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Evaluation of heavy metals in surface water of major rivers in Penang,


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INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCES Volume 6, No 5, 2016

© Copyright by the authors - Licensee IPA- Under Creative Commons license 3.0

Research article ISSN 0976 – 4402

Evaluation of heavy metals in surface water of major rivers in Penang,


Malaysia
Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N.
School of Physics, Universiti Sains Malaysia, 11800 Pulau Pinang, Malaysia
alsaffarms@gmail.com
doi: 10.6088/ijes.6062

ABSTRACT

Water pollution has an adverse effect on both human and aquatic life; therefore, the
assessment and critical observation of water pollution and its consequences have become
vital. In this study, total concentrations of Cr, Fe, Pb, Cd, Cu, Mn, Ni, and Zn in water
samples were measured by Inductively Coupled Plasma Optical Emission Spectroscopy
(ICP-OES) to evaluate the surface water quality of Sungai Muda, Sungai Jarak, Sungai
Kerian, and Sungai Kongsi, which are major rivers in Penang, Malaysia. Water properties
such as electrical conductivity and pH level were also examined in situ to determine their
quality for irrigation purpose. The concentrations of heavy metals were noted to be within
the ranges 2–3, 11–549, 7–52, 1–2, 4–6, ND–30, and ND–28 for Cr, Fe, Pb, Cd, Cu, Ni,
and Zn, respectively, whereas Mn was not detected in all water samples. These
concentrations were found to be in the allowable range according to the Malaysian
standards for water quality, except for the concentration of Pb in Sungai Kerian. The
concentrations were also determined to be within the limits set by the WHO for drinking
water; however, the level of Ni and Pb in Sungai Jarak and that of Pb in Sungai Kerian
and Sungai Muda exceeded the permissible limits. The conductivity of surface waters was
noted within the range of 72.9 – 1586.3 µS cm–1 , whereas the pH values were in the range
of 6.63 - 7.16. The metals content in surface water as well as water properties were within
safe limits for irrigation in the study area.

Keywords: Heavy metals, Surface water, Risk assessment, Penang rivers.

1. Introduction

Industrialization, population growth, and technological developments in recent years have


led to a huge increase and accretion of heavy metals in the environment (Liu et al., 2009).
Heavy metals, such as Cd, Cr, and Pb, are highly toxic even at minute quantities; these
metals enter the environment mainly through human activities. However, some heavy
metals, such as Cu, Fe, and Mn, benefit the environment in limited quantities by
providing nutrition to plants; these metals are formed naturally, but their overproduction
can result in different toxicological effects on the environment (Alsaffar et al., 2016).
Ecotoxicology pays special attention to essential and non-essential heavy metals because
both can harm living organisms (Hejabi et al., 2011). The toxic effects of heavy metals
are generally produced when their characteristics are changed as they combine with
organic compounds to form complexes (Akbulut & Tuncer, 2011). Heavy metals enter the
environment through various means, including the weathering of rocks and soil, the
discharge of urban and industrial waste into bodies of water, and anthropogenic activities
(Alkarkhi et al., 2008). Previous investigations have indicated a positive correlation
between industrialization and the increased contamination levels of heavy metals in

Received on December 2015 Published on March 2016 657


Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

aquatic environments (Guerrero & Kesten, 1994). Moreover, the accumulation and
solubility of metals in aquatic environments are considerably affected by the pH level,
salinity, and temperature of water (Barlas et al., 2005).

Enriching soil with heavy metals can also lead to increased levels of soil pollution, such
as regularly using contaminated water for irrigation (Bhaskar et al., 2010). The increased
level of heavy metals in soil will increase the concentrations of heavy metals in crops;
consequently, the concentration of heavy metals in human diet will also increase
considerably (Malan et al., 2015). Harmful heavy metals can enter the human body either
through the food chain by consuming crops grown in heavy metal-contaminated water or
by the direct consumption of polluted water. Therefore, the quality of river water must be
regularly monitored to determine its levels of toxic metals and ensure its safety for human
consumption.

Industrialization has intensified in Malaysia, which has led to various incidents of toxic
pollution caused by industrial activities (Alkarkhi et al., 2008). Penang is one of the most
populated, developed, urbanized, and economically important states in Malaysia. Thus,
this study has been conducted to evaluate the water quality of several rivers in Penang,
namely, Sungai Muda, Sungai Jarak, Sungai Kerian, and Sungai Kongsi, by assessing
their heavy metal contents as well as water properties such as electrical conductivity and
pH level in the surface water.

