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Water Air Soil Pollut (2013) 224:1476

DOI 10.1007/s11270-013-1476-6

Distribution and Contamination of Heavy Metal in the Coastal


Sediments of Port Klang, Selangor, Malaysia
Seyedeh Belin Tavakoly Sany & Aishah Salleh &
Majid Rezayi & Naghmeh Saadati &
Leila Narimany & Ghazaleh Monazami Tehrani

Received: 5 September 2012 / Accepted: 4 February 2013 / Published online: 12 March 2013
# Springer Science+Business Media Dordrecht 2013

Abstract The coastal sediments of Port Klang in toxicity estimation indicates that living organisms
Malaysia were monitored from November 2009 to have a high risk of As exposure. Spatial distribution
October 2010 to evaluate the spatial distribution of maps of heavy metals would aid in the identification
heavy metals As, Cu, Cd, Cr, Ni, Pb, Zn, Pb, Mn, Al of pollution sources and vulnerable sites.
and Fe. Sediment samples were collected from 21
stations, covering three subsidiary ports, namely Keywords Heavy metals . Sediment pollution . Port
West Port, North Port and South Port, at three-month Klang . Malaysia
intervals. The geo-accumulation index and the enrich-
ment factor were estimated to assess contamination
status based on background values. Additionally, the 1 Introduction
sediment quality guide was applied to evaluate the
adverse biological effects of heavy metals. These re- The marine environment is being continuously loaded
sults show that the concentrations of some metals, with chemical pollutants from lithogenic and anthro-
such as As, Cd and Pb were comparatively higher than pogenic sources. In recent decades, anthropogenic
the background values. This is considered a critical sources, such as agriculture, shipping, urban and in-
environmental issue for this region. Furthermore, the dustrial activities, have resulted in alarming concen-
trations of heavy metals and organic material in
aquatic areas. These chemical pollutants can cause
S. B. Tavakoly Sany : A. Salleh : G. M. Tehrani harmful effects on both marine organisms and human
Institute of Biological Sciences, University of Malaya,
populations (Karbassi et al. 2008; Morton and
50603 Kuala Lumpur, Malaysia
Blackmore 2001; Muhammad et al. 2000; Vallejuelo
S. B. Tavakoly Sany (*) : M. Rezayi et al. 2010).
Food Science and Technology Research Institute, The assessment of sediment is more conservative
ACECR Mashhad Branch,
compared with water for determining the degree of
Mashhad, Iran
e-mail: belintavakoli332@gmail.com contamination and toxicity. Sediment acts as a contam-
inant reservoir; therefore, such analysis will reflect the
N. Saadati : L. Narimany historical variation and effects of anthropogenic and
School of Chemical Sciences and Food Technology,
lithogenic inputs into the marine ecosystem (Marchand
Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, et al. 2006; Olubunmi and Olorunsola 2010; Vallejuelo
43600 Bangi, Selangor, Malaysia et al. 2010). Moreover, the determination of dissolved
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contaminates in water is more difficult and expensive The Malaysian government has put in place regu-
than that of contaminates in sediment because of their lations, guidelines and international agreements to de-
low concentration. Furthermore, expensive pure chem- crease chemical contaminants in harbours and to treat
ical methods are essential to accurately analyze waste water flowing out of ships (Yap 2005).
dissolved contaminates in water (Pan and Wang 2011; However, these studies do not provide adequate
Phillips and Rainbow 1993; Rezayi et al. 2012). information to estimate the degree of contamination
Heavy metal contamination in sediment is a critical or toxicity levels in sediment. There are no data on the
factor for evaluating potential environment effects be- distribution of heavy metals in Port Klang, and there-
cause of the associated bio-toxicity, high environmen- fore, ecological risk assessment cannot be predicted.
tal stability and high occurrence of bioaccumulation in The area is affected by pollution from non-point
the food chain (Chon et al. 2010; Kishe and Machiwa sources, such as port development activities, shipping
2003; Pan and Wang 2011; Süren et al. 2007; Wang and land runoff from rivers and mangrove forests.
2009; Rezayi et al. 2011). Studies have shown that Another limitation is that the strong coastal currents
heavy metal toxicity and accumulation not only de- during the northeast monsoon can affect sediment
pends on metal concentrations but on other factors. quality. Spatial assessment and multiple sediment
These include the form in which the metal component samplings during the north and south monsoons have
is present, the type and concentration of other mate- been used to measure the concentrations of heavy
rials and the integration of physicochemical parame- metals. The objectives of the present study are (1) to
ters, such as temperature, dissolved oxygen (DO), investigate the spatial variation of heavy metals in
salinity, sediment grain size, pH and organic carbon sediments along the Port Klang, (2) to estimate the
(Hardman 2006; Lehr and Keeley 2005; Rai et al. potential degree of toxicity and adverse biological
1981; Wang et al. 2002). effects based on sediment quality guides (SQGs) and
In the aquatic environment, the minute quantities of (3) to examine the pathway of heavy metals and their
some metals, such as: copper, zinc, iron, manganese entry source into the Port.
and nickel are essential for biological systems to func-
tion, but their excessive concentration can be toxic to
living organisms. Other metals such as cadmium, mer- 2 Materials and Methods
cury, arsenic and lead are non-essential and therefore
have toxic effects on living organisms (Amiard et al. 2.1 Study Area and Sampling Process
1987; Barka et al. 2001; Hanna et al. 1997).
Port Klang is the location of three international ports, Port Klang is located in the Klang Strait on the west
which are surrounded by mangrove forests. The area is coast of the Malay peninsula at latitude03°00′ N and
important for tourism, fisheries, navigation and trans- longitude 101°24′ E and covers an area of over
portation. However, there is limited information on 573 km2.The Strait is divided into three main ports
heavy metal concentrations in the sediments of the called the North, South and West Ports. Klang Straits
Port Klang. The first basic study on the straits was is sheltered completely by mangrove islands on the
initiated by several research organisations in 1981, west (Fig. 1).The study area is influenced by the rainy
including the Association of Southeast Asian season occurring during the North East Monsoon
Nations, Department of Environment (Selangor) and (November to March) and the dry season (South
Environmental Management for the East Sea. Ten spe- West Monsoon, April to October). Heavy rainfall is
cific pollutants (bacteria, phenol, oil and grease contam- normally experienced during the early part of the
ination and Cd, Hg, As, Pb, Cu, Cr and nutrient monsoon while dry spells occur during the later part
concentrations) were estimated to assess environmental (Yap 2005). The average salinity has been recorded at
quality. These studies reported that the high concentra- 30.25 ‰; whereas, the average temperature was
tion of heavy metals, especially Fe and Pb in the water 30.04 °C. The average concentration of DO at the
and sediment area is probably derived from transporta- surface was 5.38 mg/l, and the monthly average sur-
tion and navigation, land-based contaminants and indus- face and bottom pH values ranged from 7.85 to 8.25,
trial discharges (Everaart and Swennen 1987; Ho et al. with lower values obtained from October to January
1993; Law and Singh 1986; Tavakoly Sany et al. 2012). because of the higher river discharge (Chong et al.
Water Air Soil Pollut (2013) 224:1476 Page 3 of 18, 1476

