Arch Environ Contam Toxicol (2008) 55:180190 DOI 10.

1007/s00244-007-9117-y

Groundwater Quality Assessment Using Chemometric Analysis in the Adyar River, South India
T. Venugopal L. Giridharan M. Jayaprakash

Received: 9 September 2007 / Accepted: 14 December 2007 / Published online: 9 January 2008 Springer Science+Business Media, LLC 2008

Abstract A multivariate statistical technique has been used to assess the factors responsible for the chemical composition of the groundwater near the highly polluted Adyar River. Basic chemical parameters of the groundwater have been pooled together for evaluating and interpreting a few empirical factors controlling the chemical nature of the water. Twenty-three groundwater samples were collected in the vicinity of the Adyar River. Box-whisker plots were drawn to evaluate the chemical variation and the seasonal effect on the variables. R-mode factor analysis and cluster analysis were applied to the geochemical parameters of the water to identify the factors affecting the chemical composition of the groundwater. Dendograms of both the seasons gives two major clusters reecting the groups of polluted and unpolluted stations. The other two minor clusters and the movement of stations from one cluster to another clearly bring out the seasonal variation in the chemical composition of the groundwater. The results of the R-mode factor analysis reveal that the groundwater chemistry of the study area reects the inuence of anthropogenic activities, rock-water interactions, saline water intrusion into the river water, and subsequent percolation into the groundwater. The complex geochemical data of the groundwater were interpreted by reducing them to seven major factors, and the seasonal variation in the chemistry of water was clearly brought out by these factors. The higher concentration of heavy metals such as Fe and Cr is attributed to the rock-water interaction and
T. Venugopal L. Giridharan (&) Department of Geology and Mining, Guindy, Chennai 600032, India e-mail: girilogu@yahoo.com M. Jayaprakash Department of Applied Geology, University of Madras, Chennai, India

efuents from industries such as tanning, chrome-plating, and dyeing. In the urban area, the Pb concentration is high due to industrial as well as urban runoff of the atmospheric deposition from automobile pollution. Factor score analysis was used successfully to delineate the stations under study with the contributing factors, and the seasonal effect on the sample stations was identied and evaluated.

The geochemical properties and chemical composition of groundwater depend on the chemistry of water in the recharge area. Anthropogenic activities as well as various geochemical processes that are ongoing in the subsurface dominate the chemistry of water. The seasonal and spatial variations in groundwater chemistry and the groundwater quality depend on these geochemical processes. The main objective of groundwater geochemical study is to identify, assess, and control the pollution sources. This study mainly focuses on water quality assessment since environmental protection policy gives top priority to water quality monitoring and assessment under management of water resources. The study of the hydrogeochemistry of groundwater requires handling of a large data set, which includes the concentrations of various ions as well as physicochemical parameters. The classication, modeling, and interpretation of the data are the most important steps in the assessment of water quality. In order to achieve this objective, multivariate statistical technique such as factor analysis has been used successfully. Factor analysis explains the correlations between the variables in terms of the underlying factors, which are not apparent (Yu et al. 2003). The fundamental utilization of this factor analysis is to study and interpret the hydrogeochemistry of aquifers by simplifying the enormous

