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Environ Monit Assess (2011) 175:633649

DOI 10.1007/s10661-010-1557-6

Investigation of the possible sources of heavy metal


contamination in lagoon and canal water in the tannery
industrial area in Dhaka, Bangladesh
Mohammad Amir Hossain Bhuiyan Nahid I. Suruvi Samuel B. Dampare
M. A. Islam Shamshad B. Quraishi Samuel Ganyaglo Shigeyuki Suzuki

Received: 19 March 2010 / Accepted: 25 May 2010 / Published online: 11 June 2010
Springer Science+Business Media B.V. 2010

Abstract This study evaluated the heavy metal


pollution level of tannery effluent-affected lagoon
and canal water in the southwestern Dhaka,
Bangladesh. The measured physicochemical parameters (electrical conductivity, chemical oxygen
3

demand, pH, SO2


4 , PO4 , Cl , and NO3 ) and
metals (As, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Ni,
Pb, and Zn) were subjected to principal component (PCA) and hierarchical cluster analyses, and
examining correlation matrix as well in order to
explain the behavior and sources of the parameters/metals. The mean concentrations of the heavy

M. A. H. Bhuiyan (B) S. Suzuki


Graduate School of Natural Science and Technology,
Okayama University, 1-1, Tsushima-Naka 3 Chome,
Okayama 700-8530, Japan
e-mail: amirhb75@yahoo.com
M. A. H. Bhuiyan N. I. Suruvi
Department of Environmental Sciences,
Jahangirnagar University, Dhaka 1342, Bangladesh
S. B. Dampare S. Ganyaglo
National Nuclear Research Institute,
Ghana Atomic Energy Commission,
P.O. Box LG 80, Legon-Accra, Ghana
M. A. Islam S. B. Quraishi
Chemistry Division, Dhaka Atomic Energy Center,
Bangladesh Atomic Energy Commission,
Dhaka 1000, Bangladesh

metals in the lagoon and canal water were very


high and, in most cases, exceeded the standard
limits recommended by the Bangladesh Government. The following elemental associations were
obtained from PCA and CA: CaCdCrFeK
MnPbZn, CoCuNi, and As, which could be
linked to anthropogenic sources (i.e., processes of
the tannery and paint industries with some contributions from the municipal waste system). Potassium, Ca, Cr, Mn, Fe, Zn, As, and Cd occurred as
important anthropogenic markers in the lagoons
and lower part of the canal. Copper, Co, and Ni
were importantly distributed in the lower part of
the canal, which also received metal inputs from
the municipal waste and other industrial sources,
including paint industry. GIS-based factor score
maps, generated to show the spatial controls of
the major processes affecting surface water hydrochemistry, suggest that the activities of paint
and tannery industries and municipal sewage are
pervasive processes in the area, whereas the contribution from pesticides (used for tanning and
disinfecting hides) has localized effects. This study
has provided the evidence that effluents discharged from the tannery and auxiliary industries
and urban sewage system are the main sources
of heavy metal pollution in the lagoon and canal
water systems in the Hazaribagh area of southwestern Dhaka. The high mean concentrations (in
mg/l) of Cr (5.27), Pb (0.81), As (0.59), and Cd
(0.13) observed in the water samples may have

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serious public health and potential environmental


hazard implications.
Keywords Tannery effluent Lagoon
Water quality Heavy metal Cluster analysis
Principal component analysis

Introduction
Industrialization and unplanned urbanization
have greatly transformed the natural environment. In recent times, the environment has become hostile, posing threat to health and welfare
due to release of pollutants from industries and
urban sewage (Ntengwe 2006). The effluents discharged from industries and urban sewage may
find their way into surface water bodies via canals
and surface run-off. These water bodies, such as
lagoons, ponds, and lakes, thus receive pollutants
and become vulnerable.
The tannery industry, which uses a variety of
chemicals in the tanning process, is recognized as
a major contributor of heavy metals to the environment and poses serious environmental threats
worldwide. The effluents discharged from tannery
industry contain a bulk amount of liquid and solid
wastes with substantial quantities of toxic chemicals (sodium sulfate, sodium hydroxide, sodium
hydrosulfate, arsenic sulfide, calcium hydrosulfate, dimethyle amine, sodium sulphydrate, and
chromium sulfate; Banglapedia 2006) and other
heavy toxic trace metals, organic matter, lime, and
sulfide (Tariq et al. 2006 and references therein).
In addition, several footwear, animal glue, and
paint industries, which are commonly clustered
with tannery industries, also release some amount
of toxic chemicals from their operations. According to Landgrave (1995), about 40,000 tons of
basic chemicals and 15,000 tons of chromium salt
(as chromium sulfate) are used every year in
the world. The general practice in most developing countries is that the untreated effluents discharged from the tanning units is stored in large
lagoons or released into open canal (Scholz and
Lucas 2003; More et al. 2001).
Tannery industries contribute immensely to
the socioeconomic development of Bangladesh.

Environ Monit Assess (2011) 175:633649

The export value earned on leather commodities


from 250 small- and large-scaled tannery industries rose from US$ 60 million in the late1980s to
US$ 250 million by the end of 2002 (Rashid 1991).
This notwithstanding, the operations of these industries are detrimental to the environment as a
huge volume of effluent is directly discharged into
lagoons and canals without pretreatment. Other
auxiliary companies, including 73 glue and paint
industries, housed in the tannery complex also directly discharge about 504,000 m3 /year of effluents
into the lagoons and canals, thereby increasing the
pollutant levels (Asaduzzaman et al. 2002). Thus,
the ecotoxicological risks posed by the tannery
effluents cannot be overemphasized. However, little attention is given to the environment, health,
and sanitary conditions in and around the tannery
complex. Adequate monitoring of effluents and
surface water quality from individual or cluster
of industries at the point of origin to terminal
reservoir needs to be conducted for better understanding of the pollution status. This will also
guide entrepreneurs to develop appropriate treatment plants for wastes, which is the moral and
environmental responsibility of each industry.
Some earlier studies have underscored the importance of multivariate or chemometric methods
and self-organizing maps in data mining of matrices from environmental quality assessment. For
instance, chemometrics have successfully been
used for various purposes, including evaluation
of environmental data in lagoon water (Marengo
et al. 1995), wastewater monitoring of the Yantra
river basin in Bulgaria (Stefanov et al. 1999), water classification (Kowalkowski et al. 2006), classification and assessment of monitoring locations
of an urban river system (Kannel et al. 2007), evaluation of the quality of water sources for human
consumption (Simeonova and Simeonov 2007);
evaluation of large environmental data sets (Astel
et al. 2007), and classification and modeling in surface water pollution estimation (Astel et al. 2008).
Among these chemometric techniques, principal
components analysis (PCA) and cluster analysis
(CA) are useful methods for identifying common
patterns in data distribution, leading to a reduction of the initial dimension of data sets and facilitating its interpretation (Franco-Ura et al. 2009).