Fig. 1 Map showing the sampling sites in the three subsidiary ports of Port Klang, Malaysia

1990; Lehr and Keeley 2005). The Klang Strait expe- Tables of Malaysia, Singapore and Brunei, 2009). A
riences semi-diurnal tides with tidal ranges between total of 21 sampling stations were selected at three
2 m during neaps and 5.5 m during springs (Tide sites (six stations in North Port, six stations in South
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Port and nine stations in West Port) (Fig. 1; Table 1). and results were divided into sand (>64 μm), silt
According to the location and bathymetry of each site, (2 μm<size<64 μm) and clay (<2 μm) fractions for
stations located inside the Klang Strait were arranged into the determination of heavy metals in the contaminated
three parallel transects at three different distances. The sediment (Rauret 1998; Tessier et al. 1979). Double-
first transect lies parallel to the berth line and industrial distilled water was first used to wash sediment samples
outlets, the second is located in the middle line of the and remove halides from sediment. All Teflon bottles
strait and the third is parallel to the mangrove line in the and crystal material were washed with water and soap
west and north port. From November 2009 to October and rinsed with Milliq and Ellix quality water prior to
2010, sediment samples were collected every three analysis. Plasma mass spectrometry was used for the
months at low tide with clean plastic spoons. The samples chemical analysis of heavy metals (Al, As, Cd, Cr, Cu,
were collected in triplicate from surface sediments (2 cm Fe, Mn, Ni, Pb, Vand Zn). The samples were dried in an
depth) because this layer controls the exchange of metals oven at 60 °C over the night, and 0.5 g of the dried
between sediment and water (Praveena Ahmed et al. sediment sample was transferred to vessels for acid
2008). The samples were stored in clean polythene bags extraction. The samples was digested in 3 ml of
and kept in an icebox at 4 °C to decrease chemical and hydrofluoric acid and 9 ml of nitric acid (HNO3) for
biological reactions. In the laboratory, the samples were 15 min using microwave heating, and 18 ml of boric
stored at −20 °C until further analysis. acid 99.99 % was added to the cooled solution followed
by centrifugation. The solution from the centrifugal
2.2 Experimental Methods operation was filtered using filter-paper (Whatman No.
0.45 μm), and the volume was topped to 50 ml with
Sediment grain size was determined using a multi- deionised water for the measurement of heavy metal
wavelength particle size analyzer (model LS 13 320), concentrations. The preparation procedure described
above for metal analyses was based on EPA method
Table 1 Location of the stations along Klang Strait 3052 (EPA 1996; Ilander and Väisänen 2007; Zhang
Sites Station Depth Description of stations
and Liu 2002). Total organic carbon (TOC) was deter-
code (M) mined in surface sediments using a carbon analyzer
(Horbia Model 8210). The procedure for TOC analysis
North N100 14.3 Industrial and liquid berth line follows Fang and Hong (1999). Standard reference ma-
Port N700 20.5 Remote terials (SRM) 2702 is a natural matrix of inorganic
N1500 10.3 Mangrove compounds collected from marine sediment with certi-
NC100 13.5 Container berths and urban fied concentration values. The National Institute of
NC700 21.6 Remote Standards and Technology and collaborating laborato-
NC1500 11.2 Mangrove ries obtained certified values for the concentrations of
West C100 12.5 Industrial and cement berth 25 elements based on chemically independent analytical
Port C500 19.5 Remote methods with the highest accuracy (Willie and May
C1000 7.8 Mangrove 2002). In this study, data quality control and heavy
L100 13.3 Industrial and liquid berth metal concentrations were evaluated with the certified
L500 20.3 Remote concentration of SRMs 2702 and matrix spike recover-
L1000 8.8 Mangrove ies. The percentage recovery was between 91.54 and
W100 15.5 Container Terminal berths 104.66 (Table 2). The standard methods suggest warn-
W500 21.1 Remote ing limits for matrix spike recoveries from 87 to 113 %;
W1000 6.8 Mangrove therefore, the range of recovery was reasonable in this
South SK100 7.5 Dry berths, urban and Klang river study (IDEM 2002; Willie and May 2002).
Port SK1000 10.5 Semi-urban and Klang river
SK2000 12.4 Semi-urban 2.3 Heavy Metal Enrichment Factor and Geo-
SL100 10.3 Liquid berth accumulation Index
SL1000 11.3 industrial
SL2000 10.4 Mangrove
Several normalisation methods have been used to assess
sediment quality, such as granoulometric normalisation,
Water Air Soil Pollut (2013) 224:1476 Page 5 of 18, 1476

