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JOURNAL OF COASTAL SCIENCES


Journal homepage: www.jcsonline.co.nr ISSN: 2348 6740 Volume 1 Issue No. 1 - 2014 Pages 22-26

Evaluation of the groundwater quality along coastal stretch between Vembar and Taruvaikulam, Tamil Nadu, India: a statistical approach
S. Selvakumar*, N. Chandrasekar, Y. Srinivas, T. Simon Peter, N.S. Magesh
Centre for Geotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu 627 012, India

ABSTRACT `
The present study investigates the groundwater quality from Vembar to Taruvaikulam coastal area to provide an overview of the relationship and sources of physicochemical parameters. A total of 23 groundwater samples were collected and analyzed for various physico-chemical parameters such as pH, electrical conductivity (EC), total dissolved solids (TDS), calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+), bicarbonate (HCO32-) , chloride (Cl-) and sulphate (SO42-). The ionic concentrations confirm most of the groundwater samples belong to order of (Na+) > (Mg2+) > (Ca2+) > (K+) and (Cl-) > (SO42-) > (HCO32-). Spearmans correlation matrix, principal component analysis (PCA) was used to distinguish the main contamination sources in the study area. The significant correlation (r=>0.5) of EC, TDS, sodium, magnesium and chloride indicates saline intrusion, insignificant correlation (r=<0.5) on calcium and bicarbonate ions attribute to a fresh water source. Four varimax components were extracted from PCA, which explained 55.3, 19.20, and 0.98% of the variation in the groundwater quality in present study area. The components obtained from PCA indicated that seawater intrusion, industrial pollution, geological activities and anthropogenic activities exists in the study area.
*Corresponding author, E-mail address: geoselvas@gmail.com Phone: +91 9751616732 2014 Journal of Coastal Sciences. All rights reserved

ARTICLE INFO
Received 20 November 2013 Accepted 3 March 2014 Available online 6 March 2014 Keywords Groundwater quality Correlation analysis Principal Component Analysis Seawater intrusion

1. Introduction
As groundwater is mainly used for drinking, irrigation, industrial and other domestic purposes, a detailed geochemical analysis is extremely important, as although certain constituents became toxic beyond particular concentrations, although they may be beneficial at lower amounts. The natural chemical quality of groundwater depends on geological as well as geographical arrangement in the region. The contamination caused by seawater intrusion is a major problem in the coastal aquifers, which occurs due to over extraction of groundwater resulting in seawater infiltration into the aquifer through the unsaturated zone (Sarath Prasanth et al. 2012; Krishnakumar et al. 2012; Chandrasekar et al. 2013). Many studies have been reported on groundwater quality analysis. In this context, statistical analysis is very useful due to its relative importance in evaluating the combination of large chemical variable dataset. Principal component analysis (PCA) and Speramans correlation matrix have been frequently applied to analyze the pollution parameters in groundwater. Senthilkumar et al. (2008) proposed multivariate analysis is very useful due to its large chemical variable dataset and they are used as an analytical tool to reduce and organize large hydro-geochemical datasets into groups with similar characteristics. Abdul Halim et al. (2010) proposed PCA to classify groundwater and identify major mechanisms influencing the groundwater chemistry. The principal component analysis has been successfully applied to sort out various hydro-geochemical processes from commonly collected groundwater quality data (Hitchon et al. 1971). Mrklas et al. (2005) have used principal component analysis (PCA) for simplifying the analysis of complex
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chemical relationships. Moreover, PCA is used as a tool to organize the data and to differentiate between different chemical environments in a region. In comparison, PCA is frequently employed in hydrochemical studies, geology and hydrogeological applications (Akbal et al. 2011; Najar et al. 2012). Elkarail and Obied (2013) have used Speramans correlation matrix to identify the groundwater quality in the Red-sea coast in Sudan. They have evaluated the processes govern changes in the groundwater composition mainly associated with over abstraction, biodegradation, carbonate saturation and seawater intrusion. These analyses are useful for interpreting the groundwater quality data and relating them to specific changes in hydrogeological process. Hence, an application of the principal component analysis can be used as an important tool in the hydro-geochemical analysis of any region and helps to plan suitable management measures in time to control and improve the groundwater quality. The objective of this study is to investigate the spatial variations in groundwater quality and to identify the source of pollution. Correlation matrix and principal component analysis were used to evaluate the information concerning the similarities between the sampling stations and to ascertain the contribution of potential factors or pollution sources among various physico-chemical parameters at 23 different sampling stations of the coastal region between Vembar to Taruvaikulam. Based on the information obtained, a holistic interpretation of the results and the use of selected parameters as source tracers for contamination were improved.
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2. Study area
The present study area is located in the southern part of Tamil Nadu, which lies between north latitudes 889 to 9 08 and east longitude 7816 to 7836 and has a coastal length of 42 km (Figure 1). Sandy beaches are perceived along Vembar, Vaippar and Taruvaikulam coastal areas. The backshore of Kallar, Veppallodai and Taruvaikulam segment largely consists of salt pans. Back water zone are extensively present between Vembar and Kalaignapuram area. The dune patterns are developed by vigorous aeolian processes resulting in the migration of dunes with frequent changes in their shape and pattern from time to time, but generally trends almost parallel to the coastline. The sand sheet in the coastal zone extends from Vembar to Kalaignapuram and Taruvaikulam. The sand sheet is implanted with rich black sand deposits. Patches of Teri sand deposits are observed