Environ Monit Assess (2011) 175:633649

Regarding metal pollution, PCA and CA are


widely used in water quality assessment and monitoring (Tariq et al. 2005, 2006, in press; Bhuiyan
et al. 2010a). PCA and CA help to arrange metals
or analyzed parameters in different factors/groups
on the basis of contribution from the expected
source. Depending on the co-variances of the analyzed parameters, the multivariate technique is
able to provide useful information on their origin.
In this contribution, the pollution status of lagoons and adjoining canal water in the southwestern part of Dhaka city, which are adversely
impacted by tannery and other chemical industries together with municipal sewage effluents,
is presented. The study evaluates the degree of
hazardous metal contents as well as the mutual relationships between metal levels and dependence

635

in order to identify their sources, using PCA, CA,


and correlation matrix.

Study area
The cluster of tannery industries in Bangladesh
is located in the Hazaribagh area of southwestern Dhaka (Fig. 1). This area lies within longitude 90 22 90 22 48 E and latitude 23 43 34
23 43 49 N. It is a component of Buriganga River
floodplain which is bordered at the northeast by
Pleistocene terrace (Madhupur Tract) and slopes
towards the southeast. The tannery campus is surrounded by residences, except the southwestern
part. More than 0.2 million people live adjacent to

Fig. 1 Sampling layout in the study area (modified after Banglapedia 2006)

pH

6.10
0.05
7.25
0.04
6.92
0.05
6.95
0.04
7.19
0.05
6.19
0.01
6.00
0.02
6.19
0.03
6.20
0.04
7.10
0.05
6.30
0.01
7.00
0.07
7.30
0.02
6.50
0.02
6.70
0.10
7.50
0.10
7.20
0.12
6.30
0.13

Site

DE1
SD
DE2
SD
DE3
SD
DE4
SD
DE5
SD
DE6
SD
DE7
SD
DE8
SD
DE9
SD
DE10
SD
DE11
SD
DE12
SD
DE13
SD
DE14
SD
DE15
SD
DE16
SD
DE17
SD
DE18
SD

7.17
0.04
8.44
0.04
8.25
0.05
7.98
0.05
8.12
0.04
9.10
0.07
11.10
0.01
10.20
0.03
12.10
0.05
8.50
0.01
15.10
0.02
13.50
0.03
15.10
0.04
16.90
0.01
19.10
0.06
12.80
0.01
11.50
0.08
14.20
0.09

EC
(mS cm1 )

602
4
756
4
669
4
724
4
698
4
719
8
750
9
795
10
831
11
957
6
912
10
1,011
14
1,119
11
919
16
871
18
921
11
710
10
790
12

COD
892
25
1,163
55
661
23
640
22
1,066
50
815
9
850
10
915
9
865
6
925
13
911
11
895
15
975
11
805
8
810
5
901
9
868
10
715
7

SO2
4
6.46
0.45
12.30
1.10
28.79
2.05
34.11
2.65
13.76
1.12
27.10
0.10
25.50
0.11
29.20
0.12
31.50
0.11
33.30
0.12
37.10
0.15
38.50
0.10
37.50
0.07
41.50
0.18
52.10
0.20
45.50
0.20
38.10
0.21
35.60
0.22

PO3
4
4,140
345
6,840
510
3,675
242
2,883
156
5,432
421
5,219
111
5,219
112
5,411
110
5,129
114
5,318
117
5,350
108
5,565
117
5,630
129
5,011
109
4,538
120
4,215
122
3,211
110
2,836
131

Cl1
2.67
0.21
6.23
0.44
47.33
3.47
119.00
5.00
10.54
0.95
77.10
0.12
91.10
0.13
67.10
0.10
105.00
0.15
83.10
0.16
177.10
0.10
125.10
0.80
152.00
0.12
194.00
0.20
88.00
0.21
58.00
0.20
46.00
0.23
95.00
0.24

NO1
3
2.41
0.15
2.21
0.13
2.01
0.16
2.51
0.17
2.50
0.08
52.90
0.13
40.50
1.20
56.20
1.50
60.80
1.60
65.10
1.50
49.40
3.10
45.30
2.10
55.30
1.20
46.60
2.20
72.10
3.50
38.50
1.30
42.70
1.40
35.30
1.50

K
24.32
1.98
23.18
1.45
22.22
1.20
25.22
1.10
24.22
1.40
35.30
0.14
48.30
0.15
55.10
0.10
45.20
0.17
56.10
0.18
72.30
0.11
64.50
0.20
73.20
0.10
81.20
0.22
95.40
0.20
65.00
0.24
49.60
0.25
25.10
0.26

Ca
0.02
0.00
0.02
0.00
0.02
0.00
0.03
0.00
0.25
0.03
3.49
0.01
5.41
0.02
12.89
0.03
9.90
0.01
8.40
0.05
13.10
0.02
20.20
0.01
14.19
0.08
5.30
0.09
5.10
0.10
3.10
0.11
0.99
0.01
1.40
0.01

Cr
0.10
0.01
0.08
0.01
0.06
0.00
0.30
0.02
0.24
0.01
0.19
0.01
0.10
0.02
0.15
0.01
0.59
0.01
1.10
0.05
0.69
0.02
0.74
0.03
1.22
0.01
1.20
0.05
0.95
0.01
0.39
0.01
0.49
0.02
0.90
0.03

Mn

Table 1 Physicochemical parameters and metal concentration (in mg/l) in lagoon and canal water

0.23
0.01
0.21
0.01
0.22
0.01
0.32
0.01
0.44
0.02
0.39
0.07
5.90
0.02
6.30
0.02
11.10
0.10
15.50
0.11
12.20
0.12
9.30
0.13
8.10
0.14
5.50
0.15
7.10
0.10
0.92
0.07
1.62
0.01
2.10
0.10