Table 2 Average concentration (in milligrammes per has the same geochemical reaction under oxic and
kilogramme dry weight, except Al and Fe as weight per cent)
anoxic conditions with other heavy metals in sediment
standard deviation and percent recovery (%REC) of certified
references and also because the natural concentration is more
uniform compared with Al (Goldberg et al. 1979;
Metals Certified Measured±SD %REC Schiff and Weisberg 1999; Siddique et al. 2009). The
Cu 117.7 118.34±2.56 100.54
stability of Fe in sediment is lower than Al due to the
mobility and ability of this element to accumulate in
Cd 0.817 0.810±0.09 99.14
the food chain (Daskalakis and O’Connor 1995; Din
Zn 485.3 492.39±35.56 101.46
1992; Rubio et al. 2000; Zwolsman et al. 1996), which
Pb 132.8 128.98±6.56 97.12
indicates that Fe is affected by anthropogenic contam-
Mn 1,757.0 1,838.93±102.34 104.66
inants. Aluminium was selected as a normalising ele-
Ni 75.4 74.56±2.34 98.88
ment in this study because this metal is commonly
Co 27.76 25.21±1.3 90.81
inactive in marine sediment with little or no chemical
Cr 352.0 388.84±48.21 110.46
reaction and, therefore, is not easily affected by an-
V 357.6 371.13±31.23 103.76
thropogenic contamination and digenetic changes
As 453.0 475.26±47.32 104.91
(Rubio et al. 2000). Zubir indicated that Al has a
Al 8.4 % 7.69±0.39 91.54 strong liner correlation with other trace metals
Fe 7.91 % 8.14±0.22 102.90 (with r2, 0.89–0.93) in the Melaka Strait coastal water
(Din 1992). EF is the concentration ratio of measured
heavy metals to normalising elements (Al, Fe, Cs, Rb,
organic carbon (OC) normalisation, enrichment factor Li and Si) in sediment samples that is divided by the
(EF) and geo-accumulation index, but only a few have ratio of metal background to the normalising elements
been accepted for estuarine and coastal waters. (Rule 1986).
Granulometric normalisation analysis was used to as-
sess anthropogenic effects on the sediment, but this EF ¼ ðCmetal =Cnormaliser Þ=ðCmetal =Cnormaliser Þbackgroundvalues ð1Þ
method is not sufficient to assess the degree of contam-
ination. This method also has a reduced ability to indi- Where (Cmetal/Cnormaliser)soil are the metal concen-
cate the accurate concentration of contamination in trations in the sediment sample and (Cmetal/Cnormaliser)
marine sediment because of the extensive separation of background values is the natural background of the heavy
individual grain sizes (Ravichandran et al. 1995). It is metals and normalising elements. According to the EF,
incorrect to use the (OC) method for sediment sediment is classified into groups by river, estuary and
normalisation because OC is considered a pollutant coastal environments. EF values of 0.5≤EF≤1.5 indi-
without any geochemical approach (Kersten et al. cate that the metals may be completely derived from
1994; Rubio et al. 2000). The heavy metal EF and natural or lithogenic processes. EF values of more than
geo-accumulation are specific indices that are used to 1.5 indicate that a large portion of trace metal is
estimate the anthropogenic effect of heavy metals on derived from non-natural processes or anthropogenic
estuarine and coastal waters. sources (Feng et al. 2004; Siddique et al. 2009; Zhang
These indicators provide simple ways to assess the et al. 2009). Han et al. (2006) defined the new ER
contamination status of surface sediments (Sinex and value classification as follows: EF≤2 indicates that
Helz 1981; Vallejuelo et al. 2010; Zhang et al. 2007). metal contamination might be entirely from natural
EF is estimated based on total resistant elements, such sources, an EF value of 2–5 indicates that a moderate
as Al, Li, Fe, Rb, Sc and Cs (Balls et al. 1997; Odabasi portion of heavy metals originated from an anthropo-
et al. 2002; Rubio et al. 2000). genic source or non-natural process, an EF of 5–20
In recent decades, Al and Fe were widely used as indicates that a significant portion are from anthropo-
normalising element to estimate the EF (Ackermann et genic sources, an EF of 20 to 40 indicates that a high
al. 1983; Loring et al. 1995; Rubio et al. 2000). portion of contamination is derived from anthropogen-
Several comparative arguments exist on the use of Al ic sources, and an EF>40 indicates an extremely high
or Fe as normalising elements. Some studies have portion of contamination. In this research, the average
selected Fe as the normalising element because Fe concentration of heavy metals from 1996 to 2007 is
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used to estimate the background value from Hakanson 2.5 Statistical Analysis
(1980). The geo-accumulation index (Igeo) introduced
by Muller (1979) is used to better understand the Statistical analyses were performed using Microsoft
degree of contamination in surface sediments, and Excel and SPSS 17 software (SPSS, Chicago, IL). To
these results reflect the effect of lithogenic sources statistically evaluate the data, Kendall’s tau-b correla-
(Nobi et al. 2010; Sinex and Helz 1981; Singh et al. tion analysis and the Kruskal–Wallis test (level of
2003; Vallejuelo et al. 2010). significant is 0.05) were employed to understand the
relationship between heavy metals in sediment and
Igeo ¼ Log2ðCn=1:5BnÞ ð2Þ other parameters. Geo-statistical analysis was
performed using Surfer 8 software (GPS value of
Where Cn is heavy metal concentration in sediment stations) based on geospatial methods to better under-
of study area, Bn is the geochemical background value; stand contaminant pathways and to provide a compre-
1.5 is the background matrix correction in factor due to hensive contour map of the spatial distribution of
lithogenic effects. The contamination level was classified contaminants over a large area (Cressie 1990; Sparks
in six scales: Igeo≤0=unpolluted, Igeo<1=unpolluted 2000)
to moderately polluted, Igeo<2=moderately polluted,
Igeo<3=moderately to strongly polluted, Igeo<4=
strongly polluted, and Igeo<5=strongly to very strongly 3 Results and Discussion
polluted. Igeo>5=very strongly polluted (Leorri et al.
2008; Loska et al. 1997). 3.1 Variation in the Concentration of Surface Sediment
Components
2.4 Sediment Quality Assessment
Analysis of sediment grain size demonstrated that
There are several methods to assess sediment quality fine-grained sediments predominated in almost all sta-
and describe the contamination adverse effects. These tions (41.1–95.39 %) (Fig. 2). The highest amount of
include contamination using indexes (comparison be- fine fractions were found in stations close to the man-
tween polluted station and background level or polluted grove shore and mouth of the Klang River, whereas
stations), such as the EF and geo-accumulation, and the the highest portion of the sand fraction occurred in
SQGs that are applied to assess toxicity risk (Caeiro et stations C500 (54.03) and L500 (58.89). Grain size
al. 2005). This method indicates that the relationship variation is controlled by several factors in marine
between the concentrations of contaminants in sediment environments, including sedimentary processes, sedi-
samples and adverse biological effects is based on the ment transportation and distance from material sources
specific values of effect range low (TEL) and effect (He et al. 2009; Qin et al. 1989). The area of fine
range medium (PEL). The TEL value has been estimat- sediment along the mangrove shoreline reflected the
ed as the concentration of contaminants with a relatively
low effect on biological communities, and PEL is a
concentration of contaminants with high adverse effects.
Occasional adverse effects are expected to occur from
metal concentrations between TEL and PEL (Hübner et
al. 2009; Long et al. 1995; Long and Morgan 1990). The
possible toxicity concerning metals was described by
PEL quotients (PELqs). The PELq factor is the average
of the ratios between the heavy metal concentration in
the sediment sample and the related PEL value (Alvarez
Guerra et al. 2007; Leorri et al. 2008). This factor de-
scribes the sediment contamination range as non-toxic
(PELq<0.1), slightly toxic (0.1<PELq>0.5), moderate-
ly toxic (0.5<PELq>1.5) and heavily toxic (PELq>1.5) Fig. 2 Percentage contribution of different sized fractions in
(Vallejuelo et al. 2010) sediments at stations in Port Klang, Malaysia
Water Air Soil Pollut (2013) 224:1476 Page 7 of 18, 1476

