ARTICLE IN PRESS

Ecotoxicology and Environmental Safety 72 (2009) 301 309

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

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

a r t i c l e in fo

abstract

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

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 200506, with
monitoring at ve 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 signicant 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 inow of efuent from
industrial, domestic, agricultural and saline seeps into the lake at site 1 and also resulting from people
living in boats and shing at sites 2 and 3.
& 2008 Elsevier Inc. All rights reserved.

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

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 anthropogenic 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, efuent discharges, use of agricultural
chemicals, eroded soils and land use. Environmental pollution,
mainly of water sources, has become public interest. The underdeveloped countries have been suffering the impact of pollution
due to disordered economic growth associated with the exploitation 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 difcult to interpret), a monitoring

 Corresponding author. Fax: +92 222 771560.

E-mail addresses: tgkazi@yahoo.com (T.G. Kazi), bilal_ku2004@yahoo.com

(M.B. Arain), mkhanjamali@yahoo.com (M.K. Jamali),
nussaratjalbani_21@yahoo.com (N. Jalbani), hassanimranafridi@yahoo.com
(H.I. Afridi), rajaadilsarfraz@gmail.com (R.A. Sarfraz),
jab_mughal@yahoo.com (J.A. Baig), aqshah07@yahoo.com (A.Q. Shah).
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
difcult 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 understanding of water quality and ecological status of the study
region. These techniques allow the identication of the possible
sources that inuence 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
efuents 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, Pakistans
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
lakes water in downstream areas is also important for farmers
and shermen, who depend on the lake for irrigation and shery.
As a result of extensive evaporation of water from the lake due to

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T.G. Kazi et al. / Ecotoxicology and Environmental Safety 72 (2009) 301309

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
physicochemical parameters in water samples for 2 years
(200506) 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 inuence 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 (26130 N: 67160 E). It is a vast natural
depression anked 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 2.53.75 m and it covers an area of

233 km2. Flood barriers were constructed in 1932 from its

northern and northeastern boundaries. The human activities have
been changing signicantly the original regime of the lake over
the last 50 years. The most important activities are construction
and enlargement of the articial channels linking the river to the
lake and the construction of ood 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 signicant due to dry seasons
in 200005.
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 rst site is located in the area of entering main
efuents from MNVD. Sites 2 and 3 which are located at the
downstream side of lake, where mostly the boating occurs for
shing 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

Fig. 1. Map of Manchar Lake and Pakistan.

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that allowed for sampling at various water depths (06 in and

424 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 nally soaked in 10% nitric
acid for 24 h, nally 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 1C 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 solutions of all 16 elements were prepared by dilution of 1000 ppm
certied 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 ve sampling sites, were ltered through polycarbonate lter (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 HNO3 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 105110 1C. Total
hardness and Ca hardness were measured by EDTA complexometry 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 (AgNO3) titration, using
potassium chromate (K2CrO4) solution as an indicator. The BOD5
was determined by the Winkler azide method and COD by the
dichromate reux method. PO4-P was measured by molybdateascorbic acid method, SO4 was determined spectrophotometrically by barium sulfate turbidity method, NH4-N measured with
Nesslers reagent and total nitrogen was determined by Kjeldahls
method (Clesceri et al., 1998; AOAC, 1995). NO3-N and NO2-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 determination of major cations by further 20-time dilution with
ultrapure water, Ca, Na and K were measured by ame photometry, while Mg was determined by the ame atomic absorption
spectrometer (FAAS). For trace and toxic elements, the volume of
water samples was reduced four-fold at 60 1C on an electric hot
plate. Cu, Fe and Zn were determined by FAAS using an acetyleneair ame, while Al was determined by acetylene-nitrous oxide
ame. Cd, Co, Cr, Mn, Ni and Pb were analyzed using electrothermal 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

303

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
Biochemical oxygen demand
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

pH
EC
Salinity
TS
TDS
TSS
T-Hard
Ca-Hard
DO
BOD
COD
F
Cl
T-Alk
PO4
SO4
NO2-N
NH4-N
TKN
NO3-N
Na
K
Ca
Mg
Fe
Al
Cd
Pb
As
Cr
Ni
Co
Cu
Mn
Zn
Se

