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Ecotoxicology and Environmental Safety 72 (2009) 301– 309

Ecotoxicology and Environmental Safety 72 (2009) 301– 309 Contents lists available at ScienceDirect Ecotoxicology

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

Safety journal homepage: www.elsevier.com /locate/ecoenv Assessment of water quality of polluted lake using

Assessment of water quality of polluted lake using multivariate statistical techniques: A case study

T.G. Kazi , M.B. Arain, M.K. Jamali, N. Jalbani, H.I. Afridi, R.A. Sarfraz, J.A. Baig, Abdul Q. Shah

Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan

article info

Article history:

Received 30 October 2007 Received in revised form 21 February 2008 Accepted 23 February 2008 Available online 18 April 2008

Keywords:

Physico-chemical parameters Water quality Cluster analysis Principal component analysis Manchar Lake (Pakistan)

abstract

Multivariate statistical techniques, cluster analysis (CA) and principal component analysis (PCA) were applied to the data on water quality of Manchar Lake (Pakistan), generated during 2005–06, with monitoring at five different sites for 36 parameters. This study evaluated and interpreted complex water quality data sets and apportioned of pollution sources to get better information about water quality and to design a monitoring network. The chemical correlations were observed by PCA, which were used to classify the samples by CA, based on the PCA scores. Three significant sampling locations (sites 1 and 2), (site 4) and (sites 3 and 5) were detected on the basis of similarity of their water quality. The results revealed that the major causes of water quality deterioration were related to inflow of effluent from industrial, domestic, agricultural and saline seeps into the lake at site 1 and also resulting from people living in boats and fishing at sites 2 and 3.

& 2008 Elsevier Inc. All rights reserved.

1. Introduction

Water quality is considered the main factor controlling health and the state of disease in both man and animals. Surface water quality in a region is largely determined both by natural processes (weathering and soil erosion) and by anthropogenic inputs (municipal and industrial wastewater discharge). The anthropo- genic discharges constitute a constant polluting source, whereas surface runoff is a seasonal phenomenon, largely affected by climate within the basin ( Singh et al., 2004 ; Vega et al., 1996 ). Niemi et al. (1990) reported human activities are a major factor determining the quality of the surface and groundwater through atmospheric pollution, effluent discharges, use of agricultural chemicals, eroded soils and land use. Environmental pollution, mainly of water sources, has become public interest. The under- developed countries have been suffering the impact of pollution due to disordered economic growth associated with the exploita- tion of natural resources. Large investigations have been carried out on anthropogenic contamination of ecosystems ( Szymanowska et al., 1999 ; Issa et al., 1996 ). However, due to spatial and temporal variations in water quality (which are often difficult to interpret), a monitoring

0147-6513/$ - see front matter & 2008 Elsevier Inc. All rights reserved. doi: 10.1016/j.ecoenv.2008.02.024

program, providing a representative and reliable estimation of the quality of surface waters, is necessary ( Dixon and Chiswell, 1996 ). These results are a large and complex data matrix comprised of a large number of physico-chemical parameters, which are often

difficult to interpret and to draw meaningful conclusions. The application of different multivariate statistical techniques, such as cluster analysis (CA), principal component analysis (PCA), factor analysis (FA) and discriminate analysis (DA), helps in the interpretation of complex data matrices for a better under- standing of water quality and ecological status of the study region. These techniques allow the identification of the possible sources that influence water systems and offers a valuable tool for reliable management of water resources as well as rapid solution for pollution problems ( Reghunath et al., 2002 ; Simeonov et al.,

2004 ).

In Pakistan, drinking water comes from groundwater and surface water including rivers, lakes and reservoirs. The present free style way of disposal of agricultural, industrial and domestic effluents into natural water bodies results in serious surface and groundwater contamination. Run-off from agricultural land and saline seeps subject the most vulnerable water bodies to pollution and increased salinity, so the freshwater lakes are highly impacted. One example for this is the Manchar Lake, Pakistan’s largest freshwater lake. It is the main source of domestic water for the communities living around the lake. Groundwater in this vicinity is saline and is not suitable for drinking ( WHO, 1998 ). The lake’s water in downstream areas is also important for farmers and fishermen, who depend on the lake for irrigation and fishery. As a result of extensive evaporation of water from the lake due to

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high temperature and low rain in this region, the increase of salts, heavy metals and other pollutants are responsible factors for the poor quality of the lake ecosystem. Until now there has been no systematic environmental study carried out for the Manchar Lake. So, there is no information available to enable us, to make valid comparison to the results of our study. The present study is a part of a comprehensive program conducted to evaluate the toxicological effects of contaminated water of Manchar Lake, which had caused up to 60 deaths, mostly of children in Hyderabad during 2004 ( Siddiq, 2004 ). The objective of the present study is to analyze the 36 physico–chemical parameters in water samples for 2 years (2005–06) from the polluted lake, collected on monthly basis. The large data set obtained was subjected to the PCA and CA multivariate techniques to evaluate information about the similarities and dissimilarities present among the different sampling sites, to identify water quality variables for spatial dissimilarity, and to ascertain the influence of the pollution sources on the water quality parameters.