effect of mangrove forest on increasing the sedimen- correlation (0.4<r, p<0.01) with fine particles, e.g., Al
tary processes. The mangrove forest acts as a sediment (r=0.541), Cd (0.406), Cu (0.447), Fe (0.418), Ni
trap and provides a mechanism to sink suspended (0.432), V (0.411), Zn (0.493), and TOC (0.716)
solids by decreasing the hydrodynamic energy (tidal (Table 3).
current and baroclinic circulation), which provides The TOC content of sediment samples were esti-
time for the sinking and re-deposition of fine grain mated at 21 stations and these results are summarised
sizes (Woodroffe 1992; Wolanski et al. 1992; in Table 4. The TOC varied between 5.35–24.88 and
Furukawa et al. 1997; Kathiresan 2003; Cunha- was synchronous with fine grain size sediment in most
Lignon et al. 2009). Moreover, fine grain size sedi- parts of the study areas, with the peak value at the
ments along the mangrove line were likely transported south port around the mouth of Klang River and lower
by land-based runoff. Other stations with a high per- concentrations at stations C500 and L500. Generally,
centage of fine grain sizes were close to the Klang the fine grain sized sediment, specifically the clay
River in the South Port, which indicates the effect of colloid, exhibits a significant trend for adsorbing
the river transport. Klang River contributed signifi- TOC, and the concentration increases as the average
cantly to the distribution of sediment particles, and grain size decreases (He et al. 2009). Some heavy
the weak hydrodynamic energy increased the sedi- metals showed positive correlations with TOC, such
mentation rate of fine grain size sediment. as Al (r=0.582), Cd (0.504), Cu (0.557), Fe (0.438),
Sediment grain size plays a significant role in the Ni (0.404), V (0.462) and Zn (0.406) (Table 3). TOC,
concentration and distribution of heavy metals in coastal such as humic material, has a high adsorption and
and estuarine sediment. The concentration of heavy complex influence on the re-deposition of heavy
metals is widely enriched in fine particles compared with metals. Furthermore, anthropogenic heavy metals are
sand size particles because fine-grained sediment signif- widely absorbed on the surface or combined with TOC
icantly adsorbs heavy metals from water for deposition in suspended solids and deposited on bottom sedi-
in the bottom sediment. In addition, the fine fraction also ments (Zhang et al. 1996; Chapman 1992).
has a high capacity to retain heavy metals compared to Variations in the heavy metal concentrations on
other fractions (Abrahim et al. 2007; Nobi et al. 2010; He surface sediments were classified into four box–whis-
et al. 2009; Lim et al. 2006). Thus, this fine fraction is ker plots (Fig. 3), while the range of values are listed
frequently used to assess contaminant variation and for in Table 4. These results showed that the concentration
toxicity tests in environmental research. In the present of all metals (except for Cu, Ni and Fe) varied widely
study, some metals and TOC exhibited a positive at each station.

