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Studies on heavy metals in industrial effluent, river and groundwater of Savar

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 INTERNATIONAL JOURNAL OF GEOMATICS AND GEOSCIENCES
Volume 5, No 1, 2014
© Copyright 2010 All rights reserved Integrated Publishing services
Research article ISSN 0976 – 4380

Studies on heavy metals in industrial effluent, river and groundwater of

Savar industrial area, Bangladesh by Principal Component Analysis
Faisal B.M.R1, Ratan Kumar Majumder2, Mohammed Jamal Uddin1, Mohammed Abdul
Halim3
1- Department of Environmental Sciences, Jahangirnagar University, Dhaka-1342,
Bangladesh.
2- Nuclear Minerals Unit, Atomic Energy Research Establishment, Dhaka-1349,
Bangladesh.
3- Process Research ORTECH inc., 2350 Sheridan Park Drive, Mississauga, ON, L5K 2T4,
Canada
ratankm@yahoo.com

ABSTRACT
A total number of twenty water samples of which seven groundwater, six river water and
seven effluent samples were collected from Savar industrial area in Bangladesh for heavy
metals analysis using ICP-MS system. The average concentration of Fe, Mn, Cr, Zn, As, Ni
and Pb were 929.97, 101.01, 6.08, 33.36, 9.18, 2.03 and 3.99 mg/L in groundwater; 286.48,
37.65, 0.13, 9.18, 1.39, 1.53 and 1.26 mg/L in river water and 606.64, 72.71, 5.04, 25.05,
1.72, 2.37 and 1.56 mg/L in effluent, respectively. The average concentration of Cr, Mn,
Ni, Fe, Pb, Zn and As exceed WHO and DoE, Bangladesh limits in relation to river water
and groundwater. The order of average heavy metal content was
Fe>Mn>Zn>Cr>Ni>As>Pb in effluent water, Fe>Mn>Zn>Cr>Pb>Ni>As in groundwater
and Fe>Mn>Zn>Ni>As>Pb>Cr in river water. Multivariate statistical analyses such as
principal component, cluster analysis and correlation matrix shows significant
anthropogenic and geogenic intrusions of Fe, Mn, Cr, Zn, As, Ni, and Pb in river and
groundwater in the study area. Significant positive correlation between Cr vs Zn, Cr vs As,
Mn vs Fe, Mn vs As, and Zn vs Pb indicates their common origin, especially from
industrial effluents and municipal wastes that are responsible for the enrichment of these
variables as moving together in river water. On the other hand, strong positive correlation
between Cr vs As and Ni vs Pb in groundwater reveal the anthropogenic sources of these
variables. The high concentration of heavy metals in groundwater and river water may
cause serious threat to public health as well as the aquatic environment.

Keywords: Industrial effluent, Wastewater, Heavy metals, Principal component analysis,

Statistical analysis.

1. Introduction

The industries in Savar area include garments, textile miles, leather goods, metal products,
electronic goods, paper products, chemicals and fertilizers and miscellaneous products
(Khan et al., 2011). In the study area the industries discharge waste water with heavy
metals, toxic chemicals, dissolved lime, chromium sulfate, alkali, hydrogen sulfide, sulfuric
acid, bleach, dyes, oil, formic acid, suspended solids, organic matter, pesticides,
polychlorinated biphenyls (PCBs), dioxins, poly-aromatic hydrocarbons (PAHs),
petrochemicals, phenolic compounds and microorganisms (Fakayode, 2005) etc. Besides,
the uneducated farmers randomly use fertilizers and pesticides in agricultural lands. The

Submitted on June 2014 published on August 2014 182

Studies on heavy metals in industrial effluent, river and groundwater of Savar industrial area, Bangladesh
by Principal Component Analysis
Faisal B.M.R et al

industries discharge large amounts of effluents everyday which are being directly
discharged into the surrounding land, agricultural fields, irrigation channels, surface water
and finally rivers after partial treatment or without any treatment. The uncontrolled
dumping of huge industrial wastes of point and non-point sources is even extremely
hazardous when the pollutants are heavy metals and cannot be treated easily by
conventional methods. Industries cause environmental degradation thought the life cycle of
a product starting from exploration of raw materials and energy resources to disposal of
waste and end products ( Suzuki et al.,1998). Surface waters are most vulnerable to
pollution due to their easy accessibility for disposal of waste waters. River plays a major
role in assimilation or carrying off the municipal and industrial wastewater and runoff from
agricultural land.