pH unit
mS/cm
%
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L

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

standardization, procedural blank measurements and triplicate

samples. The ionic balance of each sample was within 75%.
2.5. Data treatment by statistical method
All mathematical and statistical computations were made
using Excel 2003 (Microsoft Ofces) 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 nding 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 classication 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 Wards 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 standardization (z-scale) was made on each chemical prior to the statistical
analysis (Simeonov et al., 2004). Standardization tends to
minimize the inuence of difference on variance of variables
and eliminates the inuence of different units of measurements
and renders the data dimensionless. The calculation was
performed based on the correlation matrix of chemical components 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 components 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 classied the 36
physico-chemical parameters into three groups: in the rst
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, NO3, NH4, PO4, 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 ve sampling sites into three
statistically signicant clusters, as sites (12) and (35) 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
signicant variations, presenting averages for all sampling sites.
The range of TDS and conductivity in lake water was found in the
range of 35804440 mg/L and 5.016.22 mS/cm, respectively. The
major ions, F, Cl, NO3, SO4, PO4, 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 262805 mg/L. The level of Fe and Al were found
in the range of 1.527.21 and 0.914.27 mg/L, respectively,
corresponding to 1020-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 35.0171, 2.412.1, and 39.0172 mg/L, respectively. The
total phosphate and nitrogen values were found in the range of
0.2620.719 and 44.9128 mg/L, respectively, in lake water
samples. Chloride concentrations ranged in all water samples
found as 8862210 mg/L. Low DO values, in the range of
2.57.4 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 37.1104.8 and
79208 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 ve 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 inuence each one. The rst
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, throughout 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 claries the abnormality of the sampling sites 1 and 2,
which make one group as cluster 1, which receive polluted
efuents 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
classication 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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305

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
Mean
Std.

7.9 8.7
8.08
0.18

7.4 8.7
8.02
0.24

7.6 8.7
8.17
0.26

8.0 8.9
8.35
0.20

7.4 8.7
8.10
0.27

EC (mS/cm)

1.5

Range
Mean
Std.

4.7 10.8
6.22
1.37

4.60 9.60
5.97
1.23

4.11 9.21
5.58
1.53

3.87 9.00
5.01
1.12

4.11 9.05
5.47
1.09

Salinity (%)

0.1

Range
Mean
Std.

0.301 0.656
0.386
0.080

0.276 0.615
0.366
0.079

0.26 0.60
0.351
0.094

0.202 0.500
0.298
0.071

0.250 0.562
0.334
0.071

TS (mg/L)

Range
Mean
Std.

4300 9742
5753
1274

4088 9128
5489
1161

4074 8811
5293
1485

3319 7813
4630
1066

3755 7620
5027
1017

TDS (mg/L)

1000

Range
Mean
Std.

3362 7136
4440
941

3224 7269
4237
951

2978 6435
4057
1021

2778 5738
3579
750

2822 6422
3842
855

TSS (mg/L)

Range
Mean
Std.

878.5 2606
1113
371

863.9-1859
1035.1
271

716.9-2376
1052
531

468.9 2246
850.9
410

622.7 1939
985.2
311

Ca-Hard (mg/L)

100

Range
Mean
Std.

517.8 1107
667.1
139

465.2 1094
638.8
137

449.5 1080
620.1
176

394.0 910.4
535.9
115

437.4 975.2
589.6
134

DO (mg/L)

Range
Mean
Std.

2.4 5.4
3.7
0.87

3.4 6.5
3.9
0.62

2.5 6.8
4.3
1.33

4.8 7.4
5.2
0.76

3.5 7.2
4.7
1.25

BOD (mg/L)

Range
Mean
Std.

41.4 92.03
58.44
15.53

45.9 104.8
64.08
13.55

41.9 100.2
61.46
13.86

37.1 81.17
50.75
11.55

41.6 97.93
56.49
14.17

COD (mg/L)

10

Range
Mean
Std.

100.1 208.6
131.4
26.70

97.5 196.9
120.9
28.63

93.7 202.7
125.3
26.92

79.7 178.3
106.2
23.69

84.5 190.1
115.2
24.88

F (mg/L)

1.5

Range
Mean
Std.

0.55 1.14
0.71
0.14

0.516 1.084
0.68
0.14

0.50 1.06
0.66
0.17

0.46 0.92
0.57
0.12

0.47 1.00
0.62
0.13

Cl (mg/L)

250

Range
Mean
Std.

1055 2210
1410
279.6

999.9 2097
1333
272.2

925.6 2089
1285
334.6

885.9 1759
1128
220.7

954.7 2006
1223
262.2

T-Alk (mg/L)

200

Range
Mean
Std

132.7 306.9
179.7
40.40

122.5 294.9
171.2
39.04

117.2 268.5
156.7
58.74

100.6 236.0
141.1
31.67

119.5 268.3
157.4
34.39

PO4 (mg/L)

Range
Mean
Std.

0.352 0.716
0.52
0.11

0.322 0.719
0.50
0.11

0.270 0.694
0.48
0.14

0.277 0.645
0.46
0.10

0.262 0.601
0.42
0.09

SO4 (mg/L)

250

Range
Mean
Std.