2. Experimental

2.1. Sampling site

Manchar is the biggest shallow-water natural lake of Pakistan ( Fig. 1 ) situated at a distance of about 18 km from Sehwan Sharif, Jamshoro district, Sindh (26 1 3 0 N: 67 16 0 E). It is a vast natural depression flanked by the Khirthar hills in the west, the Laki hills in the south and the river Indus in the east. The mean depth of Manchar Lake is approximately 2.5–3.75 m and it covers an area of

233 km 2 . Flood barriers were constructed in 1932 from its northern and northeastern boundaries. The human activities have been changing significantly the original regime of the lake over the last 50 years. The most important activities are construction and enlargement of the artificial channels linking the river to the lake and the construction of flood embankments to the north. The Main Nara Valley Drain (MNVD), brings agricultural, municipal, industrial and saline water, constitutes a constant polluting sources for the lake, whereas surface runoff is a seasonal phenomenon, and it has not been significant due to dry seasons in 2000–05.

2.2. Sample collection and pre-treatment

The sampling network was designed to cover a wide range of determinates of key sites, which reasonably represent the water quality of the lake system, accounting for the tributary and inputs from wastewater drains that have impact on the water quality ( Fig. 1 ). The first site is located in the area of entering main effluents from MNVD. Sites 2 and 3 which are located at the downstream side of lake, where mostly the boating occurs for fishing and local domestic waste also drains to this site as shown in Fig. 1. Site 3 has an outlet of lake water via canal, providing water to agricultural lands. Site 4 is near the hilly area from where mostly fresh water enters into the lake during rainy season. Site 5 is connected to Indus River and has dual aspects, for supply of fresh water when water is available in the Indus River and also as an output of lake water when the level of the Indus River is low. The samples were collected from 8:00 AM to 1:00 PM during the 2-year study. Water samples were collected using open water grab sampler (1.5 L capacity) equipped with a simple pull-ring

using open water grab sampler (1.5 L capacity) equipped with a simple pull-ring Fig. 1. Map

Fig. 1. Map of Manchar Lake and Pakistan.

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that allowed for sampling at various water depths (0–6 in and 4 24 in), from 5 to 7 sites of same station randomly. To evaluate the lake water quality, water samples were kept in a 2 L polyethylene plastic bottles cleaned with metal free soap, rinsed many times with distilled water and finally soaked in 10% nitric acid for 24 h, finally rinsed with ultrapure water. All water samples were stored in insulated cooler containing ice and delivered on the same day to laboratory and all samples were kept at 4 1 C until processing and analysis ( Clesceri et al., 1998 ).

2.3. Chemicals and reagents

Ultrapure water obtained from ELGA lab water system (Bucks, UK) was used throughout the work. All chemicals and reagents were analytical grade, Merck (Darmstadt, Germany) and were checked for possible trace metal contamination. Standard solu- tions of all 16 elements were prepared by dilution of 1000 ppm certified standard solutions, Fluka Kamica (Buchs, Switzerland) of corresponding metal ions. Argon gas with 99.99% purity, used as sheath gas for the atomizer and for internal purge.

2.4. Analytical procedure

Water quality parameters, their units and methods of analysis are summarized in Table 1. The temperature, pH, electrical conductivity (EC), salinity and DO of each water sample were measured at the sampling points by a mercury thermometer, digital pH, EC and DO meter, respectively. In laboratory the duplicate aqueous samples of about 1000 ml of each batch collected from five sampling sites, were filtered through poly- carbonate filter (0.45 mm pore size) and the samples were divided into two parts. One part was used for analysis of anions and physico-chemical parameters, while second part treated with 2 ml of concentrated HNO 3 for metal analysis. All water samples were analyzed for different physico-chemical parameters within 48 h, COD determined on the same sampling day while BOD have done promptly to avoid no changes in bacterial concentration. TS, TDS and TSS were determined gravimetrically at 105–110 1 C. Total hardness and Ca hardness were measured by EDTA complexo- metry titration, the indicators are Eriochrome Black T and Murexide at pH 10 and 12, respectively ( Eaton et al., 1995 ). Total alkalinity determined by acid titration using methyl-orange as endpoint and chloride by silver nitrate (AgNO 3 ) titration, using potassium chromate (K 2 CrO 4 ) solution as an indicator. The BOD 5 was determined by the Winkler azide method and COD by the dichromate reflux method. PO 4 -P was measured by molybdate- ascorbic acid method, SO 4 was determined spectrophotometri- cally by barium sulfate turbidity method, NH 4 -N measured with Nessler’s reagent and total nitrogen was determined by Kjeldahl’s method ( Clesceri et al., 1998 ; AOAC, 1995 ). NO 3 -N and NO 2 -N were analyzed by brucine and diazotization methods, respectively ( Kazi and Katz, 1987 ). Fluoride was measured using ion selective electrode ( Clesceri et al., 1998 ). The acid-treated water samples were analyzed for the deter- mination of major cations by further 20-time dilution with ultrapure water, Ca, Na and K were measured by flame photo- metry, while Mg was determined by the flame atomic absorption spectrometer (FAAS). For trace and toxic elements, the volume of water samples was reduced four-fold at 60 1 C on an electric hot plate. Cu, Fe and Zn were determined by FAAS using an acetylene- air flame, while Al was determined by acetylene-nitrous oxide flame. Cd, Co, Cr, Mn, Ni and Pb were analyzed using electro- thermal atomic absorption spectrometer (ETAAS), while As and Se were determined using hydride generation method (HGAAS). The quality of the analytical data was ensured through careful

