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Application of Statistical Analysis for the
Hydrogeochemistry of Saline Groundwater in Kodiakarai,
Tamilnadu, India
I. Anitha Mary*, T. Ramkumar, and S. Venkatramanan
Department of Earth Sciences
Annamalai University
Annamalainagar 608 002, India
geoanitha@gmail.com
ABSTRACT
ANITHA MARY, I.; RAMKUMAR, T., and VENKATRAMANAN, S., 2012. Application of statistical analysis for the
hydrogeochemistry of saline groundwater in Kodiakarai, Tamilnadu, India. Journal of Coastal Research, 28(1A), 8998.
West Palm Beach (Florida), ISSN 0749-0208.
The hydrogeochemical characteristics of shallow groundwater in the coastal areas of Kodiakarai have been investigated
using geochemical analysis and statistical techniques. The geochemical data (electric conductivity, pH, total dissolved
solids, Ca, Mg, Na, K, NO
3
, SO
4
, Cl, and HCO
3
) of the water sample indicates that this water not suitable for drinking.
The spatial distribution pattern indicates the total dissolved solids and electric conductivity were highly concentrated on
the northeastern side, and that of sodium and chloride on the southwestern and northeastern side. The statistical
treatment of the data (cluster, factor analysis) indicates three types of groundwater in the study area and that seawater
incursion is the dominant process that influences the quality of the groundwater in the coastal region.
www.JCRonline.org
ADDITIONAL INDEX WORDS: Spatial distribution, correlation matrix, cluster analysis, factor analysis (PCA),
seawater intrusion, Kodiakarai.
INTRODUCTION
Water is a finite resource, and it is becoming a scarce
commodity in many parts of the world. In countries with scarce
water resources, competition among agriculture, industry, and
domestic uses of limited water is a constraining factor for
economic development. These undesirable effects are expected
to become more serious as climatic changes cause more
desertification, greater erosion in watersheds, and sea level
elevation in coastal areas. In the last 20 years, groundwater
salinization has become an urgent environmental problem
worldwide and constitutes one of the most widespread forms of
water contamination. The problem is particularly serious in
coastal areas, where rapid population growth and intensive
economic activity has increased the need for freshwater
supplies. This need is mainly being satisfied by pumping
groundwater fromcoastal aquifer systems. However, in coastal
regions, groundwater quality patterns are complex because of
the input from many different water sources. These include
precipitation (possibly polluted or saline as a result of strong
evaporation), seawater, ascending deep groundwater, and
anthropogenic sources such as wastewater or irrigation return
flow (Ramkumar et al., 2010; Venkatramanan et al., 2009).
Proper management of available groundwater reserves is
impossible without knowledge of the spatial distribution of
fresh and saline groundwater and the processes that determine
their evolution (Glynn and Plummer, 2005). Understanding the
spatial variations in chemical composition of groundwater that
result from different types of input is extremely difficult,
especially if concentrations have varied over time or if
boundary conditions have changed (Hussein, 2004). Descrip-
tions of the processes and factors that control saline water
evolution over time is an academic challenge but of important
practical use for water resource evaluation and seawater
intrusion studies. Processes and chemical reactions associated
with saltwater intrusion in coastal aquifers have been
investigated by several authors. Abdul Rahimand Abdul Ghani
(2002), Luo (2000), Richter and Kreitler (1993), Samsudin et al.
(2008), and Shammas and Jacks (2007) used geochemical
techniques to identify sources of groundwater salinization.
Petalas and Diamantis (1999) describe the origin and distribu-
tion of saline groundwater in the coastal area of Rhodope,
Greece, using several hydrochemical diagrams. Chadha (1999),
Cloutier et al. (2008), Guler et al. (2002), Meng and Maynard
(2001), Yidana and Yidana (2009), and Zeng and Rasmussen
(2005) propose a new hydrochemical diagram for classification
of natural waters and identification of hydrochemical processes
using various multivariate statistical analysis.
In this study, groundwater samples from an alluvium where
intensive agricultural activities are in practice were geochem-
ically investigated to evaluate the factors regulating the
groundwater quality. Cluster analysis of geochemical data
shows that the clustered groups are well correlated to the
aquifer conditions and adequately represent the levels of
DOI: 10.2112/JCOASTRES-D-09-00156.1 received 6 November 2009;
accepted in revision 25 July 2010.
* Corresponding author.
Published Pre-print online 20 October 2010.
Coastal Education & Research Foundation 2012.