The heavy metals are very harmful, toxic and poisonous even in ppb (parts per billion)
range (Trivedi, 2003). These toxic heavy metals released in aquatic environment may enter
into the food chain through bio-magnification which may cause various health problems in
humans. Ultimately metallic components leach to groundwater and lead to contamination
due to accumulation and may cause series problems for living things. Another recent
investigation reported that elevated levels of heavy metals in vegetables are found from the
areas having long term uses of treated or untreated wastewater (Sharma et al., 2009). The
objectives of this study are to investigate heavy metals content in groundwater, river water
and industrial effluent in the study area and to evaluate the surface water and ground water
quality in terms of heavy metals concentration in the study area.

2. Study area

The study area is lies between 23044″ to 24000″ north latitude and 90014″ to 90029″ east
longitude (Figure 1). The area comprise of many isolated water bodies occupying the low
lying and depressed areas connected or not connected to the river system. The Bansi-
Daleshwari and Turag rivers comprise the drainage network of the study area. The average
rainfall distribution pattern in various months shows a distinct conformation with the
climatic pattern prevailing, with strong monsoon influence. The average annual rainfall in
dry and wet season in the area is about 25 and 380 mm, respectively (Rahman et al., 2012).
Hydrology of the study area is governed by rainfall intensity and distribution, permanent or
ephemeral water bodies and rivers or canals. The land of Savar industrial area is composed
of Pleistocene Red Clay and recent alluvium soil overlying Dupi Tila aquifer. The major
part of the land is used for the cultivation of agricultural products and the rest is used for
industrial activity.

3. Material and methods

3.1 Sample collection

In present study, 6 river water, 7 groundwater and 7 effluent samples were collected during
January 2010 for the analysis of heavy metals. The location of each sample point was
determined with the help of a GARMIN handheld GPS receiver. The sampled tube wells
were purged for 10 minutes prior to sampling. Well depths were noted from the record
preserved by the well owners. The samples were collected in high-density polypropylene
bottles and were shipped to Japan by express mail and stored at 4 ºC in dark until analysis.
Filtered (<0.45 µm cellulose acetate filter) and acidified (with supra pure 0.7N HNO3 to

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Faisal B.M.R et al

reach a pH <2) water samples were collected for heavy metal analyses following the
procedure outlined by Bhattacharya et al., 2002.

Figure 1: Locations of sampling site with photograph in study area

3.2 Laboratory analysis

Water samples were diluted several times to adjust for the operating range and were then
analyzed. The concentration of heavy metals (Fe, Mn, Pb, Zn, Cu, Cr and As) in water
samples were analyzed by inductively coupled plasma and mass spectrometry (ICP-MS),
which was linearly calibrated with custom multi-element standards (SPEX CertiPrep, Inc.,
NJ, USA) at the Center of Advanced Instrumental Analysis, Kyushu University, Japan.

3.3 Statistical analysis

Principal Component Analysis (PCA) was done on the original data set (without any
weighting or standardization) following the theories and methodologies stated by Dreher,
2003. After the application of PCA, a varimax normalized rotation was applied to minimize
the variances of the factor loadings across variables for each factor. Cluster Analysis (CA)
was performed on chemical parameters on both data sets using the weight-pair group
average based on Pearson Coefficient. In this study, CA was performed in Wards Mode by
Statistica 7 for the analysis of heavy metal in water samples (Halim et al., 2011). Pearson’s
product moment correlation matrix was used to identify the relationship among metals and
to support the results obtained by multivariate analysis (Bhuiyan et al., 2010).

