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1 23 Environmental Earth Sciences ISSN 1866-6280 Environ Earth Sci DOI 10.1007/s12665-012-2038-8 Heavy metal contamination in water and sediment of the Port Klang coastal area, Selangor, Malaysia Seyedeh Belin Tavakoly Sany, Aishah Salleh, Abdul Halim Sulaiman, A. Sasekumar, Majid Rezayi & Ghazaleh Monazami Tehrani
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Page 1: 2 3 Environmental Earth Sciences

1 23

Environmental Earth Sciences ISSN 1866-6280 Environ Earth SciDOI 10.1007/s12665-012-2038-8

Heavy metal contamination in water andsediment of the Port Klang coastal area,Selangor, Malaysia

Seyedeh Belin Tavakoly Sany, AishahSalleh, Abdul Halim Sulaiman,A. Sasekumar, Majid Rezayi & GhazalehMonazami Tehrani

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1 23

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Page 3: 2 3 Environmental Earth Sciences

ORIGINAL ARTICLE

Heavy metal contamination in water and sediment of the Port

Klang coastal area, Selangor, Malaysia

Seyedeh Belin Tavakoly Sany • Aishah Salleh •

Abdul Halim Sulaiman • A. Sasekumar •

Majid Rezayi • Ghazaleh Monazami Tehrani

Received: 17 January 2012 / Accepted: 1 October 2012

� Springer-Verlag Berlin Heidelberg 2012

Abstract This investigation presents the temporal and

spatial distribution of heavy metals (As, Cd, Cr, Cu, Ni, Pb,

Hg, and Zn), in water and in sediments of Port Klang,

Malaysia. Water and sediment samples were collected from

21 stations at 3-month intervals, and contamination factor

ðCfÞ and contamination degree ðCdÞ were calculated to

estimate the contamination status at the sampling stations.

Cluster analysis was used to classify the stations based on

the contamination sources. Results show that concentra-

tions of As, Cd, Hg, and Pb in sediment and As, Cd, Hg,

Pb, Cr, and Zn in water were significantly higher than the

background values at which these metals are considered

hazardous. The main sources of heavy metal contamination

in Port Klang were industrial wastewater and port

activities.

Keywords Heavy metals �Water and sediment pollution �

Port Klang � Malaysia

Introduction

The main goal of most contamination-oriented studies of

water and sediments is to describe or assess existing con-

ditions and to estimate whether the aquatic systems have

been anthropogenically or naturally affected. Low con-

centrations of many elements occur naturally in the earth’s

crust and are mined widely for use. Great amounts of

several elements like toxic heavy metals (cadmium, lead,

chromium and mercury) are discharged into marine envi-

ronments as contaminants by anthropogenic activities (Gao

et al. 2009; Nduka and Orisakwe 2011; Kassim et al. 2011).

Historically, water and sediment quality have been

monitored based on the collection and laboratory analysis

of samples. Several researches showed that concentrations

of heavy metals in sediment are far higher than the con-

centration of dissolved metals in the water bodies (Sultan

and Shazili 2009). Marine sediment acts as both sink and

source for heavy metals (Nobi et al. 2010; Gao et al. 2009;

Gleyzes et al. 2002). The main pathways of heavy metals

partitioning include adsorption, complexation, precipita-

tion and biological uptake. Adsorption is usually the pre-

dominant process, because metals have strong affinities for

iron and manganese hydroxides, particulate organic matter,

and a lesser extent to clay minerals. Consequently, metals

tend to accumulate in bottom sediments (Nobi et al. 2010;

He et al. 2009; Rezayi et al. 2011).

In aquatic systems, monitoring of the dissolved phase is

not sufficient to evaluate distribution, concentration, bio-

accumulation, and availability of these elements. It is nec-

essary to estimate heavy metal concentrations in the

dissolved and solid phases to monitor accurately the metal

contamination in temporal and spatial scales. Heavy metal

cycling in the marine environment is a serious problem as

these metals are stable and a majority of them have toxic

S. B. T. Sany (&) � A. Salleh �A. H. Sulaiman � A. Sasekumar � G. M. Tehrani

Institute of Biological Sciences, University of Malaya,

50603 Kuala Lumpur, Malaysia

e-mail: [email protected]

S. B. T. Sany � M. Rezayi

Food Science and Technology Research Institute,

ACECR Mashhad Branch, Mashhad, Iran

M. Rezayi

School of Chemical Sciences and Food Technology,

Faculty of Science and Technology,

Universiti Kebangsaan Malaysia,

43600 Bangi, Selangor, Malaysia

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DOI 10.1007/s12665-012-2038-8

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effects on living organisms (Nobi et al. 2010; He et al. 2009;

Pekey 2006; Ismail and Beddri 2009). Bioavailability,

mobility, and toxicity of metals depend on their specific

chemical form or binding, which are changed by several

physical and chemical factors, such as pH, temperature,

redox potential, and organic ligand concentrations. These

factors can convert metals from a solid phase to a liquid

phase and sometimes cause pollution of surrounding water

bodies (Sahuquillo et al. 2003; Nobi et al. 2010).

The Port Klang is located in the west coast of Peninsular

Malaysia, in the narrow Klang Strait; this area is important

for fisheries, tourism, navigation, and transportation. After

1981, Klang Strait experienced rapid commercial and

industrial development, which caused an increase in pop-

ulation, leading to contamination and deterioration of the

marine environment quality. This rapid deterioration of the

Port Klang marine environment drew international atten-

tion. Thus, several regulations, guidelines and international

agreements were ratified by research organizations (Asso-

ciation of Southeast Asian Nations and Department of

Environment) to reduce and remedy contamination caused

by several anthropogenic activities, such as harbors, in-

dustrials sites, and tourism, that released high amounts of

contaminants into the marine environment. Nevertheless,

the current information on concentration of contaminants

in Port Klang’s environment is inadequate.

The major objectives of this study are to estimate the

concentration levels of metals including As, Cu, Cr, Cd, Ni,

Pb, Hg and Zn, in the surface waters and sediments, and to

provide baseline data of these metals to assess the responses

of the Port Klang marine environment to anthropogenic

pollution in future.