Fe

0.12
0.02
0.51
0.02
0.40
0.01
0.23
0.01
0.32
0.01
0.21
0.01
0.43
0.01
0.50
0.02
0.39
0.02
0.52
0.01
0.72
0.05
0.30
0.01
1.10
0.02
0.91
0.03
0.45
0.01
0.20
0.02
0.38
0.01

<0.005

Co
0.02
0.00
0.20
0.01
0.90
0.01
0.03
0.01
0.14
0.02
0.19
0.01
0.11
0.01
0.21
0.01
0.49
0.02
0.50
0.05
0.33
0.01
0.25
0.01
1.10
0.02
0.90
0.01
0.43
0.02
0.15
0.01
0.17
0.01
0.23
0.01

Ni

0.11
0.01
0.75
0.01
0.03
0.01
0.04
0.01
0.20
0.01
0.12
0.01
0.32
0.03
0.40
0.01
0.20
0.01
1.20
0.06
0.52
0.02
0.78
0.05
0.92
0.03
1.50
0.10
0.62
0.01
0.42
0.02
0.12
0.01

<0.005

Cu
0.04
0.01
0.02
0.01
0.08
0.01
0.26
0.07
0.14
0.02
0.11
0.01
0.31
0.02
0.50
0.03
0.75
0.02
1.11
0.05
1.75
0.06
2.50
0.07
2.15
0.05
1.51
0.01
0.90
0.01
0.11
0.11
0.44
0.02
0.60
0.03

Zn
0.70
0.01
0.65
0.06
0.69
0.05
0.26
0.01
0.42
0.01
0.69
0.02
0.55
0.03
0.73
0.01
0.78
0.05
0.85
0.02
1.10
0.07
0.90
0.08
0.65
0.01
0.78
0.01
0.92
0.01
0.44
0.02
0.10
0.01
0.22
0.01

As

<0.01

0.12
0.01
0.26
0.03
0.30
0.02
0.21
0.02
0.25
0.03
0.33
0.01
0.40
0.02
0.21
0.06
1.21
0.01
2.10
0.08
2.50
0.09
2.10
0.10
1.90
0.11
0.50
0.01
0.20
0.01
0.75
0.04

0.03
0.01
0.02
0.01
0.09
0.01
0.08
0.00
0.10
0.01
0.12
0.01
0.14
0.01
0.15
0.01
0.19
0.01
0.20
0.01
0.21
0.02
0.25
0.01
0.28
0.01
0.18
0.01
0.20
0.01

<0.01

<0.01

Cd

<0.02

<0.02

Pb

636
Environ Monit Assess (2011) 175:633649

637

Methodology
Sample collection

DE19
SD
DE20
SD
Mean
Range

6.00
8.60
0.14
0.20
6.60
9.50
0.15
0.01
6.67 11.36
6.00 7.17
7.50 19.10
Bangladesh 9.00 12.00
standard

699
11
935
15
819
602
1,119
200

775
22.40
12
0.20
850
31.50
13
0.40
865
31.10
640
6.46
1,163 52.10
400
8.00

3,764
124
3,111
125
4,624
2,836
6,840
600

61.00
49.40
0.25
2.60
28.00
38.10
0.60
1.70
81.67
37.99
6.23
2.01
194.00 72.10
10.00

33.30
0.70
31.30
0.80
47.5
22.22
95.40

0.79
0.04
0.88
0.05
5.27
0.02
20.20
0.50

0.81
0.14
0.10
0.01
0.52
0.06
1.22
5.00

0.11
0.01
0.33
0.05
0.41
0.11
1.10

the tannery campus and 20,000 people are directly


exposed to the hazards within the tannery complex (Asaduzzaman et al. 2002). The northsouth
canal, which runs parallel to the flood control
embankment (Fig. 1), is connected to the tannery
runoff for ultimate discharge into the Buriganga
River. The effluent is temporarily stored in lagoons and later discharged into the river via a
sluice gate (Fig. 1). The topographic elevation
of this site is 1.5 m above mean sea level and
is perennially inundated by monsoon flood and
urban runoff during monsoon.

0.51
0.01
1.30
0.01
4.68
0.21
15.50
2.00

0.22
0.01
0.10
0.01
0.33
0.02
1.10
1.00

0.11
0.01
0.55
0.05
0.44
0.03
1.50
0.50

0.24
0.01
0.53
0.01
0.70
0.02
2.50
5.00

0.35
0.01
0.12
0.01
0.59
0.10
1.10
0.20

1.91
0.15
0.82
0.06
0.81
0.12
2.50
0.10

0.16
0.01
0.10
0.01
0.13
0.02
0.28
0.05

Environ Monit Assess (2011) 175:633649

Twenty water samples (prefixed DE) were collected from key locations within the Rayer Bazar
lagoon and Hazaribag-Mohammadpur canal into
plastic bottles, which had been pre-conditioned
with 5% nitric acid and rinsed with distilled deionized water. Prior to sampling, the pre-cleaned
sample bottles were immersed about 10 cm below
the water surface. The samples were collected at a
100 m interval from the outlet of the tannery zone
to the mouth of the Buriganga River. Sampling
was done at mid dry season (March) when the
canal and lagoon were at low water levels. During
monsoon sampling in the canal and surrounding
floodplains were not possible as these areas were
submerged by flood.
Methods for physicochemical analysis
The pH of samples was determined in situ
using a microprocessor pH meter (HANNA Instruments, model: PH 211). Electrical conductivity (EC) was measured with a conductivity
meter (HANNA Instruments, model: HI 8033).
The collected water samples were filtered using a pre-conditioned plastic Millipore filter
unit equipped with a 0.45 m filter membrane
(Gelman Inst. Co, London) and preserved in
a refrigerator at 4 C for subsequent elemental analysis. Chemical oxygen demand (COD)
was measured by the dichromate reflux method
(Michael 1975; Clesceri et al. 1998). Anions

638
3

(SO2
4 , PO4 , Cl , and NO3 ) were analyzed by
colorimetric methods, following the procedure
of APHA (1995).