time of sampling. Care was taken to avoid sample contamination by external means. Each bottle was labeled with its corresponding sampling station and time of sampling. The location of the sampling stations was fixed using Garmin E-trex 12 channel Global Positioning System (GPS). Hanna portable water quality meter (Model No. HANNA HI-9828) were used to conduct in situ measurements of physical parameters such as pH, electrical conductivity (EC), total dissolved solids (TDS).The samples were immediately filtered with 0.45m cellulose acetate membrane filter (Whatman Milipores) after being transported to the laboratory. The collected samples were preserved in a refrigerator at 40C to avoid microbial growth, flocculation, and reduce any adsorption on the polythene bottles. Samples were preserved according to standard methods for the examination of water and waste water (APHA 2005) for following analysis.

Fig. 1 Location map of the study area

in the north of Melmandai and Vembar coastal area. The drainage pattern of the area is mainly controlled and influenced by the presence of perennial rivers like Vembar, Vaippar and Kallar. The Vaippar river basin extends for about 6255 sq.km and the Kallar is a small river and receives water supply mostly from NE monsoon. The climate of the area experiences humid tropical and the annual average rainfall is 662.2 mm with a wind velocity varies from 2.8 to 35.5 km/hr.

3.2. Chemical analysis Calcium(Ca2+) and magnesium (Mg2+) concentrations were determined by complexation reaction using EDTA (Ethylenediamine-teracetate) with ammonium purpurate as an indicator for the determination of Ca2+ content alone, and Eriochrome Black-T was used as an indicator for both Ca2+ and Mg2+content. Sodium (Na+) and Potassium (K+) were estimated by Flame photometer. Total hardness of the groundwater was calculated using the method proposed by Hem (1985) and Ragunath (1987).
TH ( asCaCO 3 ) = Ca 2 + + Mg 2+ meq / l 50

3. Materials and Methods


3.1. Field sampling and preservation

Groundwater samples were collected from 23 open dug wells and Chloride (Cl-) content was determined with the standard silver bore wells of different locations and were homogenized. During nitrate (0.01N) titration method and in the presence of 1mL of sampling, the pre cleaned acid washed HDPE (High density potassium chromate (5%) as an indicator. The determination of polyethylene) bottles were normalized by rinsing thoroughly at the carbonate and bicarbonate concentrations was carried out by
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titration using 0.01N sulfuric acid and in the presence of phenolphthalein indicator for the rst and methyl-orange for the second. Sulfate (SO4) estimation was done using UVspectrophotometer. The reaction error (E) of all the 23 water samples was less than the accepted limit of 5 % and samples. 3.3. Statistical analyses All statistical analyses were performed using the IBM SPSS Statistics 19. PCA was applied to the datasets that had been pre-clustered by extracting the eigen values and eigen vectors from a square matrix produced by multiplying the data matrix. The most significant components were extracted to reduce the contribution of variables with minimum significance. Then, the obtained components were further subjected to varimax rotation to generate varimax factors and maximize the differences between the variables, thus facilitating easy interpretation of the datasets. The positive scores (>+1) reflect areas highly affected and extreme negative scores (<-1) reflect areas essentially unaffected by the process. PCA can be expressed using following equation: Yji = fjlzil + fj2zi2 +..... + fjm+ zim + eij