Materials and methods

Study area and sample collection

The Klang Strait covers an area of about 573 km2 and is

located in the western tropical coastal region (03�00 N to

101�240E) of Malaysia (Fig. 1). This port is divided into

three subsidiary commercial ports (North, South, and West

Port) that are sheltered by surrounding mangrove forests.

Several notable activities in this area include farming,

industrial factories (palm oil, cement, food, and electrical),

and shipping.

Klang Strait is located within the tropics experiencing

two seasons within the year, the northeast (November to

March) and the southeast monsoons (April to October) (Yap

2005). Heavy rainfall, annual flooding and high river flows

are commonly experienced during the northeast monsoon or

wet season, while dry periods occur later during the season.

The mean annual water temperature is 30.04 �C, whereas

the mean salinity has been reported to be 30.25 %. The

annual mean surface and bottom pH values vary between

7.58 and 8.25, and the mean surface dissolved oxygen (DO)

was recorded as 5.38 mg/l (Yap 2005). This area is marked

by a semi-diurnal tide, which ranges from 2 m during neaps

to 5.5 m during spring (Chong et al. 1990).

Assessment of the heavy metal status in Klang Strait

coastal water is a difficult task due to the great variability

in environment conditions. This area is affected extensively

by nonpoint sources, different depth, tidal condition and

strong marine current, due to the northeast monsoon. These

limitations have effect on metals concentration, although

the sediment situation in this area is independent of tidal

influence (Yap 2005). Several concepts have been used to

reduce the impacts of these limitations, such as increasing

number of stations, temporal assessment, and multiple

sediment samplings during the north and south monsoon.

Sediment samples were collected from November 2009

to October 2010 in 21 locations at the three subsidiary ports

and this included six stations in North Port, six stations in

South Port, and nine stations in West Port. These stations

were arranged into three parallel transects from the coast-

line at three different distances (Fig. 1). A multi-parameter

probe (YSI 556 MPS) was used to measure physical

parameters namely, temperature, salinity, dissolved oxygen

and pH from the surface water layer at a depth of 50 cm

(Table 1).

The samples were collected every 3 months in triplicate

from 2 cm depth of the sediment during low tides. Poly-

ethylene bags were used to store the sediment samples,

which were kept in an icebox at 4 �C to reduce biochem-

ical reactions. In the laboratory, the sediment samples were

kept in a freezer at -20 �C until further analysis. The water

samples were collected from surface water and stored in

500 ml polyethylene bottles that were pre-cleaned with

deionized water and rinsed with ambient water before

collection of the samples. Water samples were filtered

through 0.45 lm millipore filters and acidified to pH\ 2

using concentrated nitric acid, and then stored in the dark at

4 �C. The metal concentrations were measured by ICP-MS.

Analytical procedures

Sediment samples were oven dried (60 �C) over the night,

and passed through a 2 mm mesh sieve to remove coarser

particles. The sediment granulometry was analyzed using a

multi-wavelength particle size analyzer (model LS 13 320)

from Beckman Coulter company. The percentages of three

fractions of grain sizes were estimated: Clay (\2 lm), silt

(2 lm\ size\ 64 lm) and sand ([64 lm). A carbon

analyzer (Horiba Model 8210) was used to estimate the total

organic carbon (TOC) following the specific procedure of

Fang and Hong (1999). About 0.5 g of the dried sediment

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Fig. 1 Location of sampling stations in west coastal water of Malaysia

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was digested in 9 ml nitric acid (HNO3), 3 ml hydrofluoric

acid (HF) and 3 ml hydrochloric acid (HCl) in a teflon

vessel, and heated in a microwave.

After cooling, 18 ml of 5 % boric acid was added to the

vessel content to remove the fluoride residue. The vessel

content was centrifuged, followed by filtration into 50 ml

volumetric flasks, and volume was brought to 50 ml by the

double deionized water for measuring the heavy metals

(Yap 2005). Heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn)

were measured by plasma mass spectrometry (ICP-MS) at

the department of chemistry and geology of the University

of Malaya. Most of the metals measured had levels above

detectable limits. ICP-MS was calibrated by external

standard solutions to measure metals and the calibration

was improved using Re and In as internal standards.

Stock reference solutions of 1000 mg/l were diluted to

prepare working standards and the matrix matched with

similar acidity, both procedures being important to make

various concentration ranges. The entire chemical com-

pound used had the actual quality and soap was applied to

wash and rinse the crystal material and teflon bottles prior

to analysis. Laboratory blanks, field duplicates, and stan-

dard reference materials (SRM) 2702 were applied to

improve quality assurance during laboratory analysis.

SRM 2702 is a natural standard reference of inorganic

material collected from marine sediment with the certified

concentration. In this study, the percentage of recovery

varied between 91 and 104. The standard methods indi-

cated warning limits for matrix spike recoveries from 87 to

113 %; thus, the range of recovery was reasonable in this

study (EPA 1996; Ilander and Vaisanen 2007). Potential

contamination was detected by reagent blanks, during the

analytical and digestion procedure.

Contamination factor and contamination degree

To describe the contamination of a toxic compound, a

contamination factor ðCifÞ was defined according to Eqs. 1

and 2 (IDEM 2002; Parris et al. 1998; Schantz et al. 2005).

Cif ¼

Xn

i¼1

Ci0 � 1

Cif

ð1Þ

Cd ¼Xn

i¼1

Cif : ð2Þ

Where, Cif = the contamination factor, Ci

0�1 = the

average content of the compound in question (i) from

surface sediment (0–1 cm) at the accumulation area. The

value should be estimated in lg g-1 ds (ppm), Cin = the

background value of the compound, n = the number of

heavy metals, Cd = the contamination degree

Table 1 The mean concentration of physicochemical parameters during sampling periods

Site Description of stations Code of

Station

Fine

fraction (%)

Sand

(%)

TOC % Depth(m) Salinity

(%)

pH DO

(mg l-1)

T

(�C)