Elemental analysis
Elemental analysis of water samples was performed by a Perkin-Elmer Atomic Absorption
Spectrophotometer (AAS; Model 3110). The accuracy and precision of the AAS analytical
method were validated by triplicate analyses of
SRM-1640 (groundwater), a NIST standard reference material. The precision was better than 8%
for all analyzed elements. The minimum detection
limits (in mg/l) of heavy metals in the analyzed
water samples were: 0.05 (K), 0.03 (Ca), 0.048
(Mn), 0.038 (Fe), 0.005 (Cu, Co), 0.02 (Zn), 0.01
(As, Cr, Ni, Cd), and 0.02 (Pb).
Statistical analysis
The measured parameters were subjected to hierarchical cluster analysis (HCA) and principal
component analysis/factor analysis using SPSS
16.0 statistical package. Prior to such analyses,
the raw data were normalized to avoid misclassifications due to the different order of magnitude
and range of variation of the analytical parameters
(Aruga et al. 1995).
Principal component analysis transforms the
original variables of a data set into new, uncorrelated variables or axes, known as the principal components, which are linear combinations
of the original variables (Shrestha and Kazama
2007). Exploratory factor analysis is used for reducing the complex set of variables to smaller
number of factors (Howitt and Cramer 2005). The
physicochemical and metal data were subjected to
principal component analysis for exploration of
the extent of metal pollution and source identification. Varimax rotation was used to maximize the sum of the variance of the factor
coefficients which better explained the possible
groups/sources that influenced the water systems
(Gotelli and Ellison 2004).
The correlation coefficient matrix measures
how well the variance of each constituent can be
explained by its relationship with others (Liu et al.

Environ Monit Assess (2011) 175:633649

2003). The factor scores from the R-mode PCA


were used with ArcGIS to determine the spatial
variations of the dominant processes influencing
the surface water hydrochemistry in the area. Discussions on the interpolation techniques, such as
kriging, and integrated use of factor analysis and
kriging methods in the analysis of hydrochemical
data have been provided in literature (e.g., Yidana
et al. in press).
Cluster analysis is an exploratory unsupervised
data analysis tool for solving classification problems for variables and objects. The main objective
is to sort cases (monitoring points) into groups
or clusters so that the degree of association is
strong between members of the same cluster and
weak between members of different clusters. Each
cluster describes, in terms of the data collected,
the class to which its members belong (Einax et al.
1997). The squared Euclidean distance was used
to measure similarity among clusters while Wards
method was used as an agglomeration technique
(Einax et al. 1997). It has been suggested in literature that the use of either Euclidean or squared
Euclidean distance as a similarity measure in
combination with Wards linkage algorithm often
yields optimal classification results (e.g., Gler
et al. 2002; Banoeng-Yakubo et al. 2009; Bhuiyan
et al. 2010a, b; Boamponsem et al. 2010; Yidana
and Yidana 2010; Yidana et al. in press).
The hydrochemical data were examined by
both R-mode and Q-mode HCA. The R-mode
HCA was used to establish relationships between
the variables (analyzed parameters), whereas the
Q-mode HCA was used to classify the cases
(samples), measured by the variables, into statistically defined groups. Dendrograms were generated for the R-mode and Q-mode HCA, with
the phenon lines set to a rescaled linkage distance of about 8.5 to show statistical similarity.
The so-called phenon line is a horizontal line
drawn across a dendrogram at a certain similarity
level to delimit groups of the same rank, and
it is thus useful in determining groups or clusters. The subjective selection of the partitioning
level, where the phenon line can be moved up
or down on the dendrogram to decrease or increase the number of clusters, makes HCA a semiobjective method (Guler et al. 2002; Yidana et al.
in press).

Environ Monit Assess (2011) 175:633649

Results and discussions


Water quality
The physicochemical and total metal concentrations of the lagoon and canal water as well as the
permissible limits of Bangladesh Government are
presented in Table 1. The ranges of physicochemical parameters (in mg/l) are COD, 6021,119;
3

SO2
4 , 6401,163; PO4 , 6.4652.1; Cl , 3,111

6,840; NO3 , 2.67177.1 and EC, 7.1719.1 S/cm


and pH 6.07.5. With the exception of pH, all
other physicochemical parameters are quite high
and exceed the industrial effluent standards recommended by the Bangladesh Government (Huq
1997). The ranges of total metal contents (in mg/l)
in lagoon and canal water samples are as follows:
Ca, 22.295.4; K, 2.0172.1; Cr, 0.0220.2; Mn,
0.061.22; Fe, 0.2115.5; Co, 0.031.1; Ni, 0.021.1;
Cu, 0.031.5; Zn, 0.022.5; As, 0.101.1; Pb, 0.12
2.50; and Cd, 0.010.28, respectively (Table 1).
The mean concentrations follow a decreasing order of Ca > K > Cr > Fe > Pb > Zn > As > Mn
> Cu > Co > Ni > Cd.
The concentrations of Zn, Cu, and Ni are below the permissible limits of industrial effluent
quality recommended by the Bangladesh Government (Huq 1997). However, the concentrations
of hazardous metals (Cr, As, Pb, and Cd) are
notable and exceed the permissible limits. These
high concentrations observed in the water samples
may have serious human health and potential environmental hazard implications.
Among the toxic metals, Cr, Pb, and As are
responsible for many acute and chronic diseases,
such as skin and mucous membrane irritation,
sensitization, corrosion, dermatitis, and chronic
ulceration (Bosnic et al. 2000). Other healthrelated problems include hemorrhapic diathesis
and blood loss into the gastro-intestinal tract. This
causes cardiovascular shock and may extend to
liver necrosis, tubular necrosis of kidney, and poisoning of blood-forming organs (Asaduzzaman
et al. 2002).
Pollution source identification
The calculated factor loadings, cumulative percent
and percentages of variance explained by each

639

factor in R-mode PCA are listed in Tables 2, 3, 4,


and 5. Four factors with eigenvalues >1 were extracted from the varimax-rotated factor analysis of
all parameters in the data set. The retained factors
which led to a reduction of the initial dimension
of the data set and explained about 85% of the
total variance are mentioned as PC in Tables 2
and 3. The communalities shown by the variables,
considering four factors, varied from 63% for Mn
2
3
to 95% for Cd and PO3
4 (Table 2). SO4 , PO4 ,

and NO3 were significantly loaded on two factors.