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4. Result and discussion

The results of heavy metal concentrations in effluent, groundwater and river water samples
collected from the Savar industrial area, Bangladesh are presented in Table 1. The
concentrations of heavy metals Cr, As, Mn, Ni, Zn and Fe in the analysed water samples
exceeded the WHO (2011) and Department of Environment (DoE) limits of Bangladesh.
The average concentrations of Fe, Mn, Cr, Zn, As, Ni, and Pb in groundwater were 929.97
mg/L, Mn 101.01mg/L, 6.08 mg/L, 33.36 mg/L, 9.18 mg/L, 2.03 mg/L and 3.99 mg/L
respectively which exceeded both WHO (2011) and DoE Bangladeshi standard. In river
water also the average Fe, Mn, Cr, Zn, As, Ni and Pb concentration 286.48 mg/L, 37.65
mg/L, 0.13 mg/L, 9.18 mg/L, 1.39 mg/L, 1.53 mg/L and 1.26 mg/L respectively exceeds
both the WHO and DoE safe limits for Bangladesh.

Based on the average concentrations of heavy metals, the order of heavy metal
concentration in groundwater was Fe>Mn>Zn>Cr>Pb>Ni>As and
Fe>Mn>Zn>Ni>As>Pb>Cr in river water. The average concentrations of Pb, Mn, Fe, Ni
and Zn were high in groundwater compare to river water (Table 1). These may be due to
the percolation of surface water into the subsurface aquifer system in study area. Another
reason is that the rivers in study area are not flowing so heavy metals in surface area from
various industrial activities accumulate in groundwater due to percolation from river bed.
Due to runoff heavy metals from other sources like agriculture practice may found in
surface water and then leached down into groundwater. The above result suggests that the
study area is facing water pollution especially with dangerous heavy metals Fe, Mn, Cr, Zn,
As, Ni, and Pb which may result from increased rate of non-treatment industrial waste and
unplanned agricultural activities in the study area.

The concentration heavy metals in groundwater samples in relation to DoE and WHO
standard showed that Pb content in groundwater samples exceeded the DoE and WHO
standards (0.1 mg/L and 0.01 mg/L, respectively) for six groundwater samples. The highest
Pb content (11.22mg/L) was detected at the depth of 40 m (Table 1) and the high Pb
content in groundwater could be due to untreated industrial effluent, battery production and
scrap battery recovery facilities as well as phosphate fertilizers and pesticides from
agricultural activities in the study area. Seven groundwater samples have exceeded the
WHO (5 mg/L) health based limits with respect to Mn concentration. The highest Mn
concentrations (251.1mg/L) in groundwater were detected at depth of 45 m (Table 1). The
high concentrations of Mn in groundwater may be due to the presence of different valencies
of Mn (Mn (II) and Mn (IV)) in shallow depths. However, Mn (II) is possibly dominant
over Mn (IV) due to its higher mobility.

The content of Fe in groundwater is found in between 177.5 mg/L to 2224 mg/L at the
depths ranging from 15 m to 105 m in study area. All the groundwater samples exceeded
the WHO limit (0.02 mg/L) for Ni in drinking water (Table 1). The variation of Ni
concentration was observed from 0.785-4.38 mg/L at depth of 18-105 m in groundwater
and the highest concentration of 4.38 mg/L was found at the depth of 45m in study area. All
the groundwater samples exceeded the DoE standards (2.0 mg/L) and WHO (0.3 mg/L)
standard in relation to Fe concentration. The highest Fe concentration of 2224 mg/L is
found at depth of 55m (Table 1). The main source of elevated level of Fe in groundwater is
due to reductive dissolution of Fe-oxyhydroxide in the presence of organic matter (Halim et
al., 2009). Finally, with respect to Zn, As and Cr all the groundwater samples exceeded the
respective WHO limit of 3 mg/L, 0.01 mg/L and 0.05 mg/L at various depth from 15-105m

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given in Table 1. The high concentrations of heavy metals in groundwater may be due to
vertical percolation of heavy metals in to the underlying Dupi Tila aquifer in the study area.