North Port Liquid berth line NL100 58.20 41.79 12.49 14.30 30.15 8.05 6.23 30.27

Remote NL700 49.63 50.36 10.13 20.5 30.81 8.00 6.26 30.25

Mangrove NL1500 73.77 26.22 17.04 10.3 31.24 8.09 6.10 30.29

Container berths NC100 59.78 40.21 11.41 13.5 30.81 8.08 6.22 30.09

Remote NC700 50.89 49.10 10.08 21.6 31.02 8.02 6.29 30.19

Mangrove NC1500 65.19 34.80 14.71 11.2 31.36 8.11 6.04 30.25

West Port Cement berth and industrial outlets WC100 53.57 46.42 10.24 12.5 30.86 8.09 6.09 30.08

Remote WC500 45.96 54.03 7.74 19.5 30.98 8.01 6.33 30.17

Mangrove WC1000 63.42 36.57 11.98 7.8 30.86 8.07 5.86 30.16

Liquid berth and industrial outlets WL100 56.33 43.66 9.14 13.3 30.44 8.04 6.20 30.06

Remote WL500 41.10 58.89 7.55 20.3 30.58 8.00 6.27 30.14

Mangrove WL1000 70.81 29.18 12.76 8.8 30.75 8.04 6.07 30.06

Container berths WT100 52.31 47.68 10.63 15.5 30.51 7.97 6.28 29.94

Remote WT500 50.69 49.30 10.15 21.11 30.63 7.96 6.38 30.16

Mangrove WT1000 70.36 29.63 15.49 6.8 30.77 8.01 6.26 30.15

South Port Mouth of Klang River SK100 95.39 4.60 22.65 7.5 26.10 7.98 5.51 29.79

Mouth of Klang River SK1000 93.16 6.83 21.55 10.5 26.12 7.99 5.50 29.99

Semi-urban SK2000 64.69 35.30 15.59 12.4 30.11 8.05 6.05 30.02

Liquid berth SL100 69.50 30.49 13.79 10.3 29.45 8.09 5.82 30.10

Industrial SL1000 69.72 30.27 14.91 11.3 29.54 8.09 5.83 30.10

Mangrove SL2000 57.73 42.26 11.89 10.4 30.50 8.03 6.19 30.26

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There are several approaches to estimate an accurate

natural background level in all projects. This discussion

can be treated in different methods: one is to use a general

geological reference value such as an element’s concen-

tration in the earth crust, which was introduced by Ture-

kian and Wedepohl in 1961. The other way is to use data

older than 10 years as equivalent to pre-industrial or pre-

civilization values. In the first method, all local variations

are ignored, and in the second method, all local differences

are emphasized. Hakanson (1980) proposed a method to

estimate a natural background value based on the second

approach. In this study, the background value for sediment

was measured based on the Eq. 3 because there were pre-

vious data of sediment quality in west coast area of Pen-

insular Malaysia from 1992 until 2006. Water quality was

assessed based on marine water background value pre-

sented by Hakanson (1980).

Cin ¼ xþ sx: ð3Þ

Where, Cin is the natural background value, x is the mean

of pre-industrial data or old previous studies, and sx is one

(1) standard deviation. This contamination factor ranged as

low ðCif\1Þ, moderate ð1�Ci

f\3Þ, considerable ð3�Cif

\6Þ, and very high ðCif � 6Þ. The contamination degree

ðCdÞwas estimated based on the sum of all contamination

factors. The specific terminology is used to describe the

contamination degree of sediment—low contamination

degree ðCd\8Þ, moderate contamination degree ð8�Cd

\16Þ, considerable contamination degree ð16�Cd\32Þ,

and a very high contamination degree ðCif � 32Þ.

Microsoft Excel and SPSS 17 software were used to

perform statistical analyses. The two-way ANOVA test

(level of significance is 0.05) was employed to understand

the variation of the heavy metal concentration with respect

to different seasons and stations. Kendall’s tau-b correla-

tion analysis was constructed to understand the relationship

between heavy metals in sediment and other parameters.

Standard deviation was estimated to evaluate variation or

dispersion from the average of physicochemical parameters

based on repeating the analyses 16 times over the four

separate months.

Results and discussion

Some physicochemical parameters of water and surface

sediment have been determined to evaluate a possible

relationship between these parameters (Table 1). The pH is

a main indicator to assess water quality and pollution in

marine and coastal systems. According to the guidelines,

the acceptable range for pH is 6.5–8.5. In this study, pH

ranged 7.96–8.11, which indicates the alkaline nature of the

Port Klang coastal waters where mainly influenced by

Klang River discharge and land based runoff. Temperature

and dissolved oxygen ranged 29.79–30.29 �C and

5.50–33 mg l-1, respectively. There were no significant

differences in temperature and dissolved oxygen at all

stations. Salinity ranged between 26.10 and 31.36 %, the

lowest salinity value was recorded at stations SK100 and

SK1000, because of their location close to the fresh water

flow of the Klang River.

In the present study, according to reports of the

Malaysian Metrological Service (MMS) between 2009 and

2011, the monthly average rainfall ranged from a minimum

of 190 mm in August to a maximum of 410 mm in April

and May; the average was 266.91 mm. November, April

and May were the months with the greatest number of

raining days (400–410 mm). Other researchers have

reported that the river discharge at Klang Strait is highly

correlated with rainfall patterns, and as expected, the

maximum river discharges were measured in November

2009 and April and May 2010.

Analysis of sediment grain size demonstrated that fine-

grained sediment (\64 lm) predominated at almost all

stations (41.1–95.39 %). The maximum of fine fractions

were measured at stations close to the mangrove line and

mouth of Klang River, while the highest portion of the sand

fraction was recorded at stations WC500 (54.03) and

WL500 (58.89). According to the two-way ANOVA, there

are significant differences (p\ 0.05, df = 21, f = 8.82,

sig = 0.00) between distribution of fine-grained sediment

at different stations; however, there is no significant dif-

ference (p\ 0.05, df = 3, f = 0.82, sig = 0.66) between

its concentration at different seasons.

Several factors affect grain size variation in a marine

system, such as sediment transportation and sedimentary

process (Bowen 1966; Hakanson 1980). In this study, areas

with high percentage of fine sediment were found near the

mangrove forest. This may be due to the land-based runoff

and sedimentary process of mangrove forests. Several

studies showed that mangrove forests can increase the

suspended solid deposition by decreasing the water

dynamic energy and provide enough time for deposition of

fine grain sediment (Qin et al. 1989). Moreover, the high

percentage of fine-grained sediment was at stations close to

the Klang River, which is good evidence to confirm the

effect of the river transport mode on the distribution of

sediment particles.

