International Research Journal of Environment Sciences__________________________________ ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 42 Assessment of Water Quality Parameters using Multivariate Chemometric Analysis for Markanda River, IndiaRout Chadetrik and Bhatia Upain Kumar Department of Civil Engineering, Maharishi Markandeshwar University, Mullana-133207, Ambala, Haryana, INDIA Available online at: www.isca.in, www.isca.me Received 16th August 2015, revised 7th October 2015, accepted 9th November 2015 AbstractThe present study uses several univariate and multivariate statistical techniques to evaluate and interpret a water quality data set obtained from the Markanda River within the state of Himachal Pradesh and Haryana, India. Data was collected from August-November 2013 and 2014 for eight parameters used to assess the status of the water quality, namely pH, electrical conductivity, total dissolved solids, total hardness, chloride, sulphate, biochemical oxygen demand and chemical oxygen demand. Water quality was monitored at 8 sampling stations along the Markanda river. The data were first analysed using univariate statistical tools, followed by principal component analysis and hierarchical cluster analysis that reduced the data dimensions for better interpretation. This study also presents the usefulness of different statistical methods for evaluation and interpretation of river water quality data for the purpose of monitoring the effectiveness of water resource management. Higher values of EC, BOD and COD indicate that river water is not safe for drinking purposes as prescribed by Bureau of Indian Standards (BIS). Keywords: Markanda river, principal component analysis, biplot, cluster analysis, chemometry. Introduction The demand for water has multiplied manifold with rapid growth in population, agricultural and industrial activities all over the world which is severely affecting the available water resources now-a-days. Increasing demand of water is degrading the water quality of rivers worldwide, resulting in huge loss of the vital goods and ecosystem services. Several rivers of northern India like the Markanda, Dishradwati, Ghaggar, Ravi, Yamuna, Saraswati, Satluj and the Ganga rivers as mentioned in the ancient Sanskrit literature, have generated much interest among the research community. In recent past years several studies related to monitoring of Indian rivers have been made by various researchers2-13. Therefore, the research work is an attempt to assess the physico-chemical parameters of river Markanda which is used for drinking, irrigation and industrial activities. Material and Methods Description of the study area: The Markanda river located in the foothills of the Siwalik hills and Gangetic plains of Haryana, is the most well-known stream between the Yamuna and the Ghaggar river systems14. The river originates from Nahan in Himachal Pradesh. Its basin spreads between 30° 00 and 30° 40 North latitudes and 76° 32 and 77° 24 East longitudes in the Siwalik foothills, North West India. The basin covers an area of 1547 km. The area falls under subtropical and semi-arid region with the annual average rainfall of 1100 mm in the hilly region and 750 mm in normal areas. The geological strata the basin consists of sedimentary rocks of Tertiary to Quaternary alluvium deposits. Rocks and alluvium deposits belongs to Tertiary and Quaternary age, which occupy the northern and south part of the basin respectively15. The sampling was carried out at eight designated sampling stations selected on the basis of accessibility where peoples are using the river water for domestic purposes. The coordinates of sampling locations are as follows: (M1) 30º 3042.2 N and 77º 22 01.2 E (M2) 30º 3050.1 N and 77º 2057.4 E (M3) 30º 3105.7 N and 77º 2001.7 E (M4) 30º 3147.4 N and 77º 1827.9 E (M5) 30º 3100.0 N and 77º 1447.4 E (M6) 30º 3022.5 N and 77º 1318.8 E (M7) 30º 2947.2 N and 77º 1240.0 E (M8) 30º 1633.3 N and 77º 0127.1 E. Statistical analysis: Principal component analysis (PCA) has been done on the original data set using MATLAB software. The analytical results were compiled using Microsoft Excel, and SPSS 19.0 software was used to perform cluster analysis (CA) on the data. The data were normalized to the Z score (with a mean of “0” and a standard deviation of “1”) and then classified using Ward’s method. The correlation coefficient distance was used in the CA. The water quality parameters that correlated well were identified and grouped for further analysis. Pearson’s correlation matrix has been used to identify