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Groundwater Quality Assessment Using Chemometric Analysis in the Adyar

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Arch Environ Contam Toxicol (2009) 56:654–669
DOI 10.1007/s00244-009-9310-2
Assessment of Water Quality Using Chemometric Tools:
A Case Study of River Cooum, South India
L. Giridharan Æ T. Venugopal Æ M. Jayaprakash
Received: 23 June 2008 / Accepted: 1 March 2009 / Published online: 20 March 2009
Ó Springer Science+Business Media, LLC 2009
Abstract Multivariate statistical techniques were applied
to identify and assess the quality of river water. Thirty
samples were collected from the River Cooum, and basic
chemical parameters—such as pH, effect concentration,
total dissolved solids, major cations, anions, nutrients, and
trace metals—were evaluated. To evaluate chemical vari-
ation and seasonal effect on the variables, analysis of
variance and box-and-whisker plots were performed.
Cluster analysis was applied, and pre-monsoon and post-
monsoon major and minor clusters were classified. The
relations among the stations were highlighted by cluster
analysis, which were represented by dendograms to cate-
gorize different levels of contamination. Cluster analysis
clearly grouped stations into polluted and unpolluted
regions. The analysis classified the upper part of the river
course into one unpolluted cluster; the middle and lower
parts of the river clustered together, reflecting the presence
of pollution. Factor analysis revealed that water quality is
strongly affected by anthropogenic activities, rock–water
interaction, and saline water intrusion. Seasonal variations
in water chemistry were clearly highlighted by both cluster
and factor analysis. Factor-score diagrams were used suc-
cessfully to delineate the stations under study by the
contributing factors, and seasonal effects on the sample
stations were identified and evaluated. These statistical
approaches and results yielded useful information about
water quality and can lead to better water resource
management.
L. Giridharan (&)
T. Venugopal
M. Jayaprakash
Department of Applied Geology, University of Madras, Chennai,
India
e-mail: girilogu@yahoo.com
123
The chemical composition of river water and its properties
depends on several factors, such as geochemical nature of
the soil, precipitation, anthropogenic activities, etc. Spa-
tiotemporal variation of hydrochemical parameters and
river water quality largely depends on these factors. The
quality of surface water in a particular region is basically
governed by natural processes, e.g., precipitation rate,
weathering processes, soil erosion, and anthropogenic
effects, such as urban, industrial, and agricultural activities
(Jarvie et al. 1998). Smith (2001) presented a detailed
analysis of pollution loads caused by storm water events in
an urban watershed. Ferrier et al. (2001) emphasized that
quantitative and qualitative characteristics of a hydrologic
system reflect the geomorphologic attributes of a water-
shed, modified by the influences of variations in climate
and anthropogenic activities. Stow et al. (2001) presented a
long-term study of water quality in a watershed with mixed
land use by deriving regressions for time-series analysis. In
many surface aquifers, domestic sewage and industrial
effluents are the chief polluting sources, and surface runoff
is a seasonal phenomenon that is largely influenced by the
climate prevailing in the basin (Liao et al. 2006).
Characterization and interpretation of various physico-
chemical parameters of river water requires handling a
large data set. Complexity is mainly associated with the
interpretation of a large number of measured variables,
with high variability arising from various factors, e.g.,
natural and anthropogenic (Simeonov et al. 2002). Multi-
variate statistical analysis offers a powerful means of
identifying similarities among the variables present in the
chemical composition of water (Vega et al. 1998; Ben-
graıne and Marhaba 2003). To identify the likely factors
causing variations in hydrochemical composition, multi-
variate statistical methods, such as principal component
factor analysis, can be useful tools. Such analysis is
Arch Environ Contam Toxicol (2009) 56:654–669
especially useful because it highlights the relative signifi-
cance of the combinations of chemical variables that can be
evaluated. Subsequent interpretation is simplified because
these statistical tools reduce and categorize complex sets of
data into groups with similar characteristics. Factor anal-
ysis attempts to explain correlations between observations
in terms of underlying factors, which are not directly
observable (Yu et al. 2003).
In this study, data were further characterized and eval-
uated using cluster analysis. Hierarchical cluster analysis is
an objective technique, employed to identify natural
groupings in a set of data, that classifies entities having
similar properties (Yeung 1999). This unsupervised pat-
tern-recognition technique uncovers the intrinsic structure
or underlying behavior of a data set without making a priori
assumption about the data. It classifies objects of the sys-
tem into categories or clusters based on their nearness or
similarity to one another (Vega et al. 1998). In this study,
classification based on the sampling site was performed
with cluster analysis using Ward’s method (linkage
between groups); Euclidian distance was used as a simi-
larity measure; and the clusters were synthesized into
dendograms.
Statistical analysis has been successfully applied by
many investigators to sort out hydrogeochemical processes
from commonly collected hydrochemical data (Hitchon
et al. 1971; Seyhan et al. 1985; Ruiz et al. 1990; Grande
et al. 2003; Kamman et al. 2005; Causape et al. 2006; Ryu
et al. 2006). Several investigators have successfully dem-
onstrated the utility of multivariate statistical analysis in
identifying and characterizing pollution sources and
apportioning natural versus anthropogenic contributions
(Cave and Reeder 1995; Villaescusa-Celaya et al. 2000;
Facchinelli et al. 2001; Yu et al. 2003; Liao et al. 2006). In
this study, the effect of certain factors on river water—such
as agricultural, industrial, domestic, rock–water interaction,
and saline water intrusion—were studied by applying the
previously mentioned multivariate statistical techniques.
Study Area
In this study, water samples from the River Cooum were
collected at 30 stations to evaluate the nature and quality of
the water (Fig. 1). The River Cooum originates from the
Kesevaram Dam, in the village of Kesavaram, which lies
approximately 48 km west of Chennai. Although the River