2. Material and Method

2.1 Sites Description

Penang State, which is located on the northwest coast of Peninsular Malaysia (5°8'–5°35'
N latitude and 100°8'–100°32' E longitude), is divided into two parts, namely, Penang
Island and Seberang Perai (Figure 1). Rivers are the major sources of water for
agricultural purposes in this state (Haque et al., 2010). Almost 34,707 ha of land has been
used for agricultural purposes (16% fruits, 37% paddy, 39% oil palm, and 8% others) in
Penang (Penang Institute, 2015) .

Figure 1: Map of selected water samples in Penang


Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 658
International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

The Seberang Perai Rice Irrigation Scheme is one of the main areas for planting rice in
Malaysia. This scheme is divided into five sub-schemes, and the irrigation water supplied
to each sub-scheme is obtained from Sungai Muda, Sungai Jarak, and Sungai Kerian
either through gravity intake or pumping (Haque et al., 2010). Sungai Kongsi provides
water to the Island Rice Irrigation Schemes (Alsaffar et al., 2016). Extensive land use and
industrialization in the northwest coast of Peninsular Malaysia result in higher
concentrations of heavy metals in the waters of this area than in the other parts of the
coast (Ahmad et al., 2003).

2.2 Sampling and Analytical Methods

Water samples were collected from four different locations along each river in May 2015.
Figure 1 depicts the sampling point distribution. The samples were collected into acid-
washed 1liter plastic bottles from approximately 10 cm below the surface water. All
sampling bottles were washed by 10% HNO3 overnight, followed by rinsing with
distilled water, then with three rinses of stream water before collection. At the sampling
sites, the samples were filtered through 0.45 μm pore diameter membrane filters and
immediately acidified to approximately pH 2 with high-purity HNO3 to prevent metal
absorption into the walls of the bottles (APHA, 1999). All collected samples were then
transported to the laboratory and stored at 4 °C until analysis.

In vitro, four subsamples from each river were combined in a 50 ml uncontaminated


plastic container to form a composite sample for metal analysis. The concentrations of Cr,
Fe, Pb, Cd, Cu, Mn, Ni, and Zn metal in the water samples were determined through
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES, Optima 8000;
Perkin Elmer, USA). The user manual was used to set and calibrate the instrument. The
system calibration for metals in water samples was estimated by determining metal
contents in certified reference materials (Quality Control Standard 21, USA), whereas
ultra-pure water (UPW) was used as analytical blank. For an accurate assessment of the
metals, all samples were analyzed thrice, and the independent calibration verification
standard and calibration blank were observed after each test.

By contrast, the pH and electrical conductivity (EC) of surface water were determined in
situ. A pen-type pH meter (Lutron pH-222) with glass electrode was used to determine
the pH of water. A portable conductivity meter (Hach, sensION 5) was used to determine
the EC and the temperature of the surface water. EC and pH tests were conducted on site
by placing the probe of each meter at approximately 3 cm below the surface water for
approximately 3 min until it stabilized, and the readings were recorded immediately.

3. Result and Discussion

3.1 Water Characteristics

The solvent power of water can be determined by observing the pH level of water and
thus the probabilities of chemical reaction with sediments can be determined. If the pH
level of water exceeds the permissible range, then the watered crops may suffer from
nutritional imbalance, which can adversely affect aquatic organisms and human beings
(Sabo, 2013). Low pH levels tend to increase the toxicity of metals in water (Salati &
Moore, 2010). Water with pH levels ranging from 6.5 to 8.4 is considered suitable for
irrigation (Carrow et al., 2008). The mean values of pH, EC and Temperature of surface
Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 659
International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

water for selected rivers in Penang are presented in Table 1. The pH values were ranged
from 6.63 - 7.16 with highest value at Sungai Muda and lowest at Sungai Kongsi.
Therefore, the pH values of water in all rivers falls within the limit set for irrigation
purposes.

Table 1: Mean value of pH, EC and Temperature of surface waters

River pH EC µS cm-1 Temperature ºC


Sungai Muda 7.16 72.9 30.7
Sungai Jarak 7.12 264.5 30.9
Sungai Kerian 6.98 79.1 31.1
Sungai Kongsi 6.63 1586.3 30.1

The capability of water to conduct electricity is determined by its electrical conductivity