Journal of Coastal Research 28 1A 8998 West Palm Beach, Florida January 2012
groundwater contamination by seawater intrusion and agri-
cultural activities. The results suggest that the clustering
approach based on geochemical data can be applied to the
assessment of groundwater quality in the coastal region.
STUDY AREA
The study area, Kodiakarai, is a part of the Vedaranniyam
taluk of Nagai district, Tamilnadu, South India. It is located
11 km to the south of Vedaranniyam. This is also called Point
Calimere. The study area is located between north latitude
10u169000 east longitudes 79u499000 in the survey of India
toposheets number 58N/15 (Figure 1). The study area is
characterized as (i) western gently undulating county, (ii)
central alluvial plains of the Cauvery delta, (iii) NS and EW
trending fluvio-marine delta, and (iv) NS and EW trending
coastal Chenier plain between the southwest and Vedaran-
niyam in the southeast.
The geological formations include oldest Archean to recent
alluvium. The sedimentary section contains a number of
transgressive and regressive episodes. The area is formed of
recent unconsolidated material consisting of sand, breccias,
and fine clay to silty sand deposits. These deposits host the
main aquifer system of the area. The study area received an
average rainfall of 1013.2 mm in the present decade.
MATERIALS AND METHODS
In total, 72 groundwater samples were collected from
February to September 2007, covering the postmonsoon,
summer, and premonsoon seasons. The samples were collected
in cleaned polythene bottles from various wells. The collected
samples were analyzed for the various hydrogeochemical
parameters for pH, electric conductivity (EC), total dissolved
solids (TDS), Ca, Mg, Na, K, HCO
3
, SO
4
, Cl, and NO
3
. The
results were grouped by season. The temperature and pH were
measured with a field kit. TDS and EC were analyzed by the
electrode method. Na and K were analyzed by flame photom-
etry. Ca, Mg, Cl, and HCO
3
were estimated by the volumetric
method, and SO
4
and NO
3
analyzed by the turbidity method.
The standard methods of APHA (1998) were followed. The
results of the physicochemical analysis are given in Table 1. All
concentrations are expressed in mg/L except pHand EC, which
are given in mS/cm.
RESULTS AND DISCUSSION
Major Ion Chemistry
The analytical data of the water samples indicate that the pH
value of water samples varied from 6.4 to 8.0, indicating that
water is slightly alkaline in nature but within the limiting
value of the drinking water standard. The pH is mainly
influenced by the use of lime in agricultural fields. The small
variation in pHin the study area is due to the release of sodium
and calcium by percolating rainwater. The EC value varied
from 2391 to 4211mS/cm, and the TDS value ranged from 1530
to 3298 mg/L, showing good correlation with each other. The
summer season record high conductance was correlated to the
TDS, indicating the intrusionof residual solids into the aquifer.
Figure 1. Location map of Kodiakarai, India.
90 Anitha Mary, Ramkumar, and Venkatramanan
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
The increased value of TDS in groundwater is likely a result of
dissolution, the weathering of sediment, and the solubility of
lime and gypsum, all of which considerably increase TDS in
groundwater (Jain, Bhatia, and Vijay, 1996). The study area is
a coastal region, and seawater incursion is a main factor for the
increased amount of TDS in groundwater. This was supported
by a high value of sodium and chloride. Further the total hard-
ness of the water samples varied from 220.71 to 815.58 mg/L.
The increased level of hardness in the water is due to the excess
amount of calcium and magnesium in the groundwater.
In the present study, it was observed that sodium, potassium,
calcium, and magnesium were higher in summer samples than
those from the postmonsoon and premonsoon seasons; sodium
and magnesium were lower during the postmonsoon than
premonsoon season; for calcium and potassium it was the
opposite. This indicates the seasonal influence of the cations in
this environment. The relative abundance of sodium and
magnesium during postmonsoon and summer indicate the
influence of monsoon rainwater, which leads to an increase in
these elements from sediment, thereby increasing their concen-
tration in the groundwater during the postmonsoon and
summer seasons. Weathering of plagioclase feldspar and the
nature of dissolved atmospheric carbon dioxide, which releases
sodium and calcium, progressively increases the sodium and
calcium concentrations. With respect to anions, chloride and
sulfate dominated during the summer and premonsoon seasons,
and nitrate was dominant during the postmonsoon season.
Sulfate showed less variation between the wells between the
seasons. On the other hand, the concentrations of chloride and
nitrate showed more variation in the wells between the seasons.
The conspicuous variation observed for this parameter is mainly
a result of agricultural activity and the influence of seawater in
the shallow aquifer system. A high correlation between sodium
and chloride was observed, confirming the influence of seawater
on the groundwater. The low concentration of bicarbonate
during the postmonsoon season indicates the influence of
freshwater addition to the groundwater.