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and complex groundwater data into a set of factors, few in number, which can explain a large amount of the variance of the analytical data and the source of origin of the chemical composition (Ruiz et al. 1990). Shuxia et al. (2003) utilized the combined effect of multiple water quality variables to evaluate the water quality and the nature and degree of contamination of the groundwater. The statistical analytical technique was successfully applied by Lawrance and Upchurch (1983) to demarcate the zones of natural recharge to groundwater in the Floridan aquifer. The hydrogeological process in the Santiago Basin of Chile and Derbyshire Dome of England were evaluated using factor analysis by Ashley and Lloyd (1978). Reeder and others (1972) also employed this approach to evaluate the likely weathering processes controlling the chemical composition of surface waters of the Mackenzie River drainage basin in Canada. Factor analysis has been successfully applied by many other authors to resolve the hydrochemical problems of groundwater (Dawdy and Feth 1967; Hitchon et al. 1971; Lawrence and Upchurch 1976; Seyhan et al. 1985; Usunoff and Guzman 1989; Razack and Dazy 1990; Briz-kishore and Murali 1992; Grande et al. 1996; Sanchez-Martos et al. 2001; Ahmed et al. 2005). Factor analysis involves three important stages (Gupta et al. 2005). Determination of the correlation matrix, which contains various interrelated chemical parameters, provides vital information about various geochemical variables. Eigenvalues and eigenvectors of the correlation matrix are extracted and the least important among them are then discarded. The number of variables retained in the factors or communalities is obtained by squaring the elements in the factor matrix and summing the total within each variable. The magnitude of communalities depends on the number of factors retained. Varimax rotation was then adopted. Lower eigenvalues do not help much in interpretation of the data and hence lower eigenvalues are not considered for factor extraction. In general, factors showing eigenvalues [1 are used for interpretation of the results, and in the present work, also, factor extraction has been done with the minimum acceptable eigenvalue[1 (Harman 1960; Kaiser 1960). In this study, the multivariate statistical technique (Rmode factor analysis) was applied to evaluate the spatiotemporal variations in the normalized data matrix of the groundwater in the proximity of the highly polluted Adyar River (Chennai, India). The basic aim of this paper is (i) to evaluate the seasonal effect on the environmental factors implicated in their evolution; (ii) to establish the relations, associations, and causes for the interdependence among the various elements present in the groundwater; and (iii) to determine the possible source of their origin. It is of vital importance to identify and characterize the factors that determine the distribution and augmentation of the concentration of ions in the water. Cluster analysis is also used to delineate the stations, which brings out the relationship

among the factors responsible for the chemical budget of groundwater.

Materials and Methods Study Area In this study, the groundwater in the proximity of the Adyar River was taken for geochemical analysis (Fig. 1a). The Adyar River starts at Malaipattu Dam (80.000 latitude and 12.930 longitude) near Manimangalam village, Sriperumbathur Taluk, about 15 km west of Tambaram, near Chennai. Though it originates from the above point, it assumes the appearance of a stream only after it receives surplus water from the Chembarambakkam tank. It ows through Kancheepuram, Tiruvallur, and Chennai districts for a distance of about 50 km and enters into the Bay of Bengal near Adyar. The river receives a sizable quantity of sewage from the neighborhood after it reaches Nandambakkam near Chennai. This river is almost stagnant and does not carry enough water except during rainy season (NW monsoon). Rapid industrialization and urbanization

Fig. 1 (a) Base map and (b) pollution sources of Adyar River

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(Fig. 1b) along the river course during the 1980s and 1990s increased the pollution of the river watershed, which led to the present-day deteriorated condition of the water level. It has been observed that in the upper part of the river, there is no settlement along the bank of the river, and hence, this part is not polluted by domestic efuents. But the chance of pollution due to agricultural activities is still there. In the chosen area, nitrate and phosphate fertilizers are found to be in use near the upper part of the river. The bulk use of these fertilizers leaves behind unused wastes that are driven off by rain and enter the river, which causes excess nitrate and phosphate pollution. Several studies have reported that the release of nitrates from agricultural activities contaminated the groundwaters (Mukherjee and Pandey 1994; Chandu et al. 1995; Prasad 1998; Pacheco 2001). Groundwater near the midstream is found to be contaminated by the domestic sewage water directed into the river course (Nammalwar and Pakshirajan 1995) and the groundwater in the proximity of the lower part of the water is observed to be polluted by saline water intrusion (Fig. 1b).

Geology of the River Basin The major part of the Adyar River basin is covered by alluvium soil, with tertiary and Gondwana rocks at depth. The alluvium soil varies from 10 to 20 m in thickness and is mostly granular. In the downstream area of the river basin, coastal sand predominates, while the middle and upper parts are dominated by sand and silt. Charnockites are also found in some part of the basins. The geological succession of the basin is given in Table 1.

