April 2011, Volume 2, No.

2
International Journal of Chemical and Environmental Engineering

Spatial Variation and Binding Behavior of Cu and

Pb in Surface Sediments of Klang River
Abolfazl Naji*, Ahmad Ismail
Department of Biology, Faculty of science, University Putra Malaysia (UPM), Serdang, Selangor 43400, Malaysia
* Corresponding author: Abolfazlnaji@gmail.com (Naji, A.)

Abstract
In this investigation, concentration, distribution and risk associated with trace metals connected with urban and industrial discharge
were studied to assess an overall classification of Cu and Pb as well as their risk status in the surface sediments of Klang River.
Sequential extraction technique (SET) was used to evaluate the four (exchangeable, acid-reducible, oxidisable-organic and residual)
fractions in surface sediment. The total concentrations of metals were ranged (9.47-66.74 µg g -1) for Cu and (24.78-62.35 µg g -1) for
Pb. The fractionation of studied metals (except Cu) in most stations were in the order of residual > acid-reducible > oxidisable-organic
> exchangeable. The degree of surface sediments contamination was computed for Risk Assessment Code (RAC), Individual
Contamination Factors (ICF) and Global contamination factor (GCF). The result of these indices showed that none of studied metals
had high potential risk to fauna and flora of the Klang River, although those stations near-by anthropogenic influx had high adverse
impact in contrast with the rest stations.

Keywords: Spatial variation; Metals; Surface sediments; Risk Assessment Code (RAC).

1. Introduction Fractionation is the process of classification of an analyte

Klang River is one of the most important river in
Malaysia (3˚13َ 01.33ََ َ, 101˚ 40َ 54.92َ َ) (Fig1).
It flows through Kuala Lumpur and Klang Valley and
eventually flows into the Straits of Malacca. The
importance of the Klang River is due to: (1) it is situated
in the most urbanized and heavily populated area that
more than 4.4 million people (16% of the national
population) living around here. (2) Most industrial area of
Selangor state is located along this river. (3) It flows into
the one of the busiest international shipping lanes in the
word.
Since industrial revolution started in the mid-1800s,
the biogeo-chemical cycle of inorganic contamination
(e.g. metals) naturally present in the environment has
been greatly accelerated by human activities [1].
Heavy metal contamination of sediments can critically
degrade aquatic systems [2]. In sediments, metals can be
present in a number of chemical forms, exhibiting
different physical and chemical behaviors with respect to
chemical interactions, mobility, biological availability,
and potential toxicity [3-4] Metals in oxic sediments are
mainly distributed in different operationally defined
geochemical phases, such as carbonates, total organic
carbon (TOC), and Fe-Mn oxides, which have diverse
binding abilities with various metals and have contrasting
influences on the metal bioavailability [5]. The toxicity
of the metal particularly depends on their chemical forms
rather than on their total contents, and therefore,
speciation studies increasingly gain importance [6].
or a group of analytes into a certain matrix according to
physical (size, solubility) or chemical (bonding,
reactivity) properties [7]. In order to assay the
fractionation of heavy metals from sediments, various
sequential extraction procedures have been applied.
In this investigation, the sequential extraction
technique (SET) was used to fractionate resistant fraction
(lithogenous) from nonresistant (non-lithogenous)
fraction. The procedure of SET consists of four
(exchangeable, acid-reducible, oxidisable organic and
residual) fractions.
The mathematical summation of exchangeable, acid-
reducible, and oxidisable-organic fractions constitutes the
nonresistant phase [8]. Even thought there are two
disadvantage of using sequential extraction technique, e.g.
non-specificity of extractants and metal re-absorption, this
technique is still widely reported in the literature [9].
In Malaysia, metals fractionations were reported in
river sediments [10-13]. But there is no information on
the basis of metals in the Klang River. Hence, the study
described in this paper would be of great value in this
area. The main objectives of this study were: (1) to
investigate the fractionation of Cu and Pb in surface
sediments of the Klang River, (2) to assay their mobility
and bioavailability in order to provide preliminary
baseline data for control of pollution, and (3) to determine
possible sources of anthropogenic inputs of trace metals
in this river.
 35%) in a water bath at 90˚C. After cooling, the metal
released from the organic complexes was
continuously shaken for 3 h with 50 ml of 1.0M
104' 101'
ammonium acetate (NH4CH3COO) acidified to pH
South China Sea 2.0 with HCl, at room temperature.
N 6
(4) Fraction 4: Resistant. The residue from (3) was
digested in a 10 ml combination (ratio of 4:1) of
Kuala Lumpur concentrated HNO3 (AnalaR grade, R&M Chemicals
65%) and HCLO4 (AnalaR grade, R&M Chemicals
3 70%).
Gombak The residue of each step was rinsed to 20 ml double-
Batu Dam
Indonesia
1
2
Hulu Langat distilled water (DDW) and filtered through Whatman®
3 No.1 filter paper into pre-cleaned 100 ml volumetric
4 Klang Gato Dam
5
Kuala Lumpur
flasks. The supernatants liquid of each fractions after
6
filtration were stored for metal determination, except
7 fraction 1 that is sensitive and must be analyze
8
immediately. The samples were measured for trace metals
19
18
9 concentration by using an air-acetylene flame atomic
16