Cooum originates from this dam, excess water from the
Cooum tank (79.82° latitude and 13.02° longitude) joins
this course at approximately 8 km, and this point is con-
sidered the head of the River Cooum. In the upper part of
the river stretch, many agricultural activities are being
carried out. The river receives a sizeable quantity of sewage
655
from its neighborhood after it reaches Vanagaram near
Chennai. It flows through the Kancheepuram, Tiruvallur,
and Chennai districts for a distance of approximately 68 km
and, after flowing through the heart of Chennai, it enters
into the Bay of Bengal. This river is almost stagnant and do
not carry enough water except during the rainy season. This
period runs from October to December and is referred to as
the ‘‘northeast monsoon season’’ in Tamil Nadu. Chennai
receives the bulk of its rainfall from this monsoon.
It has been observed that in the upper part of the river,
there is no settlement along the bank of the river; hence this
part is not polluted by domestic effluents. However,
because of intense agricultural activities, the possibility of
pollution caused by fertilizers and pesticides is highly
expected. Currently fertilizers play a vital role in crop
growth. The bulk use of these fertilizers leaves behind
unused wastes, which are driven off by rain and enter into
aquifers. Several investigators have reported on the release
of nitrates from agricultural activities, which contaminat-
ing river waters (Prasad 1998; Pacheco 2001). In the
middle and lower stretches of the River Cooum, domestic
sewage water is directed into the river and appears as a
sewage water stream.
Analytical Methodology
The presented data include the results from two sampling
periods (September 2005 [pre-monsoon period] and Feb-
ruary 2006 [post-monsoon period]) at 30 locations along
the Cooum River basin performed to evaluate seasonal
variations in chemical compositions. For collection, pres-
ervation, and analysis of the samples, standard methods
(Rainwater and Thatcher 1960; Brown et al. 1970; Amer-
ican Water Works Association 1971; Hem 1985; American
Public Health Association 1995) were followed. The effect
concentration and pH of water samples were measured in
the field immediately after collection of the samples using
pH and conductivity meters. Before each measurement, the
pH meter was calibrated with reference buffer solution (pH
levels 4 and 7). Na? and K? were measured using a flame
photometer (Systronics Flame Photometer 128). Silica
content was determined with the molybdate blue method
using an ultraviolet (UV) light–visible spectrophotometer.
Total dissolved solids (TDS) were measured using the
evaporation and calculation methods (Hem 1991). Ca2?
and Mg2? were determined titrimetrically using standard
ethylenediaminetetraacetic acid. Chloride was estimated by
AgNO3 titration. Sulphate was analysed using the turbidi-
metric method (Clesceri et al. 1998). Nitrate, nitrite,
phosphate, and fluoride were analysed using a UV light–
visible spectrophotometer (Rowell 1994). Standard solu-
tions for the previously mentioned analysis were prepared
123
656
Fig. 1 Base map of Cooum
River depicting sample
locations and pollution sources
from the respective analytic reagent-grade salts. Trace
metals were determined by a graphite furnace atomic
absorption spectrophotometer (AAnalyst 700; Perkin–
Elmer). Multielement Perkin–Elmer standard solutions
were used for the estimation of trace metals.
Statistical Methodology
Factor analysis was applied to the data matrix to reduce the
data to an easily interpretable form. Before applying factor
analysis, the data were standardized according to the cri-
teria presented by Davis (2002). Standardization of
variables is performed to remove the influence of different
units of measurement on the data by making them
dimensionless. Normalization of data is essential in factor
analysis because it involves the computation of a correla-
tion coefficient matrix, which requires equal distribution in
all variables. Factors are extracted by varimax rotation,
which gives values closest to –1, 0, and ?1, suggesting the
negative, zero, and positive contribution, respectively, of a
variable toward a factor (Briz-Kishore and Murali 1992).
Commonality attached to each row of the matrix gives an
appreciation of how well each variable is explained by
‘‘m’’ factors. If many commonalities B0.8, more factors
are required (Klovan 1975). By examining the factor
loadings and their eigenvalues, those variables belonging to
a specific process can be identified. In certain cases, some
variables may load high in [1 factor. Finally, factor scores
are evaluated to illustrate the station-wise variation of the
factors (Klovan 1975).
Standardization of the values was performed after we
measured skewness in the variables. The measure of
123
Arch Environ Contam Toxicol (2009) 56:654–669
skewness compares the manner in which variables are
distributed in a particular series with variables having a
symmetrical distribution. Analysis of kurtosis and skew-
ness are vital because most statistical methods require
variables to conform to normal distribution (Papatheodorou
et al. 2006). Computation of the correlation coefficient
matrix is the first step in factor analysis between stan-
dardized variables. Eigenvalues quantify the contribution
of a factor to total variance. The contribution of a factor is
significant when the eigenvalue is greater than unity
(Kaiser 1960). Initial factors are extracted and subjected to
mathematical rotation. Varimax rotation procedure is used
to maximize differences between the variables, thus facil-
itating easy interpretation of the data. The first factor
accounts for as much variance as possible in the data set.
The second factor accounts for as much residual variance
as possible, and so forth. Factor loading indicates the
degree of closeness between the variables and the factor.
The largest loading, either positive or negative, suggests
the meaning of the dimension: Positive loading indicates
that the contribution of variables increases with increased
loading in a dimension, and negative loading indicates that
the contribution of variables decreases with decreased
loading (Lawrence and Upchurch 1983). The study of
factor scores reveals the extent of influence of each factor
on overall water chemistry at all locations of sampling
stations. Extreme negative scores reflect areas essentially
unaffected by that particular factor, and positive scores
reflect the areas most affected. Near-zero scores indicates
areas affected to an average degree. In the present article,
the station-wise variation of factors is indicated by line
diagrams.
Arch Environ Contam Toxicol (2009) 56:654–669 657