Statistical Methodology Cluster analysis is a powerful tool for identifying and evaluating similar groups from the hydrochemical data. The term cluster analysis encompasses a number of different algorithms and methods for grouping objects of similar kind into respective categories. This tool sorts different objects into
Table 1 Geological succession of the Adyar River basin Group Age Lithology Soil, alluvium (sand and silt)

Quaternary Sub, Recent Tertiary Mesozoic

Pleistocene Black clay Eocene to Pliocene Sandstone and shale fossil ferrous Lower Cretaceous to Lower Jurassic Silt, gray stone, and black shale Charnockite, granite, gneiss Brown sandstone

Azoic

Precambrian

groups such that the degree of association between the objects is maximal if they belong to the same group and minimal otherwise. This method groups samples into distinct populations that may be signicant in the hydrogeological context, as well as from the statistical point of view. In this study, the classication based on the sampling site was performed through cluster analysis using Wards (1963) method with Euclidian distance as a similarity measure and synthesis into dendogram plots. The Euclidean distance is the geometric distance in multidimensional space. Wards method is known to be distinct, as it uses an analysis of variance approach to evaluate the distances between clusters. This method minimizes the sum of squares (SS) of any two (hypothetical) clusters that have been derived at each step. Factor analysis is unique since the patterns of relationship among many dependent variables are studied with the goal of discovering the nature of the independent variables which affect them, even though those independent variables are not measured directly. Factor analysis was applied to the data matrix in order to reduce the data to an easily interpretable form. Before applying factor analysis, the data were standardized according to the criteria presented by Davis (2002). Standardization of the variables is performed in order to do away with the inuence of different units of measurement on the data by making them dimensionless. The standardization of the values was done after the measurement of skewness in the variables. The measure of skewness indicates the difference in the manner in which the variables are distributed in a particular series compared with a symmetrical distribution. The result of skewness showed that the variables were within the skewness index. Transformation of the data is required if the variables shows high skewness. Transformation makes the variation within the variables minimal, which is essential to get better results from factor analysis. Computation of the correlation coefcient matrix is the rst step in factor analysis between standardized variables. The eigenvalues quantify the contribution of a factor to the total variance. The contribution of a factor is signicant when the eigenvalue is greater than unity (Kaiser 1960). Initial factors are extracted and they are subjected to mathematical rotation. Varimax rotation procedure is used in order to maximize the difference between the variables, facilitating easy interpretation of the data. The rst 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 highest loading, either positive or negative, suggests the meaning of the dimension; positive loading indicates that the contribution of the variables increases with increasing loading in a dimension, and negative loading indicates a decrease (Lawrence and Upchurch 1982). The study of factor scores

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reveals the extent of inuence of each factor on the overall water chemistry at all locations of sampling stations. Extreme negative scores reect areas essentially unaffected by that particular factor and positive scores reect areas most affected. Near-zero scores indicate areas affected to an average degree. In the present study, the stationwise variation of factors is indicated by line diagrams. Boxwhisker plots (Fig. 2) of individual variables were plotted in order to evaluate the chemical variation and the seasonal effect on the variables. These plots were constructed to evaluate different patterns associated with spatial variations in the groundwater quality.

Analytical Methodology In order to evaluate the seasonal variations in chemical compositions, groundwater samples were collected during September 2005 and January 2006, representing pre- and postmonsoon seasons. The water samples were collected from wells adjacent to the river (within 100 m) at a depth of 10 to 20 ft. The samples were collected in new 1-liter HDPE bottles rinsed three or four times with the water sample before lling it to capacity and then labeled accordingly. Prior to analysis in the laboratory, the samples were stored at a temperature below 4C. For sample collection, preservation, and analysis, standard methods (Rainwater and Thatcher 1960; Brown et al. 1970; AWWA 1971; Hem 1991; APHA 1995) were followed. Using pH and SEC meters, the EC and pH of water samples were measured in the eld immediately after the collection of the samples. Before each measurement, the pH meter was calibrated with a reference buffer solution of pH 4. Alkali metal ions (Na+ and K+) were measured using a ame photometer (Model 128 Systronics Flame Photometer). Silica content was determined by the Molybdate Blue method using a UV-visible spectrophotometer. Total dissolved solids (TDSs) were measured by evaporation and calculation methods (Hem 1991). Ca2+ and Mg2+ were determined titrimetrically using standard EDTA. Chloride was estimated by AgNO3 titration. Turbidimetric technique was used for the analysis of sulfate (Clesceri et al. 1998). Nitrate, nitrite, phosphate, and uoride were analyzed using the UV-visible spectrophotometer (Rowell 1994). Standard solutions for the above analysis were prepared from the respective salts of analytical reagent grade.