They were, however, retained in the final factor
model due to their high communalities values
(more than 90%) which showed how well the
variances of these parameters were explained by
the set of factors. Therefore, their high loadings on
two factors could probably be explained by their
derivation from two sources. The factor scores
for all samples and their distributions are shown
in Tables 4 and 5. Factor scores represent cumulate contribution of all parameters loaded on
a particular factor/principal component. Positive
and negative scores in PCA indicate that most
water samples were either essentially affected or
unaffected by the presence of the extracted loads
on a specific factor/component, respectively.
The first principal component (PC1) in the
lagoon and canal water data sets explains more
than 41% of total variance, and is heavily loaded

on EC, COD, PO3


4 , NO3 , K, Ca, Cr, Mn, Fe,
Zn, Pb, and Cd. These parameters retain high
scores in DE10 to DE15 (Table 4), and may be
considered as most important parameters in these
samples. Components in PC1 are derived from
mixed sources such as the tanning, re-tanning,
and basification stages of leather production of
tannery industries, and municipal sewage. MnO is
used in tanning process to allow the chromium or
aldehyde to bind to skin protein (Tariq et al. in
press).
PC2, explaining about 21% of total variance,

has high loadings for PO3


4 , NO3 , Co, Ni, and Cu
which may be derived from municipal sewage and
paint industries (e.g., Roxy paint industry, Pailac
paint company) that share common drainage with
the tannery industries. Raw materials used in the
paint industries are color pigment, mineral thinner, tarpin oil, petroleum gum and synthetic resin,
talcum powder, chalks, ammonia, water, and pre-

640
Table 2 Varimax rotated
factor loadings and
communalities of water
quality parameters
(significant values are in
bold type face)

Environ Monit Assess (2011) 175:633649


R-mode
Parameters

PC1

PC2

PC3

PC4

Communalities

pH
EC
COD
SO4
PO4
Cl
NO3
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Pb
Cd
Eigenvalue
% of variance
Cumulative %

0.132
0.707
0.697
0.114
0.603
0.093
0.623
0.901
0.792
0.901
0.759
0.832
0.367
0.288
0.460
0.839
0.021
0.739
0.931
7.843
41.270
41.280

0.252
0.435
0.362
0.439
0.724
0.034
0.669
0.168
0.295
0.190
0.224
0.226
0.839
0.699
0.756
0.348
0.200
0.480
0.230
4.011
21.120
62.390

0.062
0.114
0.213
0.623
0.242
0.951
0.079
0.054
0.324
0.278
0.041
0.322
0.011
0.404
0.142
0.011
0.872
0.161
0.155
2.705
14.240
76.630

0.911
0.048
0.397
0.580
0.068
0.168
0.235
0.144
0.092
0.067
0.076
0.051
0.125
0.113
0.194
0.041
0.244
0.058
0.006
1.586
8.350
84.980

0.915
0.704
0.82
0.93
0.95
0.943
0.897
0.864
0.828
0.93
0.634
0.85
0.854
0.748
0.841
0.826
0.86
0.806
0.944

serving agents (Asaduzzaman et al. 2002). The


factor scores of the R-mode PCA show that these
parameters are importantly distributed in samples
DE3, DE14, and DE15 (Tables 2, 3, 4, and 5),
which are located immediately below the connect-

Table 3 Varimax rotated


factor loadings and
communalities for metals
only (significant values
are in bold type face)

ing points of municipal sewage line. PC2 could


be explained in lesser extent as anthropogenic
(municipal and industrial) sources.
PC3, accounting for 14% of total variance, is

loaded on SO2
4 , Cl , and As. These parame-

R-mode
Parameter

PC1

PC2

PC3

Communalities

K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Pb
Cd
Eigen value
% of variance
Cumulative %

0.880
0.776
0.882
0.777
0.821
0.326
0.231
0.380
0.836
0.053
0.723
0.914
5.797
48.31
48.31

0.255
0.317
0.274
0.206
0.259
0.858
0.797
0.866
0.349
0.095
0.509
0.292
2.946
24.552
72.862

0.018
0.355
0.222
0.025
0.346
0.053
0.367
0.086
0.055
0.957
0.173
0.179
1.421
11.84
84.702

0.84
0.828
0.902
0.647
0.861
0.844
0.823
0.902
0.825
0.927
0.811
0.954

Environ Monit Assess (2011) 175:633649


Table 4 Factor scores for
the R-mode factor
analysis (significant
values are in bold type
face)

641

Sampling site

PC1

PC2

PC3

PC4

DE1
DE2
DE3
DE4
DE5
DE6
DE7
DE8
DE9
DE10
DE11
DE12
DE13
DE14
DE15
DE16
DE17
DE18
DE19
DE20

1.093
1.907
2.623
1.001
0.875
0.367
0.253
0.344
0.492
0.665
0.852
0.937
1.082
0.667
0.772
0.310
0.502
0.461
0.258
0.272

2.938
0.481
2.403
0.390
0.793
0.089
0.530
0.197
0.211
0.117
0.403
0.300
0.362
1.111
0.923
0.201
0.479
0.074
0.552
0.380

0.333
1.455
0.048
2.010
0.335
0.378
0.491
0.827
0.719
0.703
0.936
0.558
0.652
0.458
0.288
0.459
1.675
1.615
0.777
1.551

0.976
1.690
0.559
0.298
1.264
1.098
1.274
0.758
0.845
0.624
0.564
0.486
1.321
0.380
0.128
1.496
1.209
0.704
1.228
0.722

ters may have emanated from the chemicals (e.g.,


different sulfate and chloride salts and acids) and
pesticides (arsenic sulfide) used for tanning and
disinfecting hides. Arsenic sulfide and chlorine
are widely used as pesticides to prevent further
decay of skin (Banglapedia 2006; Asaduzzaman
et al. 2002). The effect of these components is
significant in DE2, DE8 to DE11, and DE15. PC3
can be explained as effluent discharge (anthropogenic) from tannery industry.
PC4 accounts for 8.35% of the total variance
and is mostly contributed by pH and SO2
4 , which
are derived from organic wastes/matter (e.g., vegetables residue, animal blood, soft parts of animal
skin, municipal wastes etc.). PC4 may be considered as anthropogenic source component (tannery processes). High scores of PC4 are observed
in samples DE2, DE5, DE10, DE13, DE16, and
DE17, suggesting that pH and SO2
4 are important
parameters in these samples.
In order to further investigate elemental
patterns, PCA was performed on the metal
data set only. Here, three factors are retained
again accounting for 85% of the total variance.
The communalities displayed by the metals are
high values and similar to the previous results
(Table 3). Three factors, PC1, PC2, and PC3,

were extracted, which explained more than 48%,


24.5%, and 12% of total variance, respectively
(Tables 2, 3, 4, and 5). The elemental loadings on
PC1, PC2, and PC3 in the metal data set were