(EC). This factor can be used to determine the concentrations of dissolved solids,
particularly electrolytes, and is directly related with salt concentrations and total dissolved
solids (TDS) in water (Hayashi, 2004). Water salinity hazard, which is measured by EC,
exerts the greatest influence on crop productivity. Water with high EC can prevent plants
from competing for ions. Water temperature also has a direct influence on its EC, that is,
a high temperature leads to a high EC. The EC of water must always be less than 2000 µS
cm–1 ; otherwise, salinity problems may arise if EC ranges from 2000 to 3000 µS cm–1
(Fipps, 2003). In the present study, the EC values of waters were ranged from 72.9 µS
cm–1 at Sungai Muda to 1586.3 µS cm–1 at Sungai Kongsi (Table 1). The results show that
Sungai Kongsi has the highest EC in comparison to other rivers. This may be due to the
effect of seawater when returned and mixed with river water during the tidal process,
since the most testing sites of Sungai Kongsi are close to the coast (Figure 1). However,
all surface waters from the rivers were determined in safe limits and consequently do not
have any harmful effect on agricultural land and crops.

3.2 Heavy Metals Content in Water

Table 2 shows the concentrations of heavy metals in water samples collected from the
rivers in Penang. The maximum limits that are provided by the Malaysian standards for
water quality (EQA, 1974), the limits of WHO for drinking water qua lity (WHO, 1993),
and the irrigation water quality standards (Fipps, 2003) are used as guidelines to
determine the upper limit for heavy metal pollution in these samples (Table 3).

Table 2: Mean value of heavy metals in surface waters (µg l-1 )

River Cr Fe Pb Cd Cu Mn NI Zn

Sungai Muda 3 549 17 1 4 ND ND ND


Sungai Jarak 3 11 34 2 5 ND 30 28
Sungai 2 321 52 1 6 ND ND 4
Kerian
Sungai 2 18 7 1 5 ND ND 2
Kongsi
ND: not detected
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International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

Table 3: Maximum limits of heavy metals in water (µg l-1 )


Guide Cr Fe Pb Cd Cu Mn NI Zn

Malaysia A 200 1000 50 10 100 200 200 100


WHO 50 1000 10 3 2000 500 20 5000
Irrigation 100 5000 5000 10 200 200 200 2000

Cr contents in natural waters are usually very low (Tuzen & Soylak, 2006). However, an
increasing number of refractory, metallurgical, and chemical industries discharge Cr
concentrations into bodies of water. Natural Cr compounds are generally in the trivalent
state (Cr(III)); they function as micronutrients for humans and have a vital role in the
metabolism of lipids and sugars (Oliveira, 2012). Nevertheless, anthropogenic activities
can release hexavalent-form Cr concentrations (Cr(VI)) into bodies of water, which are
declared carcinogenic for human health by different regulatory and non-regulatory
agencies (Tchounwou et al., 2012). Cr(VI) is not only harmful for humans but also for
microorganisms, aquatic animals, and plants (Oliveira, 2012). The collected samples have
very low Cr concentrations ranging from 2 to 3 µg L–1 (Table 2). However, this
concentration is greater than that from previous studies on Malaysian rivers (0.05 µg L –1
and 0.8 μg L–1 ) (Gupta et al., 1998). Nevertheless, the cumulative amount of Cr
concentrations in the sample does not exceed the upper acceptable limits for water quality
(Table 3).

Fe benefits the human body in small amounts by forming some biomolecules and
hemoglobins; however, it becomes highly poisonous when ingested in large amounts
(Abbaspour et al., 2014). Fe can take different forms in water, with each form exhibiting
different stability and solubility levels that directly affect its absorption by animals and
humans (Sundaray et al., 2012). The two main forms of Fe are insoluble ferric (Fe +3 ) and
soluble ferrous (Fe+2 ) (Acton, 2013). The concentration of Fe in the collected waters
ranged between 11 µg l–1 in Sungai Jarak and 549 µg l–1 in Sungai Muda (Table 2). The
concentrations of the metals in Sungai Muda (549 µg l–1 ) and Sungai Kerian (321 µg l–1 )
revealed that Fe is the most abundant metal in the water sa mples. The high levels of Fe in
both rivers can be attributed to the iron and steel manufacturing activities, municipal
drainage, and landfill leachates that flow into the rivers. The results also demonstrate that
Fe values are highly variable in water samples as documented in previous studies; Fe
values range from < 5 to over 3600 μg l–1 for Finnish stream water (Lahermo et al., 1996),
whereas the values range from <10 to over 1000 μg l–1 (Neal & Robson, 2000) and <100
to over 1500 μg l–1 (Kritzberg & Ekström, 2012) for United Kingdom and Swedish rivers
water, respectively. Although Fe has the highest mean concentration value (i.e., 224.8 μg
l–1 ) among all of the heavy metals detected in the collected water samples, its
concentration value is lower than the background values (Table 3).