The TOC content of sediment ranged between 5.35

and 24.88 % and its concentrations were significantly dif-

ferent either at stations (p\ 0.05, df = 21, f = 10.10,

sig = 0.00) or in seasons (p\ 0.05, df = 3, f = 3.62,

sig = 0.018). The distribution of TOC follows the same

pattern as fine-grained sediment in most parts of Port Klang

with high concentrations of TOC recorded at stations

SK100 and SK1000 near the mouth of Klang River and the

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lower percentage at stations WC500 and WL500. There

was high correlation (0.716) between the TOC and fine-

grained sediment in study area. In November 2009, the

TOC percentage increases with decreasing mean grain size

because the fine particle size, particularly the clay colloid,

has a high tendency to adsorb TOC.

Spatial and temporal variation of heavy metals

In water, the spatial variation of dissolved metals concen-

tration during the sampling periods and the ranges of val-

ues recorded are given in Table 2. There was distinct

temporal variation of heavy metals concentration during a

year (Fig. 2). Figure 2 shows that all metals have high

fluctuations during four samplings times in surface water,

and the highest mean metal concentration was recorded in

May 2010 and November 2009. The large value of standard

deviation (Fig. 2 and Table 2) reflected a wide variation of

dissolved metals concentration in temporal and spatial

scales in a two-way ANOVA test (Woodroffe 1992; Wo-

lanski et al. 1992; Furukawa et al. 1997; Kathiresan 2003;

Cunha-Lignon et al. 2009). This test indicates significant

temporal and spatial difference (p\ 0.05, sig = 0.00) in

dissolved metal concentration in water.

The mean concentrations of heavy metals in surface

sediment are summarized in Table 3 with their ranges.

Fig. 3 shows temporal variations of heavy metal concen-

trations during a year. The results showed that concentra-

tions of metal in surface sediments were significantly

(p\ 0.05, sig = 0.00) changed in temporal and spatial scale

in a two-way ANOVA test. The metal concentration in both

water and sediment showed a wide variation in temporal and

spatial scale. This is attributed to differential derivation of

these contaminations from lithogenic and anthropogenic

sources such as untreated effluents discharges from indus-

tries, port activities and domestic sewage.

The highest metal levels in sediment and water samples

were measured in South Port, at the SK100 and SK1000

stations, which are close to the mouth of the Klang River.

According to several studies, several contaminants such as

untreated waste, municipal effluents, and industrial wastes

are being discharged directly into the river (Yap 2005),

thus the Klang River discharges can be considered a major

route of contamination in the Port Klang. The water and

sediment in South Port easily exchange with the polluted

Klang River fresh water because the water currents in the

vicinity of South Port are weak; therefore, there is enough

time for the absorption of heavy metals by suspended

Table 2 The mean and standard deviation (±) concentrations of the heavy metals in the surface water during sampling periods (lg l-1)