144.9 313.1
186.1
38.7

139.0 288.09
176.70
37.4

24.78 288.8
162.2
63.50

118.2 245.5
150.4
33.97

125.6 271.9
162.2
35.55

NO2-N (mg/L)

Range
Mean
Std.

2.41 5.50
3.37
0.75

2.28 5.11
3.22
0.71

2.37 4.84
3.09
0.78

2.01 4.21
2.68
0.58

2.11 4.66
2.92
0.65

NH4-N (mg/L)

Range
Mean
Std.

5.85 13.22
8.48
1.7

5.57 12.6
8.04
1.7

5.48 12.10
7.82
2.1

4.77 10.36
6.82
1.4

5.36 12.46
7.35
1.7

TKN (mg/L)

Range
Mean
Std.

58.7 128.1
94.2
21.5

44.9 117.5
86.7
27.5

55.5 120.1
89.3
20.9

52.2 105.4
74.7
16.7

52.7 111.2
81.2
18.2

NO3-N (mg/L)

50

Range
Mean
Std.

5.03 12.7
8.4
1.9

5.31 11.3
8.2
2.1

5.59 13.0
8.8
1.9

4.46 11.0
7.2
1.6

4.72 11.4
7.6
1.7

Na (mg/L)

200

Range
Mean
Std.

355.2 804.7
474.5
109

327.2 760.4
51.9
108

316.2 758.3
433.6
136

262.4 625.2
381.1
93.8

306.1 720.8
418.4
100

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T.G. Kazi et al. / Ecotoxicology and Environmental Safety 72 (2009) 301309

Table 2 (continued )
Parameters

WHO limits

St1

St2

St3

St4

St5

K (mg/L)

12

Range
Mean
Std.

18.141.2
23.9
5.1

17.139.2
22.5
4.7

17.835.7
21.6
5.2

14.533.1
18.9
4.3

15.236.9
20.5
4.6

Ca (mg/L)

100

Range
Mean
Std.

181382
245.5
50.9

171377
234.9
49.5

172373
228.3
65.9

143314
197.1
41.3

152370
217.0
49.7

Mg (mg/L)

50

Range
Mean
Std.

129.1291.0
167.2
38.8

119.1268.6
157.7
35.7

120.0280.0
154.3
48.5

106.8257.9
134.0
32.5

105.6248.7
145.6
33.0

Fe (mg/L)

0.3

Range
Mean
Std

1.686.88
3.4
1.7

1.715.52
3.0
1.2

1.586.25
2.8
1.3

1.527.21
3.0
1.7

1.595.28
2.6
1.3

Al (mg/L)

0.2

Range
Mean
Std.

1.014.27
2.1
1.1

0.913.86
1.92
0.93

0.9674.06
1.87
0.96

1.063.92
2.01
0.96

0.9313.83
1.93
0.95

Cd (mg/L)

Range
Mean
Std.

2.9011.8
5.8
3.1

2.712.1
5.3
2.7

2.81.2
5.3
2.9

2.69.1
5.0
2.2

2.48.7
5.1
2.1

Pb (mg/L)

10

Range
Mean
Std.

43.1172.2
89.4
46

43.7171.2
82.3
43

39.2170.7
82.0
44

40.4161.4
81.2
41

43.7142.2
77.2
34

As (mg/L)

10

Range
Mean
Std

43.2171
86.1
47

35.4150
83.8
38

42.7140
77.4
34

42.1158
80.2
38

39.3141
76.5
34

Cr (mg/L)

50

Range
Mean
Std.

4.216.1
8.2
4.0

4.415.4
7.8
3.7

4.315.7
7.4
4.2

4.116.4
7.7
3.2

3.216.2
7.1
3.4

Ni (mg/L)

20

Range
Mean
Std.

20.276.4
38.1
18.1

15.158.5
36.0
15.2

17.267.4
33.4
16.2

15.261.5
34.6
15.2

17.158.5
32.7
14.1

Co (mg/L)

40

Range
Mean
Std.

23.088.0
42.97
21.4

19.084.0
39.32
21.2

17.077.0
38.30
17.4

19.073.0
38.03
17.2

21.064.0
36.06
14.8

Cu (mg/L)

2000

Range
Mean
Std.

11.240.2
21.1
10.2

11.636.1
19.2
8.74

9.440.6
17.2
10.4

9.136.3
18.7
9.24

8.238.4
18.3
10.1

Mn (mg/L)

100

Range
Mean
Std.

34.0151.0
77.0
40.2

3.0143.0
75.3
38.2

35.0141.0
70.1
35.4

32.0137.0
72.1
33.2

29.0131.0
68.3
36.5

Zn (mg/L)

10

Range
Mean
Std.

