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Environ Earth Sci
DOI 10.1007/s12665-013-2826-9
ORIGINAL ARTICLE
Risk assessment of polycyclic aromatic hydrocarbons
in the West Port semi-enclosed basin (Malaysia)
Seyedeh Belin Tavakoly Sany • Rosli Hashim •
Aishah Salleh • Omid Safari • Ali Mehdinia •
Majid Rezayi
Received: 1 February 2013 / Accepted: 23 September 2013
Ó Springer-Verlag Berlin Heidelberg 2013
Abstract Sediment samples collected from the West
Port, the west coastal waters of Malaysia, were analyzed by
standard methods to determine the degree of hydrocarbon
contamination and identify the sources of polyaromatic
hydrocarbons (PAHs). Concentrations of PAHs in the port
sediments ranged from 100.3 to 3,446.9 lg/kg dw. The
highest concentrations were observed in stations close to
the coastline, locations affected by intensive shipping
activities and industrial input. These were dominated by
high-molecular-weight PAHs (4–6 rings). Source identifi-
cation showed that PAHs originated mostly pyrogenically,
from the combustion of fossil fuels, grass, wood, and coal
or from petroleum combustion. Regarding ecological risk
estimation, only station 7 was moderately polluted, the rest
of the stations suffered rare or slight adverse biological
effects with PAH exposure in surface sediment, suggesting
that PAHs are not considered as contaminants of concern in
the West Port.
S. B. Tavakoly Sany (&)  R. Hashim  A. Salleh
Institute of Biological Sciences, University of Malaya,
50603 Kuala Lumpur, Malaysia
e-mail: belintavakoli332@gmail.com
S. B. Tavakoly Sany  M. Rezayi
Food Science and Technology Research Institute,
ACECR Mashhad Branch, Mashhad, Iran
O. Safari
Faculty of Natural Resources and Environment,
Ferdowsi University of Mashhad, Mashhad, Iran
A. Mehdinia
Department of Marine Science, Marine Living Group,
Iranian National Institute for Oceanography,
P. O. Box 14155-4781, Tehran, Iran
Keywords PAHs  Ecological risk  West Port 
Sediment  Malaysia
Introduction
Over recent decades, there have been many chemistry
assessments on environment contamination; however,
petroleum pollution over time is of particular interest to
many research institutions. Petroleum compounds are
classified into three main categories, which include ali-
phatic hydrocarbons, polycyclic aromatic hydrocarbons
(PAHs), and biomarkers (Chuanyuan et al. 2011; Khairy
et al. 2009). Important categories of petroleum pollution
are groups of chemical compounds, which include two or
more fused benzene rings called polycyclic aromatic
hydrocarbons (PAHs; Neff 1979).
Marine and coastal ecosystems are one of the main
sinks for PAHs, which tend to adsorb onto suspended
particulate matter and settle in the sediment (Hong et al.
1995; Khairy et al. 2009; Sánchez-Avila et al. 2010).
Stranded PAHs attached to suspended sediments can
become available to organisms dwelling in sediments
(shellfish and cockles), which are able to bioaccumulate
PAHs actively. Following the consumption of contami-
nated dwelling organisms, these PAHs become concen-
trated in the human body. More importantly, PAHs may
pose major human health concerns because of their
mutagenic and genotoxic potential on the natural ecosys-
tems, which is especially true for many estuary and
coastal areas where high anthropogenic effects and various
pollution sources exist (Dsikowitzky et al. 2011; Kupry-
ianchyk et al. 2012; Saadati et al. 2013).
Petroleum hydrocarbons originate primarily from
anthropogenic activities and from natural sources. PAHs in
123