STATION As Cu Cr Cd Ni Pb Hg Zn

NL100 15.8 ± 11.4 2.88 ± 1.61 3.5 ± 2.42 0.44 ± 0.1 1.86 ± 0.9 3.54 ± 0.8 0.01 ± 0.001 49.5 ± 30.3

NL700 13.3 ± 9.5 1.71 ± 0.66 2.83 ± 1.5 0.44 ± 0.1 1.61 ± 0.7 3.79 ± 0.9 0.01 ± 0.001 45.0 ± 25.5

NL1500 15.3 ± 7.89 1.63 ± 0.71 2.41 ± 1.6 0.42 ± 0.2 1.54 ± 0.7 3.96 ± 0.5 0.01 ± 0.001 44.1 ± 24.8

NC100 20.0 ± 14.9 2.53 ± 1.37 4.28 ± 2.5 0.85 ± 0.6 2.47 ± 0.9 2.32 ± 0.7 0.01 ± 0.001 59.6 ± 40.1

NC500 18.6 ± 14.3 1.19 ± 0.63 3.74 ± 2.3 0.36 ± 0.2 1.83 ± 0.8 1.64 ± 0.8 0.01 ± 0.001 57.7 ± 37.9

NC1000 21.6 ± 13.2 1.54 ± 1.03 3.41 ± 2.1 0.33 ± 0.2 1.79 ± 0.9 2.01 ± 0.7 0.01 ± 0.001 57.5 ± 38.9

WC100 28.0 ± 10.0 2.63 ± 2.26 3.89 ± 2.9 0.41 ± 0.1 2.29 ± 1.4 5.14 ± 0.6 0.03 ± 0.01 47.5 ± 28.2

WC500 32.4 ± 24.2 1.67 ± 1.37 3.91 ± 2.3 0.33 ± 0.2 3.13 ± 2.3 3.56 ± 0.7 0.02 ± 0.01 26.0 ± 5.63

WC1000 23.4 ± 17.3 2.33 ± 1.07 3.44 ± 2.2 0.35 ± 0.2 1.58 ± 0.7 4.70 ± 2.7 0.02 ± 0.01 41.5 ± 19.6

WL100 32.6 ± 6.45 1.67 ± 1.37 5.82 ± 1.6 0.39 ± 0.3 2.29 ± 1.4 6.15 ± 1.3 0.04 ± 0.01 55.9 ± 9.76

WL500 16.6 ± 2.20 1.17 ± 0.94 4.29 ± 1.9 0.38 ± 0.2 1.17 ± 0.3 3.58 ± 0.8 0.03 ± 0.01 56.9 ± 17.1

WL1000 27.0 ± 9.26 2.96 ± 0.84 3.91 ± 1.9 0.470.3 2.10 ± 0.9 4.87 ± 1.1 0.02 ± 0.01 48.7 ± 19.3

WT100 23.2 ± 16.1 3.46 ± 1.48 6.37 ± 1.4 0.40 ± 0.1 2.38 ± 1.5 5.63 ± 1.6 0.04 ± 0.01 52.8 ± 34.9

WT500 35.6 ± 12.4 1.83 ± 1.53 5.33 ± 1.0 0.34 ± 0.2 2.29 ± 1.4 3.74 ± 1.8 0.04 ± 0.01 54.1 ± 29.4

WT1000 34.9 ± 12.7 2.83 ± 2.52 5.16 ± 0.9 0.79 ± 0.6 3.13 ± 2.2 2.92 ± 0.6 0.04 ± 0.01 55 ± 28.3

SK100 46.7 ± 19.3 5.12 ± 1.99 7.24 ± 1.6 1.06 ± 0.3 4.62 ± 2.8 6.94 ± 1.3 0.06 ± 0.001 88.3 ± 31.4

SK1000 47.7 ± 17.2 5.29 ± 1.50 7.33 ± 1.3 1.07 ± 0.4 5.42 ± 3.0 7.17 ± 1.1 0.06 ± 0.01 87.3 ± 31.1

SK2000 18.3 ± 12.4 2.46 ± 1.21 3.97 ± 1.2 0.39 ± 0.1 1.96 ± 1.0 3.27 ± 0.5 0.01 ± 0.001 50.3 ± 28.3

SL100 23.2 ± 6.82 3.29 ± 1.5 5.1 ± 0.85 0.4 ± 0.1 2.87 ± 1.6 5.06 ± 0.9 0.03 ± 0.001 53 ± 25.1

SL1000 23.1 ± 6.92 2.79 ± 1.57 4.75 ± 0.9 0.36 ± 1 2.630.9 4.61 ± 1.1 0.03 ± 0.01 54 ± 24.0

SL2000 15 ± 9.62 1.68 ± 0.86 3.9 ± 1.11 0.35 ± 0.2 2.13 ± 1.2 2.87 ± 0.6 0.01 ± 0.001 42.2 ± 18.4

Minimum 13.3 ± 9.5 1.67 ± 1.37 2.41 ± 1.6 0.33 ± 0.2 1.17 ± 0.3 1.64 ± 0.8 0.01 ± 0.001 26.0 ± 5.63

Maximum 47.7 ± 17.2 5.29 ± 1.50 7.33 ± 1.3 1.07 ± 0.4 5.42 ± 3.0 7.17 ± 1.1 0.06 ± 0.001 88.3 ± 31.4

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solids for deposition on surface sediments. Heavy metals

are not easily deposited in bottom sediments with strong

water currents (Tam and Wong 2000). The high percentage

of fine-grained sediment is the other main parameter, which

causes increased metal concentrations in this study site.

Fine-grained sediment is the main parameter which con-

trols the concentration of heavy metals in the marine

environment. Fine sediments adsorb heavy metals from

water and have a significant capacity to retain heavy metals

(Nduka and Orisakwe 2011). Some metals in this study

have a significant positive correlation (0.4\ r, p\ 0.01)

with fine particles, e.g., Cu (r = 0.447), Cd (0.406), Ni

(0.432), Zn (0.493).

The significant temporal variation of heavy metal con-

centration is probably due to seasonal fluctuations. This

significant difference in metal concentration is unusual

during this short period of sampling. However, several

studies indicated that chemical properties of metal, water,

and sediment, which are associated with other environ-

mental factors such as atmospheric deposition, high

dynamics of marine water, tidal and seasonal currents, and

change of pollution load of anthropogenic source, can

Fig. 2 Temporal variation of the heavy metal in surface water lg l-1 (the grey bar shows the average concentration and the black line of each

bar is standard deviation value)

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cause this temporal variation in mobility, bioavailability

and enrichment of heavy metals during a short time. For

example, several studies recorded that in the rainy season

(during monsoon), concentration of heavy metals in sedi-

ment is lower than in the dry season; this could be related

to high disturbance of the sediment created by huge waves

during monsoon. Rainwater causes increased mobility and

dilution, which decrease heavy metal concentrations in

sediment (Lim et al. 2006; Li et al. 2009). Moreover,

during the rainy season most of pollutants load of anthro-

pogenic activities including shipping and fishing decrease

or stop in some locations. Subsequently, after this reduc-

tion of anthropogenic activities, the level of metals input by

the vessels might be decreased leading to occurrence of

low metals concentration in sediment. In dry season, by the

increase of anthropogenic activities, metals input starts to

increase. The sediment is more stable, leading metals level

to rise up again (Zhang et al. 2010; Olubunmi and Olo-

runsola 2010; Aydin onen S et al. 2011).

In this research, some metals (Cd, Ni, Zn, Hg, As and

Cr) showed significant reduction in their concentration in

sediment with increasing rainfall in November 2009 and

May 2010 (Fig. 3). This implies that these metals are

bound to the exchangeable phase of the minerals in the

sediment and probably more easily influenced by dilution

due to heavy rainfall and strong marine currents, which

occur during the north-east monsoon and inter-monsoon

periods. Likewise, this could be related to reduction of

anthropogenic activities during this period. The concen-

tration of Zn and Cu showed the significant increase in

their concentration with increasing rainfall, it is suggested

that these metals mainly originate from land-based runoff

and river discharges in Klang Strait coastal water.

In seawater, the highest concentration of all metals

(except Hg) was synchronous with heavy rainfall in

November 2009 and May 2010 (Fig. 2) because heavy

rainfall causes increased land-based runoff and river dis-

charges, which are polluted by several contaminants.

Atmospheric deposition is another route for metals to enter

the seawater as it can transport a large amount of chemicals

for hundred of mile far from their place of origin (Zhang

et al. 2010; Aydin onen S et al. 2011).