the relationship among the water quality parameters to support the results obtained by multivariate analysis. Collection and characterization of water samples: River water samples were collected on monthly basis from 8 selected locations in 1-L airtight sampling bottles. All the water samples were analyzed immediately after collection of the samples in the Environmental Engineering Laboratory of Maharishi International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 43 Markandeshwar University, Mullana, Ambala, Haryana. All the water quality parameters (pH, EC, TDS, TH, Cl, SO2-, BOD and COD) were analyzed according to the standard methods16. The monitoring was made over a period of 8 months (August-November, 2013 and 2014), comprising of one session i.e. post-monsoon. All measurements were done in triplicates. Analytical reagent (AR) grade chemicals were used throughout the study without any further purification. Distilled water was used for experimental purpose. A comparison of water quality parameters of the Markanda river as observed with drinking water quality standards (Indian) was given in table-1. Results and Discussion pH: The pH values of the river water samples varied from minimum 7.09 at sampling station 1 to maximum 8.32 at sampling station 8 (table 1 and 2). The results shows that pH values of the river water collected from eight different sampling stations were found within the desirable permissible limit (6.5-8.5) of drinking water quality standards of BIS (table 1). Similar results were obtained in studying the effect of dye effluents on pH of river Kshipra, Ujjain City17. Statistical summary for pH in river water samples is presented in table-2. Electrical conductivity (EC): The EC values of the river water samples varied from minimum 0.30 mS/cm at sampling station 1 to maximum 0.6 mS/cm at sampling station 5 (table-1 and 2). The results shows that EC values of the river water collected from 8 different sampling stations were not satisfying the maximum permissible limit (0.3 mS/cm) of drinking water quality standards of BIS (table 2). Statistical summary for EC in river water samples is presented in table3. Total dissolved solids (TDS): The TDS content of the analysed river water samples varied from minimum 183 mg/l at sampling station 1 to maximum 330 mg/l at sampling station 5 (table-1 and 2). High content of dissolved solids affects the density of water, influences osmoregulation of freshwater organisms, hence reduces solubility of oxygen, and utility of water for drinking18. The results shows that TDS content of river water collected from eight different sampling stations were satisfying the prescribed limit (500 and 2000 mg/l) of drinking water quality standards of BIS (table-2). Statistical summary for TDS in river water samples is presented in table-3. Total hardness (TH): The total hardness content of river water samples varied from minimum 80 mg/l at sampling station 1 to maximum 410 mg/l at sampling station 6 (table-1 and 2). The results shows that total hardness content of river water collected from eight different sampling stations were within the prescribed maximum permissible limit (600 mg/l) of drinking water quality standards of BIS (table-2). Statistical summary for total hardness in river water samples is presented in table-3. Chloride (Cl): The chloride content of the analysed river water samples varied from minimum 7.9 mg/l at sampling station 1 to maximum 55.8 mg/l at sampling station 8 (table-1 and 2). The results shows that chloride content of river water collected from eight different sampling stations were within the prescribed limit (250 and 1000 mg/l) of drinking water quality standards of BIS (table-2). Statistical summary for Cl in river water samples is presented in table-3. Table-1 Water quality parameters (average) at different sampling stations of river Markanda Sample No pH EC TDS TH Cl SO2- BOD COD 1 7.09 0.30 183 80 7.9 8 2 9 2 7.94 0.37 221 248 21.7 14.7 10 64 3 8.08 0.39 235 155 13.5 16.5 8 75 4 8.19 0.33 199 392 30.9 10.6 10 50 5 7.45 0.60 330 290 15.8 12 6 45 6 7.55 0.31 192 410 27.5 7.0 13 90 7 8.19 0.35 210 304 32.4 28 5 48 8 8.32 0.46 282 375 55.8 11.5 4 40 International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 44 Sulphate (SO2-): The sulphate content of the analysed river water samples varied from minimum 7 mg/l at sampling station 6 to maximum 28 mg/l at sampling station 7 (table-1 and-2). The results shows that sulphate content of river water collected from eight different sampling stations were within the prescribed permissible limit (200 