Table 1 Water quality parameters associated with their abbreviations, units and analytical methods used

Variables

Abbreviations Units

Analytical methods

PH Electrical conductivity Salinity Total solids Total dissolved solids Total suspended solids Total hardness Calcium hardness Dissolved oxygen

pH

pH unit pH-meter

EC

mS/cm

Electrometric Electrometric Gravimetric Gravimetric Gravimetric Titrimetric Titrimetric Prob metod Winklar azide method Dichromate method Ion selective electrode Titrimetric Titrimetric

Salinity

%

TS

mg/L

TDS

mg/L

TSS

mg/L

T-Hard

mg/L

Ca-Hard

mg/L

DO

mg/L

Biochemical oxygen demand BOD

mg/L

Chemical oxygen demand Fluoride Chloride Total alkalinity Phosphate Sulphate Nitrite nitrogen Ammonical nitrogen Total kjeldahl nitrogen Nitrate nitrogen Sodium Potassium Calcium Magnesium Iron Aluminum Cadmium Lead Arsenic Chromium Nickel Cobalt Copper Manganese Zinc Selenium

COD F Cl T-Alk PO 4 SO 4 NO 2 -N NH 4 -N TKN NO 3 -N Na K Ca Mg Fe Al Cd Pb As Cr Ni Co Cu Mn Zn Se

mg/L

mg/L

mg/L

mg/L

mg/L

Spectrophotometric Spectrophotometric Spectrophotometric Spectrophotometric Titrimetric Spectrophotometric Flame photometer Flame photometer Flame photometer FAAS FAAS FAAS ETAAS ETAAS Hydride generation AAS ETAAS ETAAS ETAAS FAAS ETAAS FAAS Hydride generation AAS

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

m g/L

m g/L

m g/L

m g/L

m g/L

m g/L

m g/L

mg/L

mg/L

m g/L

standardization, procedural blank measurements and triplicate samples. The ionic balance of each sample was within 7 5%.

2.5. Data treatment by statistical method

All mathematical and statistical computations were made using Excel 2003 (Microsoft Office s ) and STATISTICA 6 (StatSoft, Inc. s ). Multivariate analysis of the lake water quality data set was performed through principal component and cluster analysis techniques ( Liu et al., 2003 ).

2.5.1. Principal components analysis (PCA)

PCA is designed to convert the original variables into new, uncorrelated variables (axes), called the principal components, which are linear combinations of the original variables. The new axes lie along the directions of maximum variance. PCA provides an objective way of finding indices of this type so that the variation in the data can be accounted for as concisely as possible ( Sarbu and Pop, 2005 ). PCA provides information on the most meaningful parameters which describe the whole data set interpretation, data reduction and to summarize the statistical correlation among constituent in the water with minimum loss of original information ( Helena et al., 2000 ).

2.5.2. Cluster analysis (CA)

The CA technique is an unsupervised classification procedure that involves measuring either the distance or the similarity

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between the objects to be clustered. The resulting clusters of objects should then exhibit high internal (within cluster) homogeneity and high external (between clusters) heterogeneity. Hierarchical agglomerative clustering is the most common approach, which provides instinctive similarity relationships between any one sample and the entire data set, and is typically illustrated by a dendrogram (tree diagram) ( McKenna, 2003 ). The dendrogram provides a visual summary of the clustering processes, presenting a picture of the groups and their proximity, with a dramatic reduction in dimensionality of the original data. The Euclidean distance usually gives the similarity between two samples and a distance can be represented by the difference between analytical values from the samples ( Otto, 1998 ). In this study, hierarchical agglomerative CA was performed on the normalized data set by means of the Ward’s method, using squared Euclidean distances as a measure of similarity. In this research work PCA was applied to summarize the statistical correlation among components in the water samples. Concentration order among all physico-chemical parameters differ greatly and the statistical results should be highly biased by any parameter with high concentration. Therefore standardiza- tion ( z -scale) was made on each chemical prior to the statistical analysis ( Simeonov et al., 2004 ). Standardization tends to minimize the influence of difference on variance of variables and eliminates the influence of different units of measurements and renders the data dimensionless. The calculation was performed based on the correlation matrix of chemical compo- nents and the PCA scores were obtained from the standardized analytical data. Cluster analysis was applied to detect spatial similarity for grouping of sites under the monitoring network.