Table 3 Correlation coefficient between heavy metals, TOC and fine particular size fraction

Al As Cd Cr Cu Fe Mn Ni Pb V Zn Fine fraction TOC

Al 1.00
As 0.26 1.00
Cd 0.38 0.32 1.00
Cr 0.37 0.27 0.26 1.00
Cu 0.33 0.15 0.29 0.32 1.00
Fe 0.63 0.35 0.39 0.52 0.29 1.00
Mn 0.13 0.23 0.19 0.11 0.03 0.10 1.00
Ni 0.29 0.32 0.30 0.29 0.34 0.34 0.18 1.00
Pb 0.31 0.58 0.36 0.22 0.21 0.39 0.16 0.27 1.00
V 0.30 0.29 0.51 0.36 0.22 0.34 0.31 0.24 0.28 1.00
Zn 0.68 0.26 0.55 0.32 0.38 0.58 0.08 0.38 0.27 0.27 1.00
Fine fraction 0.54 0.37 0.40 0.28 0.44 0.41 0.10 0.43 0.20 0.41 0.49 1.00
TOC 0.58 0.36 0.50 0.25 0.55 0.43 0.11 0.40 0.23 0.46 0.40 0.71 1.00
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Table 4 Range of the metal concentration (in milligrammes per kilogramme dry weight, except Al and Fe as weight percentage) in
different stations

Site

POINT Al Fe Mn As Cu Cr Cd Pb Ni V Zn TOC

North N100 Minimum 8,546.83 4,183.00 195. 43.30 12.40 39.50 0.42 41.20 4.50 30.23 29.00 10.00
Port Maximum 18,983.4 6,480.00 286.0 109.2 23.80 53.87 1.10 92.67 17.60 70.30 77.00 15.58
N700 Minimum 6,740.43 2,380.00 137.0 36.40 10.34 27.00 0.22 31.30 4.16 22.34 26.60 7.09
Maximum 12,983.4 4,700.00 210.0 91.00 16.93 50.98 1.00 73.40 9.60 47.00 47.00 19.00
N1500 Minimum 12,597.9 4,672.00 245.0 42.00 14.20 37.90 0.50 47.60 6.23 40.40 30.50 14.00
Maximum 24,804.5 8,278.00 289.1 121.2 30.40 49.11 1.30 98.90 13.89 71.25 83.00 21.74
NC100 Minimum 11,303.5 4,000.00 230.0 22.30 12.80 28.90 0.51 42.57 8.45 30.09 23.45 8.03
Maximum 16,784.5 9,247.00 289.0 46.00 20.80 52.67 1.32 62.60 17.90 67.50 72.00 14.94
NC700 Minimum 10,024.4 2,760.00 177.1 21.00 10.34 20.34 0.35 31.85 4.43 27.12 26.00 7.75
Maximum 20,875.3 6,890.00 216.6 41.00 14.70 46.70 1.40 60.25 10.0 62.50 62.90 13.06
EC1500 Minimum 10,768.5 4,095.59 299.0 25.52 12.34 31.45 0.58 32.70 9.34 42.67 28.45 11.00
Maximum 23,923.3 8,081.00 352.0 76.70 24.89 45.87 1.32 68.93 14.90 73.90 73.80 19.34
West C100 Minimum 7,845.87 2,855.98 162.8 27.20 11.50 50.35 0.32 45.67 6.20 29.45 30.40 6.94
Port Maximum 12,584.4 6,298.00 289.7 47.60 24.26 66.98 1.20 64.90 14.30 69.34 70.50 13.38
C500 Minimum 7,401.68 5,135.00 96.80 24.50 8.60 31.60 0.40 35.70 6.45 49.10 20.40 5.35
Maximum 10,123.4 10,560.0 234.0 95.60 13.93 66.90 1.18 75.30 10.93 77.90 60.90 10.83
C1000 Minimum 9,684.34 3,400.00 244.7 40.27 10.21 33.46 0.42 43.03 7.20 33.40 22.34 9.36
Maximum 13,608.3 6,298.00 390.5 124.7 17.54 58.50 1.30 58.90 14.50 73.34 57.70 18.94
L100 Minimum 8,783.50 3,000.00 179.1 43.90 12.34 28.50 0.20 44.95 7.89 21.30 20.70 7.00
Maximum 12,808.4 6,382.12 325.6 125.0 16.78 48.90 0.40 67.20 17.80 62.00 51.40 11.54
L500 Minimum 7,103.68 3,150.00 128.6 29.30 10.20 22.00 0.16 41.56 8.70 16.30 18.90 5.98
Maximum 10,474.9 6,652.00 220.7 63.90 16.98 51.90 0.52 64.30 18.20 50.30 49.00 8.94
L1000 Minimum 10,804.6 4,016.00 142.0 38.63 11.40 38.80 0.14 46.80 10.30 30.67 21.98 10.17
Maximum 16,032.8 6,730.80 365.5 57.45 20.99 61.50 1.10 66.10 20.80 72.70 52.87 18.04
W100 Minimum 15,318.6 6,626.53 201.6 43.40 14.03 54.80 0.40 50.90 10.34 64.30 28.70 9.00
Maximum 23,830.4 10,660.0 342.7 134.2 21.80 66.17 1.60 104.87 19.40 130.00 73.60 12.0
W500 Minimum 8,087.30 4,001.00 174.0 43.78 10.34 33.56 0.21 36.60 6.12 26.50 17.00 6.00
Maximum 20,999.4 10,156.0 321.0 87.20 14.90 50.30 1.80 62.13 12.70 73.28 46.87 12.95
W1000 Minimum 12,102.6 4,000.00 280.2 54.23 11.50 40.90 0.50 62.23 10.34 31.30 21.40 12.00
Maximum 24,930.4 10,370.0 468.0 137.5 28.90 52.90 1.90 89.98 14.87 127.34 70.67 19.03
South SK100 Minimum 20,578.2 10,020.0 193.3 84.34 29.20 63.00 1.14 78.23 8.67 65.45 76.45 20.00
Port Maximum 42,586.5 17,569.0 282.0 142.3 57.01 83.20 1.94 97.80 23.50 127.20 192.90 25.74
SK1000 Minimum 20,478.4 10,002.0 181.0 78.45 25.03 57.34 0.96 60.34 8.74 63.23 74.34 19.00
Maximum 40,849.4 15,908.0 248.5 138.0 51.92 73.10 2.10 98.56 21.40 121.72 189.45 24.88
SK2000 Minimum 15,287.0 6,023.00 167.0 30.30 14.40 40.50 0.83 60.20 6.56 28.40 38.60 13.70
Maximum 22,287.3 11,023.0 238.0 54.60 19.45 53.70 1.10 91.30 12.40 52.40 69.60 17.60
SL100 Minimum 10,484.5 3,567.34 118.3 37.98 12.20 39.50 0.40 36.23 6.50 35.49 22.67 12.04
Maximum 20,776.4 9,292.00 208.0 112.2 18.45 78.81 1.45 66.09 17.50 72.10 70.80 16.16
SL1000 Minimum 11,103.4 4,604.32 128.4 40.31 14.50 41.59 0.54 54.56 8.50 35.74 28.85 8.36
Maximum 19,439.3 8,802.03 219.1 63.20 24.89 60.19 1.46 96.02 15.09 74.02 72.20 21.35
SL2000 Minimum 10,104.8 3,103.70 118.0 30.00 11.23 34.00 0.52 37.89 3.96 24.56 31.70 6.56
Maximum 21,056.4 6,241.00 209.0 57.60 19.30 48.00 0.73 68.30 10.30 46.30 61.80 14.70
Water Air Soil Pollut (2013) 224:1476 Page 9 of 18, 1476