21 20
17
15 10
Petaling
absorption spectrophotometer (Perkin-Elmer Model
14

13
Klang
Fig. 1 Study area and geographical location of 21 stations in Klang
River.
2. Material And Method
2.1. Sampling
Surface sediment samples were collected at 21 sites
between January and February 2009 along Klang River
(Fig. 1). Three surface sediment (0-5 cm) samples were
collected by using a clean plastic spoon. The surface
sediments of each sample were placed in polyethylene
plastic bag and labeled. They were then kept in an ice
box. As soon as the field work was finished, samples
were brought to the Ecotoxicology Laboratory at
University Putra Malaysia and preserved at -10˚c for
future analysis. Unfixed samples for assessment were
dried by using an air-circulating oven at 80˚ C, and sieved
through 63µm mesh size, and kept in an acid-washed
container for future use.
2.2. Sequential extraction
Fractionation of Cu and Pb in surface sediments was
analyzed by using the modified sequential extraction
technique [8, 14].
(1)Fraction 1: Easily, freely or leachable and
exchangeable (EFLE). About 10 g of sample was
continuously shaken for 3 h with 50 ml 1.0M
ammonium acetate (NH4CH3COO), pH 7.0 at room
temperature.
(2) Fraction 2: Acid-reducible. The residue from (1) was
continuously shaken for 3 h with 50 ml 0.25M
hydroxyl-ammonium chloride (NH2OH.HCl)
acidified to pH 2 with HCl, at room temperature.
(3) Fraction 3: Oxidisable-organic. The residue from (2)
was first oxidized with 15ml H2O2 (R&M Chemicals
11
AAnalyst 800).
12
Klang River Basin
2.3. Quality control
To prevent uncertain contaminations, all laboratory
equipments used were washed with phosphate-free soap,
double rinsed with distilled water and left in 10% HNO3
for 24 hr and all equipments were then rinsed tow times
with double distilled water and left semi-closed to dry at
room temperature. Certified Reference Material (CRM)
(International Atomic Energy Agency, Soil-5, Vienna,
Austria) was determined as a precision check. Percentage
of recoveries (n=5 for each metal) for certified and
measured concentration of those metals were ranged from
94% for Cu to 98% for Pb. Calibration curves for each
trace element were determined with 1,000 mg/l (BDH
Spectrosol®) stock solution. The reagent and procedural
blanks were monitored for each fraction after five
samples during the analysis as part of the quality accuracy
program.
2.4. Statistical analysis
All Statistical analyses were computed by using
Package for Social Science (SPSS) version 16. The
graphs were performed with Microsoft Excel for
Windows.
3. Results and Discussion
3.1.. Cu sequential fractionation
Copper is a micronutrient, essential for most
physiological growth for aquatic and terrestrial organisms
[15]. Geochemical fractions of Cu in surface sediment of
The Klang River are tabulated in the Table 1 and Fig.2.
The total Cu concentration ranged from 0.28 to1.55 µg g-
1. The exchangeable fraction of Cu range from 0.28 to
1.55 µg g-1 with mean percentage of 2.28%. The acid-
reducible fraction ranged from 0.01 to 0.65 µg g-1 with
mean percentage of 0.7%. The oxidisable-organic fraction
ranged from 3.87 to 44.43 µg g-1 with mean percentage of
92
 53.01%. The resistant fraction ranged from 5.13 to 33.75 main traffic had high non-lithogenous percentage of this
µg g-1 with mean percentage of 44%. The fractionation of element such as stations 5, 8, 17, 18, 19 and 20.
Cu in the surface sediments of Klang River was in the
order of oxidisable-organic > residual > exchangeable >
100%
acid-reducible. This investigation showed more than 50%