3. Results

The basic statistics of lake water quality are based on 2160 total water samples (5 sampling sites 3 replications 6 sampling frequency 24 months) are summarized in Table 2 , which gives the range, mean and the standard deviation of the results for each of the 36 parameters. The sampling sites were the grouping (dependent) variables, while all the measured parameters constituted the independent variables. The result of the PCA base on the correlation matrix of chemical compo- nents is expressed in Table 3 , and station wise shown in Fig. 2 . Three components of PCA analysis showed 97.6% of the variance in the data set of lake water. The eigenvectors classified the 36 physico-chemical parameters into three groups: in the first component all physico-chemical parameters, major, trace and toxic elements in lake water; the second component is loaded with trace and toxic metals while the third component shows TSS, major cations, TKN, NO 3 , NH 4 , PO 4 , Fe, Al, Cd, Pb, Cr, Co and Zn. Cluster analysis was applied on lake water quality data, to detect spatial similarity and dissimilarity for grouping of sampling sites (spatial variability) spread over the lake stretch. The resulted dendogram ( Fig. 3 ), grouped all the five sampling sites into three statistically significant clusters, as sites (1–2) and (3–5) have low mutual dissimilarities as compared to site 4 has 28% of total dissimilarity. The analytical data set was standardized in order to compare the aspects of the variation of each physico-chemical parameters on different sampling sites as shown in Fig. 4 . The TDS and EC during the annual season cycle showed no significant variations, presenting averages for all sampling sites. The range of TDS and conductivity in lake water was found in the range of 3580–4440 mg/L and 5.01–6.22 mS/cm, respectively. The major ions, F, Cl, NO 3 , SO 4 , PO 4 , Na, Ca, Mg and K were higher than their concentrations in several surface water bodies in the world

( Silva and Rezende, 2002 ). The range of Na was found in all the sampling site as 262–805 mg/L. The level of Fe and Al were found in the range of 1.52–7.21 and 0.91–4.27 mg/L, respectively, corresponding to 10–20-folds higher than WHO recommended values for drinking water. High concentrations of toxic elements (As, Cd and Pb), which were detected in 100% of the samples, ranged 35.0–171, 2.4–12.1, and 39.0–172 m g/L, respectively. The total phosphate and nitrogen values were found in the range of 0.262–0.719 and 44.9–128 mg/L, respectively, in lake water samples. Chloride concentrations ranged in all water samples found as 886–2210 mg/L. Low DO values, in the range of 2.5–7.4 mg/L, were found while high levels of COD and BOD were observed in all study sites. The range in BOD and COD of water samples collected from all sites were found to be 37.1–104.8 and 79–208 mg/L, respectively.

4. Discussion

4.1. Spatial similarity and site grouping

Principal component analysis was applied to the normalized data sets (36 variables) separately for the five different sampling sites and demarcated by the CA technique to compare the compositional patterns among the analyzed water samples and to identify the factors that influence each one. The first component (PC1) accounted for over 78.6% of the total variance in the data set of the lake water, in other words, the physical parameters, major cations, anions and heavy metals in the solution demonstrate similar behavior in the lake water samples ( Table 3 ). In a macroscopic point of view all the physico-chemical parameters behave similarly, i.e. high concentration of major elements as well as toxic metals in main body of whole lake except minor change at site 4, where the slight variation in pollution loading has some temporal effects. We have already mentioned that the wet season in this area is very short, and has little effect on values of variables at this site. The strong positive loading on BOD and COD were observed, whereas, a negative loading on DO. It is, thus, a group of purely organic pollution indicator parameters. This also suggests that the anthropogenic pollution, which is the major lake pollution problem, is mainly due to the discharge of wastewater as a regular source, through- out the year. The trend obtained was also supported by the analysis of the results on the raw data set. The second component (PC2), explaining 16.4% of the total variance has strong positive loadings for trace and toxic metals, thus basically represents the metals of pollution group. The third component (PC3) of PCA shows only 2.5% of the total variation has positive loading of major cations. The high values of Fe, Al and Pb are above the permissible limit of WHO values for drinking water ( WHO, 2004 ). The result of CA base on the PCA scores is shown in Fig. 3 . The dendogram clarifies the abnormality of the sampling sites 1 and 2, which make one group as cluster 1, which receive polluted effluents from non-point sources, i.e., from agricultural, industrial and domestic activities via MNVD as shown in Fig. 1. Besides cluster 1, the mutual dissimilarity among other sites made as cluster 2 (site 4) and cluster 3 (sites 3 and 5) correspond to relatively high pollution, low pollution and moderate pollution regions, respectively. It implies that for rapid assessment of water quality, only one site in each cluster may serve as good in spatial assessment of the water quality as the whole network. It is evident that the CA technique is useful in offering reliable classification of surface waters in the whole region and will make possible to adequately serve for spatial assessment in an optimal manner. Thus, the number of sampling sites and cost in the monitoring network will be reduced without loosing any

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Table 2 Range, mean and standard deviation (Std.) of water quality parameters at different sites of Lake Manchar during 2005– 06

 

Parameters

WHO limits

St1

St2

St3

St4

St5

pH

6.5– 8.5

Range

7.9– 8.7

7.4– 8.7

7.6– 8.7

8.0– 8.9

7.4– 8.7

 

Mean

8.08

8.02

8.17

8.35

8.10

Std.

0.18

0.24

0.26

0.20

0.27

EC

(mS/cm)

1.5

Range

4.7– 10.8

4.60– 9.60

4.11– 9.21

3.87– 9.00

4.11– 9.05

 

Mean

6.22

5.97

5.58

5.01

5.47

Std.

1.37

1.23

1.53

1.12

1.09

Salinity (%)

0.1

Range

0.301– 0.656

0.276– 0.615

0.26– 0.60

0.202– 0.500

0.250– 0.562

 

Mean

0.386

0.366

0.351

0.298

0.334

Std.