In this study, Klang Strait was divided into three concentration of all metals (except for Mn), TOC
specific geochemical sites (North, West and South and fine grain sized sediment were observed in
Ports) to describe the distribution of metals and South Port. Metal analysis showed that there was
TOC. At the North Port site, the mean value of the considerable variation among the different stations,
metals (Cu, Mn, Pb, Cr, Ni, Cd, Zn, As, V, Al, Fe (in which was evidenced by a non-parametric Kruskal–
microgrammes per gramme)) and TOC were 16.24, Wallis test. This test indicates that there were signifi-
241.37, 53.85, 39.67, 9.63, 0.82, 47.48, 55.41, 46.52, cant differences (p<0.05) between the heavy metal
13,312.05, 5,373.43 and 12.18 %, respectively. At concentrations at some stations. Furthermore, the spa-
West Port, these values were 14.58, 256.2, 58.35, tial distribution maps indicated this significant
47.39, 12.11, 0.71, 39.22, 60.70, 53.34, 12359.49, variation. These results indicate that heavy metal con-
5,993.85 and 10.46 %, respectively. At South Port, centrations in Klang Strait were affected by several
these values were 23.6, 189.5, 67.89, 53.07, 12.53, sources of contamination (Fig. 4).
1.02, 74.37, 66.31, 57.03, 20,179.4, 8,730.9 and Studies elsewhere indicate that several factors such
16.4 %, respectively. as erosion, sedimentation, sediment type, water dy-
namics, urbanisation, industrialisation, river discharge
3.2 Spatial Distribution and geochemical reactions affect the distribution and
constitution of heavy metals in coastal and estuarine
Figure 4 shows the spatial distribution of heavy waters (Olubunmi and Olorunsola 2010; Pan and
metals, sediment grain size and TOC. The highest Wang 2011; Nobi et al. 2010; Vallejuelo et al. 2010;

Fig. 3 Box–whisker plots


of the heavy metal concen-
trations (in milligrammes
per kilogramme weight, ex-
cept Al and Fe as weight per
cent) in sediments in the
Klang Strait (the whisker
show the minimum and
maximum concentration,
and the line of each plot is
the median value)
1476, Page 10 of 18 Water Air Soil Pollut (2013) 224:1476

Fig. 4 Spatial distribution of heavy metals, TOC and fine-grain-sized sediment in Port Klang, Malaysia (in milligrammes per
kilogramme dry weight, except Al and Fe as weight percentage)
Water Air Soil Pollut (2013) 224:1476 Page 11 of 18, 1476

Fig. 4 (continued)

Zhang et al. 2009; Siddique et al. 2009; Naji et al. Likewise, the highest concentrations of these com-
2010). pounds were estimated at the SK100 and SK1000 sta-
At the South Port, the distribution of all metals, TOC tions, which are parallel to the mouth of the Klang River.
and silt-clay sediments exhibited a homogeneous pat- This study support the view that the Klang River may
tern that decreased from the north to south direction. be the main source of contamination and influence the
1476, Page 12 of 18 Water Air Soil Pollut (2013) 224:1476