Fig. 2 Box-whisker plot representing chemical and seasonal variation of variables

Results and Discussion The analytical results of the chemical analysis and the statistical parameters such as minimum, maximum, mean, and standard deviation are presented in Table 2 for both

premonsoon and postmonsoon. The pH values of groundwater are found to be acidic in premonsoon but change to alkaline during postmonsoon. TDS values are high in both seasons and the postmonsoon shows enhanced values at most of the stations. There is a considerable increase in the concentration of ions during the postmonsoon, which may

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be attributed to the leaching of salts from the soil and also to anthropogenic activities. During postmonsoon, the water table in the study area is nearer to the surface and active leaching and subsequent inltration would have changed the chemical composition of the groundwater. A higher concentration of TDSs is observed in the groundwater near the lower part of the river basin, which is near the Bay of Bengal. The results show that the contribution of Na and Cl to the TDSs is high. Among the trace metals Fe, Pb, and Cr values in the groundwater are higher than the permissible limit. In general, the geochemical results show the effect of monsoon on the overall chemical composition of the groundwater.

Cluster Analysis Grouping of sampling points in accordance with the concentration of the constituent ions is done by cluster analysis. Cluster analysis is a helpful tool for organizing a particular set of data from various points into clusters or groups and determining the relationship between the various points (McGarial et al. 2000). Cluster analysis is also helpful in determining the seasonal effect on each station.

The movement of stations from one cluster to another reveals the effect of monsoon. In order to determine the number of clusters which describe the underlying process that leads to spatial variation, dendograms in cluster analysis offer a useful tool. Both premonsoon and postmonsoon (Figs. 3a and b) two major clusters or groups are obtained from the data. Each major group is subdivided into two minor clusters. Cluster 1 (stations 17, 911, 1316) of the premonsoon season is characterized by an unpolluted to moderately polluted region. This area lies in the upper stretch of the river and the groundwater in this area is not very polluted. Cluster 2 (stations 12, 17, 19, 20) of the premonsoon season could be categorized as highly polluted, as these show high TDSs. The wells in these stations are nearer to the downstream region of the river except for station 12, which is found to be highly polluted with industrial and domestic efuents. Cluster 3 (stations 8 and 18) of the premonsoon season is a typical grouping, with one groundwater station near the upper stretch of the river and the other near the downstream of the river. In the groundwater near the upper stretch, only station 8 shows high TDSs. Station 18 also shows a similar TDS value and both these stations are found to be highly polluted. Cluster 4 (stations 2123) of the premonsoon season were related

Table 2 Summary statistics of the analytical data Parameter Premonsoon Mininum pH EC (lS/cm) TDS (mg/L) Ca2+ (mg/L) Mg2+ (mg/L) Na+ (mg/L) K (mg/L) HCO3- (mg/L) SO2- (mg/L) 4 Cl- (mg/L) F- (mg/L) NO- (mg/L) 3 NO- (mg/L) 2 PO3- (mg/L) 4 SiO2 (mg/L) Cu (mg/L) Co (mg/L) Zn (m/L) Fe (mg/L) Pb (mg/L) Cr (mg/L)
+

Postmonsoon Maximum 6.73 5120.31 3277.00 208.00 120.60 795.00 44.17 1037.00 292.00 1210.00 2.03 45.93 1.07 4.67 32.50 0.098 0.074 0.066 4.618 0.618 0.457 Mean 6.31 2708.02 1733.13 124.96 55.60 311.94 12.90 375.48 238.58 435.39 1.18 18.67 0.25 1.09 29.44 0.064 0.034 0.024 0.791 0.186 0.103 r 0.023 1126.50 720.96 35.80 32.25 193.47 13.78 210.45 30.26 268.79 0.39 11.32 0.22 1.11 2.05 0.019 0.025 0.016 0.925 0.164 0.104 Minimum 7.48 656.25 420.00 48.00 12.00 31.82 0.00 170.80 32.42 150.00 0.15 1.02 0.09 0 9.2 0.011 0.003 0.005 0.065 0.008 0.012 Maximum 8.96 13759.38 8806.00 424.00 686.00 1120.00 64.80 732.00 272.00 3470.00 0.91 75.91 3.61 0.13 28.3 0.088 0.068 0.250 3.986 0.548 0.650 Mean 8.29 3558.15 2277.22 197.70 134.17 391.25 11.31 368.86 176.74 956.96 0.50 21.07 0.7 0.06 26.47 0.051 0.028 0.035 0.598 0.139 0.113 r 0.4 3031.41 1940.10 114.43 142.48 331.14 17.60 148.17 68.27 903.16 0.20 22.15 1.03 0.03 3.82 0.022 0.023 0.053 0.788 0.148 0.155