Extraction precentage of Cu
of Cu was associated with oxidisable-organic. Association 80%

between Cu and organic matter is one of the most 60%

important factors in controlling of Cu in sediments [16]. 40%

Organic matter is the most significant sink for Cu in
20%
sediments [17-18]. The Cu in the Oxidisable fraction is
associated with biogenic carriers, which have settled 0%
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
through the water column [19-20]. Once the particulate Sampling station
material is precipitated at the surface of sediments, the
Exchangeable Acid-reducible Oxidisable organic Residual
Oxidisable-organic fraction undergoes phase
transformations as the organic carriers decompose [15].
The present investigation determined that most Cu ion in Fig. 2. Sequential chemical distribution of Cu.
surface sediments is associated with oxidisable-organic
(53.01%) and residual (44%) fractions. The Cu 100%

Extraction precentage of Pb
concentrations in the most sampling stations were
80%
dominated by the nonresistant fraction. The high level of
nonresistant of Cu can be due to industrial activities, 60%

dumping and road run-offs in the Klang River. Between 40%

the nonresistant fractions, the mean percentages of
20%
exchangeable, acid-reducible and oxidisable-organic
constituted 4.07, 1.25 and 94.67%, respectively. The high 0%
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
percentage of oxidisable-organic fraction identified that
Sampling station
the organically-bound materials such as humic and fulvic
can be easily available for biological uptake [21]. The Exchangeable Acid-reducible Oxidisable organic Residual

concentration of Cu in the acid-reducible fraction (0.01to

0.65) was low. It is because of low affinity of Cu in acid- Fig. 3. Sequential chemical distribution of Pb.
reducible fraction in surface sediments of Klang River.
On the other hand, Iron and manganese-oxides constituted
in acid-reducible fraction have high scavenging
Table 1 Sequential chemical Concentration of Cu (µg/g) in surface
efficiencies for trace metals but they are sediments of Klang River
thermodynamically unstable under anoxic circumstances Station Cu Total
No.
[22]. Exchangeable Acid-reducible Oxidisable-organic Resistant

1 0.35 ( 3.65) 0.11(1.21) 3.87(40.92) 5.13(54.23) 9.46

3.2. Pb sequential fractionation 2 0.62 (2.98) 0.19 (0.94) 11.7(56.71) 8.12(39.37) 20.63
3 1.39 (3.46) 0.29(0.71) 26.1(64.57) 12.60(31.26) 40.38
Most often Pb because of its high toxicity has 4 1.08 (3.23) 0.38(1.13 ) 21.6(64.54) 10.40 (31.1) 33.46
5 1.55 (2.86) 0.65 (1.19) 37.3(68.8) 14.71(27.17) 54.12
contamination concern. The geochemical distributions 6 0.67 (2.41) 0.39(1.41) 15.6(56.26) 11.11(39.9) 27.77
and mean concentrations of Pb are shown in Table 2 and 7 1.02 (3.1) 0.37(1.4) 19.21(58.43) 12.28(37.3) 32.88
8 0.88 (1.98) 0.46 (1.02) 20.68(46.22) 22.73(50.8) 44.75
Fig. 3. The total concentration of Pb ranged from 24.78 to 9 1.36 (3.72) 0.59 (1.62) 15.08(41.22) 19.62(53.5) 36.65
62.35 µg g-1. The exchangeable fraction of Pb ranged 10
11
0.38 (1.73)
0.37 ( 0.56)
0.13(0.6)
0.37(0.56)
9.23(41.17)
44.43(41.6)
12.43(56.0)
21.57(32.3)
22.17
66.74
from 0.59 to 4.07 µg g-1 with mean percentage of 4.06%. 12 0.85 (2.25) 0.18(0.47) 15.03(66.5) 21.62(57.4) 37.68
13 0.81 (1.92) 0.14(0.34) 22.73(39.9) 18.83(44.2) 42.51
The acid-reducible fraction ranged from 0.38 to 4.16 µg 14 1.48 ( 2.66) 0.14(0.26) 31.39(53.52) 22.80(40.8) 55.81
g-1 with mean percentage of 3.59%. The oxidisable- 15
16
0.73 ( 2.08)
0.96 ( 1.73)
0.13(0.37)
0.23(0.41)
18.52(56.27)
20.78 (53.2)
15.52(44.4)
33.77(60.6)
34.9
55.74
organic fraction ranged from 2.81 to 28.9 µg g-1 with 17 1.15 ( 2.96) 0.22(0.52) 23.97(37.3) 17.39(40.5) 42.73
18 0.87 ( 1.57) 0.12(0.21) 36.16(56.2) 18.61(33.4) 55.76
mean percentage of 25.09%. The resistant fraction ranged 19 0.42 ( 0.82) 0.15(0.3) 26.87(64.9) 21.93(44.4) 49.37
from 14.29 to 49.64 µg g-1 with mean percentage of 20
21
0.51 ( 1.1)
0.28( 1.48)
0.14(0.3)
0.01(0.06)
22.27 (54.5)
8.30 (43.3)
23.03(50.1)
10.68(55.2)
45.95
19.27
67.26%. The fractionation of Pb in the surface sediments Range 0.28-1.55 0.01-0.65 3.87-44.43 5.13-33.75 9.47-
66.74
was in descending order of residual > oxidisable-organic Note: The values in parentheses Shows percentage of elemental
> exchangeable > acid-reducible. More than 60% of the concentration
total concentration of Pb was dominated by residual
fraction in surface sediments of the Klang River. Pb
associated largely in the residual fraction and can be less
bioavailable except under harsh condition. Since one of
the main sources of Pb in the environment is automotive.
Our result showed that those stations near-by intensive