other metals. These results are most likely due to the


low concentration of biogenic carbonates in South
Port sediments. Dissolved concentration of Mn con-
trols the absorption and substitution in calcite. Most
particulate Mn is easily bound to seawater carbonates
(Wartel et al. 1991; Wartel et al. 1990). Studies have
also reported a strong correlation between the concen-
tration of biogenic carbonates and Mn in coastal sed-
iments of Taiwan and the East China Sea (Fang and
Hong 1999; Fang et al. 2009).
In North Port, the distribution of As and Zn gener-
ally showed a same pattern that varied from a high to
low concentration from north to south. The high con-
Fig. 5 Box–whisker plots of the EF of heavy metals in sedi- centration of Cu, Pb and Cr also occurred in the east
ment (the whisker shows the minimum and maximum concen- and northwest direction. These areas are adjoining to
tration, and the line of each plot is the mean value)
land runoff and industrial outlets, which can directly
release organic and inorganic pollutants.
concentration and distribution of metals and TOC be- The distribution of Al, Fe, Mn, Cd and V showed
cause water and suspended solids were easily exchanged the same pattern with fine particle sized sediments and
between South port and the polluted Klang River. The TOC distribution. The highest concentration occurred
river contains industrial effluents and untreated munici- in the western part of strait and along the mangrove
pal waste (Naji et al. 2010; Balamurugan 1991; forest fringes, which was related to the higher concen-
Greenwood, Jr. 2007). The water currents in the vicinity tration of TOC and fine grain size in mangrove sedi-
of South Port are weak; therefore, there is enough time ment. In this study, there was a positive correlation
for the absorption of heavy metals by suspended solids (0.4<r; p<0.01) between fine particle size and the
for deposition on surface sediments. Heavy metals are following metals: Al (r = 0.541), Cd (0.406), Fe
not easily deposited in bottom sediments with strong (0.418), V (0.411), Cu (0.447) and TOC (0.716).
water currents (He et al. 2009). The fine particle size The distribution of Ni was unique because it was
dominant in the South Port zone could be due to Klang high along the mangrove coastline and east direction
River sedimentation and the weak water currents be- of North Port. Generally, the lowest concentration of
cause fine-sized grains are more easily deposited in areas metals (except for Al and As) was found close to the
with weak water currents (Qin et al. 1989). stations N700 and NC700 in North Port. This may be
According to the correlation analysis, there was no due to the strong water currents which decrease the
correlation between Mn and other metals, and Mn chemical reactions (adsorption and complexation) be-
showed a different spatial distribution relative to the tween metals and sediments. Moreover, these stations
had substrates with a high percentage of sand grain
sized sediments compared with other stations.
At the West Port area, the spatial distributions of
As, Pb, V, Al, Fe, Zn, Cu and Ni were generally
homogenous with a low to a high concentration from
the north to the south. The high concentration of these
metals was determined around stations W100. This
distribution may be related to the large container ter-
minal (Table 1) and the inflow of land runoff in south
of West Port, which may have caused an increase in
the metal concentration. Moreover, Ni showed the
Fig. 6 Box–whisker plots of the geo-accumulation indexes for
sediments in Port Klang where (the whisker shows the minimum
highest concentration around the L1000 and L500
and maximum concentration, and the line of each plot is the stations. These stations were probably influenced by
median value) both the sedimentation area (mangrove line) and the
Water Air Soil Pollut (2013) 224:1476 Page 13 of 18, 1476

Table 5 Comparison of heavy metals concentration in Klang Strait with background value, igneous and SQG

Concentration of heavy metal (mg/kg) Al Fe Mn As Cu Cr Cd Pb Ni V Zn

the average concentration of heavy metal in 14,724 6,547 231.43 60.36 17.43 46.4 0.82 59.45 11.44 52. 51.05
Klang Strait
Heavy metals Back ground value in Klang 85,100 41,922 349.18 18.79 23.21 53.71 0.18 39.8 32.77 71.59 141.22
Strait (Yap 2005)
Igneous rock (Bowen 1966) 82,000 56,300 950 1.8 55 100 0.2 12.5 75 135 70
SQG-based on Macdonald et al. (1996, 2000)
TEL 7.24 18.7 52 0.68 30.2 15.9 124
PEL 41.6 108 160 4.2 112 42.8 271

industrial waste from the industrial outlets that are 3.3 Enrichment Factor and Geo-accumulation Index
located along the coastline. The higher concentration (Igeo): Pollution Levels
of Cr exhibited a higher trend to east of the strait
(along the coast line). The concentration of Cd, Mn, The metal EF was also applied to evaluate the anthro-
TOC and fine-grain size decreased from the mangrove pogenic contribution of heavy metals in surface sedi-
line to the coastline, and this pattern was similar to the ments. In this study, heavy metals had different EF
distribution patterns at North Port. ranges (Fig. 5). The EF value of Fe was lower than 2,
As a result, the different distribution patterns indicating that Fe may have entirely originated from
showed that multiple sources widely contributed to natural processes or crustal materials. The enrichment
the heavy metal load in the Klang Strait. These sources value of Cu, Cr, Mn, Ni, V and Zn were between 2<
include the large-scale inflow from the industries, such EF<5, indicating that the sediment of Klang Strait had
as the palm oil, cement and food manufactures that are moderate anthropogenic inputs of these heavy metals.
located along the coastline of North and West Port, There was significant enrichment of Pb, As and Cd in
vessel-based discharges, Klang River outflow, land sediments, which suggests that a high proportion of
runoff, sedimentation and siltation. these metals were from anthropogenic sources.
In the general, significance correlation analysis re- The geo-accumulation index was used to evaluate the
veal that TOC and fine grain size sediment had syn- pollution levels of heavy metals on surface sediment
ergic effects on the distribution of heavy metals, that (Fig. 6). Most of the Igeo values for heavy metals were
is, the percentage of fine grain sized sediment and not detectable except for except for Cd and As. Cd and
TOC increased in tandem. This resulted in an increase As exhibited moderately polluted levels with mean
of some metal concentrations, especially in South values of 1.33±0.9 and 1.12±0.63, respectively.
Port. TOC and fine-grain size are natural controls of According to background value concentrations,
heavy metal accumulation in the study area. these results showed that heavy metal contamination