Spatial Distribution Pattern
The spatial distribution pattern of electric conductivity and
total dissolved solids during the study period is shown in
Figures 2ac and 3ac. The exception is during the monsoon
season when a higher concentration of TDS and higher EC
were observed in the northeast direction. This spatial pattern
clearly indicates that large values of TDS and EC in
groundwater correspond to the influence of seawater in some
coastal wells. This phenomena is widely observed thoughout
the world in freshwater aquifers lying close to the sea coast.
The spatial distribution pattern of sodium during the
postmonsoon season (Figures 4 ac) shows a higher concen-
tration on the northeastern and southeastern sides, particu-
larly at wells 14, 6, and 9. These well lie near the coastal area,
and seawater influences the distribution pattern. On the
southern and northern sides, the spatial distribution of sodium
and chloride is determined by seawater intrusion; irrigation
return flow from agricultural activity also plays a significant
role in determining the sodium and chloride content. The
spatial distributionof chloride during the study periodis shown
in Figures 5ac and is similar to the spatial distribution of
sodium. During the postmonsoon season, higher concentra-
tions of chloride are observed on the northeastern and
southeastern coastal side (wells 17). During the summer
and premonsoon seasons, high levels of chloride are observed
on the southeastern and northeastern side. The maximum
concentration is observed on the southwestern side (well 6).
Correlation Matrix
Correlations between major cations and anions were carried
out using Pearsons correlation. A correlation analysis is a
bivariate method applied to describe the degree of relation
between hydrochemical parameters. A high correlation coeffi-
cient (near 1 or 21) means a good relationship between two
variables, and a value near 0 means there is no relationship
between themat a significance level of ,0.05. More precisely it
can be said that parameters showing r . 0.7 are considered to
be strongly correlated, whereas when r has a value between 0.5
and 0.7, moderate correlation is said to exist. During the
postmonsoon season, good correlation exists between EC-Cl,
TDS-Cl, HCO
3
-EC, TDS-HCO
3
, EC-TDS, and K-Na. Poor
correlation exists between EC-Mg, Cl-Na, HCO
3
-Na, Mg-
HCO
3
, and K-EC with other ions because of the dilution
process. Cl shows good correlation with Na, TDS, and EC,
Table 1. Physicochemical parameters of the groundwater samples.
Water Quality Parameter (mg/L)
Concentration in Study Area (mg/L)
Postmonsoon Summer Premonsoon
Min. Max. Average Min. Max. Average Min. Max. Average
pH 6.4 7.3 6.9 6.7 8.0 7.33 6.6 7.8 7.12
EC (mS/cm) 2391 4221 3330.4 3099 5153 4010.9 2561 4404 3509.7
TDS 1530 2695 2129.5 1983 3298 2566.6 1639 2818 2241.2
TH 220 695 447.7 245 815 503.6 224 671 456.5
Calcium (Ca) 29 65 43.2 38 82 61.01 30 92.7 53.7
Magnesium (Mg) 29.9 133.5 82.4 31.1 156.9 85.3 32.2 125.1 79.7
Sodium (Na) 544.8 909.9 684.7 618.3 990 779.4 511.2 892.6 686.3
Potassium (K) 17.1 42.3 26.3 23.5 67.8 45.4 19 43.8 33.05
Bicarbonate (HCO
3
) 61 96 75.04 74 108 89.8 64.6 98.7 78.72
Sulfate (SO
4
) 397.8 822.5 580.5 404.1 892.9 656.7 513.4 878.6 669.3
Chloride (Cl) 318.5 913.4 708.17 547.9 1143.5 878.4 304.8 980.6 704.1
Nitrate (NO
3
) 2.2 9.07 5.68 3.63 8.45 6.18 2.77 8.6 5.69
Hydrogeochemistry of Saline Groundwater in Kodiakarai, India 91
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
Figure 2. Spatial distribution of EC (a) postmonsoon, (b) summer, (c) premonsoon.
92 Anitha Mary, Ramkumar, and Venkatramanan
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
Figure 3. Spatial distribution of TDS (a) postmonsoon, (b) summer, (c) premonsoon.
Hydrogeochemistry of Saline Groundwater in Kodiakarai, India 93
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
Figure 4. Spatial distribution of Na (a) postmonsoon, (b) summer, (c) premonsoon.
94 Anitha Mary, Ramkumar, and Venkatramanan
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
Figure 5. Spatial distribution of Cl (a) postmonsoon, (b) summer, (c) premonsoon.