93
Table 2 Sequential chemical Concentration of Pb (µg/g) in surface 3.3.2. Individual and global contamination factor
sediments of Klang River The bioavailability and toxicity of trace metals depend
Station Pb Total
No. Exchangeable Acid-reducible Oxidisable organic Residual on their type of chemical forms. The Individual and
global contamination factor was calculated to evaluate the
1 1.32(5.33) 1.71(6.91) 3.33(13.42) 18.42(74.34) 24.78
2 2.39(5.45) 3.06(6.83) 6.90(15.71) 31.63(72.01) 43.98 metals contamination and their bioavailability in surface
3 2.31(4.08) 3.17(5.61) 11.13(19.7) 39.93(70.61) 56.54
4 3.44(6.77) 3.98(7.83) 8.26(16.26) 35.13(64.14) 50.81
sediments of Klang River. The individual contamination
5 3.02(4.9) 4.16 (6.75) 17.60(28.53) 36.91(59.81) 61.69 factors (ICF) for the various sampling sites were
6 2.07(5.34) 0.91(2.36) 9.59(24.77) 26.13(67.53) 38.70
7 2.98(6.98) 2.78(6.5) 8.81(26.59) 28.20(65.94) 42.77 calculated from the result of the fractionation study by
8 3.67(6.28) 1.62(2.78) 15.11(25.88) 37.96(65.05) 58.36
9 4.07(6.53) 3.67(5.89) 4.96(7.95) 49.64(79.63) 62.34
dividing the sum of the first three extractions (i.e.
10 0.59(1.57) 0.77(1.92) 10.97(29.3) 25.13(67.19) 37.46 exchangeable, acid-reducible and oxidisable organic
11 2.39(4.45) 0.68(1.27) 2.81(5.25) 47.73(89.03) 53.61
12 0.67(1.31) 0.67(1.3) 12.93(25.1) 37.19(72.27) 51.46 forms) by the residual fraction for each sampling station.
13 0.71(1.31) 0.65(1.2) 12.72(23.4) 40.31(74.1) 54.39
14 0.98(2.05) 0.61(1.29) 6.73(14.15) 39.27(82.52) 47.59
The global contamination factor (GCF) for each sampling
15 1.64(3.74) 0.56(1.27) 9.14(20.89) 32.41(74.09) 43.75 station was computed by summing the ICF for Cu, and Pb
16 1.19(1.93) 1.14(1.84) 17.23(27.88) 42.23(68.35) 61.79
17 2.26(3.9) 2.48(4.28) 17.01(29.3) 36.27(62.51) 58.02 obtained for sampling stations [23].
18 1.17(1.98) 0.54(0.9) 23.23(39.2) 34.38(57.95) 59.32
19 0.87(1.57) 0.38(0.68) 25.13(45.3) 29.12(52.45) 55.50
20 3.40(6.32) 2.94(5.47) 28.90(53.74) 18.53(34.46) 53.77
21 0.94(3.53) 0.65(2.43) 10.83(40.55) 14.29(53.49) 26.71
Range 0.59-4.07 0.38-4.16 2.81- 28.9 14.29-49.64 24.78-62.35 The ICF and GCF were expressed as following
Note: The values in parentheses Shows percentage of elemental expression:
concentration
C nonresistan t
3.3.. Contamination assessment ICF metal=
C resis tan t
3.3.1.. Risk assessment code (RAC)
n