and 400 mg/l) of drinking water quality standards of BIS (table-2). Similar results were obtained in studying the sulphate content of river Kapila, Nanjangud, Karnataka19. Statistical summary for SO2- in river water samples is presented in table-3. Biological oxygen demand (BOD): The biological oxygen demand of the analysed river water samples varied from minimum 2 mg/l at sampling station 1 to maximum 13 mg/l at sampling station 6 (table-1 and 2). The results shows that BOD content of river water collected from eight different sampling stations were exceeding the prescribed limits (2 mg/l) of drinking water quality standards of BIS (table-2). Similar results were obtained in studying the BOD of river Ghataprabha, Belgaum, Karnataka20. Statistical summary for BOD in river water samples is presented in table 3. Chemical oxygen demand (COD): The chemical oxygen demand of the analysed river water samples varied from minimum 9 mg/l at sampling station 1 to maximum 90 mg/l at sampling station 6 (table-1 and 2). This indicates that pollution load in the river is due to untreated industrial effluents, agricultural runoff and sewage water entering into it from the surrounding areas. Increase in COD could be attributed to an increase in the addition of both organic and inorganic contaminant21. The results shows that COD content of river water collected from eight different sampling stations were exceeding the maximum limit (20 mg/l) of drinking water quality standards of WHO. Statistical summary for COD in river water samples is presented in table-3. Principal component analysis: PCA was performed on covariance correlation matrix data, such that the considered data set can be explained. Analyzing the results (table-5), the cumulative percent variance of PC1 and PC2 is more than 96% and from the third component the cumulative percentage variance is more than 99% therefore, PC1 and PC2 has taken for consideration. The loading values &#x-3.3;女0.75 signifies “strong”, the loading with values in between 0.5-0.75 indicate “moderate” while loading values between 0.3-0.50 denote as “weak”22. Using the above classification, two variables in each component (1 and 2) have strong positive loading. Considering the first two components, higher coefficient is observed for pH and total hardness (TH) with 0.7592 and 0.865 in PC1 and electrical conductivity (EC) and total dissolved solids (TDS) with 0.861 and 0.886 in PC2. The coefficients for chloride (Cl) with 0.717, BOD with 0.622, COD with 0.686 in PC1 and BOD with 0.598 in PC2 (negative sign is omitted) have moderate loading. The coefficients for other parameters are very less. Biplots of all the physico-chemical parameters are shown in figure-1. The six biplots of pH, EC, TDS, TH, Cl and SO2- are falling in the first i.e. positive coordinate (figure-1) which indicates similar trend will follow between them and the other two biplots i.e. BOD and COD are falling in the second coordinate (figure 1), which indicates similar trend will also follow between them.The group of water quality parameters (pH, EC, TDS, TH, Cl and SO2-) which are falling in the first coordinate will not affected by the parameters of second coordinate (BOD and COD) and vice-versa. Hence the quality of river water can be well differentiated by taking the six parameters having higher coefficients. Variables, with higher PC1 and PC2 values indicating that concerned parameters are responsible for development of poor water quality along all the sampling locations of river Markanda. The reason for poor water quality is probably due to disposal sewage and industrial effluents into the river without any treatment. Table-2 Comparison of average water quality parameters of river Markanda with drinking water quality standard (Bureau of Indian Standards) Parameters Observed Range of Samples Indian Standards (BIS) Minimum Maximum Desirable limit Maximum limit pH 7.09 8.32 6.5-8.5 No Relaxation EC (mS/cm) 0.03 0.60 - 0.3 TDS (mg/l) 183 330 500 2000 TH (mg/l) 80 375 300 600 Cl- (mg/l) 7.9 55.8 250 1000 SO2- (mg/l) 7.0 16.5 200 400 BOD (mg/l) 2 13 2 2 COD (mg/l) 9 90 - - International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 45 Table-3 Statistical analysis of physico-chemical parameters of Markanda river water pH EC TDS TH Cl SO2- BOD COD N 8 8 8 8 8 8 8 8 Min 7.09 0.3 183 80 7.9 7 2 9 Max 8.32 0.6 330 410 55.8 28 13 90 Mean 7.85 0.388 231.5 281.75 25.68 13.53 7.25 52.62 Std. error 0.154 0.035 17.83 41.35 5.27 2.34 1.29 8.63 Variance 0.191 0.0098 2543.71 13681.36 222.98 43.97 13.35 596.55 Stand. dev 0.437 0.099 50.43 116.96 