Hydrogeochemistry of Saline Groundwater in Kodiakarai, India 95
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
which indicates seawater incursion and leaching of secondary
salts. The lower concentration of calcium compared with
sodium and chloride is a result of the cation exchange process
that occurs naturally when seawater is introduced into the
freshwater aquifer system (Appelo and Postma 2005).
During the summer season, sodium is positively correlated
with chloride, EC, and TDS, indicating seawater incursion due
to continuous pumping activities in the study area. Poor
positive correlation of Cl-Mg and Mg-K indicates a lesser
dilution process. During this period, sodium correlates well
with chloride, indicating that coastal groundwater is highly
affected by seawater. This kind of result was observed by Aris,
Abdullah, and Kim, 2007). During the premonsoon season, a
good correlation exists between K-Cl, Cl-TDS, Cl-EC, TDS-
HCO
3
, K-TDS, and Na-EC, indicating seawater incursion and
leaching of secondary salts. Bicarbonate levels during pre-
monsoon season correlate significantly with other elements
compared with the other two seasons. This is related to the
rainwater infiltration and decay of organic matter. The
correlation matrix of the three seasons clearly indicates
seawater incursion present in the aquifer (Table 2).
Factor Analysis
The Kaiser criterion (Kaiser, 1960) was applied to determine
the total number of factors for each data set in this analysis.
Table 2. Correlation coefficients of hydrochemical data of groundwater.
pH EC TDS Ca Mg Na K HCO
3
Cl
Postmonsoon
pH 1.00
EC 20.48 1.00
TDS 20.48 0.72 1.00
Ca 0.38 20.40 20.40 1.00
Mg 20.14 0.23 0.23 0.11 1.00
Na 20.37 0.39 0.39 20.63 20.08 1.00
K 20.27 0.31 0.31 20.67 0.01 0.95 1.00
HCO
3
0.05 0.68 0.68 20.63 0.29 0.34 0.39 1.00
Cl 20.40 0.86 0.86 20.36 20.05 0.08 20.05 0.58 1.00
Summer
pH 1.00
EC 0.41 1.00
TDS 0.41 0.86 1.00
Ca 20.11 20.65 20.65 1.00
Mg 0.65 0.52 0.52 0.00 1.00
Na 0.45 0.70 0.70 20.79 0.16 1.00
K 20.28 0.53 0.53 20.28 0.22 20.09 1.00
HCO
3
0.47 0.77 0.77 20.59 0.45 0.78 0.04 1.00
Cl 0.10 0.88 0.88 20.55 0.16 0.50 0.68 0.48 1.00
Premonsoon
pH 1.00
EC 20.65 1.00
TDS 20.65 0.92 1.00
Ca 0.08 20.22 20.22 1.00
Mg 0.11 0.44 0.44 20.10 1.00
Na 20.11 0.52 0.52 20.46 0.08 1.00
K 20.42 0.72 0.72 20.31 0.41 0.12 1.00
HCO
3
20.23 0.74 0.74 20.64 0.55 0.75 0.54 1.00
Cl 20.72 0.87 0.87 20.08 0.22 0.14 0.79 0.42 1.00
Table 3. Varimax rotated factor loadings.
Factor
Postmonsoon Summer Premonsoon
1 2 3 1 2 3 1 2
pH 20.53 0.00 20.48 0.47 20.76 0.25 20.60 20.53
EC 0.89 20.36 0.04 0.98 0.10 0.12 0.96 0.12
TDS 0.89 20.36 0.04 0.98 0.10 0.12 0.96 0.12
Ca 20.71 20.42 20.04 20.73 20.16 0.52 20.40 0.62
Mg 0.16 20.30 20.73 0.50 20.41 0.71 0.46 20.23
Na 0.65 0.68 0.01 0.80 20.27 20.50 0.53 20.61
K 0.60 0.74 20.15 0.43 0.77 0.43 0.78 0.20
HCO
3
0.75 20.13 20.48 0.83 20.31 20.16 0.81 20.53
Cl 0.72 20.56 0.29 0.81 0.47 0.05 0.82 0.49
Explanatory variable 4.24 1.88 1.10 5.11 1.78 1.32 4.78 1.68
Precipitation total 0.47 0.21 0.12 0.57 0.20 0.15 0.53 0.19
96 Anitha Mary, Ramkumar, and Venkatramanan
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
Under this criterion, only factors witheigenvalues greater than
or equal to 1 will be accepted as possible sources of variance in
the data, with the highest priority ascribed to the factor that
has the highest eigenvector sum. The rationale for choosing 1 is
that a factor must have a variance at least as large as that of a
single standardized original variable to be acceptable. When
the seemingly complete factor model was developed using this
criterion, the first four factors that account for at least 80% of
the variance were selected for the next analysis. This was to
ward off factors that by virtue of their low loadings do not
constitute unique sources of variance in the hydrochemistry
and could therefore be dispensed with. Factor analysis was
performed using the statistical package SPSS.