marine and coastal waters are mostly derived from indus-
trial discharge, atmospheric fallout, oil operations, petro-
leum transport, harbor activities, wastewater discharge,
natural seepage, and biogenic origin.
The West Port is newly constructed, still being devel-
oped, and the busiest port on the west coast of Malaysia.
This port is surrounded by the west coast of Malaysia and
by the Straits of Malacca in Southeast Asia. Nowadays,
ocean-going ships enter this port from the Far East and the
Middle East to upload and download goods (Tavakoly
Sany et al. 2013; Yap 2005). The West Port has also
experienced rapid development of industrialization,
urbanization, and motorization over recent decades (Yap
2005). Thus, this area is exposed to the threat of contam-
inants, mainly derived from anthropogenic activities, and it
is likely that this threat will increase in the future (Alongi
2002).
In 1982, the west coastal area of Malaysia was cate-
gorized as moderately polluted with petroleum hydrocar-
bons, according to the standard classification of the FAO
(the Food and Agriculture Organization), which also
indicated that the petrogenic pollutants in this area orig-
inated from oil spill events and from ship ballasting or
bilge pumping due to tanker and non-tanker operations
(Marchand et al. 1982; Yap 2005). Likewise, it is recor-
ded elsewhere that the concentration of petroleum pro-
ducts (due to the industrial and city sources) on the west
coast of Malaysia is significantly higher than on the east
coast (Pauzi Zakaria et al. 2001; Raza et al. 2013). Thus,
in this research a hypothesis can be defined, based on the
serious threat posed by PAHs contamination of the West
Port.
Risk assessment of petroleum in coastal waters of the
West Port is a difficult task, because this area is greatly
influenced by non-point sources, such as shipping activi-
ties, port development, and land discharges. Another lim-
itation is that the strong marine current, due to the northeast
monsoon, can affect sediment quality.
This paper represents the first extensive study with the
following objectives: to estimate the occurrence and
distribution of PAHs in the sediment of the West Port, to
identify the origin of PAHs in the port, and to conduct
an environmental risk assessment to recognize the pos-
sible adverse ecological effects to the benthic community
due to exposure to PAHs concentrated in the West Port
sediments. With regard to the importance of the West
Port as an international shipping route, an industrial
center, and an ecological habitat, it is necessary to do
chemical research to evaluate environmental properties,
control pollution occurrence, and protect living
organisms.
123
Environ Earth Sci
Materials and methods
Study area and sample collection
The West Port is one of Malaysia’s principal gateways and its
busiest port, with 22 berths. The West Port has been developed
along the Klang Strait and is well sheltered by several man-
grove islands and mudflats, which form a natural enclosure. In
this research, the study area is restricted to a narrow channel
between Klang Island and Che Mat Zin Island on the west of
Indah Island. Ten stations were selected from three transects
parallel to the coastline at three different distances (see Fig. 1;
Table 1), as well as one station, which was selected as a
control point 21 km away from the West Port in a remote area.
The study area lies within a humid tropical area with a rainy
season (North monsoon, November–March) and a dry season
(South monsoon, April–October). In the West Port, the aver-
age salinity is 30.25 % (±1.36), the average temperature is
30.04 8C (±0.62), the average surface dissolved oxygen is
5.38 mg/L (±0.17), and the monthly average surface and
bottom pH values are between 7.85 and 8.25.
Sediment samples were taken with a Peterson grab
sampler (0.07 m2) at two dates per season. The top 1 cm
layers were removed with a stainless steel spoon for sub-
sequent analysis. The samples were transported on ice to
the laboratory. All the samples were packed into aluminum
boxes and immediately stored at -20 °C until required. For
PAHs analysis, three replicates of grab samples were taken
to investigate the spatial and temporal distribution.
Experimental methods
Chemical and reagents
A standard solution the 16 USEPA (United State Environ-
mental Protection Agency) priority PAH and a five-surrogate
standard (acenaphthene-d10, chrysene-d12, perylene-d12,
naphthalene-d8 and phenanthrene-d10) were purchased
from Ultra Scientific Inc. (North Kingstown, RI, USA). A
standard reference material (SRM) was obtained from
National Institute of Standards and Technology (NIST,
Gaithersburg, MD, USA) Neat (99%) hexamethylbenzene
was purchased from Aldrich Chemical Company (Milwau-
kee, WI, USA). All solvents (acetone, dichloromethane,
methanol and hexane) applied to analyses were of analytical
grade and redistilled twice. The alumina (120–200 mesh) and
silica gel (80–100 mesh) were extracted for a period of 72 h
in a Soxhlet apparatus, activated in the oven at 150 and at
180 °C for a period of 12 h, respectively, and then deacti-
vated by using distilled water in a ratio of 3 % (m/m).
Deionized water was obtained from a Milli-Q system.
Environ Earth Sci
Fig. 1 Location of the sampling stations in West Port Malaysia
Extraction and fractionation
Sediment samples were sieved at 125 lm to remove large
particles and debris. Sediment samples were homogenized
and freeze-dried before extracting. For the extraction proce-
dure, about 5 g of dried sediment samples were Soxhlet
extracted by dichloromethane (150 mL) for a period of 72 h.
A mixture of surrogate standard was added to all the samples
as recovery surrogate standards. Elemental sulfur was
removed from the extracts by using activated copper granules.
After extraction, the extract was concentrated with a rotary
vacuum evaporator. The volume of extract was adjusted to
2–3 mL, and solvent exchanged into 10 mL n-hexane, which
was further decreased to approximately 1–2 mL.
123
 Environ Earth Sci