Table 5 Factor scores for the R-mode factor analysis (significant values are in bold type face)
Sampling site

PC1

PC2

PC3

DE1
DE2
DE3
DE4
DE5
DE6
DE7
DE8
DE9
DE10
DE11
DE12
DE13
DE14
DE15
DE16
DE17
DE18
DE19
DE20

0.838
2.212
2.602
0.681
0.928
0.289
0.309
0.350
0.498
0.831
0.805
0.988
0.938
0.625
0.773
0.221
0.439
0.434
0.380
0.040

3.393
0.081
1.964
0.679
0.201
0.009
0.692
0.048
0.248
0.227
0.367
0.199
0.562
1.057
0.769
0.209
0.092
0.054
0.402
0.343

0.989
0.751
0.482
1.399
0.366
0.124
0.361
0.666
0.731
1.040
1.018
0.553
0.527
0.513
0.659
0.408
1.812
1.414
0.949
2.064

642

K, Ca, Cr, Mn, Fe, Zn, Pb, and Cd; Co, Cu, and
Ni; and As, respectively, and elemental patterns
were similar to that obtained for all parameters
metal data set (the physicochemical parameters
and metals).
The relationships among the analyzed parameters are also visualized in the factor loadings plots
of PC1 vs. PC2 and PC1 vs. PC3 (Fig. 2). For all
parameters, four main clusters are obtained from
the plotting of PC1 vs. PC2 (Fig. 2a). Cluster 1
contains parameters EC, COD, Ca, K, Fe, Mn,
Zn, Pb, Cd, and Cr and cluster 2 consists of PO3
4 ,

NO3 , Cu, Ni, and Co. Cluster 3 includes As, Cl ,


and SO2
4 whereas pH independently remains in
cluster 4. Similar groupings of parameters are observed on the plot of PC1 vs. PC3 (Fig. 2b). For
the metal data set, the PC1 vs. PC2 and PC1 vs.
PC3 plots show similar results of three distinct
clusters (Fig. 2c, d), which confirm the clustering
phenomenon observed in Fig. 2a and b.
For a better understanding of the sources of
metals in the water courses, R-mode cluster
analysis was also performed to visualize the re-

Environ Monit Assess (2011) 175:633649

lationships between physicochemicalmetal and


metalmetal groupings in data sets. The results
are graphically presented in Fig. 3. Elements/parameters belonging to the same cluster/group are
likely to have originated from a common source.
The CA results largely agree with the PCA results. The R-mode CA retains three main clusters
for data sets of all parameters and metal samples
separately, with the phenon line set to a rescaled
linkage distance of about 8.5. For all parameters,
cluster 1 consists of COD, EC, K, Ca, Fe, Mn,
Zn, Cd, and Cr (Fig. 3a). This cluster is almost
similar to PC1 in PCA analysis. Cluster 2 contains

PO3
4 , NO3 , Pb, Cu, Co, and Ni and cluster 3
consists of Cl , As, SO2
4 , and pH. However, pH
is slightly different from the other cluster members, as depicted by its long linkage distance; this
observation is strongly supported by PC3 in PCA
analysis. The metalmetal CA presented in Fig. 3b
shows similar clustering, where cluster 1 contains
Cu, Co, and Ni; cluster 2 is made up of K, Cd, Cr,
Fe, Zn, Ca, Mn, and Pb; and cluster 3 contains As
only.

Fig. 2 Plots of first three principal component loadings, PC1 vs. PC2 and PC1 vs. PC3 for all analyzed parameters (a, b) and
metals only (c, d)

Environ Monit Assess (2011) 175:633649

643

Fig. 3 Dendrogram showing the hierarchical clusters of analyzed parameters and samples using all parameters (a, c) and
metals only (b, d). Dashed lines in dendrograms represent Phenon lines

The R-mode PCA and CA have yielded the


following elemental associations in the water
data set: CaCdCrFeKMnPbZn, CoCu
Ni, and As, which are mainly derived from anthropogenic sources. These anthropogenic sources are
linked to the processes of the tannery and paint
industries with some contribution from municipal
waste.
GIS-based factor score maps were developed
for the three factors/principal components extracted from the PCA of the metal data set. The
factor scores for each factor and the corresponding geographical coordinates of the sampling positions were used to create interpolation surfaces.
These interpolation maps show spatial variations

of the influence of each of the three dominant


processes in the study area. Figures 4, 5, and 6
represent factor score maps for factors 1, 2, and
3, respectively. In Fig. 4, the area has factor scores
ranging from 2.58 to 0.65 and above. Within this
range of scores, about 40% of the study area has
positive factor scores, and about 80% has scores
in the range of 0.56 to 0.65. This suggests that
the processes involved in tanning, re-tanning, and
basification stages of leather production of tannery industries, and municipal sewage have moderate to high effects on the hydrochemical data in
the study area. Generally, the effects of factor 1
increase from southeastern to northwestern parts
of the study area. The highest impact of factor

644

Environ Monit Assess (2011) 175:633649

Fig. 4 Factor score map


for factor 1

1 occurs at the mouth of Buriganga River and


Rayer Bazar lagoon area, which receive contributions from both tannery effluents and municipal
sewage, unlike the southeastern portion which is
mainly impacted by the tannery effluents
Figure 5, the factor score map for factor 2,
shows the extent of influence of both industrial
and municipal activities on surface water hydrochemistry in the Hazaribag tannery area. Factor scores range between 3.39 and 1.76, and
over 70% of the study area has positive factor
scores, indicating the importance of factor 2 in
the area. The factor scores generally increase in
Fig. 5 Factor score map
for factor 2

the southeastnorthwest direction, similar to the


trend depicted in Fig. 4. The high impacts of factor
2 occur at the lagoon area, where it stores water
from the various sources through the canal runoff.
The Hazaribag tannery effluents discharged into
the canal (from southeast) are ultimately discharged into the lagoon. The municipal sewage
of Rayer Bazar-Mohammadpur areas is also released into the lagoon by sewage outlets located
at the northeastern corner of the study area (near
sampling points DE8, DE10, and DE11).
The factor scores for factor 3 are displayed in
Fig. 6, and they range from 1.76 to 0.68 and