5.95 1679.69 1075.00 56.00 16.40 136.30 0.00 224.80 204.00 110.00 0.48 4.21 0.01 0.24 26.60 0.012 0.002 0.006 0.066 0.012 0.012

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Arch Environ Contam Toxicol (2008) 55:180190 Fig. 3 Dendogram showing the relationship among the groundwater samples during (a) premonsoon and (b) postmonsoon seasons

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to saline water-inuenced stations, as these are nearer to the estuary, showing a high TDS value as well as high concentrations of Ca, Mg, SO4, Na, and Cl. In postmonsoon season, the cluster analysis shows a marked change in the grouping of stations. The seasonal effect is visible in cluster 1 (stations 810, 12, 13, 15, 17, 1820), as it shows higher concentrations of geochemical constituents

compared to those of premonsoon season, reecting the leaching effect of the rock-water interaction as well as the pollutants due to anthropogenic activities. The groundwater in cluster 2 (stations 17, 14, 16) is adjacent to the upper part of the river. Dilution of the groundwater and seepage from the less polluted river water contribute to this grouping of stations. Cluster 3 (stations 11, 21, 22) is a

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mixture of pollutant-inuenced (station 11) and salineinuenced stations. Station 11 shows a high TDS value due to anthropogenic activities such as laundering near the river banks and direction of the industrial efuents into the river water directly. The fourth cluster, which consists of a single station (station 23), can be considered an estuarine, saline water-inuenced station.

Factor Analysis Factor analysis is a statistical technique designed to analyze the interrelationships within a set of variables by reducing the complex data to an easily interpretable form (Davis 2002). In this work, R-mode factor analysis is chosen, which allows interpretation of the data more scientically. Factor loadings, communalities, and eigenvalues (Table 3) were examined to evaluate the variables belonging to a specic chemical process and also to nd out the dominance and contribution of the major elements in the total data set. Factor 1 (anthropogenic and silicate weathering) of the premonsoon, which explains 33.2% of the total variance, has high loadings of the ions Na, Mg, K, Cl, PO4, and HCO3-. The percentage abundance of the above variables indicates that their source of origin may be expected from (i) the dissolution of silicate minerals and (ii) anthropogenic sources such as residential water softeners or agricultural activities (Vengosh and Keren 1996; Wayland et al. 2003). Factor score diagrams reveal the extent of inuence of each factor on the overall water chemistry at all locations of sampling stations. Factor 1 of the premonsoon season (Fig. 4a) is least signicant at the origin, and it shows some positive values at station 8 but gains importance only from station 18 to the conuence point. This shows that the groundwater near the downstream is affected with regard to this factor. The lower part of the Adyar River is found to be highly polluted due to the mixing of industrial efuents and domestic sewage at various points and the backwaters from the ocean near the conuence point (Ramesh et al. 1995). The river water is found to be stagnant in this region, which facilitates the rock-water interaction. Moreover, the stagnancy of the water increases the residence time of the ions, which augments percolation of the polluted water into the nearby aquifers. Factor 2 (iron, chromium factor) of the premonsoon season, which accounts for 13.2% of the total variance, has high loadings on the variables Fe and Cr. The factor score diagram (Fig. 4b) reveals that the groundwater near the upper part of the river shows some positive scores, indicating that these wells are affected with regard to this factor. Since in this region, except for agricultural activity, no anthropogenic activities were being carried out, the high