101°190 21.0200 E

101°180 58.3800 E
101°180 48.1400 E
101°180 34.5600 E
101°180 20.9900 E
101°170 18.7600 E

101°160 55.5500 E
101°120 44.7000 E
Clean-up and fraction procedures were performed with a

101°190 9.0600 E

101°170 7.5700 E
Longitude 1:2 alumina/silica gel column. PAHs were obtained by
eluting with 60 mL of hexane/dichloromethane (1:1). The
PAHs fraction was concentrated again using a rotary
evaporator, and the volume was concentrated to 1 mL. The
fraction was further reduced to 0.2 mL under a stream of
filtered purified nitrogen gas. An aliquot of 0.2 mL of each
extract was applied to gas chromatography–mass spec-
2°580 44.0000 N
2°58 54.12 N

2°58 14.90 N
2°58 23.07 N
2°55 34.43 N
2°55 39.38 N
2°550 45.0200 N
3° 6 55.95 N
2°590 3.1200 N
2°580 6.3400 N
00

00

00

00

00
trometry (GC–MS) analysis. Likewise, hexamethylbenzene

00
Latitude

was added as an internal standard prior to GC–MS analysis.

0

0 Instrumental analysis

The PAHs were estimated by a Hewlett-Packard 5890

series gas chromatograph interfaced with a 5972 mass-
TOC (%)

selective detector (MSD) for the selective ion monitoring

7.74

9.14
7.55
10.24

11.98

12.76
10.63
10.15
15.49
10.46

(SIM) mode. A fused silica capillary column (50 m,

0.32 mm, 0.17 lm) coated with HP-5MS (film thickness
0.25 mL) was used for separation with helium as carrier
gas at a flow rate of 2 mL/min with a head pressure of 12.5
psi, and a linear velocity of 39.2 cm/s at 290 °C. The
Fine sediment (%)

temperature was programmed from 80 to 290 °C at 4 °C/

min and held at the final temperature for 30 min. The
injector temperature and transfer line temperature were 250
53.57
45.96
63.42
56.33
41.10
70.81
52.31
50.69
70.36
51.60

and 180 °C, respectively. The mass spectrometer was

operated at electron energy of 70 eV with an ion source
temperature of 250 °C.
The interface temperature and injection were pro-
grammed at 290 °C. The oven temperature was initially
Container berths

isothermal at 80 °C for 5 min, programmed from 80 to

Cement berth

Liquid berth
Description

290 °C at 3 °C/min, and held at the final temperature

Mangrove

Mangrove

Mangrove
Remote

Remote

Remote

Remote

(290 °C) for 30 min. A 1 mL sample was manually

injected in the splitless injector with a 1 min solvent delay.
The mass spectrometer was operated at an electron impact
of 70 eV with an ion source temperature of 250 °C. The
ranges of mass scanning were between 50 and 500 m/z.
3-WC1000