Environ Monit Assess (2011) 175:633649

645

Fig. 6 Factor score map


for factor 3

above. It is noteworthy that the spatial pattern


observed in Fig. 6 is generally controlled by As
(Table 3) which can be derived from pesticides
(arsenic sulfide) used for tanning and disinfecting
hides in the tannery industries. The trend of factor
scores in Fig. 6 is slightly different from those portrayed in Figs. 4 and 5. In general, the factor scores
increase from northeastern to southwestern sections of the study area, with some high scores also
occurring at the southeastern part. About 45% of
the area has positive factor scores, and about 60%
has scores ranging from 0.54 to 0.68, suggesting moderate to high effects. The positive factor
scores shown at the southeast corner are probably
due to the proximity of the areas to the pollution
source (tannery industries). As explained earlier,
effluents from the tannery industry and auxiliary
industries, and municipal sewage lines are discharged into the lagoon. Hence, the high score
values at the lagoon area are not unexpected.
Interestingly, very low factor scores of factor 3 are
observed outside the Dhaka city flood protection
embankment, in the Buriganga floodplain area,
where it is frequently flashed by tidal water of
Buriganga River.
It is clear, from the spatial distributions of the
three factor scores, that the activities of paint and
tannery industries and urban sewage are competitive processes influencing surface water hydrochemistry in the area. On the other hand, the

contribution from pesticides has localized effects.


Field observations seem to confirm this, as no
strict measures have been put in place to regulate
the effluents discharged from the industries and
municipal sewage lines in the area.
Spatial similarities and sampling site grouping
Q-mode CA has been used to evaluate the spatial
similarities and site groupings among the sampling
sites, where sampling sites belonging to a particular cluster exhibit similar characteristics with
respect to the analyzed parameters.
Three major clusters were extracted from all
analyzed parameters for the 20 sampling sites
(Fig. 3c). Cluster 1 consists of three sampling
points (DE1, DE2, and DE5) and cluster 2 consists of ten sampling points (DE3, DE4, DE6
DE8, and DE16DE20). Cluster 3 consists of
seven sampling sites (DE9DE15). These sites are
located within the lagoon, but also receive inputs from municipal sewage system which is connected to the tannery drains. When CA was run
for only the metal data set, three major clusters
were also obtained (Fig. 3d). Cluster 1 consists
of five sampling sites (D1DE5). Cluster 2 contains eight sampling sites (DE6DE8 and DE16
DE20) whereas cluster 3 contains sites DE9
DE15. There is good agreement between the CA
results of all parameters and that of metals only,

646

with the exception of DE3 and DE4 which fall in


different groups in the two CA analyses.
The factor scores from the R-mode PCA performed on the metal data set was also used
to identify sampling site similarities/groupings
(Fig. 7). On the plot of the first two principal
components, PC1 vs. PC2, PC1 divides the sampling points into two main groups: D1DE5 and
DE6DE20. PC2 separates the first group into
subgroups: DE1, DE2 and DE3, and DE4 and
DE5 (Fig. 7a). Similar groupings are observed
in the plot of PC1 vs. PC3 (Fig. 7b). However,
in Fig. 7b, PC3 divides DE6DE20 into DE6
DE15 and DE16DE20. The R-mode PCA and
R-mode CA appear to agree with each other.
The subgroups depicted by the PCA also occur as
primary clusters and/or sub-clusters in CA. Thus,
the sampling sites may be grouped into three
statistical important clusters: D1DE5; DE6DE8
and DE16DE20; and DE9DE15.
The average concentrations of the analyzed
water quality parameters in the three categorized
groups are presented in Table 6. Group 1, consisting of D1DE5, has the highest values of pH
(6.88) and SO2
4 (884 mg/l), which differ slightly
from the corresponding values in the other two
groups. Group 1, however, has the lowest concentrations for most of the parameters, except
As and Cl . The sampling stations are situated
at the extreme upstream of the canal and very
close to the tannery campus. Group 3 comprises
samples DE9DE15, and has the highest concentrations of all analyzed parameters, except pH
(Table 6). The mean concentrations
and SO2
4
(mg/l) of heavy metals at these sampling sites are

Environ Monit Assess (2011) 175:633649

as follows: Cr (10.88), Mn (0.92), Fe (9.83), Co


(0.63), Ni (0.57), Cu (0.79), Zn (1.52), As (0.85),
Pb (1.49), and Cd (0.18). These sites are located
at lagoon areas and correspond to relatively high
polluted sites, compared to other sample groups.
Group 3 stations receive pollution from point and
nonpoint sources, which are highly influenced by
industrial and urban sewage system of Dhaka City
Corporation.
Group 2 consists of samples DE6DE8 and
DE16DE20 and is moderately enriched with
metals, except As. It corresponds to relatively
moderate pollution sites. In group 2, sampling
points are situated in the middle of the canal
and Buriganga floodplain areas of the study area,
which are contaminated by domestic and sewage
effluents. The floodplain area is regularly flashed
with tidal water of Buriganga River.
Correlation matrix
The Pearsons correlation matrix for the analyzed
parameters of the water data set is presented in
Table 7. The inter-element relationships between
metals support the results obtained from PCA
as well as reveal new associations. The metal-tometal correlation coefficient matrix shows strong
and significant correlations. There are strong
( p < 0.01) and significant ( p < 0.05) correlations
between most of the metals in the water samples.
The elemental associations may be summarized as
follows: CaCdCrFeKMnPbZn, CoCu
NiPbZn, CdCoCuPbZn, CoFeMnNi
Zn, AsCoCuZn, and AsCaCrFe. These associations of metals clearly indicate that the lagoon and canal water have assimilated various

Fig. 7 Plots of PC1 vs. PC2 and PC1 vs. PC3 showing groupings among sampling sites