Fe concentration in these waters could not be assigned to the anthropogenic activities, but rather the soil-water interaction should be the reason for the higher value of Fe observed in this region. Factor 3 (calcium factor) of the premonsoon season, accounting for about 9.6% of the total variance, is explicitly a calcium factor with a positive loading in SO4. The factor score diagram (Fig. 4c) reveals that the groundwater near the lower part of the river shows high positive scores. The inuence of saline water is high in the lower part of the river and this may be the reason for the enrichment of Ca and SO4 in the nearby groundwaters. Factor 4 (cobalt, zinc factor) of the premonsoon season is found to have high loadings in cobalt and zinc. The factor score diagram (Fig. 4d) shows signicant factor scores at station 2 and in the groundwaters near the middle part of the river. During premonsoon, factor 5 is explicitly a uoride factor. The factor score diagram (Fig. 4e) shows that some stations near the middle and lower parts of the river show highly signicant factor scores, indicating that these wells are affected with regard to this factor. Contribution from anthropogenic activities would have decided the premonsoon values (Saxena et al. 2003; Subbarao 2003). Factor 6 (lead factor) of the premonsoon efuent factor has high loadings in lead. The factor score diagram (Fig. 4f) shows that the groundwater near the middle and lower parts of the river shows highly signicant factor scores. The industries located near the course of the river and their efuents which are directed into the river should have increased the concentration of these ions and the nearstagnancy of the river at this region facilitates the percolation into the adjacent groundwater. Factor 7 of premonsoon is explicitly a copper factor. The factor score diagram (Fig. 4g) demonstrates a distributive pattern. Since the lithology of the area does not support the rock bearing such minerals, it is highly logical to assign these factors to anthropogenic activities (Akpan 2002). Factor 1 (saline factor) of the postmonsoon, which explains 35.9% of the total variation, has high loadings in the ions Ca, Mg, Na, K, SO4, and Cl. The factor score diagram (Fig. 5a) shows signicance at station 11 near the midstream of the river and at three stations near the conuence point, i.e., stations 21, 22, and 23. Factor 1 played a major role only at the downstream stations. This leads to the conclusion that, during postmonsoon, saline water intrusion played a major role at the downstream. The percentage loading of ions also supports the above view. During postmonsoon, factor 2 (domestic sewage and runoff factor), which explains 14% of the variance, is explicitly a Pb, nitrite, and nitrate factor. The factor score diagram (Fig. 5b) reveals that the groundwater near the middle part of the river shows high positive scores, reecting that the wells in this region are affected with respect to this factor. The concentrations of various

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Arch Environ Contam Toxicol (2008) 55:180190 Table 3 Rotated component matrix: (a) premonsoon and (b) postmonsoon

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(a) Premonsoona Factor 1

PH EC TDS Ca Mg Na K HCO3 SO4 Cl F NO3 NO2 PO4 Si Cu Co Zn Fe Pb Cr Eigenvalue % variance -0.359 0.958 0.958 0.105 0.893 0.964 0.766 0.680 0.602 0.869 0.038 -0.040 -0.088 0.747 -0.186 -0.073 0.173 -0.034 0.019 -0.084 -0.190 60.97 330.21

Factor 2
0.689 -0.090 -0.089 0.012 0.035 -0.122 -0.094 -0.073 -0.150 -0.160 0.020 -0.361 -0.238 0.004 -0.047 -0.016 -0.002 0.316 0.734 -0.133 0.868 20.78 130.25

Factor 3
-0.355 0.105 0.104 0.905 -0.214 0.023 -0.136 -0.258 0.509 0.350 -0.089 0.321 0.484 0.212 -0.156 0.179 -0.102 0.333 -0.028 0.212 0.099 20.02 90.64

Factor 4
0.147 0.123 0.124 0.062 0.012 0.003 -0.183 0.294 0.198 -0.037 0.130 0.564 0.219 -0.074 0.163 0.173 0.745 0.702 -0.412 -0.053 0.219 10.68 80.01

Factor 5
0.073 0.113 0.113 0.018 0.072 0.038 -0.211 0.143 0.092 -0.007 0.816 0.287 0.152 0.084 -0.814 -0.028 -0.134 0.029 0.036 0.149 0.002 10.39 60.60

Factor 6
0.032 0.037 0.039 0.097 0.127 -0.040 -0.201 0.020 0.052 -0.023 0.327 -0.145 -0.596 -0.160 0.171 0.134 -0.233 0.221 -0.099 0.859 0.016 10.31 60.22

Factor 7
-0.206 -0.018 -0.020 0.145 -0.068 -0.050 0.001 0.463 0.040 -0.185 -0.203 0.199 -0.006 0.291 -0.178 0.853 0.053 0.204 0.136 0.147 -0.025 10.01 40.80

(b) Postmonsoonb Factor 1

PH EC TDS Ca Mg Na K HCO3 SO4 Cl F NO3 NO2 PO4 SI Cu Co Zn Fe Pb Cr Eigen value % variance -0.491 0.969 0.969 0.729 0.940 0.897 0.839 0.399 0.616 0.906 0.249 0.101 0.059 0.190 0.125 0.061 -0.085 -0.030 -0.090 -0.053 -0.094 70.53 350.88