0.080

0.079

0.094

0.071

0.071

TS

(mg/L)

Range

4300– 9742

4088– 9128

4074– 8811

3319– 7813

3755– 7620

 

Mean

5753

5489

5293

4630

5027

Std.

1274

1161

1485

1066

1017

TDS (mg/L)

1000

Range

3362– 7136

3224– 7269

2978– 6435

2778– 5738

2822– 6422

 

Mean

4440

4237

4057

3579

3842

Std.

941

951

1021

750

855

TSS (mg/L)

Range

878.5– 2606

863.9-1859

716.9-2376

468.9– 2246

622.7– 1939

 

Mean

1113

1035.1

1052

850.9

985.2

Std.

371

271

531

410

311

Ca-Hard (mg/L)

100

Range

517.8– 1107

465.2– 1094

449.5– 1080

394.0– 910.4

437.4– 975.2

 

Mean

667.1

638.8

620.1

535.9

589.6

Std.

139

137

176

115

134

DO (mg/L)

Range

2.4– 5.4

3.4– 6.5

2.5– 6.8

4.8– 7.4

3.5– 7.2

 

Mean

3.7

3.9

4.3

5.2

4.7

Std.

0.87

0.62

1.33

0.76

1.25

BOD (mg/L)

6

Range

41.4– 92.03

45.9– 104.8

41.9– 100.2

37.1– 81.17

41.6– 97.93

 

Mean

58.44

64.08

61.46

50.75

56.49

Std.

15.53

13.55

13.86

11.55

14.17

COD (mg/L)

10

Range

100.1– 208.6

97.5– 196.9

93.7– 202.7

79.7– 178.3

84.5– 190.1

 

Mean

131.4

120.9

125.3

106.2

115.2

Std.

26.70

28.63

26.92

23.69

24.88

F (mg/L)

1.5

Range

0.55– 1.14

0.516– 1.084

0.50– 1.06

0.46– 0.92

0.47– 1.00

 

Mean

0.71

0.68

0.66

0.57

0.62

Std.

0.14

0.14

0.17

0.12

0.13

Cl

(mg/L)

250

Range

1055– 2210

999.9– 2097

925.6– 2089

885.9– 1759

954.7– 2006

 

Mean

1410

1333

1285

1128

1223

Std.

279.6

272.2

334.6

220.7

262.2

T-Alk (mg/L)

200

Range

132.7– 306.9

122.5– 294.9

117.2– 268.5

100.6– 236.0

119.5– 268.3

 

Mean

179.7

171.2

156.7

141.1

157.4

Std

40.40

39.04

58.74

31.67

34.39

PO

4 (mg/L)

Range

0.352– 0.716

0.322– 0.719

0.270– 0.694

0.277– 0.645

0.262– 0.601

 

Mean

0.52

0.50

0.48

0.46

0.42

Std.

0.11

0.11

0.14

0.10

0.09

SO

4 (mg/L)

250

Range

144.9– 313.1

139.0– 288.09

24.78– 288.8

118.2– 245.5

125.6– 271.9

 

Mean

186.1

176.70

162.2

150.4

162.2

Std.

38.7

37.4

63.50

33.97

35.55

NO

2 -N (mg/L)

3

Range

2.41– 5.50

2.28– 5.11

2.37– 4.84

2.01– 4.21

2.11– 4.66

 

Mean

3.37

3.22

3.09

2.68

2.92

Std.

0.75

0.71

0.78

0.58

0.65

NH

4 -N (mg/L)

Range

5.85– 13.22

5.57– 12.6

5.48– 12.10

4.77– 10.36

5.36– 12.46

 

Mean

8.48

8.04

7.82

6.82

7.35

Std.

1.7

1.7

2.1

1.4

1.7

TKN (mg/L)

Range

58.7– 128.1

44.9– 117.5

55.5– 120.1

52.2– 105.4

52.7– 111.2

 

Mean

94.2

86.7

89.3

74.7

81.2

Std.

21.5

27.5

20.9

16.7

18.2

NO

3 -N (mg/L)

50

Range

5.03– 12.7

5.31– 11.3

5.59– 13.0

4.46– 11.0

4.72– 11.4

 

Mean

8.4

8.2

8.8

7.2

7.6

Std.

1.9

2.1

1.9

1.6

1.7

Na (mg/L)

200

Range

355.2– 804.7

327.2– 760.4

316.2– 758.3

262.4– 625.2

306.1– 720.8

 

Mean

474.5

51.9

433.6

381.1

418.4

Std.

109

108

136

93.8

100

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Table 2 ( continued )

 

Parameters

WHO limits

St1

St2

St3

St4

St5

K (mg/L)

12

Range

18.1–41.2

17.1–39.2

17.8–35.7

14.5–33.1

15.2–36.9

 

Mean

23.9

22.5

21.6

18.9

20.5

Std.

5.1

4.7

5.2

4.3

4.6

Ca (mg/L)

100

Range

181–382

171–377

172–373

143–314

152–370

 

Mean

245.5

234.9

228.3

197.1

217.0

Std.