During postmonsoon season, Factor 1 accounts for 34.96% of
the variance of the sample concentration, and it presents the
highest percentage in relation to the other factors. The
variables present in this factor are EC, TDS, Cl, Na, HCO
3
,
and K. It indicates seawater incursion, ionic exchange, and
carbonate weathering. Factor 2 explains 30.72%of the variance
and is mainly associated with Na and K. These are constituents
resulting fromthe dissolution of evaporate minerals within the
aquifer. Factor 3 is not associated with other elements; it
clearly indicates that an ionic exchange process dominates in
factor 3.
During the summer and premonsoon seasons, more or less
the same kind of result was observed, but variations occurred
in one or two wells because of seasonal changes. During the
summer season, factors 1 and 2 show a good relationship with
EC, TDS, HCO
3
, Na, and Mg, which is indicative of sewage
organic matter decomposition in the study area. The concen-
trationof Na andCl canbe ascribed to the incursionof seawater
into the aquifer system. Factor 3 has a good relationship with
Ca and Mg, which indicates carbonate mineral weathering and
significance of natural water recharge and sediment water
interaction. During the premonsoon season, the same kind of
results are observed, though the study factor analysis clearly
indicates seawater incursion into the coastal aquifer (Table 3).
Cluster Analysis
Cluster analysis groups a system of variable into clusters on
the basis of similarities or dissimilarities such that each cluster
represents a specific process in the system. Results from the R-
mode HCA for each region were reported in the form of a
dendrogram. On the basis of the connecting distances between
parameters and their positions on the dendrogram, distinctive
clusters of the variables were defined for each of the three
locations along the basin. Though this procedure is subjective,
the distinction between clusters in this analysis is quite clear
from the dendrogram.
During the postmonsoon season, three groups are visible
from the cluster analysis. Group 1 comprises pH, Ca, HCO
3
,
Mg, and K, and represents the weathering of calcite in organic
sediments; the high level of HCO
3
clearly represents decay of
organic matter, which enriches the water with HCO
3
ions, and
the contribution of water that contain MgCl
2
. Group 2 is made
up of Na and Cl; it clearly indicates seawater incursion, which
leads to incursion of Na and Cl into the groundwater. Group 3
indicates that EC and TDS represent seawater incursion.
During the summer and premonsoon seasons, the same kind of
result was observed. This pattern indicates that throughout
the study period (postmonsoon, summer, premonsoon) seawa-
ter incursion is present in the groundwater aquifer (Figures 6
ac).
CONCLUSIONS
The hydrogeochemical nature of the groundwater in the part
of the Kodiakarai region area was studied. We collected 72
Figure 6. Dendrogram of the 11 chemical parameters of 9 cases (a)
postmonsoon, (b) summer, (c) premonsoon.
Hydrogeochemistry of Saline Groundwater in Kodiakarai, India 97
Journal of Coastal Research, Vol. 28, No. 1A (Supplement), 2012
groundwater samples from a selected location covering the
postmonsoon, summer, and premonsoon seasons; their chem-
ical and physicochemical characters were studied to determine
the quality of the groundwater and the suitability of water for
various purposes in addition to understanding the nature of
variations of groundwater quality. Throughout the study
period the spatial distribution is clearly determined with
reference to EC, TDS, Na, and Cl. The maximumconcentration
observed is near the coastal area, indicating sea water
incursion and salt pan deposits. Irrigation return flow also
plays a major role in controlling groundwater quality in the
Kodiakarai region. A dendrogram of the nine cases and nine
variables are plotted and grouped into three main clusters. The
values of correlation coefficients and their significance levels
will help in selecting the proper treatments to minimize the
contamination of the groundwater in the study area.
Factor analysis is useful over graphical representations to
understand the chemical facies present in groundwater. The
study reveals that the groundwater fromthe Kodiakarai area is
great influenced by seawater intrusion, lithology, and environ-
mental factors in its genesis. There is an increasing awareness
among the people to maintain the groundwater at its highest
quality andpurity levels, and the present study may prove to be
useful in achieving this goal.
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