Heavy metals in the sediments can pose hazard to

GCF=  CF
i 1
i

aquatic biota through (1) being released into overlaying The individual and global contamination factors for
water, which may cause acute toxicity; (2) being directly Cu and Pb in the surface sediments of are shown in Table
digested by bottom feeders or being transferred through 4.The result of ICF showed that contamination degree of
bioaccumulation in food web [24]. Cu was higher than the rest studied metals. On the basis
The metals in the sediments are bound with different of the Ikem (2003), ICF reflects the risk of contamination
strengths to the fractions [5]. In the present investigation, of a water body by a pollutant. Therefore, Cu had highest
the Risk Assessment Code (RAC) has been used to risk to water body. Likewise, the bioavailability of metals
evaluate the risk of heavy metals concentration in surface from sediment into the water column will be influenced
sediments of the Klang River. The RAC assess the by factors such as pH, chemical forms of the heavy
potential release of metals in solution based on the metals, and the physicochemical characteristics of the
percentage of exchangeable and carbonate fractions in water column [23]. The mean individual concentration
sediments [25]. This classification is tabulated in Table factor in the surface sediments were ranged in the
3[4]. descending order of Cu > Pb.
The global contamination factor analyzed from ICF
Table 3 Risk assessment code
values showed that stations 3(confluence of Batu River
Risk Metal in exchangeable and
easy to mobilize fractions (%) and Gombak river) and 5(confluence of Klang River and
No risk <1 Gombak River) in upstream and most downstream
Low risk 1-10 stations were high impacted by trace metal pollutants. The
Medium risk 11-30 obtained result is in accordance with Luoma and Rainbow
High risk 31-50
Very high risk ≥75
statement in which the trace metals trend to accumulate in
a hotspot near the inputs [26]. GCF is significant because
it reflects the overall potential risks posed by the toxic
The amount of Cu in the exchangeable and carbonate
elements [23]. According to Naji et al., since GCF value
fractions ranged from 1.1 (station 11) to 5.34 % (Station
dose not compare with any guidelines. It, therefore,
9) and Pb ranged from 2.25 (Station 19) to 14.60%
cannot assay comprehensively the effects of the
(Station 4). On the basis of classification of the RAC, in
combination of metals contamination [27]. The results
all stations the risk associated with Cu in surface
identified that those stations located near-by municipal
sediment was low risk. While, Pb was medium risk in
and industrial area had high potential risk to the Klang
upstream stations (vicinity of intensive main traffic
River environment. Notably, determination of degree of
stations). Also, down stream stations can classified as low
metal contamination is one of the most important aspect
risk.
to reduce and control of pollution in aquatic environment.

94
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Table 4 Individual and global contamination factors of Cu and Pb U deposition in sediments of Patroon Reservoir, Albany County,
in the surface sediments of Klang River NY, USA. Environmental Pollution, 123 (2003) 383–391.

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4 2.22 0.45 2.94 concentration and organic matter in sediments and metal studies of
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[10] J.L. Howard, W.J. Vandenbrink, Sequential extraction analysis of

4. Conclusion
Rivers in mega cities are more often vulnerable to
metals contamination because of widespread point and
non-point sources near-by of them. The mean percentages
of anthropogenic portions of the investigated metals were
decreased in the order of Cu (56.01) > Pb (33.22). It
showed that Pb in Klang River surface sediments existed
in the resistant fractions (sedimentary matrix), while Cu
existed in the non-resistant fractions. The mean
exchangeable (EFLE) concentration of Cu and Pb were
less than the rest fractions. Since exchangeable fraction is
most labile, the small portion of exchangeable fraction of
studied metals indicated that the poor bioavailability of
these metals in the Klang River. The contamination
assessment of surface sediments was computed for Risk
assessment code (RAC), Individual Contamination
Factors (ICF) and Global contamination factor (GCF).
The result determined that none of studied metals had
high potential risk to fauna and flora of this area. This
study was the first study in accordance with chemical
fractionation of metals in surface sediments of the Klang
River. Also, it located in the most sensitive area of
Malaysia. It, therefore, can be informative data to control
and reduce pollution in Klang River.
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