50.9

49.5

65.9

41.3

49.7

Mg (mg/L)

50

Range

129.1–291.0

119.1–268.6

120.0–280.0

106.8–257.9

105.6–248.7

 

Mean

167.2

157.7

154.3

134.0

145.6

Std.

38.8

35.7

48.5

32.5

33.0

Fe (mg/L)

0.3

Range

1.68–6.88

1.71–5.52

1.58–6.25

1.52–7.21

1.59–5.28

 

Mean

3.4

3.0

2.8

3.0

2.6

Std

1.7

1.2

1.3

1.7

1.3

Al (mg/L)

0.2

Range

1.01–4.27

0.91–3.86

0.967–4.06

1.06–3.92

0.931–3.83

 

Mean

2.1

1.92

1.87

2.01

1.93

Std.

1.1

0.93

0.96

0.96

0.95

Cd ( m g/L)

3

Range

2.90–11.8

2.7–12.1

2.8–1.2

2.6–9.1

2.4–8.7

 

Mean

5.8

5.3

5.3

5.0

5.1

Std.

3.1

2.7

2.9

2.2

2.1

Pb ( m g/L)

10

Range

43.1–172.2

43.7–171.2

39.2–170.7

40.4–161.4

43.7–142.2

 

Mean

89.4

82.3

82.0

81.2

77.2

Std.

46

43

44

41

34

As ( m g/L)

10

Range

43.2–171

35.4–150

42.7–140

42.1–158

39.3–141

 

Mean

86.1

83.8

77.4

80.2

76.5

Std

47

38

34

38

34

Cr ( m g/L)

50

Range

4.2–16.1

4.4–15.4

4.3–15.7

4.1–16.4

3.2–16.2

 

Mean

8.2

7.8

7.4

7.7

7.1

Std.

4.0

3.7

4.2

3.2

3.4

Ni (m g/L)

20

Range

20.2–76.4

15.1–58.5

17.2–67.4

15.2–61.5

17.1–58.5

 

Mean

38.1

36.0

33.4

34.6

32.7

Std.

18.1

15.2

16.2

15.2

14.1

Co ( m g/L)

40

Range

23.0–88.0

19.0–84.0

17.0–77.0

19.0–73.0

21.0–64.0

 

Mean

42.97

39.32

38.30

38.03

36.06

Std.

21.4

21.2

17.4

17.2

14.8

Cu ( m g/L)

2000

Range

11.2–40.2

11.6–36.1

9.4–40.6

9.1–36.3

8.2–38.4

 

Mean

21.1

19.2

17.2

18.7

18.3

Std.

10.2

8.74

10.4

9.24

10.1

Mn ( m g/L)

100

Range

34.0–151.0

3.0–143.0

35.0–141.0

32.0–137.0

29.0–131.0

 

Mean

77.0

75.3

70.1

72.1

68.3

Std.

40.2

38.2

35.4

33.2

36.5

Zn ( m g/L)

10

Range

377–1387

396–1580

340–1390

364–1455

361–4240

 

Mean

788

731

711

721

701

Std.

300

415

335

356

338

Se (m g/L)

10

Range

32.7–118

32.7–92.4

30.6–77.2

32.7–82.4

30.6–74.5

 

Mean

81.2

62.2

38.5

43.4

38.5

Std.

10.4

10.4

10.2

9.1

8.6

significance of the outcome. The same aspects are also reported by other researchers ( Simeonov et al., 2004 ; Kim et al., 2005 ).

4.2. Chemistry of lake water

The minimum and maximum values of all physico-chemical

parameters of water samples collected from five sampling sites are presented in Table 2 , the results are compared to the values of World Health recommended maximum permissible limits ( WHO,

2004

).

4.2.1.

Physical parameters

Air and water temperatures showed a very characteristic annual cycle, with higher values during the summer (30–49 1 C),

and lower values in the winter season (12–28 1 C). The pH values of collected water samples were within those defined by WHO guidelines of 6.5–8.5 ( WHO, 2004 ). The high level of EC, due to significant amount of dissolved salt, was observed in all sites of lake under study. The annual rainfall in this basin is as little as o 100 mm, so very little variation was obtained in values of conductivity in the rainy season. High conductivity in dry season represents water with high electrolyte concentration due to evaporation. The EC values exceeding the WHO (2004) guidelines ( Table 2 ) for drinking water, the 12–15- folds higher EC is attributed to the high salinity and high mineral content in all sampling sites. It also corresponds to the highest concentrations of dominant ions, which are the result of ion exchange and solubilisation in the aquifer ( Sanchez-Perez and Tremolieres, 2003 ). The high level of major cations (Na, Ca and

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Table 3 Eigenvector and eigenvalues on the correlation matrixes of concentration of physico-chemical parameters in Lake Manchar