Table 1: Heavy metals content of effluent, river water and groundwater in Savar study area
Sample ID Depth Cr Pb Mn Fe Ni Zn As
(m) (mg/L) (mg/L (mg/L) (mg/L) (mg/L) (mg/L)
(mg/L) )
Effluent
S(E)-01 2.017 2.675 246.5 1040 2.367 50.02 1.757
S (E)-03 9.726 0.9103 33.09 1234 2.367 29.45 BDL
S(E)-04 14.74 1.518 19.31 1182 1.763 21.72 0.8897
S(E)-15 4.085 1.294 87.41 238.6 4.926 14.04 2.11
S(E)-18 1.777 1.491 63.99 190 2.827 33.72 BDL
S(E)-19 1.145 1.355 13.63 74.69 0.8143 9.781 BDL
S(E)-20 1.755 1.646 45.07 287.2 1.533 16.61 2.142
Average 5.04 1.56 72.71 606.64 2.37 25.05 1.72
River water
S(R)-07 0.1033 1.044 11.78 122.4 2.108 7.914 1.082
S(R)-08 0.1343 1.19 10.38 228.5 BDL 9.68 1.275
S(R)-09 0.1435 1.561 46.69 152.8 1.131 10.53 BDL
S(R)-10 0.1222 1.241 85.14 467.4 1.677 8.581 BDL
S(R)-11 0.1125 1.338 39.43 531.4 1.504 9.46 1.821
S(R)-12 0.1521 1.189 32.46 216.4 1.246 8.896 BDL
Average 0.13 1.26 37.65 286.48 1.53 9.18 1.39
Groundwater
S(G)-14 15 BDL 0.8076 44.83 1715 1.619 5.692 BDL
S(G)-16 18 BDL 1.571 117.7 238 0.785 9.085 BDL
S(G)-17 20 BDL 1.101 200.9 323.9 0.699 6.663 BDL
S(G)-05 40 5.174 11.22 14.87 783.4 4.006 50.61 0.0868
S(G)-02 45 0.426 10.34 251.1 1048 4.38 8.695 0.6006
S(G)-13 55 BDL 1.12 73.91 2224 1.849 9.384 BDL
S(G)-06 105 12.64 1.759 3.768 177.5 0.9 143.4 BDL
Average 6.08 3.99 101.01 929.97 2.03 33.36 0.34
DoE surface 0.1 0.1 5.0 2.0 1.0 5.0 0.2
water standard
WHO water 0.05 0.01 0.5 0.3 0.02 3.0 0.01
quality standard
BDL –Below Detection Limit

4.1 Correlation matrix

Inter-element relationships in river water matrix provide information on sources and

pathways of variables in geo-environment. In general, correlations between heavy metals
agree with the results obtained by PCA and CA which are useful to confirm some new
associations between parameters that were not clearly stated in previous analysis.
According to the values of correlation coefficients in river water (Table 2), a significant
positive correlation exists between Cr vs. Zn (0.56), Cr vs As (0.66), Mn vs Fe (0.60), Mn
vs As (0.68), and Zn vs Pb (0.87). The strong correlation among these variables indicates

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by Principal Component Analysis
Faisal B.M.R et al

their common origin, especially from industrial effluents, municipal wastes and agricultural
inputs that are responsible to enrich these variables in river water. The significantly positive
correlation of Zn, As, Pb with Cr and Fe, As with Mn indicates that the variables were
derived from similar sources as moving together.

Table 2: Correlation matrix of heavy metals in river water samples

Cr Mn Fe Ni Zn As Pb
Cr 1.00
Mn 0.07 1.00
Fe -0.31 0.60 1.00
Ni 0.16 -0.49 -0.17 1.00
Zn 0.56 0.04 -0.03 0.26 1.00
As 0.66 0.68 -0.05 -0.45 0.19 1.00
Pb 0.41 0.41 0.13 -0.20 0.87 0.44 1.00

Correlation matrix (Table 3) of heavy metals in groundwater indicates strong positive

correlation of Cr with As (0.77) and Ni with Pb (0.94). The positive correlations within
these variables reveal their common source in groundwater especially from industrial and
agricultural activities in the study area. On the other hand significant negative correlation
also found between Pb vs As (-1.00) Ni vs As (-0.94), Pb vs Cr (-0.80) and Ni vs Cr (-0.69)
in groundwater, which indicates the anthropogenic and geogenic sources of these variables
in the study area.