Factor 2
-0.595 0.122 0.122 0.422 0.055 0.015 -0.224 0.059 0.161 0.198 -0.069 0.911 0.796 0.037 -0.004 0.289 -0.447 -0.015 -0.215 0.312 -0.158 20.94 140.01

Factor 3
-0.207 0.069 0.069 0.163 -0.005 0.108 0.045 0.296 0.465 0.042 0.160 0.110 0.110 0.012 0.957 -0.068 0.187 0.070 -0.914 0.117 -0.145 20.30 100.95

Factor 4
0.240 0.057 0.057 0.229 -0.076 0.260 -0.022 -0.122 -0.101 0.278 0.793 0.030 0.440 0.220 0.155 0.731 -0.058 0.032 -0.017 0.554 0.151 10.71 80.16

Factor 5
0.154 0.046 0.046 -0.004 -0.017 0.227 0.161 0.243 0.202 0.043 -0.077 0.233 -0.025 0.778 0.058 0.044 0.218 -0.071 -0.005 -0.664 -0.727 10.39 60.62

Factor 6
0.014 0.016 0.016 -0.099 0.044 -0.055 -0.113 0.286 -0.008 -0.020 -0.204 -0.131 -0.054 -0.203 0.066 0.324 0.696 0.870 -0.130 -0.188 -0.177 10.17 50.57

Note. Extraction method: principal component analysis. Rotation method: varimax with Kaiser normalization
a

Rotation converged in eight iterations

Rotation converged in seven iterations

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188 Fig. 4 Factor score line diagrams: premonsoon

Arch Environ Contam Toxicol (2008) 55:180190

industries along the course of the middle part of the river and their activities should have increased the higher concentration of lead in the river, which would have percolated into the adjacent aquifers. The atmospheric depositions resulting from automobile pollution (Varrica 2003; Rajnikant and Shamsh 2003) and the urban runoff due to precipitation may also lead to the increase in the concentration of Pb in the aquifers. Nitrate is stable in groundwater because of the dissolved oxygen (Hamilton and Helsel 1995), and in the middle part of the river, domestic sewage water was directed into the river. In many watersheds, there is a well-dened exchange of water from groundwater and surface water (Moldan and Cerny 1994). Since nitrates are highly mobile, as they do not interact

with the matrix materials (Bulger et al. 1989), the nitrate ion concentration in the adjacent aquifers increases by percolation (Kayabali et al. 1999; Ramesh et al. 1995). Hence, the higher concentration of nitrates in the groundwater may be attributed to the movement of nitrate ions from the river water into the adjacent aquifers. During postmonsoon, factor 3 (silicate factor), which explains 10.9% of the total variance, has high loadings in the ions silicate and sulfate. The factor score diagram (Fig. 5c) reveals that the groundwater near the middle part of the river is found to be affected with regard to this factor. High loading on silicate could be associated with the leaching action of rainwater on the adjacent aquifer soils. Weathering of rocks with carbonic acid releases SiO2,

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Arch Environ Contam Toxicol (2008) 55:180190 Fig. 5 Factor score line diagrams: postmonsoon

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bicarbonate, and kaolinite (Gupta et al. 1994; Rajmohan 2004). During postmonsoon, factor 4 (uoride factor) has high loadings in the ions uoride, copper, and lead. The factor score diagram (Fig. 5d) reveals that the groundwater near the middle and lower parts of the river shows signicant positive scores. The lithology of the study area has no signicant uoride-bearing minerals and hence it is logical to assign the high uoride to the anthropogenic activity and, to a lesser extent, to chemical weathering (Saxena et al. 2003; Subbarao 2003). Factor 5 of the postmonsoon season is explicitly a phosphate factor. The factor score diagram (Fig. 5e) reveals a distributive pattern with respect to this factor. The surface runoff of the unused fertilizer remains near the upper part of the river, which explains the highly signicant factor scores in this region. In the case of the middle and lower parts of the river, the domestic efuents containing water softeners contribute to the higher concentrations of these ions in the groundwater (Rajmohan 2005). Factor 6 (zinc, cobalt factor) of the postmonsoon season shows high loadings in zinc and cobalt. The factor score diagram (Fig. 5f) shows signicant values in the groundwater near the lower part of the river.

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