Parameters

PC1

PC2

PC3

EC

0.188

0.065

0.191

Salinity

0.186

0.112

0.071

TS

0.188

0.096

0.047

TDS

0.190

0.076

0.051

TSS

0.172

0.180

0.089

T-Hard

0.189

0.087

0.066

Ca-Hard

0.185

0.124

0.046

DO

0.024

0.312

0.248

BOD

0.120

0.283

0.205

COD

0.176

0.137

0.262

F

0 .18 6

0.114

0.036

Cl

0.190

0.081

0.033

T-Alk

0.185

0.051

0.264

PO 4

0.169

0.088

0.199

SO 4

0.188

0.009

0.239

NO 2 -N NH 4 -N

0.188

0.096

0.065

0.189

0.092

0.006

TKN

0.178

0.133

0.237

NO 3 -N

0.132

0.259

0.420

Na

0.186

0.107

0.063

K

0 .19 0

0.078

0.039

Ca

0.184

0.125

0.041

Mg

0.188

0.100

0.019

Fe

0.145

0.276

0.075

Al

0.098

0.327

0.113

Cd

0.183

0.100

0.220

Pb

0.166

0.173

0.336

As

0.152

0.231

0.202

Cr

0.142

0.260

0.106

Ni

0.157

0.239

0.069

Co

0.170

0.179

0.219

Cu

0.135

0.268

0.262

Mn

0.152

0.223

0.143

Zn

0.162

0.223

0.118

Se

0.172

0.182

0.169

Eigenvalue

26.742

5.566

0.871

Variability (%)

78.653

16.370

2.563

Cumulative %

78.653

95.023

97.586

10 5 Site 4 Site 1 0 Site 2 Site 5 Site 3 -5 -10
10
5
Site 4
Site 1
0
Site 2
Site 5
Site
3
-5
-10
-5
0
5
10
PC2 (16.37 %)

PC1 (78.65 %)

Fig. 2. Scores of the first two principal components (PC1 and PC2) PC1 and PC2 explained 95.02% of the total variance.

Mg) and concentration of major anions Cl and SO 4 in lake water increase EC, is consistent with other study ( Zacheus and Martikainen, 1997 ). Alkalinity values varied between 0.20% and 0.66% among all sampling sites. This variation is similar to that for the variation of values of EC in under study water samples. A similar relationship was reported by Thomaz et al. (1992) for the Varzea Lake, Brazil.

90 80 70 60 50 40 30 20 10 0 Dissimilarity Site 1 Site 2
90
80
70
60
50
40
30
20
10
0
Dissimilarity
Site 1
Site 2
Site 4
Site 3
Site 5

Fig. 3. Dendogram for cluster analysis based on the PCA score. The dissimilarity defined by Euclidean distance and the combination of cluster is based on Ward method.

The monitoring of oxygen concentration in aquatic system is an important subject ( Galal-Gorchev et al., 1993 ), as the biological, chemical and physical processes involved in the increase or decrease of oxygen in lake are so numerous and complex that there is no model that can be used without a careful analysis of local characteristics. The highest value of COD was recorded at the sampling site 1 and lowest at sites 4 and 5. COD is widely used for determining waste concentration and is applied primarily to pollutant mixtures such as domestic sewage, agricultural and industrial waste. In the case of BOD, the higher values were observed at sites 2 and 3, due to local anthropogenic pollution produced by people who lived in boats day and night for fishing, and also addition of local domestic waste at this site. Total nitrogen and phosphate concentrations ( Table 2 ) varied greatly as a result of lake water contamination resulting from domestic wastage and agricultural sources from the upstream agricultural areas where frequent use of the phosphate and nitrogen fertilizers are common. Our results are also consistent with those of the study on the Tiete River, which contains high values of nitrogen due to anthropogenic activities such as fertilizer usage, organic pollutants releases and discharge of water from domestic sources ( Silva et al., 1999 ). The higher values of chloride in water samples exceeded the WHO proposed drinking water quality criteria ( WHO, 2004 ). According to Versari et al. (2002) , chloride concentrations higher than 200 mg/L are considered to be a risk for human health and may cause unpleasant taste of water.

4.2.2. Dissolved metals in lake

The mean concentrations of elements in water samples

collected in 2005–06 are presented in Table 2 . The average levels showed that concentrations of major, trace and toxic elements due to anthropogenic contamination (domestic, industrial and agri- cultural wastes) in water do not vary among sampling sites. The trend obtained was also supported by the analysis of the results on the raw data of water samples. Among the 16 elements determined in Manchar Lake water except Cu, Cr, Co and Mn, other elements (Na, K, Ca, Mg, Fe, Al, Ni, As, Se, Pb and Cd) have higher values as compared to the permissible level of these elements in drinking water ( WHO, 2004 ). These values of elements indicate that deterioration of the lake is mainly due to the input of agricultural and domestic waste. Metals generally had uniform distribution in all samples, and there was little seasonal variability. In the summer season at sampling site 4, there was a low level of elements due to dilution

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TDS BOD COD Alkalinity TKN 2 1 0 -1 -2 Site 1 Site 2 Site
TDS
BOD
COD
Alkalinity
TKN
2
1
0
-1
-2
Site 1
Site 2
Site 3
Site 4
Site 5
Na
K
Ca
Mg
Fe
Al
Standard Units
2 1 0 -1 -2 Standard Units
2
1
0
-1
-2
Standard Units
Site 1 Site 2 Site 3 Site 4 Site 5 Cd Pb As Se 2
Site 1
Site 2
Site 3
Site 4
Site 5
Cd
Pb
As
Se
2
1
0
-1
-2
Site 1
Site 2
Site 3
Site 4
Site 5
Standard Units