14.93 6.63 3.65 24.42 25 prcntil 7.475 0.315 193.75 178.25 14.075 8.65 4.25 41.25 75 prcntil 8.19 0.442 270.25 387.75 32.02 16.05 10 72.25 Skewness -0.771 1.619 1.281 -0.715 1.103 1.675 0.155 -0.27 Kurtosis -0.718 2.604 0.925 -0.485 1.698 3.377 -0.85 0.755 Coeff. var 5.57 25.55 21.78 41.51 58.13 48.98 50.41 46.41 Table-4 Correlation matrixes among the physico-chemical characteristics of river waterpH EC TDS TH Cl SO2- BOD COD pH 1 EC 0.018 1 TDS 0.094 0.991 1 TH 0.469 0.114 0.147 1 Cl 0.698 0.094 0.194 0.732 1 SO2- 0.518 0.028 0.023 -0.062 0.117 1 BOD 0.163 -0.239 -0.253 0.517 -0.0067 -0.207 1 COD 0.304 -0.084 -0.07 0.437 0.069 0.048 0.873 1 International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 46 Table-5 Factor loading for Markanda river water qualityComponents Variables 1 2 3 4 5 6 7 8 pH 0.7592 0.214 -0.494 0.119 -0.308 -0.149 -0.029 0 EC 0.048 0.861 0.460 0.2 0.020 -0.044 0.006 0 TDS 0.105 0.886 0.420 0.151 -0.054 0.020 0.008 0 TH 0.865 0.066 0.16 -0.340 0.309 -0.080 -0.051 0 Cl 0.717 0.354 -0.305 -0.482 -0.037 0.167 0.057 0 SO2- 0.189 0.232 -0.673 0.623 0.259 0.016 0.022 0 BOD 0.622 -0.598 0.443 0.179 0.004 -0.137 0.074 0 COD 0.686 -0.410 0.351 0.428 -0.078 0.213 -0.038 0 Eigenvalue 13987.9 2495.95 491.62 89.6 36.27 0.821 0.026 0 % Variance 81.79 14.594 2.8746 0.52388 0.212 0.0048 0 0 Cumulative % Var. 81.79 96.384 99.286 99.995 99.999 100 100 100 Figure-1 Scatter plots of the principal component analysis of river water pH EC TDS TH Cl - SO 2 - BOD COD 1 2 3 4 5 6 7 8 - 4.8 - 3.6 - 2.4 - 1.2 1.2 2.4 3.6 4.8 Component 1 - 6.0 - 4.8 - 3.6 - 2.4 - 1.2 1.2 2.4 3.6 4.8 Component 2 International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. International Science Congress Association 47 Cluster analysis results: The cluster analysis results are illustrated in the hierarchical clustering dendrograms shown in figure-2. The cluster analysis results for the river water indicate that the physico-chemical parameters could be split into three main groups. The first group (cluster I) included EC and TDS; the second group (cluster II) included BOD and COD; and the third group (cluster III) included pH, TH, Cl and SO2- (figure 2). The cluster results indicate that three different factors were responsible for the development of the water quality in the Markanda river. EC and TDS (cluster I) have one source; BOD and COD (cluster II) are derived from another source; and pH, TH, Cl and SO2- (cluster III) are associated with other sources. Correlation matrix analysis: Water collected from River Yamuna and correlation matrix was used to know the correlationship between physico-chemical properties of river water23. Correlation matrix was prepared24 between eight different water quality parameters and is presented in table 4. The highest positive correlation is observed between electrical conductivity (EC) and total dissolved solids (TDS) with 0.991. There is also strong positive correlation exists between BOD and COD (0.873), total hardness and chloride (0.732), pH and chloride (0.698), pH and sulphate (0.518) and total hardness and BOD (0.517). Other physico-chemical parameters having insignificant positive as well as negative correlation (table 4). Conclusion This study assessed some physico-chemical properties of Markanda River from eight different locations, during the months of August to November 2013 and 2014. Based on the eight environmental parameters such as pH, electrical conductivity, total dissolved solids, total hardness, chloride, sulphate, biological oxygen demand and chemical oxygen demand for water quality, it was able to identify three main sources which are responsible for deteriorating the water quality of Markanda River at all the sampling stations. Water quality parameters like BOD and COD were exceeding the level of pollution. Therefore it is concluded that River Markanda is polluted and unsafe for human consumption. Overall, this study recommends identifying the pollution sources and monitoring the water quality parameters from time to time so that will help researcher to interpret data and implementation of remediation actions to protect the quality of the river water from deterioration. Similarity distance  \n \n \r Dendrogram with Ward's Linkage and Correlation Coefficient DistanceFigure-2 Cluster analysis based on physico-chemical characteristics of river water International Research Journal of Environment Sciences ______________________________________________ISSN 2319–1414Vol. 4(12), 42-48, December (2015) Int. Res. J. Environment Sci. 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