6-WL1000

9-WT1000
1-WC100
2-WC500

4-WL100
5-WL500

7-WT100
8-WT500
Table 1 Physicochemical description of sampling station

Quality assurance
10-CP
Code

For every set of samples, a procedural method of blanks

(solvent), sample duplicates, spiked matrixes (standards
spiked into solvent), and standard reference material
(SRM1941) samples were used to assess quality control
21 km far from Port (control station)

and quality assurance. Individual PAHs were quantified

100 m after liquid berth (outlet)

according to the retention time and m/z ratio of PAHs

1,000 m after container berth
100 m after container berth
500 m after container berth
1,000 m after cement berth

mixed standard (Sigma), and a standard calibration curve

1,000 m after liquid berth
100 m after cement berth
500 m after cement berth

500 m after liquid berth

was used to calibrate the concentrations of each of the

PAHs. None of the target compounds were detected. The
method detection limits (MDLs) for the investigated
organic pollutants were determined according to (USEPA
1984). Percentages of relative standard deviation (RSD) for
Stations

all the investigated PAHs were lower than 20.0 % in the

fortification experiment and in the replicates used to

123
Environ Earth Sci

determine the MDL. The reported results were corrected
with the recoveries of the surrogate standards. The average
recoveries of surrogate standards varied from 63.28 to
96.75. Recoveries of all the PAHs and RSD were in the
range of 78.4–95.2 and 2.6–13.5 %, respectively. The
detection limits ranged from 0.095 and 1.018 ng/g.
Measurement of total organic carbon (TOC) and sediment
grain size
Sediment grain size was determined using a multi-wave-
length particle size analyzer (model LS 13 320), and results
were divided into sand ([64 lm), silt (2 lm \
size \ 64 lm), and clay (\2 lm) (Rauret 1998). Freeze-
dried sediment samples were ground, and the treatment
procedure used 10 % (v/v) HCl to remove carbonate from
the sediment samples. The samples were then dried at
60 °C in an oven (Feng et al. 2004). The TOC was deter-
mined in surface sediments using a carbon analyzer (Hor-
bia Model 8210).
PAHs source identification
Source identification of PAHs
The PAH isomer ratio was used to infer the possible
anthropogenic sources of PAH from the natural source.
These ratios and their classification are defined in Table 2,
based on several studies such as those described in Bud-
zinski et al. (1997), Yunker et al. (2002), Zhang et al.
(2004), Wang et al. (2011) and Khairy et al. (2009).
Ecological risk assessment
The ecological toxicities of the concentrations of individual
PAHs were assessed, based on the sediment quality
guidelines (SQGs). The PEL quotient is a unique factor for
describing the probability toxicity of PAHs according to
the analyses of matching toxicity and chemical data from
1,068 sediment samples from coastal and estuaries water in
the USA (Long et al. 1995). PEL quotients (PELq) have
also been estimated as the average of the ratios between the
PAHs concentration in the sediment sample and the related
PEL (probable effects level) value (Alvarez-Guerra et al.
2007; Fdez-Ortiz de Vallejuelo et al. 2010; Khairy et al.
2009; Leorri et al. 2008).
ERMq factors were divided into four categories, which
can be used to describe the sediment as non-toxic
(PELq \ 0.1), slightly toxic (0.1 \ PELq \ 0.5), moder-
ately toxic (0.5 \ PELq \ 1.5), and highly toxic
(PELq [ 1.5). This factor is practical for comparing with
different historical episodes or other study areas and to
facilitate the decision maker’s work in sediment quality
assessment (McCready et al. 2006).
Statistical analysis
Statistical analyses were performed using Microsoft Excel
and SPSS 17 software (SPSS, Chicago, IL, USA) to sta-
tistically evaluate the data. For the data assessment, sig-
nificant difference from the control was evaluated via a
Kruskal–Wallis one-way nonparametric ANOVA (level of
significance is 0.05). Cluster analysis was used to classify a
set of data into different groups, based on similarity. This
method has been widely applied to environmental assess-
ment to classify the data into temporal and spatial scales
(Kitsiou and Karydis 2011). Geo-statistical analysis was
performed using Surfer 8 software (GPS value of stations),
based on geospatial methods to better understand contam-
inant pathways and to provide a comprehensive contour
map of the spatial distribution of contaminants over a large
area (Cressie 1990; Sparks 2000).
Results and discussion