Comparison with natural background values

and standard guidelines of metals

Table 4 summarizes the general mean metal concentration

in Port Klang water in comparison with the standard

guidelines and background values. The mean concentra-

tions of all metals were lower than threshold levels stated

Table 3 The mean and standard deviation (±) concentrations of the heavy metals in the surface sediment during sampling periods (lg g-1)

STATIONS As Cu Cr Cd Ni Pb Hg Zn

NL100 75.6 ± 27.51 17.43 ± 4.4 44.41 ± 5..04 0.79 ± 0.25 11.14 ± 4.50 58.59 ± 19.68 0.24 ± 0.07 52.3 ± 20.4

NL700 60.35 ± 23.11 13.60 ± 2.47 37.2 ± 8.2 0.67 ± 0.29 7.14 ± 2.22 47.5 ± 16.32 0.17 ± 0.05 35.2 ± 7.43

NL1500 76.2 ± 30.4 20.9 ± 5.7 44.5 ± 4.5 0.89 ± 0.29 10.5 ± 2.6 68.5 ± 20.6 0.20 ± 0.08 56.5 ± 19.7

NC100 38.05 ± 8.4 16.5 ± 2.8 39.9 ± 10.0 0.93 ± 0.3 12.4 ± 3.37 53.24 ± 6.9 0.19 ± 0.06 46.2 ± 20.3

NC500 34.1 ± 7.5 12.4 ± 1.3 30.2 ± 9.1 0.80 ± 0.32 6.2 ± 2.04 47.3 ± 10.01 0.17 ± 0.04 42.2 ± 15.6

NC1000 48.5 ± 16.9 17.6 ± 4.9 37.6 ± 4.6 0.89 ± 0.28 11.8 ± 1.88 48.9 ± 11.4 0.19 ± 0.06 50.1 ± 18.68

WC100 35.8 ± 7.9 16.1 ± 4.7 58.6 ± 6.9 0.68 ± 0.33 11.6 ± 3.01 54.9 ± 7.8 0.25 ± 0.08 49.5 ± 13.3

WC500 51.6 ± 25.4 11.35 ± 2 47.06 ± 12.5 0.81 ± 0.33 8.8 ± 1.7 52.5 ± 13.8 0.20 ± 0.05 36.4 ± 15.0

WC1000 68.13 ± 33.3 14.72 ± 2.5 48.91 ± 10.2 0.89 ± 0.34 10.49 ± 2.5 51.31 ± 5.9 0.20 ± 0.05 37.2 ± 12.5

WL100 67.5 ± 32.28 13.96 ± 1.59 37.20 ± 7.16 0.28 ± 0.07 13.03 ± 3.4 57.71 ± 7.9 0.25 ± 0.09 37.32 ± 12.31

WL500 47.7 ± 11.24 13. ± 2.35 36.08 ± 10.88 0.28 ± 0.10 12.44 ± 3.42 54.07 ± 7.95 0.30 ± 0.08 32.8 ± 10

WL1000 50.31 ± 5.53 15.69 ± 3.79 47.05 ± 8.60 0.62 ± 0.43 16.02 ± 3.97 58.23 ± 6.72 0.31 ± 0.07 35.1 ± 11.16

WT100 94.24 ± 37.13 16.81 ± 2.64 60.56 ± 4.21 0.95 ± 0.49 13.84 ± 3.07 72.1 ± 19.89 0.30 ± 0.09 49.8 ± 20.3

WT500 59.07 ± 14.02 12.1 ± 1.67 42.7 ± 5.51 0.73 ± 0.62 9.6 ± 2.3 53.46 ± 9.6 0.21 ± 0.02 33 ± 12.51

WT1000 78.3 ± 33.6 17.6 ± 6.77 45.9 ± 5.26 1.26 ± 0.57 13.38 ± 1.40 71.55 ± 9.8 0.28 ± 0.05 40.02 ± 19.6

SK100 112.8 ± 19.16 40.6 ± 11.3 74.8 ± 8.32 1.55 ± 0.27 17.83 ± 5.68 85.92 ± 6.50 0.35 ± 0.05 126.7 ± 43.5

SK1000 106.01 ± 21.23 38.5 ± 10.4 68.3 ± 5.98 1.4 ± 0.41 16.08 ± 4.46 79.4 ± 13.4 0.32 ± 0.05 126.9 ± 43.6

SK2000 42.38 ± 7.22 16.3 ± 1.7 45.07 ± 4. 0.91 ± 0.10 9.80 ± 2 74.7 ± 13.1 0.22 ± 0.01 52.8 ± 13.5

SL100 67.8 ± 21.8 14.9 ± 2.37 50 ± 10.03 0.84 ± 0.38 12.2 ± 3.93 50.8 ± 10.72 0.20 ± 0.05 52.15 ± 17.66

SL1000 50.27 ± 7.87 19.03 ± 3.94 47.68 ± 7.05 0.89 ± 0.33 12.18 ± 2.29 68.21 ± 16.27 0.21 ± 0.06 53.9 ± 16.7

SL2000 40.2 ± 8.2 16.27 ± 2.26 41.34 ± 3.8 0.57 ± 0.09 7.58 ± 2.36 52.4 ± 12.09 0.19 ± 0.001 47.57 ± 11.4

Minimum 34.1 ± 7.5 40.6 ± 11.3 74.8 ± 8.32 0.28 ± 0.07 6.2 ± 2.04 47.5 ± 16.32 0.17 ± 0.05 32.8 ± 10

Maximum 112.8 ± 19.16 11.35 ± 2 30.2 ± 9.1 1.55 ± 0.27 17.83 ± 5.6 85.92 ± 6.50 0.35 ± 0.05 126.9 ± 43.6

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in standard guidelines to regulate marine environmental

quality and which protect marine water quality. Concen-

trations of Cd, As, Pb, Cr and Zn were far higher than the

marine background values while other metal concentra-

tions were lower than the background value.

In sediment, concentrations of Cu, Cr, Ni, and Zn

were lower than thresholds of standard guideline and

background values (Table 5). Concentrations of Cd, Pb and

Hg were higher than in background value and TEL (effect

range low) in sediment and showed enrichment of metals in

surface sediment, which was far higher than those thresh-

olds in sediment.

In general, the levels of As, Cd, Cr, Pb, and Zn exceeded

their marine background values in sea water and

Fig. 3 Temporal variation of the heavy metals in surface sediment lg l-1 (the grey bar shows the average concentration and the black line of

each bar is standard deviation value)

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concentrations of As, Cd, Hg, and Pb measured were far

higher than the sediment background values and TEL

values.

Metals released into Port Klang by some anthropogenic

sources can be adsorbed on sediment particles. Moreover,

As, Cd, and Hg are easily absorbed by plants and then

enrich the sediment through the plant decomposition and

nutrient cycling (NBO 2009; Lee et al. 2007; Ke Pan and

Wang 2011).