Cluster analysis is a powerful tool for identifying and
evaluating similar groups in hydrochemical data. The
object of this analysis is to look for similar groups of items
or for variables that group together in clusters. Cluster
analysis organizes sampling entities into discrete classes or
groups such that within-group similarity is maximized and
among-group similarity is minimized (McGarial et al.
2000; Zeng and Rasmussen 2005). An unsupervised pat-
tern-recognition technique uncovers intrinsic structure or
underlying behavior of a data set, without making a priori
assumption about those data, such that the objects of the
system can be classified into categories or clusters based on
their nearness or similarity to one another (Vega et al.
1998). In this study, classification based on sampling site
was performed with cluster analysis using Ward’s method
(Ward 1963); Euclidian distance was used as a similarity
measure; and data were synthesized into dendograms.
Euclidean distance is the geometric distance in a multidi-
mensional space. Ward’s method is known to be distinct
because it uses an analysis-of-variance approach to evalu-
ate the distances between clusters. This method minimizes
the sum of squares of any two (hypothetical) clusters
derived at each step of analysis.
Results and Discussion
The basic statistical parameters of the data matrix for both
the pre-monsoon and post-monsoon periods are listed in
Table 1. During the pre-monsoon period, skewness ranges
from –0.68 to 1.53; during the post-monsoon period,
skewness ranges from –4.34 to 4.79. Skewness results for
most variables show only narrow variability, and all pre-
monsoon variables are found to be well within the skew-
ness index. During the post-monsoon period, few variables
are found to have high skewness values. Logarithmic
transformation of the data was performed to decrease
skewness in the variables. Kurtosis was also applied on the
data matrix to measure peakedness of the probability dis-
tribution. A distribution with positive kurtosis has a higher
probability of variables than the normal distribution around
the mean and also indicates a higher probability of dis-
tributed variables with extreme values. A distribution with
negative kurtosis indicates a lower probability of normally
distributed variables of values near the mean as well as
extreme values. During the pre-monsoon period, kurtosis
ranges from –1.31 to 2.5; during the post-monsoon period,
kurtosis ranges from –1.62 to 24.89. During the pre-

Table 1 Summary statistics of geochemical data

Geochemical Pre-monsoon Post-monsoon
data
Mean r Kurtosis Skewness Confidence CV Mean r Kurtosis Skewness Confidence CV
(mg/l) level (mg/l) level

pH 6.70 0.15 -0.35 -0.42 0.05 2.17 8.15 0.53 -1.62 -0.03 0.19 6.47
EC 2978.49 1059.93 0.42 0.01 379.28 35.59 1506.88 593.35 -0.70 0.39 212.32 39.38
TDS 1906.23 678.35 -0.42 0.01 242.74 35.59 964.40 379.74 -0.70 0.39 135.89 39.38
Ca 152.00 48.28 0.92 -0.47 17.28 31.76 118.73 41.93 0.47 0.87 15.01 35.32
Mg 38.98 19.68 -1.02 0.56 7.04 50.49 44.80 36.07 -0.76 0.69 12.91 80.52
Na 377.09 228.83 2.50 1.38 81.88 60.68 168.71 77.44 -0.46 0.58 27.71 45.90
K 31.26 17.62 0.15 0.81 6.30 56.36 12.25 8.36 0.37 0.97 2.99 68.29
HCO3 321.35 114.01 2.34 1.08 40.80 35.48 18.80 9.06 1.50 0.76 3.24 48.17
SO4 268.73 36.24 -0.49 0.29 12.97 13.49 111.93 45.23 -1.54 -0.23 16.18 40.41
Cl 565.53 320.14 0.31 0.66 114.56 56.61 440.73 190.81 -0.14 0.60 68.28 43.29
F 1.34 0.56 1.03 0.47 0.20 41.67 0.60 0.79 15.47 3.65 0.28 132.63
NO3 62.15 42.67 -0.94 0.58 15.27 68.66 8.36 3.80 3.01 1.27 1.36 45.45
NO2 0.57 0.34 -0.13 0.44 0.12 60.22 1.87 2.22 -0.56 0.94 0.79 118.35
PO4 8.33 5.87 -0.22 0.91 2.10 70.46 1.12 1.42 -0.10 1.23 0.51 127.11
SiO2 24.94 4.20 -0.93 -0.68 1.50 16.82 26.97 2.53 21.85 -4.34 0.90 9.38
Cu 0.07 0.01 -0.81 0.28 0.01 21.10 0.09 0.09 24.89 4.79 0.03 104.79
Co 0.06 0.03 -0.53 -0.56 0.01 40.60 0.05 0.06 21.86 4.37 0.02 114.66
Zn 0.03 0.02 1.74 1.53 0.01 78.56 0.02 0.01 2.01 1.51 0.00 65.27
Fe 0.44 0.34 -1.31 0.31 0.12 77.03 0.45 0.30 -0.10 0.80 0.11 64.95
Pb 0.44 0.25 -0.67 0.57 0.09 56.83 0.27 0.19 -0.16 0.80 0.07 70.31
Cr 0.51 0.24 -1.14 -0.05 0.08 46.25 0.25 0.14 -0.66 0.43 0.05 53.52