Table 3: Correlation matrix of heavy metals in groundwater samples

Cr Mn Fe Ni Zn As Pb
Cr 1.00
Mn 0.06 1.00
Fe 0.29 -0.11 1.00
Ni -0.69 0.19 0.27 1.00
Zn -0.57 -0.58 -0.45 -0.14 1.00
As 0.77 -0.23 0.01 -0.96 0.05 1.00
Pb -0.80 0.18 -0.06 0.94 0.01 -1.00 1.00

4.2 Principal component analysis

In PCA analysis for river water samples, all PCs extracted from the variables were retained
with eigen values greater than 1.12 that were taken into account. With respect to principal
component analysis for river water, three PCs were extracted using the correlation matrix
which reflected the processes influencing the heavy metals composition of river water
having 91.13% of total sample variance (Table 4). The variance explanations of the PCs are
50.70%, 24.39% and 16.04% for PC 1, PC 2 and PC 3 respectively. PC 1 was seen to be
strongly correlated with Ni and PC 2 with Mn and Fe. PC 1 was also seen to be negatively
correlated with Cr, Mn, Fe, Zn, As and Pb; PC 2 with Cr and Zn. On contrary, PC 3 mainly
participated in As in river water and negatively precipitated in Zn, Pb and Fe. The source of
PC 1 loading variables could be geogenic while PC 2 and PC 3 loading could be released

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by Principal Component Analysis
Faisal B.M.R et al

from anthropogenic sources, specifically derived from industrial effluents and agricultural
activities in the study area. In PCA analysis for groundwater all PCs extracted from the
variables were retained with eigen values greater than 1.13 that were taken into account.
Three PCs extracted from the correlation matrix reflects the processes influencing the
heavy metals composition of groundwater showing about 96.03% of total sample variance
(Table 5).

Table 4: Varimax normalized factor loading matrix of 7 heavy metals for river water
Parameters PC 1 PC 2 PC 3
Cr -0.73 -0.48 0.29
Mn -0.56 0.77 0.18
Fe -0.10 0.86 -0.36
Ni 0.91 -0.01 -0.06
Zn -0.71 -0.37 -0.58
As -0.80 0.13 0.58
Pb -0.86 -0.03 -0.45
Eigenvalue 3.55 1.71 1.12
% Total variance 50.70 24.39 16.04
Cumulative % 50.70 75.09 91.13

The variance explanations of the PCs are 51.78%, 28.09% and 16.17% for PC 1, PC 2 and
PC 3 respectively. PC 1 is strongly correlated with Ni and Pb and negatively correlated
with Cr and As. On contrary, PC 2 mainly participated Zn and negatively correlated with
Mn, Fe and Cr. While PC 3 is positively contributed with Fe and negatively correlated with
Mn with respect to groundwater samples. Considering the above results, the components
loading of PC 1 may have been derived from lithogenic sources and geochemical
weathering of minerals contribute to the enrichment of groundwater with these metals. On
the contrary and PC 2 and PC 3 can be considered as mixed source from both lithogenic
and anthropogenic inputs.

Table 5: Varimax normalized factor loading matrix of 7 heavy metals for groundwater
Parameters PC 1 PC 2 PC 3
Cr -0.86 -0.47 0.02
Mn 0.18 -0.63 -0.69
Fe -0.05 -0.58 0.78
Ni 0.94 -0.25 0.21
Zn 0.09 0.97 0.08
As -0.99 0.12 0.01
Pb 0.99 -0.05 -0.01
Eigenvalue 3.62 1.97 1.13
% Total variance 51.78 28.09 16.17
Cumulative % 51.78 79.86 96.03

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Studies on heavy metals in industrial effluent, river and groundwater of Savar industrial area, Bangladesh
by Principal Component Analysis
Faisal B.M.R et al

