y = -1.0283x + 0.86
R = 0.99
2
(SD) y = -1.2484x + 0.51
R = 0.96
2
-20
-10
0
10
20
30
40
50
60
70
-70 -60 -50 -40 -30 -20 -10 0 10
Na-Cl (meq/l)
C
a
+
M
g
-
A
l
k
a
l
i
n
i
t
y
-
S
O
(
m
e
q
/
l
)
4
Secondary data Primary data
process, Na/Cl ratio should be constant when EC
rises (Jankowski and Acworth 1997). The EC vs
Na/Cl scatter diagramof the groundwater samples
of the basin (Fig. 11) shows that the trend line is
inclined, and Na/Cl ratio decreases with increas-
ing salinity (EC) which seems to be removal of
sodium by ion exchange reaction. This observa-
tion indicates that evaporation may not be the
major geochemical process controlling the chem-
istry of groundwater in this study region or ion
exchange reaction dominating over evaporation.
However, the Gibbs diagrams (Fig. 6) justify that
evaporation is not a dominant process in this basin.
Effect of land use on groundwater chemistry
As mentioned earlier, the groundwater is the sole
source for domestic and agricultural activities in
the study region. Further, cultivation of paddy and
grams are economically important in the study
region, and most of the basin is covered by agri-
cultural lands and residents. Hence, groundwater
contamination by irrigation return ow, fertiliser
and farm manure application, leaching of soil
mineralised nitrogen, domestic sewage, etc is also
an important issue on groundwater contamination
in the study area. The concentrations of nitrate
and chloride in the groundwater justify the effect
of surface contamination sources (Table 1). The
nitrate concentration varies from below detection
limit (BDL) to 56 mg/l with a mean value of
17.9 mg/l. However, six samples exceed WHO
standards and are not t for drinking, which may
cause blue baby disease/methaemoglobinaemia
in children and gastric carcinomas (Comly 1945;
Gilly et al. 1984). Likewise, chloride ranges from
6.5 to 2,552 mg/l with a mean value of 342 mg/l,
and sulphate varies from BDL to 624 mg/l with
Fig. 11 Relation between
EC and Na/Cl in the
groundwater
0
1
2
3
4
5
6
0 2000 4000 6000 8000 10000
EC ( S/cm)
N
a
/
C
l
(
m
e
q
/
l
)
Secondary data Primary data
Environ Monit Assess (2010) 162:123137 135
Fig. 12 Cl vs SO
4
scatter
diagram indicates the
effect of land use on
groundwater in the
study area
(PD) y = 0.161x + 0.19
R = 0.74
2
(SD) y = 0.142x + 0.22
R = 0.69
2
0
2
4
6
8
10
12
14
0 10 20 30 40 50 60 70 80
Cl (meq/l)
S
O
(
m
e
q
/
l
)
4
Secondary data Primary data
a mean value of 77.4 mg/l. Sulphate and chloride
show strong correlation in both primary (PD) and
secondary data (Fig. 12, (PD) R
2
= 0.74, (SD)
R
2
= 0.69) and implies the effect of surface con-
tamination, especially irrigation return ow since
gypsum application is very common in the paddy
eld in the study region. Similarly, since most of
the basin is intensively irrigated, higher concen-
tration of nitrate in groundwater can be resulted
from the agricultural activities (Subramani et al.
2005a).
Conclusions
Hydrogeochemical investigations were carried out
in Chithar River basin, Tamil Nadu, India to
identify the major geochemical processes that
are responsible for the groundwater chemistry.
Groundwater chemistry of this region is inu-
enced by complex contamination sources and geo-
chemical processes. The comparison of primary
and secondary groundwater quality data exhibits
that electrical conductivity and major ion con-
centrations are higher in primary data compared
to the secondary data, which apparently suggests
the enhancement of solute load in the aquifer. In
the study region, carbonate mineral dissolution,
silicate weathering and ion exchange reactions are
the major hydrogeochemical processes responsi-
ble for the concentration of major ions in ground-
water. Dissolved silica, uoride and alkalinity
concentrations reveal the effect of rockwater in-
teraction on water chemistry. Nitrate, sulphate
and chloride concentrations and depth to water
table illustrates that water chemistry is impaired
by land-use activities, especially irrigation return
ow, synthetic fertilisers (urea, gypsum, ammo-
nium sulphate, etc) and farm manures. This study
highlights that combined application of long-term
(secondary) and recent (primary) data on ground-
water geochemical studies are more reliable and
also helpful to avoid the misleading identication
of hydrogeochemical process due to lack of data.
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