123
658
monsoon period, almost of all variables lie near zero value,
reflecting that the distribution is normal ‘‘mesokurtic.’’
During the post-monsoon period, high positive values are
obtained for silicates, fluoride, and heavy metals Cu and
Co, indicating peaked distribution. Peaked distribution of
the previously mentioned variables indicates surface runoff
of sporadic high emissions from certain point sources.
Coefficient of variation (CV) was used to compare the
variability of C 2 series. The series of data for which the
CV is large indicates that the group is more variable.
Among the variables, pH shows the minimum CV,
reflecting that there is not much variation in pH throughout
the river course during both seasons. The seasonal effect is
apparent with respect to the CVs of many variables. In
general, heavy metals show much higher CVs among the
variables during both seasons.
Analysis of variance (ANOVA) is a statistical tool that
permits the testing of significant differences between sev-
eral means by comparing variances. ANOVA tests the
variation between the mean values of the given variable. In
the present study, it was observed that among the major
ions, Mg shows p C 0.05, and all other major ions and
nutrients show p \ 0.05, indicating that seasonal effect is
significant with respect to all major ions and nutrients
except Mg. In the case of heavy metals, Cu, Co, and Fe
show p [ 0.05, whereas the other metals show p \ 0.05,
reflecting that seasonal effect is significant for Cu, Co, and
Fe. Box-and-whisker plots (Fig. 2) of individual variables
were constructed to evaluate chemical variation and sea-
sonal effect on the variables. These plots were constructed
to evaluate different patterns associated with spatial vari-
ations in river water quality. Most monsoon variables
showed deviations from normal distribution and included
outliers and extremes.
Cluster Analysis
Cluster analysis was applied to reveal the relation among
the stations and to elucidate water chemistry. It is a useful
tool in organizing a particular set of data from various
points into clusters or groups and determining relations
between the various points (McGarial et al. 2000). Cluster
analysis is also helpful in determining the seasonal effect
on each station. During the pre-monsoon period (Fig. 3a),
cluster 1 (stations 1 through 9) is characterized as an
unpolluted region that lies in the upper part of the river. In
this region, there are no settlements and no point sources of
pollution near the river stretch. Cluster 2 (anthropogenic
and saline water intrusion) (stations 17, 25, 26, and 30) is
classified as a highly polluted region. This region lies in the
eastern part of the river where settlements along the river
course are dense, and domestic effluents are directed into
the river. Moreover, the influence of saline water intrusion
123
Arch Environ Contam Toxicol (2009) 56:654–669
into river water is high at station 30. In the case of station
17, both industrial as well as domestic effluents influence
the chemical composition of the water, and all of these
stations are characterized by high TDS. Cluster 3
(anthropogenic), comprising the remaining 18 stations, lies
in the middle and lower parts of the river stretch. In this
region, it has been observed that the industrial and
domestic effluents are directed into river water. Industries
are concentrated in the suburban (middle part of the river)
and intense settlements near the river course, and the for-
mation of slums on the river bank influences the quality of
river water.
During the post-monsoon season, the data are also
classified into three major groups (Fig. 3b). Station 30
alone comes under one category and is mainly influenced
by saline water intrusion. Cluster 1 (stations 1 through 5, 7
through 9, and 13) is located in the upper part of the river
course and is apparently unpolluted. Because there is no
point source of pollution and because it receives heavy
precipitation, this water behaves almost like freshwater.
Cluster 2 (stations 11-15 and 6-10-12-14) also lies in the
upper part of the river. The TDS of the water is slightly
higher than the other grouping in the same region but lower
than the limit set by the World Health Organization. Sta-
tions 28 and 29 form cluster 3, which is located near the
eastern end of the River Cooum and the ocean, where
population density is considerably high. The quality of
river water at these stations is influenced by domestic
effluents as well as saline water intrusion. Cluster 4 (sta-
tions 16 through 26) is comprises suburban and urban
areas, where domestic and industrial effluents are directed
into the river, thus degrading water quality. Station 30
forms a separate cluster that is directly influenced by saline
water because this station lies at the river’s confluence
point. A distinct variation is caused by the seasonal effect,
which is reflected by the grouping of stations falling into
different clusters.
Correlation Studies
Analytic results of the geochemical data were analysed
using Statistical Package for Social Sciences (SPSS version
11.5; Chicago, IL) for factor analysis as described by Nie
et al. (1985). Before the data were investigated, the raw
data were standardized. Standardization of the variables is
performed to eliminate the influence of different units of
measurement on the data by making them dimensionless.
Close inspection of correlation matrix is useful because it
can reveal associations between variables that can show
overall coherence of the data set and indicate participation
of the individual chemical parameters that influence fac-
tors, a phenomenon that commonly occurs in
hydrochemistry (Helena et al. 2000). The correlation
Arch Environ Contam Toxicol (2009) 56:654–669
Fig. 2 Box-and-Whisker plot representing chemical and seasonal variation of variables
coefficient values exhibiting ?1 or –1 between the vari-
ables show that a strong correlation exists, and a value of
zero indicates that there is no relation between them. In
general, geochemical parameters showing a correlation
coefficient [0.7 are considered to be strongly correlated,
whereas values between 0.5 and 0.7 shows moderate cor-
relation. In this study, the relation between various
elements was studied.
The correlation matrix (Tables 2, 3) shows a distributive
pattern of positive and negative correlations among the
variables. During both the pre- and post-monsoon periods,
659
the correlation results are as follows: During the pre-
monsoon period, Ca2? and Na? have a positive correlation
with HCO3, and the correlation matrix of the post-monsoon
period shows that Mg2? and Na? have a significant cor-
relation with HCO3, suggesting that rock–water interaction
as well as precipitation and leaching contribute to water
chemistry.
During the pre-monsoon period, Ca2? has a low corre-
lation with SO42–; however, it does not have any
correlation at all with NO3, suggesting that agricultural
activities may not contribute to the source of these ions.
123
660
Fig. 2 continued
During the post-monsoon period, although Ca2? has some
correlation with SO42–, as in the case of the pre-monsoon
period, it does not have any correlation with NO3. If pol-
lution is related to the influence of domestic sewage, then
there will be some association of NO3, Na, and Cl ions
because all of these constituents are usually enriched in
sewage. The correlation matrix for the pre-monsoon period
shows that Na? is strongly correlated with Cl– and also that
the variation of Na? with Cl– is significantly correlated to
nitrate, reflecting that the mixing of domestic sewage water
into river water strongly contributes to water chemistry
123
Arch Environ Contam Toxicol (2009) 56:654–669
during the post-monsoon period. Although Na and Cl have
a strong correlation, the variation of Na with Cl is only
moderately correlated with NO3. This correlation result
reveals that although sewage water is polluting river water,
precipitation dilutes the effect of sewage water on the
chemical composition of the water during the post-mon-
soon period. During both periods, some pairs of
constituents show moderate to strong correlation (r [ 0.6),
e.g., the major exchangeable ions Na–Ca and Na–Mg
correlate significantly in both the pre- and post-monsoon
periods, respectively. Moreover, the pairs of constituents
Arch Environ Contam Toxicol (2009) 56:654–669
Fig. 3 a Dendogram showing the relation among pre-monsoon river water samples.b Dendogram showing the relation among post-monsoon
river water samples
—i.e., Cl–SO4, Mg–SO4 Ca-SO4, and Na–SO4—show little
or no correlation, suggesting that overall water chemistry is
not predominated by a dissolution/precipitation reaction;
rather, extraneous sources, such as pollution caused by
anthropogenic activities, dominate the water’s chemical
make-up.
Factor Analysis
Characterization and interpretation of various parameters is
often a complex problem. However, factor analysis offers a
powerful means of identifying the similarities among
variables that represent water chemistry. To identify the
likely factors causing variations in hydrochemical compo-
sitions, multivariate statistical methods of analyzing
hydrochemical data, such as factor analysis, can be useful
tools. Such an analysis is especially useful because it
reveals the relative significance of the combinations of
661
chemical variables available for evaluation. Subsequent
interpretation is simplified because these statistical tools
reduce and categorize complex sets of data into smaller
groups with similar characteristics. Factor-score diagrams
of the pre- and post-monsoon periods are presented in
Figs. 4 and 5, respectively.
The first six factors, which account for approximately
80% of variance during the pre-monsoon period and 83%
of variance during the post-monsoon period (all of which
have eigenvalues [ 1), were extracted from the principal
factor matrix after varimax rotation (Tables 4, 5).
Pre-Monson Factors
Factor 1 during the pre-monsoon period, which explains
33% of total variance, has high loadings of the ions Na, Cl,
SO4, Mg, F, and NO3. The loading pattern of the previously
mentioned variables indicates that their source of origin
123
 662