Fig. 7 PELqs values for


sediment in Klang Strait.
PELq<0.1, non-toxic;
0.1<PELq<0.5, slightly
toxic; 0.5<PELq<1.5, mod-
erately toxic; and
PELq>1.5, highly toxic
1476, Page 14 of 18 Water Air Soil Pollut (2013) 224:1476

in marine sediments of Klang Strait were attributed to 3.4 Comparison with the SQG: Adverse Biological
natural processes or mineralogical variation and hu- Effect
man activities (anthropogenic). Furthermore, marine
sediments of Klang Strait were considered to be pol- In this study, the concentration of heavy metals were
luted with Cd and As. compared with TEL and PEL values and the PELq
Cd and As originate mainly from industrial process- factor were used to estimate possible toxic effects of
es including mining, burning of fossil fuels, waste heavy metals at different stations. PELq were not
recycling, cement manufacturing, as well as paper estimated for Al, Fe, Mn, V and Co because these
and glass production (Fishbein 1981; Srikanth et al. metals generally do not have toxic effects on biolog-
1993; Yasar et al. 2001; Jennings and Rainbow 1979; ical communities in the environment (Vallejuelo et al.
Cossa et al. 2011; Pan and Wang 2011; Davis et al. 2010; Hübner et al. 2009). Table 5 shows a compari-
2009). There are several industries in Port Klang in- son between the heavy metal concentrations in the
volved in cement manufacturing, palm oil processing present study with background values in the Klang
and oil/electrical based power generation. Other Strait, indigenous rock and guideline values (TEL
sources of Cd and As might be due to atmospheric and PEL). The mean concentrations for Zn, Ni, Cr
deposition, river inflows and terrestrial runoffs, which and Cu were below the TEL value which effects are
are the main routes of metal release into marine envi- expected to be rare. Cd and Pb were found in the TEL
ronments. Organic herbicides, insecticides (lead- and PEL rang where occasional adverse effects are
Arsenate), pesticides and fertilisers applied in agricul- expected. Only As exceeded the PEL value, indicating
ture activities and industrial discharges are the land- likely high adverse effects for biological organisms. In
based anthropogenic sources of metals into rivers that the present study, only estimated Cd, Pb and As con-
could pollute coastal and estuarine areas. The high centrations are significantly greater than the back-
concentration of all heavy metals around the Klang ground and igneous rock value, while other metals
River mouth is consistent with observations that the were lower than these values. This study clearly in-
river is a main route of heavy metal release, especially dicates that the metal concentration was influenced by
for Cd and As, in Klang Strait (Law and Singh 1986). disturbances, which changed the associated geochem-
Moreover, the high concentration of Cd and As could ical concentration ratios, and that the metal concentra-
have originated from tsunami sediment deposition, tions increased from their standard range. The relative
ship waste, embarkation activities and anticorrosive concentration ratio of the metals exceeds standard
paints used on marine vessels. variation levels in the sediment when geochemical

Fig. 8 Dendogram showing


the rescaled distance cluster
of different stations of Port
Klang
Water Air Soil Pollut (2013) 224:1476 Page 15 of 18, 1476

metal concentrations experience disturbances due to are influenced by the Klang River runoff and the
environmental change (Praveena et al. 2008; Wang terminal container, which may not be covered under
and Qin 2006). the protective regulations.
The variation in estimated PELq values is shown in
Fig. 7. Three sediment samples collected in SK100,
SK1000 (South port) and W100 (West Port) were con- 4 Conclusions
sidered to exhibit moderate toxic effects. The rest of the
sediment samples were considered to be slightly toxic. The spatial distribution maps and geo-statistical index
The dendrogram results allow for a better understanding reveal that contamination of sediments is in a pristine
of the similarity between sampling stations and metal state, except for Cd and As. Furthermore, contamina-
analyses (Fig. 8). The dendrogram grouped sampling tion assessment based on the SQGs shows that the
stations into three clusters based on possible toxicity potential toxicity of all metals varied between rare
effects of heavy metals in sediment. The first and second toxic effects to occasional toxic effects, except in the
plot clusters (A and B) are in the same range of slightly case of As. This metal exhibited high toxic effects, and
toxic effects (0.1<PELq<0.5). However, the average the As concentration was significantly greater than
toxicity effects of heavy metals in the N100, N1500 PEL and the background value. Therefore, arsenic
and W1000 stations in the second cluster (B) were more (As) can be considered as a serious threat to biological
than the stations in the first cluster (A). Second cluster communities and human health.
values were closer to 0.5 compared with the first cluster In addition, Regarding the sediment quality esti-
because these stations were largely influenced by land- mates, only sediment from SK100, SK1000 and
based runoff and mangrove sedimentation. The third W100 can be considered to be moderately polluted,
cluster of the plot (C), which includes stations SK100, and other stations were classified at the slightly pollu-
SK1000 and W100, exhibited a similar toxicity effect tion level. Thus, sediments from the most polluted
(moderately toxic). The average toxicity effect of the stations were a significant source of toxic metals. In
third cluster exhibited significant differences with sta- summary, the present study has provides excellent
tions located in the other cluster. Stations SK100 and baseline data for the long-term monitoring of heavy
SK1000 are close to the Klang River mouth in South metal pollution in Klang Strait.
Port, whereas W100 was located near the West Port end
and is close to the container terminal. Acknowledgment The authors’ gratitude goes to support of
University Malaya Research Grant (UMRG) with project number
Regarding to the dendrogram results, only sediment
RG174-12SUS, HIR Grant ( UM.C/625/1/HIR/162) and Univer-
from SK100, SK1000 and W100 can be considered to sity Malaya Postgraduate Research Grant (PPP).
be polluted. This is in good agreement with the idea
that the Port Klang area recovered sediment quality,
which was most likely due to wastewater management
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