Environ Monit Assess (2011) 175:633649


Table 6 Descriptive
statistics of the three
classified sample groups
by HCA and PCA

pH
EC (mS cm1 )
COD
SO2
4
PO3
4
Cl
NO
3
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Pb
Cd

647
Group 1
(n = 5) average SD

Group 2
(n = 8) average SD

Group 3
(n = 7) average SD

6.88
7.99
689.8
884.4
19.08
4,594
37.15
2.33
23.83
0.07
0.16
0.30
0.25
0.26
0.23
0.11
0.54
0.23
0.03

6.50
10.88
789.9
836.1
31.86
4,123
65.41
44.20
42.88
3.62
0.39
2.38
0.30
0.17
0.31
0.36
0.40
0.62
0.15

6.73
14.33
945.7
883.7
38.79
5,220
132.04
56.37
69.70
10.88
0.93
9.83
0.63
0.57
0.79
1.52
0.85
1.49
0.18

0.46
0.49
58.7
234.7
11.77
1,559
49.13
0.21
1.16
0.10
0.11
0.10
0.14
0.37
0.35
0.10
0.20
0.09
0.01

contaminants from the processes of tannery and


paint industries, and municipal sewage systems.
A similar correlation agreement has been evaluated in tannery effluent of Multan, Pakistan, by
Tariq et al. (in press). The significant correlations
( p < 0.05) among Ni, Mn, Fe, and Co indicate that they may have originated from common
sources, preferably from other industrial (chemicals, paints) activities. Here, the association is
slightly different from the PCA results, where Ni,
Co, and Cu are highly correlated and recognized

0.56
1.92
92.2
66.2
7.55
1,050
22.44
7.67
13.69
4.08
0.32
2.37
0.12
0.05
0.20
0.19
0.25
0.57
0.07

0.42
3.42
95.8
61.8
6.74
372
43.55
10.09
16.45
5.39
0.26
3.39
0.29
0.31
0.46
0.65
0.14
0.90
0.05

as outputs from paint industries. As previously


mentioned, Mn and Fe are indicative of sources
of tanning processes in leather industries. This
new association probably suggests that Mn and Fe
may have been obtained from mixed sources. The
strong correlation of As with Cr and Fe indicate
their common source from tannery industries.
The R-mode PCA and CA, supported by
Pearsons correlation matrix, suggest that the ana
2
lyzed parameters EC, COD, PO3
4 , NO3 , SO4 ,
Cl , K, Ca, Cr, Mn, Fe, Zn, As, Pb, and Cd in

Table 7 Pearsons correlation matrix among metals in lagoon and canal water samples
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Pb
Cd

Ca

Cr

Mn

Fe

Co

Ni

Cu

Zn

As

Pb

Cd

1
0.727a
0.584a
0.610a
0.656a
0.417
0.265
0.461b
0.503b
0.338
0.488b
0.728a

1
0.622a
0.648a
0.606a
0.696a
0.430
0.787a
0.678a
0.541b
0.656a
0.765a

1
0.430
0.773a
0.394
0.322
0.365
0.843a
0.630a
0.503b
0.391

1
0.554b
0.508b
0.573b
0.435
0.707a
0.274
0.746a
0.719a

1
0.436
0.524b
0.440
0.702a
0.699a
0.288
0.318

1
0.480b
0.721a
0.536b
0.465b
0.527b
0.521b

1
0.531b
0.504b
0.395
0.501b
0.255

1
0.520b
0.487b
0.575a
0.557b

1
0.500b
0.755a
0.513b

1
0.259
0.080

1
0.642a

a Correlation
b Correlation

is significant at the 0.01 level


is significant at the 0.05 level

648

the water systems may have originated from combined sources of tannery industry and municipal
sewage. The strong association of Co, Ni, and Cu
indicates common sources, and these metals may
have been derived from anthropogenic sources,
especially paint industry and municipal sewage
system.

Conclusions
This study has employed principal component and
cluster analyses to investigate the sources of heavy
metal pollution of the lagoon and canal water
systems at the Hazaribagh area of southwestern Dhaka, Bangladesh. The mean concentration
of the analyzed physicochemical parameters and
metals are quite high and greatly exceed the permissible limits of Bangladesh industrial effluent
standards. Among the measured parameters, the
concentrations of Cr, As, Pb, and Cd are more
significant and somewhat alarming in evidencing
the pollution potential.
In the multivariate statistical analyses, three
groups are extracted from the sampling sites by
the Q-mode CA and PCA methods. Group 1
includes sites DE1DE5, which are located at the
proximal part of the canal and close to the tannery
complex. Group 2 includes sampling sites located
close to the lagoon (DE6DE8), and the discharging point of the canal to Buriganga River (DE16
DE20) whereas DE9 to DE15 fall in group 3.
The group 3 sites appear to be the most polluted,
followed by group 2 with group 1 being the least
polluted with respect to the analyzed parameters.
The R-mode PCA and CA, supported by Pearsons correlation matrix, suggest that the effluents
discharged from the tannery and auxiliary (e.g.,
paint) industries, and municipal sewage are the
main sources of heavy metal pollution in the lagoon and canal water systems in the Hazaribagh
area of southwestern Dhaka. GIS-based factor
score maps are developed to show the spatial variations of the contributing processes affecting surface water hydrochemistry in the study area. The
activities of paint and tannery industries and urban sewage are competitive processes influencing
surface water hydrochemistry in the area, while

Environ Monit Assess (2011) 175:633649

the contribution from pesticides has localized


effects.
In this regard, several control measures can be
recommended to mitigate the adverse conditions
of environment of this study area. For sustainable environmental management, the government
should encourage the tannery entrepreneurs to
set up the necessary treatment plants for improving the existing effluent quality. The treatment
process may offer reuse of recycled water and
reduce the usage of groundwater as well as minimize the production cost of tannery commodity. Considering the existing environmental and
public health conditions, it is also recommended
that the tannery complex be re-located elsewhere,
away from the capital city.
Acknowledgement The first author acknowledges
financial support from the Japanese Government
(MONBUKAGAKUSHO Scholarship). The authors are
indebted to Roksana Begum, Department of English,
Jahangirnagar University, Dhaka, Bangladesh, for her
sincere efforts on the English language development.
Sincere gratitude to the anonymous reviewers whose constructive comments significantly improved the manuscript.

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