123
Table 2 Pre-monsoon correlation coefficient matrix
pH EC TDS Ca Mg Na K HCO3 SO4 Cl F NO3 NO2 PO4 SiO2 Cu Co Zn Fe Pb Cr

pH 1.00
EC -0.02 1.00
TDS -0.02 1.00 1.00
Ca 0.30 0.39 0.39 1.00
Mg 0.07 0.55 0.55 0.02 1.00
Na -0.04 0.93 0.93 0.16 0.59 1.00
K 0.09 0.41 0.41 0.30 -0.04 0.27 1.00
HCO3 -0.01 0.60 0.60 0.47 0.06 0.40 0.59 1.00
SO4 0.13 0.71 0.71 0.48 0.52 0.60 0.17 0.21 1.00
Cl -0.10 0.97 0.97 0.26 0.57 0.95 0.27 0.48 0.66 1.00
F -0.16 0.59 0.59 0.39 0.32 0.48 0.20 0.34 0.53 0.57 1.00
NO3 0.02 0.58 0.58 0.04 0.37 0.52 0.22 -0.01 0.61 0.58 0.49 1.00
NO2 0.27 0.30 0.30 0.32 0.24 0.16 0.42 0.25 0.44 0.25 -0.05 0.15 1.00
PO4 0.11 0.26 0.26 0.36 -0.01 0.08 0.58 0.70 0.02 0.13 -0.14 -0.20 0.54 1.00
SiO2 0.01 0.61 0.61 0.14 0.30 0.47 0.55 0.50 0.34 0.51 0.32 0.65 0.25 0.37 1.00
Cu -0.07 -0.08 -0.08 0.10 -0.20 -0.07 0.01 0.13 0.01 -0.15 0.08 -0.14 -0.16 0.07 -0.13 1.00
Co 0.15 0.22 0.22 -0.03 0.13 0.14 0.14 0.30 0.11 0.18 -0.20 0.11 0.42 0.53 0.44 -0.23 1.00
Zn 0.20 0.24 0.24 0.02 0.18 0.23 0.05 -0.08 0.39 0.17 0.19 0.58 0.00 -0.18 0.27 0.08 0.19 1.00
Fe -0.09 -0.15 -0.15 0.25 -0.20 -0.27 0.02 0.30 -0.01 -0.22 -0.12 -0.45 0.35 0.50 -0.12 0.32 0.33 -0.26 1.00
Pb 0.10 -0.12 -0.12 0.02 -0.11 -0.25 0.21 0.09 0.06 -0.19 -0.03 -0.03 0.35 0.36 0.09 0.39 0.34 0.03 0.45 1.00
Cr 0.13 -0.19 -0.19 0.07 -0.18 -0.11 -0.27 -0.27 0.02 -0.22 0.02 -0.11 -0.40 -0.39 -0.31 0.22 -0.35 0.21 -0.23 -0.17 1.00
Arch Environ Contam Toxicol (2009) 56:654–669
 Table 3 Post-monsoon correlation coefficient matrix
pH EC TDS Ca Mg Na K HCO3 SO4 Cl F NO3 NO2 PO4 SiO2 Cu Co Zn Fe Pb Cr

pH 1.00
EC -0.72 1.00
TDS -0.72 1.00 1.00
Ca -0.59 0.67 0.67 1.00
Arch Environ Contam Toxicol (2009) 56:654–669