Pb concentration in aquatic systems is primarily increased by anthropogenic activities and


industries. It is mainly introduced into bodies of water through the disposal of batteries,
agricultural runoff from fields that use sewage sludge as fertilizers, at mospheric
deposition of exhaust from vehicles, and sewage discharge (Zweig et al., 1999). Pb is
harmful for all living organisms even at low concentrations; its harmful effects to humans
include anemia, hypertension, symptoms of peripheral nerve paralysis, and neuropathy of
the kidneys (Brochin et al., 2008). Demayo et al. (1982) identified the harmful effects of
Pb on humans and aquatic species. In this study, the mean concentration of Pb (i.e., 27.5
Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 661
International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

µg l–1 ) was ranked second in terms of the most abundant metal in water after Fe. Its
concentration was recorded between 7 and 52 µg l–1 (Table 2). Sungai Kerian had the
highest Pb concentration, whereas the lowest concentration was recorded in Sungai
Kongsi. The results reveal that Pb concentration in Sungai Kerian surpasses the upper
acceptable limit set by the Malaysian standards for water quality (Table 3). Pb
concentrations in Sungai Muda, Sungai Jarak, and Sungai Ker ian also exceeded the
permissible limits set by the WHO for drinking water. The use of leaded petrol was
regarded as the main cause of Pb detected in the Malaysian aquatic environment (Shazili
et al., 2006), which differs from one river to another because of the variation in industrial
locations and the extent of pollution flowing into the rivers. However, the concentrations
of Pb in waters are within the safe limits to be used for irrigation purpose (Table 3)
.
Cd is non-essential and highly toxic metal with adverse effects on living organisms,
particularly on their skeletons and kidneys (Deevika et al., 2012). Cd is considered a chief
contaminant in aquatic environments because this element can easily dissolve in water
(Benavides et al., 2005). Cd mainly enters bodies of water through the discharge and
dumping of effluents into rivers without any prior treatment (Umar et al., 2001). The Cd
concentrations in the collected samples only range from 1 to 2 µg L–1 (Table 2) and are all
within the permissible ranges dictated by the above mentioned standards (Table 3).

Cu with small quantities plays an important role in the human body by supporting the
proper and efficient functioning of certain enzyme systems, particularly the production of
catecholamine. In large quantities, however, Cu can be hazardous for both animals and
humans (Pearson, 1976). Cu can be found in natural waters either in its dissolved form as
Cu2+ ion or in its complex form with organic or inorganic ligands (Georgopoulos et al.,
2001). The Cu concentrations in the collected samples range from 4 to 6 µg l–1 (Table 2),
which is within the permissible range for standard wa ter quality (Table 3). The lowest
concentration is found in the Sungai Muda, whereas the highest concentration is found in
the Sungai Kerian. As shown in Table 2, the samples have a low concentration of Cu
which was the case for those of Cr and Cd as well. Such low concentrations of metals can
be attributed to several chemical or physical reasons, such as the mobility, adsorption, co-
precipitation of metals or the manifestation of certain biological occurrence from aquatic
fauna that can remove metal ions that have accumulated in water.

Mn does not exist as a free metal in nature, but is part of approximately 100 minerals,
some of which include different oxides, silicates, borates, sulfides, carbonates, and
phosphates (Nádaská et al., 2010). Mn is introduced into aquatic environments mainly
through anthropogenic sources, such as sewage sludge, emissions from alloy, iron, and
steel industries, municipal wastewater discharges, and mining and mineral processing.
Some reports have indicated that the presence of Mn in water can increase the toxicity
levels of other metals, particularly Cd (Kabata-Pendias & Mukherjee, 2007). Mn
intoxication has also been documented after the ingestion of polluted water (Hudnell,
1998). Table 2 indicates the absence of Mn in all the water samples. The redox conditions
and pH level of water directly affect Mn concentration. The solubility of Mn increases
under anaerobic and acidic conditions. Mn concentrations under aerobic conditions,
which are typical of surface water, are usually low and do not reach detection limits.
Under such situations, Mn generally takes the form of MnO 2 , which is a stable oxidized
form of Mn and is highly insoluble in this state (Nádaská et al., 2010).

Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 662


International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

Ni is an abundantly present trace metal that is introduced into the environment either
through anthropogenic activities or natural sources. Ni in natural waters generally takes
the form of Ni(H2 O)6 2+ (WHO, 2007). Ni forms a precipitate coating on particles and is
linked to organic matter for mobility in rivers. It is easily accumulated in the biota,
particularly in some aquatic plants, such as phytoplankton (Cempel & Nikel, 2006). Ni in
water is poisonous to plant life at levels as low as 500 µg L–1 (USEPA, 1976). Previous
studies have shown that many Ni compounds are carcinogenic for animals and humans;
however, their complete mechanism in the human body has not yet been comprehended
(Cempel & Nikel, 2006). The concentration of dissolved Ni in Malaysian rivers was
documented within the range of 10–900 μg l-–1 (Gupta et al., 1998). In this study, Ni was
only detected in Sungai Jarak with a concentration of 30 μg l–1 (Table 2). This value
naturally implies that industrial activities are probably responsible for the elevated level
of this metal in Sungai Jarak. Furthermore, Ni content in Sungai Jarak was noted to be
above the highest permissible value by the WHO for drinking water but below the
maximum limit of Malaysian water quality and irrigation water standards (Table 3).

Zn is a part of natural water but in very minute quantities because Zn oxides and its free
metal have very low solubility in water (Sundaray et al., 2012). Zn has an extensive use
in industry. However, atmospheric fallout as well as surface drainage are the most
contributors of Zn to aquatic environments (Hogstrand & Wood, 1996). The level of harm
that can be caused by Zn depends on the aquatic organism that is being considered as well
as the quality of water (Sundaray et al., 2012). Humans tend to consume Zn in large
quantities without damaging their bodies; however, an excessive amount of Zn can lead to
certain health issues (Plum et al., 2010). Zn detected in Sungai Jarak, Sungai Kerian, and
Sungai Kongsi have concentrations of 28, 4, and 2 µg l-–1 , respectively, but it is not
detected in Sungai Muda (Table 2). The concentration of Zn in the water in
uncontaminated areas were reported to be 1 µg l–1 or less, whereas it rarely exceeded 50
µg l-–1 in industrialized areas (Hogstrand & Wood, 1996). However, the concentrations of
Zn in all of the water samples were recorded to be less than the background limits (Table
3).

Figure 2 illustrates the dispersal of heavy metals in the various water samples taken from
several rivers in Penang. This figure exhibits that the concentration of various metals
differs from one river to another. These variations may be due to the fact that the rivers in
Penang are subjected to the effects of different industrial and anthropogenic activities,
since this area is one of the most densely populated in the country.

Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 663


International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

Sungai Muda
500
400
300
Concentration (µg/l)
50

40

30

20

10

0
Cd Cr Cu Fe Mn Ni Pb Zn
Metals

Sungai Jarak
500
400
300
Concentration (µg/l)

50

40

30

20

10

0
Cd Cr Cu Fe Mn Ni Pb Zn
Metals

Sungai Kongasi
500
400
300
Concentration (µg/l)

50

40

30

20

10

0
Cd Cr Cu Fe Mn Ni Pb Zn
Metals

Alsaffar M. S, Suhaimi Jaafar M., Ahmad Kabir N 664


International Journal of Environmental Sciences Volume 6 No.5 2016
Evaluation of Heavy Metals in Surface Water of Major Rivers in Penang, Malaysia

Sungai Kerian
500
400
300

Concentration (µg/l)
50

40

30

20

10

0
Cd Cr Cu Fe Mn Ni Pb Zn
Metals

Figure 2: Distribution of heavy metals in surface waters


4. Conclusion

In this study, we examined the distribution of heavy metals as well as water properties (i.e.
electrical conductivity and pH) in the surface water of Sungai Muda, Sungai Jarak,
Sungai Kerian, and Sungai Kongsi in the Penang State of Malaysia. The order of
abundance of the metals in the analyzed water was noted to be Fe > Pb > Cu > Cr > Cd in
Sungai Muda and Pb > Ni > Zn > Fe > Cu > Cr > Cd in Sungai Jarak, whereas their order
was Fe > Pb > Cu > Zn > Cr > Cd in both Sungai Kerian and Sungai Kongs i. Thus, Zn
was observed in Sungai Jarak, Sungai Kerian, and Sungai Kongsi and Ni was noticed
only in Sungai Jarak, while Mn was not detected in any of the samples analyzed. The
concentration of the various metals differs from one river to another probably because of
the variation in the quality of industrial and sewage wastes being added to the rivers. This
study demonstrates that industrial and anthropogenic activities that are probably
responsible for the elevated level of heavy metals in the selected rivers could be
considered in the future, especially the activities that caused a buildup of Pb and Ni in
Sungai Jarak, and Pb in Sungai Muda and Sungai Kerian. Furthermore, the surface waters
of the selected rivers do not contribute any harmful effect to agricultural land and crops.

Acknowledgments

We would like to express our gratitude to the School of Physics, Universiti Sains
Malaysia for providing research facilities to conduct this study.

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