Parameters Min Max Mean SD WHO 2004 pH (Range) 7.45 8.5 7.917 0.26 6.5-8.5 EC (S/cm) 288 8976 2537.7 2553.2 1500 TDS (mg/l) 184.32 5744.6 1624.2 1634.1 1500 Ca (mg/l) 26.4 369 103.4 84.2 200 Mg (mg/l) 28.8 622.6 139.3 135.3 150 Na (mg/l) 88.05 557.25 289.1 131.5 200 K (mg/l) 1.26 102.7 28.3 29.8 12 HCO3 (mg/l) 36.6 196.6 89.8 40.8 500 Cl (mg/l) 306.52 3021.3 888.3 636.3 600 SO4 (mg/l) 37.8 173.5 112.3 42.8 250 Table. 1 Statistical summary of hydro chemical parameters of the study area

The evaluation of groundwater and its relationship between rock types and water composition has been evaluated by the Ternary diagram, which reveals that the water type has Na-Cl facies (Fig.2) and ionic concentration of sodium, magnesium and chloride are the dominant cations and anion respectively. Generally, calcium and bicarbonate are major ions in fresh water, while chloride and sodium are most dominant in seawater.

Where y is the measured variable, f is the factor control loading, z is the factor score, e is the residual term accounting for errors or other sources of variation, i and j is the simple number and m is the total number of factors. Spearmans correlation matrix is a statistical measure of the strength of a monotonic correlation between paired data which can be employed to study the degree of relation between two variables and it is simply measure to demonstrate how well one variable predicts the other. The interpretation of the data r2 value has >0.19 is very weak, 0.20 to 0.39 is weak, 0.40 to 0.59 is moderate, 0.60 to 0.79 is strong and 0.80 to 1.0 the very stronger. The monotonic Fig. 2 Groundwater Chemistry (Ternary plot) relationship or the r2 value has >1.0 is perfect correlation, 0 to 1 is the two variables tend to increase or decrease together, 0.0 is the two Therefore, the higher concentration of chloride and sodium ions variables do not very together at all, -1 to 0 is one variable increases in the coastal groundwater attribute to significant effect of saltwater as the other decreases and <-1.0 have perfect negative or inverse intrusion. correlation.