Mg -0.45 0.76 0.76 0.12 1.00

Na -0.67 0.96 0.96 0.60 0.68 1.00
K -0.71 0.81 0.81 0.54 0.65 0.68 1.00
HCO3 -0.58 0.62 0.62 0.31 0.52 0.59 0.62 1.00
SO4 -0.58 0.79 0.79 0.72 0.44 0.78 0.52 0.45 1.00
Cl -0.69 0.98 0.98 0.60 0.79 0.93 0.83 0.59 0.67 1.00
F 0.11 0.13 0.13 -0.13 0.27 0.15 -0.08 0.02 0.33 0.06 1.00
NO3 0.01 -0.01 -0.01 -0.14 0.14 -0.05 0.03 0.09 -0.22 0.03 -0.27 1.00
NO2 -0.42 0.44 0.44 0.08 0.70 0.31 0.51 0.29 0.10 0.50 -0.10 0.44 1.00
PO4 -0.64 0.79 0.79 0.38 0.83 0.65 0.83 0.51 0.46 0.82 0.00 0.15 0.77 1.00
SiO2 -0.29 0.33 0.33 0.34 0.19 0.31 0.21 -0.10 0.25 0.33 0.08 0.24 0.20 0.22 1.00
Cu -0.24 0.15 0.15 0.07 0.25 0.03 0.20 0.01 0.16 0.13 0.04 0.09 0.36 0.32 0.05 1.00
Co -0.08 0.05 0.05 -0.11 0.25 -0.10 0.14 0.03 0.04 0.03 0.15 0.22 0.34 0.29 0.02 0.89 1.00
Zn 0.31 -0.45 -0.45 -0.29 -0.39 -0.44 -0.17 -0.19 -0.43 -0.42 -0.18 0.27 -0.18 -0.24 -0.22 -0.17 -0.06 1.00
Fe -0.35 0.43 0.43 0.40 0.15 0.51 0.13 0.03 0.44 0.39 0.14 -0.27 0.06 0.13 0.27 0.17 -0.02 -0.44 1.00
Pb 0.41 -0.40 -0.40 -0.19 -0.39 -0.29 -0.53 -0.40 -0.26 -0.38 -0.08 -0.01 -0.42 -0.55 -0.07 -0.15 -0.23 0.01 -0.05 1.00
Cr -0.21 0.34 0.34 0.03 0.27 0.38 0.37 0.52 0.14 0.36 0.01 0.30 0.20 0.36 -0.09 -0.06 0.03 0.26 0.02 -0.52 1.00
663

123
664
Fig 4 Pre-monsoon factor-
score line diagrams
arises anthropogenically, such as agriculture, industrial,
and domestic effluents. Moreover, the percentage abun-
dance of the variables suggests saline water intrusion in the
lower part of the river course. The high loadings of Na, Cl,
and NO3 indicate that pollution caused by mixing sewage
water into river water affects the chemical composition of
the water. The factor-score diagram shows that factor
scores gain significance from station no. 14 and that high
positive values are observed at the eastern part of the river,
indicating that the lower part of the river is more affected
than the central region by this factor. The intrusion of
saline water into the river course at the eastern part of the
river is reflected in the factor scores; ion loadings also
support this point. The middle part of the river runs through
the urban area and receives the bulk of domestic sewage
and industrial effluents (Ramesh et al. 1995). The factor-
score diagram and the correlation of the ions Na, Cl, and
NO3 clearly indicate that sewage water is being mixed into
the middle part of the river and that the chemical compo-
sition of river water is highly influenced by this factor.
Factor 2 during the pre-monsoon period, which accounts
for 17% of total variance, has high loadings of Co, NO2,
and PO4. The factor-score diagram shows that the eastern
and western parts of the river are not affected by this factor.
Significant scores are observed only in the central part of
123
Arch Environ Contam Toxicol (2009) 56:654–669
the river, suggesting that the composition of river water in
this region is highly influenced by these constituents.
Riverine nitrite and phosphate originate mainly from
agricultural or domestic effluents. In the region near the
middle part of the river, no agricultural activity is being
carried out; hence the high loadings of nitrite and phos-
phate must be attributed to domestic effluents. The
concentration of NO2–N indicates fresh input of organic
pollution load into the water system. In this region,
domestic effluents containing water softeners contribute to
the higher concentration of phosphates in the water (Ra-
jmohan and Elango 2005). The increased abundance of Co
in the middle part of the river, along with the high con-
centration of nutrients in a region where organic matter
pollution is high, suggests that this may be caused by
sediment fluxes or anthropogenic sources (Windom et al.
1988). The concentration of many metallurgical and
chemical industries near the course of the river adjacent to
the urban area, as well as the uncontrolled direct mixing of
the effluents into river water, accounts for the higher
concentration of this ion in the water.
Factor 3 during the pre-monsoon period, accounting for
approximately 9% of total variance, has high loadings of K,
HCO3, PO4, and SiO2 and may be considered as being
affected by silicate-weathering and anthropogenic factors.
Arch Environ Contam Toxicol (2009) 56:654–669
Fig 5 Post-monsoon factor-
score line diagrams
The weathering reaction of microcline yields K, HCO3, and
SiO2. The factor-score diagram shows that the middle part
of the river is affected with respect to this factor. It has
been observed that SiO2 is positively correlated with K and
HCO3, suggesting that the sources of these ions have the
same origin. The fact that fertilizer surface runoff remains
near the upper part of the river explains the highly signif-
icant factor scores in this region. In the case of the middle
and lower parts of the river, domestic effluents containing
water softeners contribute to the higher concentration of
phosphate ions in river water (Rajmohan and Elango 2005).
Factor 4 during the pre-monsoon period, which account
for 8% of total variance, has high loadings of NO3 and Zn.
The factor-score diagram shows high positive scores at the
middle and lower parts of the river course. It is known that
nitrate is stable in aquifers because dissolved oxygen is
present (Hamilton and Helsel 1995). It has been observed
that no agricultural activities are being carried out in the
middle and lower parts of the river; however, at many points
in this region, domestic sewage water is discharged into the
river. Domestic sewage loads are the main source of organic
matter in this region. The oxidation products of many
organic loads in the river system lead to the increased
concentration of NO3-N in river water. Previous studies of
665
this river water have also indicated higher nitrate concen-
trations in the middle and lower stretches of the river
(Ramesh et al. 1995). Many industrial activities (chemical,
paint, chrome plating, tanning industries) are being carried
out near the river course, and effluents are discharged into
the river. These industrial effluents must be the cause of the
increased abundance of Zn in this region of the river.
Factor 5 during the pre-monsoon period, which accounts
for 6.5% of total variance, is explicitly a heavy-metal
factor, with high loadings of Cu, Pb, and Fe. The factor-
score diagram shows a distributive pattern of this factor,
with many significant scores in the middle and lower parts
of the river. In addition to industrial activities, the atmo-
spheric depositions resulting from automobile pollution
(Varrica 2003; Sharma 2003) as well as urban runoff
caused by precipitation may lead to the increased con-
centration of Pb in aquifers.
Factor 6 during the pre-monsoon period, accounting for
6% of total variance, has high loadings of Ca, with some
positive values of NO2. The factor-score diagram shows a
distributive pattern, with significant scores at many sta-
tions, near the middle part of the river. Anthropogenic
activities and rock–water interaction in this region increase
the concentration of these ions in the water.
123
666 Arch Environ Contam Toxicol (2009) 56:654–669