As, Cd, Pb and Hg originate mostly from industrial

activities such as burning of fossil fuels, mining, cement

manufacturing, paper and glass production and waste recy-

cling (Zhang et al. 2010). Several industries such as palm oil,

cement manufacturing, and oil/electrical-based power

Table 4 Nature concentration and guidelines levels of metals in seawater described in the literature

Concentration of heavy metal (lg l-1) As Cu Cr Cd Ni Pb Hg Zn

The mean concentration of heavy metals in this study 24.7 2.51 8.77 0.48 2.39 8 0.02 52.9

CMC 69 4.8 1,100 40 74 210 1.8 90

CCC (Nduka and Orisakwe 2011; Rezayi et al. 2012) 36 3.1 50 8.8 8.2 8.1 0.94 81

Nature concentration of marine water (EPA 2002) 3 3 0.05 0.11 5.4 0.3 0.03 10

CMC criteria maximum concentration

CCC criteria continuous concentration

Table 5 Comparison of heavy metals concentration in the Port Klang with back ground value and sediment quality guidelines (SQG)

Concentration of heavy metal (lg g-1) As Cu Cr Cd Pb Ni Hg Zn

The mean concentration of heavy metal in this study 60.36 17.43 46.4 0.826 59.45 11.44 0.23 51.05

Heavy metals Back ground value in the Port Klang (Yap 2005) 18.79 23.21 53.71 0.186 39.8 32.77 0.08 141.22

SQG-based (MacDonal 1994) TEL (effect range Low) 7.24 18.7 52 0.68 30.2 15.9 0.13 124

PEL(effect range medium) 41.6 108 160 4.2 112 42.8 0.7 271

Table 6 Mean value of the contamination factor Cf and contami-

nation degree Cdin the surface sediment

Stations As Cu Cr Cd Ni Pb Hg Zn Cd�value

NL100 4.03 0.22 0.84 4.23 0.34 1.47 3.04 0.37 14.54

NL700 3.21 0.21 0.7 3.61 0.22 1.2 2.18 0.25 11.58

NL1500 4.06 0.21 0.84 4.81 0.32 1.72 2.56 0.4 14.92

NC100 2.02 0.19 0.75 5.02 0.38 1.34 2.4 0.33 12.43

NC500 1.82 0.16 0.57 4.28 0.19 1.19 2.16 0.3 10.67

NC1000 2.58 0.22 0.71 4.78 0.36 1.23 2.43 0.36 12.67

WC100 1.91 0.25 1.1 3.68 0.36 1.38 3.19 0.35 12.22

WC500 2.75 0.2 0.89 4.34 0.27 1.32 2.52 0.26 12.55

WC1000 3.63 0.2 0.92 4.81 0.32 1.29 2.51 0.26 13.94

WL100 3.59 0.21 0.7 1.49 0.4 1.45 3.13 0.26 11.23

WL500 2.54 0.24 0.68 1.53 0.38 1.36 3.8 0.23 10.76

WL1000 2.68 0.19 0.88 3.32 0.49 1.46 3.93 0.25 13.2

WT100 5.02 0.15 1.14 5.11 0.42 1.81 3.72 0.35 17.72

WT500 3.14 0.17 0.8 3.94 0.29 1.34 2.66 0.23 12.57

WT1000 4.17 0.16 0.86 6.78 0.41 1.8 3.5 0.28 17.96

SK100 6.21 0.21 1.41 8.31 0.54 2.16 4.33 0.93 23.86

SK1000 5.64 0.2 1.28 7.78 0.49 1.99 3.98 0.91 22.26

SK2000 2.26 0.14 0.85 4.87 0.3 1.88 2.71 0.37 13.38

SL100 3.61 0.17 0.94 4.52 0.37 1.28 2.52 0.37 13.78

SL1000 2.68 0.21 0.9 4.79 0.37 1.71 2.67 0.38 13.71

SL2000 2.14 0.18 0.78 3.08 0.23 1.32 2.38 0.34 10.45

Minimum 1.82 0.2 0.57 1.49 0.19 1.19 2.18 0.25 10.45

Maximum 6.21 0.24 1.41 8.31 0.54 2.16 4.33 0.93 23.86

Table 7 Mean value of the contamination factor Cf and contami-

nation degree Cd in the surface water

POINT As Cu Cr Cd Ni Pb Hg Zn Cd�value

NL100 6 0.96 7.00 4.00 0.34 11.80 0.33 4.96 34.68

NL700 4.45 0.57 5.67 4.00 0.30 12.63 0.33 4.51 32.47

NL1500 5.12 0.54 4.83 3.82 0.29 13.20 0.33 4.41 32.54

NC100 6.67 0.84 8.57 7.73 0.46 7.75 0.33 6.03 38.31

NC500 6.22 0.40 7.48 3.27 0.34 6.3 0.33 5.78 30

NC1000 7.22 0.51 6.83 3.00 0.33 6.72 0.33 5.75 30.70

WC100 9.34 0.88 7.78 3.73 0.42 17.15 1.00 4.75 45.05

WC500 10.81 0.56 7.83 3.00 0.58 11.88 0.67 2.61 37.94

WC1000 7.81 0.78 6.88 3.18 0.29 15.68 0.67 4.15 39.44

WL100 10.89 0.56 11.65 3.55 0.42 20.52 1.33 5.60 54.51

WL500 6 0.39 8.58 3.45 0.22 11.95 1.00 5.70 36.84

WL1000 9 0.99 7.83 4.27 0.39 16.25 0.67 4.88 44.27

WT100 7.74 1.15 12.75 3.64 1 18.78 1.33 5.28 51.12

WT500 11.87 0.61 10.67 3.09 0.42 12.47 0.92 5.42 45

WT1000 11.65 1 10.33 7.18 1 9.73 1.33 6.02 47.26

SK100 15.59 1.71 14.48 9.64 1 23.13 2.00 8.73 76.14

SK1000 15.39 1.76 14.67 9.73 1 23.90 2.00 8.73 77.39

SK2000 6.12 0.82 7.95 3.55 0.36 10.92 0.33 5.03 35.08

SL100 7.74 1.10 10.20 3.64 0.53 16.88 1.00 5.30 46.39

SL1000 7.70 0.93 9.50 3.27 0.49 15.38 1.00 5.41 43.68

SL2000 6 0.56 7.80 3.18 0.39 9.58 0.33 4.23 31.08

Minimum 4.45 0.57 4.83 3 0.22 6.3 0.33 2.61 30

Maximum 15.39 1.76 14.67 9.73 1 23.90 2.00 8.73 77.39

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generation release waste into Port Klang. Moreover, these

metals might be released by atmospheric deposition, terres-

trial runoffs, and tsunami sediment deposition, which are the

main routes of metal into marine environment. Boat docking

and corrosion of ships, organic insecticides (lead-arsenate),

pesticides, and fertilizers applied in agriculture activities are

other sources of pollution in the Port Klang coastal waters.