3771387
788
300

3961580
731
415

3401390
711
335

3641455
721
356

3614240
701
338

Se (mg/L)

10

Range
Mean
Std.

32.7118
81.2
10.4

32.792.4
62.2
10.4

30.677.2
38.5
10.2

32.782.4
43.4
9.1

30.674.5
38.5
8.6

signicance 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 ve 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 (3049 1C),

and lower values in the winter season (1228 1C). The pH values of
collected water samples were within those dened by WHO
guidelines of 6.58.5 (WHO, 2004).
The high level of EC, due to signicant amount of dissolved salt,
was observed in all sites of lake under study. The annual rainfall in
this basin is as little as o100 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 1215folds 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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90

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

0.065
0.112
0.096
0.076
0.180
0.087
0.124
0.312
0.283
0.137
0.114
0.081
0.051
0.088
0.009
0.096
0.092
0.133
0.259
0.107
0.078
0.125
0.100
0.276
0.327
0.100
0.173
0.231
0.260
0.239
0.179
0.268
0.223
0.223
0.182
5.566
16.370
95.023

0.191
0.071
0.047
0.051
0.089
0.066
0.046
0.248
0.205
0.262
0.036
0.033
0.264
0.199
0.239
0.065
0.006
0.237
0.420
0.063
0.039
0.041
0.019
0.075
0.113
0.220
0.336
0.202
0.106
0.069
0.219
0.262
0.143
0.118
0.169
0.871
2.563
97.586

PC2 (16.37 %)

10

5
Site 4
Site 1

60
50
40
30
20
10
0
Site 5

0.188
0.186
0.188
0.190
0.172
0.189
0.185
0.024
0.120
0.176
0.186
0.190
0.185
0.169
0.188
0.188
0.189
0.178
0.132
0.186
0.190
0.184
0.188
0.145
0.098
0.183
0.166
0.152
0.142
0.157
0.170
0.135
0.152
0.162
0.172
26.742
78.653
78.653

Site 3

EC
Salinity
TS
TDS
TSS
T-Hard
Ca-Hard
DO
BOD
COD
F
Cl
T-Alk
PO4
SO4
NO2-N
NH4-N
TKN
NO3-N
Na
K
Ca
Mg
Fe
Al
Cd
Pb
As
Cr
Ni
Co
Cu
Mn
Zn
Se
Eigenvalue
Variability (%)
Cumulative %

70

Site 4

PC3

Site 2

PC2

Site 1

PC1

80

Dissimilarity

Parameters

307

Fig. 3. Dendogram for cluster analysis based on the PCA score. The dissimilarity
dened 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 shing,
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.

0
Site 2
Site 5
Site 3

-5
-10

-5

0
PC1 (78.65 %)

10

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

Mg) and concentration of major anions Cl and SO4 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.

4.2.2. Dissolved metals in lake

The mean concentrations of elements in water samples
collected in 200506 are presented in Table 2. The average levels
showed that concentrations of major, trace and toxic elements due
to anthropogenic contamination (domestic, industrial and agricultural 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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T.G. Kazi et al. / Ecotoxicology and Environmental Safety 72 (2009) 301309

TDS

BOD

Alkalinity

COD

TKN

Standard Units

-1

-2
Site 1

Site 2

Na

Site 3
Ca

Site 4

Site 5
Fe

Mg

Al

Standard Units

-1

-2
Site 2

Site 1
Cd

Pb

Site 3
As

Site 4

Site 5

Se

Standard Units

of dissolved oxygen in understudy lake water was strongly

correlated with the high Fe2+ 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
1.85.06 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 signicant
relationship between the exposure to Al in water and an increased
risk of Alzheimers 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
315-fold higher than the permissible limit of As in drinking
water (10 mg/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

-1

-2
Site 1

Site 2

Site 3

Site 4

Site 5

Fig 4. Standard unit of chemical concentrations in water of the lake Manchar. The
standard units is dened as z (xu)/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 inow of
surface run off from hill torrents and agricultural wastes
(agricultural and rocks), both are rich in Al and Fe. The low level

The data of the physico-chemical parameters were transformed 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. 4a). The normalized concentrations for
all the physico-chemical parameters are almost equivalent to their
mean values above one standard deviation (1s). All physicochemical parameters show low normalized values at site 4 and 5
(below 0), whereas the values of these parameters are (o1s) at
sites 2 and 3 (Fig. 4b). 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. 4c).

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 ve 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

ARTICLE IN PRESS
T.G. Kazi et al. / Ecotoxicology and Environmental Safety 72 (2009) 301309

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 complex data sets, identication of pollution sources and understanding 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 inuence the population and
will invite socioeconomic disaster. These results should be
considered for future planning in using the lakes water for
drinking purposes.

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