Table 4 Pre-monsoon rotated

Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Factor 6
component matrix
pH -0.135 0.107 0.024 0.204 -0.149 0.814
EC 0.911 0.099 0.339 0.116 -0.073 0.044
TDS 0.911 0.099 0.339 0.116 -0.073 0.044
Ca 0.353 -0.143 0.359 -0.231 0.225 0.655
Mg 0.688 0.280 -0.295 0.076 -0.180 0.033
Na 0.881 0.026 0.157 0.122 -0.179 -0.062
K 0.131 0.156 0.826 0.144 0.020 0.104
HCO3 0.383 0.138 0.781 -0.243 0.154 0.045
SO4 0.783 0.094 -0.089 0.245 0.201 0.368
Cl 0.932 0.094 0.192 0.073 -0.156 -0.066
F 0.691 -0.327 0.157 0.127 0.206 -0.054
NO3 0.541 0.052 0.045 0.747 -0.102 -0.059
NO2 0.226 0.686 0.130 -0.057 0.105 0.438
PO4 0.012 0.546 0.659 -0.279 0.186 0.171
SIO2 0.391 0.323 0.565 0.460 -0.092 -0.128
Cu -0.045 -0.295 0.078 0.018 0.805 -0.074
Co 0.032 0.795 0.169 0.170 0.017 0.048
Zn 0.172 -0.037 -0.066 0.803 0.107 0.183
Fe -0.120 0.408 0.072 -0.476 0.635 0.079
Pb -0.190 0.446 0.076 0.177 0.700 0.044
Cr -0.130 -0.661 -0.202 0.162 0.097 0.310
Extraction method was principal Eigen value 7.01 3.56 1.89 1.74 1.36 1.27
component analysis. Rotation % Variance 33.37 16.96 8.99 8.29 6.48 6.02
method was varimax with Cumulative variance 33.37 50.33 59.33 67.62 74.09 80.11
Kaiser normalization

Post-Monsoon Factors
Factor 1 during the post-monsoon period, which explains
43% of total variance, has high loading of the ions Mg, K,
Na, Cl, PO4, HCO3, and NO2. The factor-score diagram
shows that the western part of the river is unaffected by this
factor. In this region, there is no point source of pollution,
and the intense rainfall during this period dilutes the water;
hence river water in this region behaves almost like
freshwater. The factor-score diagram shows that there is a
gradual increase from the western (upstream) to the eastern
part (downstream) of the river. The eastern part of the
study area is adjacent to the ocean, and saline water
intrusion contributes to the chemical composition of river
water. The factor-score diagram shows less significant
values from stations 12–22, demonstrating that the middle
part of the river is only moderately affected. The seasonal
effect on the chemical composition of water in this region
is highly significant because the point sources of pollution
in this urban area are highly diluted.
Factor 2 during the post-monsoon period, accounting for
13% of total variance, has high loadings of Ca, Na, SO4,
Cl, and Fe, as well as a positive loading of silicate, and thus
may be described as having been influenced by a silicate-
weathering factor. It is apparent that the seasonal effect is
highly significant for this factor. The factor-score diagram
shows significant scores in the middle part of the river; in
this region, the flow of river water is almost stagnant. This
stagnancy of river water facilitates more rock–water
interaction, thus leading to augmentation of these ions in
river water. It is observed from the correlation matrix that
pH is negatively correlated with all of these ions, sug-
gesting that an increase in hydrogen ion concentration in
the water increases the previously mentioned ions in the
chemical make-up of the water. The factor-score diagram
also depicts low positive scores at the downstream area,
showing that the water in this part is only moderately
affected by this factor. In the downstream region, saline
water intrusion increases the concentrations of these ions in
the water. The higher loading of Fe is attributed to rock–
water interaction as well as anthropogenic activities. The
high concentration of Fe observed in the middle stretch of
the river is caused by the strong association of dissolved Fe
with finer particles and colloids (Sholkovitz 1976). More-
over, effluents from the industries near the river course also
contribute Fe to river water.
Factor 3 during the post-monsoon period, which
accounts for 10% of total variance, has high loadings of Cu
and Co. The factor-score diagram illustrates that except at
one station (station 26), all other stations are only