Fig 4. Standard unit of chemical concentrations in water of the lake Manchar. The standard units is defined as z ¼ ( x u )/ S , where x is the raw concentrated data, u is the mean values and S is the standard deviation. (a) TDS, BOD, COD, Alkalinity and TKN (b) Major cations, (c) trace and toxic metals.

by entering of fresh water from large hills due to rainy season. The high level of Na was due to drainage from lands cultivated with rice and many salt seeps present in the upper basin tributaries that result in salt loading through MNVD (site 1) in the lake. The water of lake is frequently used for drinking by humans as well as animals, because the people have no other resources of drinking water. It has been reported that high consumption of salts, particularly NaCl, may be crucial for the development of hypertension and increases the risk for stroke, left ventricular hypertrophy, osteoporosis, renal stones and asthma. This study is consistent with other study that people residing in these localities have frequent renal stones and asthmatic problems ( McCarthy, 2004 ). The concentrations of Al and Fe were found to be very high in water samples collected from different sampling sites. The high level of Fe in lake water samples are mainly due to the inflow of surface run off from hill torrents and agricultural wastes (agricultural and rocks), both are rich in Al and Fe. The low level

of dissolved oxygen in understudy lake water was strongly correlated with the high Fe 2+ concentrations in water samples ( Barreto et al., 2005 ). The results of iron are also consistent with other studies on river water has Fe concentration in the range of 1.8–5.06 mg/L ( Da Silva and Sacoman, 2001 ). Exchangeable Fe usually relates to the adsorbed metals on the sediment surface can be easily remobilized into the Lake water ( Ikem et al., 2003 ). The major adverse effects of elevated concentrations of Fe are associated with aesthetic nuisances such as staining of laundry, unpleasant odor and taste. Some studies have found a significant relationship between the exposure to Al in water and an increased risk of Alzheimer’s disease ( Gardner and Gunn, 1991 ). Prolonged exposure to Al, however, can cause systemic toxicity, mainly affecting the gastrointestinal tract and causing neurological and skeletal effects. The poisoning of Al in patients with chronic renal failure is also the most important clinical problems involving trace metal toxicity ( Forbes and Hill, 1998 ). The concentration of As detected in all water samples were 3–15-fold higher than the permissible limit of As in drinking water (10 m g/L). The main adverse health effects of As are tracheae bronchitis, rhinitis, pharyngitis, shortness of breath and nasal congestions ( Xia and Liu, 2004 ). Similarly, contamination of drinking water from As may also result in blackfoot disease ( Liu et al., 2003 ; Tsai et al., 1998 ). The levels of Pb were found to be higher during 2-year lake water analyses, which are mostly higher than permissible limit of drinking water by WHO guidelines, indicating pollution in this lake. Adverse health effects of Pb include various cancers, adverse reproductive outcomes, cardiovascular and neurological diseases ( Watt et al., 2000 ). Elevated concentrations of Cd can cause nausea, vomiting, salivation and renal failure as well as kidney, liver and blood damages ( Ikem et al., 2002 ) suggested that high concentrations of Cd may even cause mutations.

4.3. Overview of the physico-chemical parameters of lake water

The data of the physico-chemical parameters were trans- formed into standard unit ( z ) to compare the aspects of the variation in water samples collected from different sites as shown in Fig. 4 . Among the normalized data, except for BOD, all other parameters were found to be very high at sampling site 1, showing high pollution at this site; it is the main contributing source of pollution in the lake ( Fig. 4 a). The normalized concentrations for all the physico-chemical parameters are almost equivalent to their mean values above one standard deviation (1s). All physico- chemical parameters show low normalized values at site 4 and 5 (below 0), whereas the values of these parameters are ( o 1s) at sites 2 and 3 ( Fig. 4 b). Se and As have similar behavior at sites 1 and 2, while other toxic metals (Pb, Cd) show moderate variations at sites 2 and 3 ( Fig. 4 c).

5. Conclusion

In this study, different multivariate statistical techniques were used to evaluate variations in surface water quality of the Manchar Lake. Cluster analysis grouped five sampling sites into three clusters of similar water quality characteristics. Based on obtained information, it is possible to design a future, optimal sampling strategy, which could reduce the number of sampling sites and associated cost. Principle component analysis helped in identifying the factors or sources responsible for water quality variations. The main cause of degradation of the lake is the discharge of industrial, agricultural wastes and of municipal sewage water from the upper northern areas of Sindh, coming through MNVD (site 1). Fishing and boating activities were also

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among the major sources responsible for lake water quality deterioration. This study illustrates the usefulness of multivariate statistical techniques for the analysis and interpretation of com- plex data sets, identification of pollution sources and under- standing variations in water quality for effective lake water management. The chemometric study enabled us to show similarities and differences among the lakes examined among variables that were not clearly visible from an examination of the analytical data in the tables. Interventions should be made to reduce anthropogenic discharges in the Lake basin; otherwise, high levels of pollution will greatly influence the population and will invite socio–economic disaster. These results should be considered for future planning in using the lake’s water for drinking purposes.

Acknowledgment

The authors would like to thank the financial support from Higher Education Commission of Pakistan.

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