Table 2 PAH isomer pair ratio measurement

Concentration and spatial distribution of PAHs
PAH isomer Ratio Source in sediments
Anthracene/anthracene \ 0.4 Petroleum
? phenanthrene PAH contamination was calculated for surface sediments
0.4–0.5 Petroleum combustion
all over the port, based on a dry weight and total PAHs
[0.5 Dominance of combustion
of coal means: the sum of 16 USEPA priority PAHs. In the West
Fluoranthene/fluoranthene \0.20 Petroleum Port, the concentration of total PAHs ranged from 100.3 to
? pyrene 0.20–0.35 Petroleum and combustion
3,446.9 lg/kg dw with an average concentration of
[0.35 Combustion
910.3 lg/kg dw (Table 3).
Phenanthrene/anthracene [10 Petrogenic
Significant variations (p \ 0.05, df = 21, sig = 0.12)
were not observed in the concentrations of total PAHs
\10 Pyrolytic
among different sampling times. Probably, seasonal vari-
Fluoranthene/pyrene \1.0 Petrogenic
ations are not effective parameters to control distribution of
[1.0 Pyrolytic
PAHs in the Klang Strait. Hence, this study tries to

123
 Environ Earth Sci

Table 3 Concentration of PAHs (lg/kg dw) in surface sediments of West Port

Station number 1 2 3 4 5 6 7 8 9 10 Mean SD Min Max

Nap 1.26 5.70 1.20 0.80 0.72 2.04 16.10 2.96 2.20 1.78 3.48 4.5 \MDL 110
Acy ND ND ND ND ND ND 645.28 ND ND ND 64.53 198.6 \MDL 650.4
Ace ND 1.04 ND ND 0.66 0.98 14.84 0.49 ND ND 1.80 4.4 \MDL 15
Flr 27.6 39.0 7.68 23.6 48.76 39.7 620.80 33.78 8.72 12.4 86.23 183.3 1.04 621.6
Phn 127 6.78 5.12 5.04 15.60 24.8 225.00 75.78 9.60 1.70 49.70 71.8 \MDL 225.6
Ant 267 71.4 8.16 10.1 37.80 233.01 308.00 181.30 3.78 4.10 112.6 118.83 \MDL 601.2
Fla 10.3 13.5 ND ND 17.65 21.5 166.50 15.80 0.00 0.00 24.53 49.23 \MDL 169
Pyr 12.7 15.7 28.1 236.5 25.10 341.02 243.75 14.03 0.00 0.00 91.75 125.6 \MDL 599
BaA 204 50.5 191 278.8 29.50 774.4 390.90 146.30 78.3 56.8 220.1 219.7 \MDL 1516.5
Chy ND ND 198. ND ND ND ND ND ND ND 19.80 60.94 \MDL 549.2
BbF ND ND ND ND ND ND 11.60 11.32 12.8 23.4 5.91 8.91 \MDL 889.6
BkF 47.6 ND ND ND 367.56 1.34 28.56 ND ND ND 44.51 111.6 \MDL 367.56
BaP ND 122 ND ND ND 0.96 825.20 59.90 ND ND 100.8 252.18 \MDL 1524
DibA ND ND 67.8 ND ND 7.26 ND ND 130.03 ND 20.53 42.7 \MDL 199.2
Bghip ND 64.2 ND ND ND ND 49.40 ND ND ND 11.36 23.6 \MDL 72
Inp ND 77.4 ND 68.74 ND ND ND 31.80 348.04 ND 52.63 105.9 \MDL 360.8
P
PAHs 698 467 507 623.7 543.35 1448.43 3545.9 573.46 594.07 13.13 910.3 958.8 100.3 3446.9
ND below the method detection limit, Nap naphthalene, Acy acenaphthylene, Ace acenaphthene, Flr fluorene, Phn phenanthrene, Ant anthracene,
Fla fluoranthene, Pyr pyrene, BaA benzo(a)anthracene, Chy chrysene, BbF benzo(b)fluoranthene, BkF benzo(k)fluoranthene, BaP benzo(a)-
pyrene, InP indeno[1,2,3,(c,d)]pyrene, DibA dibenzo(a,h)anthracene, BghiP benzo(g,h,i)perylene