123
Arch Environ Contam Toxicol (2009) 56:654–669 667

Table 5 Post-monsoon
Factor1 Factor 2 Factor 3 Factor 4 Factor 5 Factor 6
rotated component matrix
pH -0.541 -0.581 -0.135 -0.130 0.271 0.010
EC 0.753 0.621 -0.019 0.117 0.082 0.057
TDS 0.753 0.621 -0.019 0.117 0.082 0.057
Ca 0.193 0.852 -0.044 0.031 -0.288 0.014
Mg 0.919 0.047 0.137 0.000 0.286 0.102
Na 0.664 0.644 -0.167 0.119 0.157 0.054
K 0.737 0.389 0.102 0.281 -0.211 -0.028
HCO3 0.644 0.191 -0.089 0.406 -0.062 -0.270
SO4 0.370 0.775 0.030 0.072 0.234 -0.109
Cl 0.803 0.528 -0.043 0.102 0.034 0.097
F 0.023 0.079 0.071 0.027 0.927 -0.066
NO3 0.172 -0.338 0.088 0.261 -0.234 0.711
NO2 0.749 -0.147 0.332 0.002 -0.143 0.340
PO4 0.865 0.200 0.241 0.168 -0.073 0.105
SIO2 0.075 0.432 0.005 -0.144 0.089 0.775
Cu 0.117 0.119 0.951 -0.068 -0.020 0.005
Co 0.101 -0.084 0.945 0.080 0.108 0.066
Zn -0.409 -0.360 -0.061 0.594 -0.227 0.125
Fe 0.034 0.684 0.080 -0.180 0.216 0.065
Pb -0.391 -0.138 -0.244 -0.586 -0.044 0.063
Cr 0.292 0.016 -0.084 0.849 0.085 0.056
Extraction method was principal Eigen value 9.04 2.69 2.05 1.47 1.21 1.00
component analysis. Rotation % Variance 43.04 12.84 9.76 6.99 5.76 4.76
method was varimax with Cumulative variance 43.04 55.89 65.65 72.63 78.39 83.16
Kaiser normalization

moderately affected by this factor. It is apparent that the
seasonal effect is highly significant for this factor. Both of
these heavy metals have no significant lithologic origin;
hence it must be attributed to anthropogenic activities.
Factor 4 during the post-monsoon period, accounting for
7% of total variance, has high loadings of Cr and Zn. In the
suburban area and near the entry point of the urban area, a
number of industries and small tanneries are situated along
the river course. Effluents from these industries increase
the concentration of these metals in the water.
Factor 5 during the post-monsoon period, accounting for
6% of total variance, is explicitly a fluoride factor. The
factor-score diagram illustrates that water is moderately
affected by this factor throughout the stretch of the river
except at a few stations in the middle part of the river. The
lithology of the study area has no significant fluoride-
bearing minerals; hence it is logical to assign the high
fluoride level to anthropogenic activity and, to a lesser
extent, to chemical weathering (Saxena et al. 2003; Sub-
barao 2003).
Factor 6 during the post-monsoon period, accounting for
approximately 5% of total variance, has high loadings of
silicate and nitrate. The factor-score diagram shows that
the upper part of the river has significant factor scores,
reflecting that this region is affected by this factor.
Agricultural activities lead to fertilizer remaining in the
soil, and the use of NPK fertilizers is high in this region.
Fertilizer surface runoff contributes to the abundance of
nitrate in river water. Heavy precipitation and subsequent
soil–water interaction leads to increased loadings of sili-
cates in the water.
Conclusion
The application of chemometric techniques for character-
ization and evaluation of hydrochemical data has been
successfully demonstrated. Variation within and between
variables are highlighted using parametric and nonpara-
metric statistical techniques. Box-and-whisker plots
demonstrate seasonal and chemical variations of various
chemical parameters of river water. The significance of the
seasonal effect on variables is evaluated by ANOVA. The
results show that among the major ions, Mg is nonsignificant
regarding seasonal effect, whereas Cu, Co, and Fe are found
to be nonsignificant. Cluster analysis also highlights sea-
sonal variation among the stations, and results show that the
upper part of the river is grouped into one unpolluted major
cluster. The middle and lower parts of the river are grouped
into another major cluster for which industrial and domestic

123
668
sewage and saline water intrusion influence river water
chemistry. The results of factor analysis clearly illustrate the
various factors responsible for water chemistry. The con-
tribution of anthropogenic activities, such as discharge of
industrial and domestic sewage effluents into river water,
silicate-weathering reactions, and the influence of saline
water on river water, is clearly demonstrated by factor
analysis. Factor scores clearly delineate the influence of
various factors on the sample stations. The seasonal effect on
the chemical composition of river water and the underlying
factors responsible for water quality are clearly illustrated.
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