4. Results and discussion


4.1. Hydrochemical characteristics Statistical summary of hydrochemical parameters of the groundwater samples are shown in Table 1. The groundwater samples of the study area have pH values ranging from 7.45 - 8.5 with an average value of 7.92, which indicates that the groundwater is slightly alkaline in nature and found within the permissible limit suggested by WHO (2004). The electrical conductivity (EC) values ranged 288 - 8,976 S/cm with an average value of 2537.7S/cm. The total dissolved solids values vary between 184 to 5745 mg/l and average value of 1624 mg/l. The abnormal high value of EC and TDS indicates the possibility of saline intrusion in the coastal area. The order of abundance of the major cations is Na >Mg > Ca > K. In sodium, 70% of the samples exceeded the desirable limit of 200 mg/l, magnesium 61% of the samples exceeded the permissible limit of 150 mg/l and calcium, potassium was mostly found within the desirable limit. The abundance of the major anions is Cl > SO4> HCO3 and almost 87% of the samples exceeded the desirable limit of Cl (600 mg/l), but the sulfate and bicarbonate concentrations are all below WHO guidelines (WHO, 2004).
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4.2. Principal Component Analysis (PCA) The PCA was applied on the water quality dataset to identify the spatial sources of pollution within the southern coastal aquifer. With reference to the eigenvalues (>1) four components were extracted and explained 91% of the total variance (Table 2) In table 2, PC 1 accounted for 55% of the total variance. This component showed high loading of EC, TDS, Cl, Mg, Ca, Na and SO4. The electrical conductivity and total dissolved solids are generally regarded as indicator for the presence of dissolved ions; these two concentrations increases at the same dissolved ions will also increase. Salinity will also increase at the time of increase in dissolved salt concentration (Elder 1988). This statement is also supported by the strong positive component loadings for EC and TDS. The high absolute loadings for the major ions such as Cl, Mg, Ca, Na and SO4 probably shows the result of mineral water reactions and it indicates that the seawater intrusion still influence the hydrochemistry of the study area. It may also be explained by the mixing condition between freshwater and seawater (Aris et al. 2012), and occurrence of dolomitic and evaporite minerals in the aquifer. PC 2, which accounts for 19.20% of the total variance, contains high loadings for pH, K, and HCO3. Its represents the major geochemical processes taking place in the study area, which is most probably
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due to the presence and dissolution of some carbonate, activities. Insignificant correlation (r=<0.5) on calcium and agricultural, industrial and anthropogenic activities. PC3 and PC4 bicarbonate attribute to a fresh water source. which explain about 0.9 and 0.8%, of the variance of the concentration of the samples, extreme negative scores reflect areas 5. Conclusion essentially unaffected by the process. The result of the statistical analysis including Spearmens Parameters Component correlation coefficient and principle component analysis, as applied PC1 PC2 PC3 PC4 to the hydrochemical data set of groundwater in this coastal area pH -0.078 0.715 -0.002 0.675 provides an insight into the underlying factor controlling hydroEC 0.956 0.125 -0.043 0.083 geochemical processes in the region. The evaluation of groundwater TDS 0.956 0.125 -0.043 0.083 and relationship between rock types and water composition has Ca 0.749 -0.565 0.188 0.065 been evaluated by the ternary diagram. It reveals that the water type Mg 0.833 -0.492 0.067 0.151 has dominant Na-Cl facies which indicates possibility of seawater Na 0.726 0.215 -0.528 0.062 intrusion in the study area. Principal component analysis identified K 0.504 0.539 0.498 -0.268 by several intrinsic factors responsible for groundwater pollution either from natural or anthropogenic inputs. HCO3 0.593 0.440 -0.382 -0.454 Four components were extracted with a total variance of 91% Cl 0.899 -0.357 -0.031 0.122 and high loading of EC, TDS, Cl, Mg, Ca, Na and SO4. The PCA results SO4 0.707 0.400 0.386 -0.044 recommended that seawater intrusion, industrial pollution, Initial Eigen values 5.529 1.921 0.867 0.794 agricultural and anthropogenic activities. The Spearmens Percent of variance 55.293 19.2013 8.667 7.943 correlation indicate strong, positive monotonic correlation between Cumulative percent 55.293 74.506 83.172 91.115 EC, TDS with major ionic concentration of Mg2+, Na+, Cl- and SO42-. Table. 2 Summarized the PCA results including the loadings and the This has indicated seawater influence on the groundwater salinity in eigenvalues of each PC the coastal areas. This study indicates that there is an ongoing problem of salt water intrusion in the study area. 4.3 Correlation matrix Based on Spearmans correlation, it was found that the correlation between EC (Salinity) and TDS with the major components of sea water (Na, Mg, Cl, SO42-) showed significant positive correlation (TDS-Mg2+, r=0.756; TDS-Na+, r=0.565; TDS-Cl-, r=0.828 and TDSSO42- , r=0.712 (Table 3) that reflects signs of sea water influence on the groundwater salinity.
Parameters pH EC TDS Ca Mg Na K HCO3 Cl SO4 pH 1 -0.035 -0.035 -0.382 -0.124 0.078 -0.031 -0.205 -0.157 0.129 EC 1 0.999 0.514 0.756 0.565 0.721 0.398 0.828 0.712 TDS Ca

Acknowledgements
The authors would like to thank the Department of Science and Technology (DST) (WAR for WATER scheme) Govt. of India, New Delhi. This work forms a part of the major research project (Project No: DST/WAR-W/SWI/010/2010) granted to Prof. N. Chandrasekar.
Mg Na K HCO3 Cl SO4

1 0.514 0.756 0.565 0.721 0.398 0.828 0.712 1 0.701 0.109 0.457 0.130 0.574 0.440 1 0.368 0.386 0.354 0.780 0.628 1 0.275 0.497 0.782 0.428 1 0.368 0.509 0.682

1 0.393 0.414

1 0.609

Table. 3 Spearmans correlation matrix of the groundwater variables (values higher than 0.6 bold are of significant correlations) The significant correlation of Cl- ion with Na+ (Cl-- Na+, r=0.782) and Cl- with Mg2+ (Cl-- Mg2+, r=0.780) reflects the seawater intrusion to groundwater in the study area. The variation of these relationships may also be inferred to indicate the complexity of the hydrochemical components of groundwater where natural water always contain dissolved and suspended substances of mineral origin and the processes govern changes in the groundwater composition are mainly associated with over abstraction, biodegradation, carbonate saturation and seawater intrusions (Elkarail and Obied 2013). Positive correlation of Mg2+ with SO42- (Mg2+-SO42-, r=0.628) has undergone reduction, precipitation, solution and concentration as they traverse through the sedimentary rocks such as gypsum and anhydrite and K+ ion with SO42- (K+- SO42-, r=0.682). Groundwater is deteriorated due to using fertilizers in agriculture and anthropogenic
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