Metal contamination level in water and sediment

Contamination factor Cf and contamination degree Cd are

applied to assess the state of conservation of an environ-

ment and to monitor its condition (Fishbein 1981; Jennings

and Rainbow 1979; Cossa et al. 2010; Ke Pan and Wang

2011; Davis et al. 2009). Tables 6 and 7 show variations of

contamination factor and contamination degree in water

and sediment. In general, the highest values of contami-

nation degree and contamination factor were estimated at

stations SK100 and SK1000 in water and sediment. The

Cf values for all metals follow this sequences in the sedi-

ment: Cu\Ni\Zn\Cr\Pb\Hg\As\Cd while

the sequence of Cf-value in water was Ni\Hg\Cu\

Cd\Zn\As\Cr\ Pb.

The differences between contamination factor sequences

of water and sediment can be related to physicochemical

parameters, which control the rate of adsorption and

desorption of heavy metals. All heavy metals exist in

surface waters in particulate colloidal, and dissolved pha-

ses, but the dissolved concentration are generally low. The

particulate and colloidal metal can be found in hydroxides,

silicates oxides, or adsorbed to silica, clay, or organic

material. Adsorption removes the heavy metal from the

water and stores the metal in the sediment. Desorption

sends back the metal to the water column where recircu-

lation and bio-assimilation may take place (Conti and

Cecchetti 2001). Several researches showed that salinity,

pH and solubility product (Ksp) of each metal are main

parameters to control concentration of dissolved metals in

water column. For example, increased metal concentration

may be affected by increase in salinity, decrease in redox

potential, and decrease in pH. Elevated salt concentrations

create increased competition between cations and metals

for binding sites (Nduka and Orisakwe 2011). This is

typical in coastal regions and estuaries because of fluctu-

ating river flow inputs and land-based discharges, as seen

in Klang Strait coastal water. From this study, the acidity

(pH) level seemed to have no effect on the metal concen-

tration because the pH is within acceptable international

standard for surface water. Fluctuation of salinity espe-

cially in South Port may have affected rate of adsorption

and desorption of metals to and from sediments, and have

caused the different sequence of contamination factor in

water and sediment.

In sediment, the Cf values for Cu, Cr, Ni, and Zn were

less than 1 and were found at an unpolluted level at all

stations. The contamination factor for Pb appeared mod-

erate at all stations and Cf-value for Hg and As were on the

borderline between moderately polluted to high level pol-

luted. The contamination factor for Cd at all stations

(except at stations WL100, WL500) was found between

high and very highly polluted. Contamination degrees at

the WT100, WT1000, SK100 and SK1000 stations were

high whereas Cd-value indicates moderate pollution in

other stations in the Port Klang.

In water, based on the data shown in Table 7, the Cf-

value for Cu, Ni and Hg was lower than 1, and was

observed in unpolluted levels at all stations except at the

SK100, SK1000, WT100, and WT1000, which showed

moderate pollution. Contamination factors for As, Cr, Cd,

and Zn were between considerably polluted to very high

level of pollution, while Pb was at a very highly polluted

level at all stations. Contamination degrees for stations

SL2000, NC1500, and NC700 showed considerable con-

tamination whereas it was in a very high degree of con-

tamination at other stations.

In general, the highest contamination degree of all of the

metals (except for Mn) were determined at South Port at

stations SK100 and SK1000, which are parallel to the

mouth of the Klang River, and at station WT100 around the

container terminal in the West Port. As a result, the sig-

nificant contamination degree showed that multiple sources

greatly contributed to the contaminant loads in Klang

Strait. These sources included industrial inflow, such as the

palm oil, cement and food manufacturers that are located

along the coastline of North and West Port, vessel-based

discharges and Klang River. The contamination factor (Cf)

also indicated that all of the metal concentration were

influenced by anthropogenic inputs, especially very toxic

elements, such as As, Cd, Hg and Pb, which were enriched

at high levels at stations close to the berth line and the

mouth of the Klang River.

Conclusion

Heavy metal pollution in Port Klang water and sediments

has increased because of the rapid industrialization and

urbanization in recent decades. The study area was divided

into different stations, with different metal contamination

degrees. The results indicate that in South Port, stations are

located in the riparian zone of the Klang River which

predominantly flowed through South Port. It could be an

indication that the high level contamination of metals in

these stations comes from an anthropogenic source because

high concentrations of metals were released continuously

into the Klang River from chemical factories, urban

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effluents due to high density of human settlements, and

agriculture activities. Moreover, in West Port, stations

close to container terminal showed the high level of con-

tamination because these stations are influenced by indus-

trial discharge along the coastline, leakage or emissions of

petrol due to busy marine transport, and atmospheric

depositions.

The study indicates that the potential contamination of

Cd, As, Pb, and Hg were between moderate and high

contamination in sediments while the rest of the metals

were at an unpolluted level in the sediments at all stations.

Metals with above normal concentrations in sediments can

be considered as a serious threat to marine organisms and

human health, especially As, because its concentration is

significantly greater than effect range medium value. In

addition, these data revealed that some elements such as

As, Cd, Cr, Zn, and Pb, were enriched in water and their

level of contamination varied between considerable and

very high levels at all stations. In summary, the present

study provides baseline data for interpretation of variations

in heavy metal concentration in water and sediment and

traces contamination routes of metal in the Port Klang.

These data can also be used as a contribution to long-term

monitoring of heavy metal pollutants in Port Klang.

Acknowledgments This study was supported by the University

Malaya Research grant (UMRG) with project number RG174/12SUS

and by the University Malaya Postgraduate Research Grant (PPP).

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