A Cluster Analysis (CA) was carried out to visualize the groupings in measured variables
of river and groundwater. The Cluster Analysis (CA) results are shown in Figure 2 and 3.
The results of cluster analysis (CA) were performed in Ward’s mode by STATISTICA 7.0
using the heavy metals of all river water samples presented in Figure 2. Parameters
belonging to the same clusters or groups are likely to be originated from a common source.
Several common features are observed in this plot and these are very similar to that
examined in PCA. Here, two distinct clusters, which closely relate the group of trace
elements, are evident: (1) Mn, As and Fe and (2) Ni, Pb, Zn and Cr. Each of these clusters
is decoupled from one another and the rest of the parameters form their own cluster. Mn
and As form a cluster, which further sub-cluster with Fe. At the same time, Pb and Zn form
one cluster, along with sub-clustering with Zn and Ni. The cluster made in As, Mn and Fe
joins with Pb, Zn, Cr and Ni in river water. In groundwater; two distinct clusters, which
closely relate the group of trace elements, are evident: (1) Zn, Pb, Ni and Mn and (2) Fe, As
and Cr. Pb and Ni form a cluster, which further sub-cluster with Zn and Mn. While As and
Cr forms a cluster along with sub-clustering with Fe. The cluster made in Zn, Pb, Ni and
Mn joins with Fe, As and Cr in groundwater presented in Figure 3.

Ward`s method
1-Pearson r
1.8

1.6

1.4
Linkage Distance

1.2

1.0

0.8

0.6

0.4

0.2

0.0
Fe As Mn Ni Pb Zn Cr

Parameters

Figure 2: Cluster analysis based on the heavy metal concentrations in river water collected
from the studied area

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by Principal Component Analysis
Faisal B.M.R et al

Ward`s method
1-Pearson r
3.0

2.5
Linkage Distance

2.0

1.5

1.0

0.5

0.0
Zn Pb Ni Mn Fe As Cr

Parameters

Figure 3: Cluster analysis based on the heavy metal concentrations in groundwater samples
collected from the studied area

5. Conclusion

The results of the study revealed that water in Savar industrial area are considerably
contaminated by heavy metals like Fe, Mn, Cr, Zn, As, Ni, and Pb with their concentrations
beyond threshold average values of WHO and DoE safe limits in water which may give rise
to various health hazards. The significantly positive correlation of Zn, As, Pb with Cr and
Fe, As with Mn in river water indicates that these variables were derived from common
origin, especially from industrial effluents and agricultural inputs that are responsible to
enrich these variables in the river water. On the other hand strong positive correlation of Cr
with As and Ni with Pb in groundwater reveal their common source especially from various
industrial processes, agricultural inputs as well as geogenic sources in the study area. The
PCA results suggest that the observed heavy metals Fe, Mn, Cr, Zn, As, Ni, and Pb in river
and groundwater are of anthropogenic origin. Cluster analysis also confirms the PCA
results. PC 1 is loaded with Ni ; PC 2 with Mn and Fe and PC 3 with As in river water. The
component loading of PC 1 may have been geogenic while PC 2 and PC 3 loading could be
released from anthropogenic sources, specifically derived from industrial effluents and
municipal wastes in river water. PC 1 is loaded with Ni and Pb ; PC 2 with Zn and PC 3
with Fe in groundwater. The components loading of PC 1 may have been derived from
lithogenic sources and geochemical weathering of minerals in groundwater. On the contrary
and PC 2 and PC 3 can be considered as a mixed source from both lithogenic and
anthropogenic inputs in study area.

6. References

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2. Bhuiyan M.A.H., Lutfar P., Islam M.A., Samuel B., Suzuki S., (2010), Heavy metal
pollution of coal mine-affected agricultural soils in the Northern Part of Bangladesh,
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3. Dreher T., (2003), Evaluation of graphical and multivariate methods for

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5. Halim M.A., Majumder R.K., Nessa S.A., Hiroshiro Y., Uddin M.J., Shimada J.,
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6. Halim M. A., Sumayed S. M., Majumder R. K., Ahmed N., Rabbani A., (2011),
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9. Sharma R.K., Agrawal M., Marshall F.M., (2009), Heavy metals in vegetables
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10. Suzuki K.T., Sunaga Hiroyuki S., Yasunobu A., Shigehisa H., Yoshio S., Yawara
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