estimate the concentration and distribution of PAHs in
spatial scales.
The result shows a significant variation (p \ 0.05,
df = 21, sig = 0.003) in the concentrations of total PAHs
among different stations, which were evidenced by a
nonparametric Kruskal–Wallis test. This test showed that
the PAH concentrations at stations 10, 6, and 7 were not
homogeneous with the other stations.The highest concen-
tration of total PAHs was recorded in station 7
(3,545.9 lg/kg dw), which is located near the container
terminal. The surrounding areas of station 7 are strongly
influenced by port activities, and land-based runoff releases
organic compounds directly in the vicinity of these stations.
The second highest concentration of total PAHs was
recorded in station 6, which is located near the mangrove
forest with a high abundance of Rhizophora and Sonneratia
roots, which are likely to decrease water flow and increase
sediment settling (Raza et al. 2013). Also, station 6 is well
protected from sea waves. This would enhance deposition
of the PAHs in the suspended particles that are transported
through the area upstream of the West Port. The lowest
total PAHs concentration was found in station 10, which is
located 21 km away from the West Port in a remote area.
Apart from station 4, the spatial distribution of total
PAHs showed that the PAH concentrations in sediment
samples collected from near-shore areas (stations 1 and 7)
of West Port are greater than the PAH concentrations in
offshore areas (stations 3 and 9; Fig. 2; Table 3).
This finding suggests that PAHs accumulated in near-
shore areas may come from different sources. These
sources include the large-scale inflow from industries such
as the palm oil, cement and food manufacturers that are
located along the near-shore of West Port, vessel-based
discharges, and land-based runoff. More research revealed
significant differences in the sources and concentration of
PAHs in sediment samples of near-shore and offshore
areas. These imply that PAH concentrations in near-shore
areas are influenced by lateral transport such as runoff, the
transportation of water due to daily rainfall, and industrial
waste. (Boonyatumanond et al. 2006; Farrington et al.
1983; Ikenaka et al. 2005; Kumar et al. 2012; Safari et al.
2010).
The concentration composition of PAHCombust and
PAHstoxic in ten sampling stations is shown in Table 4.
High-molecular-weight (HMW) PAHs, specifically with
four or more rings (Fla, Pyr, BaA, Chy, BbF, BkF, BaP,
InP, DibA, BghiP) are typically used to assess the com-
bustion value. Concentrations of some high-molecular-
weight PAHs such as BaA, Chy, BbF, BkF, BaP, InP, and
DibA are known as toxic PAHs because of their mutagenic
and carcinogenic effect on human health and on biological
communities (Khairy et al. 2009; Mirsadeghi et al. 2011).
In this study, PAHCombust values ranged from 80 to
1,715.90 lg/kg dw with an average concentration of
637.64 lg/kg dw (Table 4). High-molecular-weight PAHs
represented between 39.34 and 95.8 % of the total

123
Environ Earth Sci
Fig. 2 Spatial variation of
PAHs compounds in surface
sediment of the West Port
concentration of PAHs, with a mean value of 74.02 %.
Moreover, the combustible PAHs constituted a significant
portion of the total PAHs at stations 7 and 6 in the West
Port (Fig. 2), which reflects a recent input of PAHs at these
stations or can be due to their low microbial degradation
rates and high particle affinities, which lead to their
accumulation in sediments. These results are the same as
those of some other researches (e.g., Al-Saad and Al-Timari
1989; Bakhtiari et al. 2011) where sedimentary PAHs showed
an abundance of high molecular weight of PAHs.
PAHstoxic values ranged from 80.30 to 1,256.3 lg/kg
dw, with a mean concentration of 507.15 lg/kg dw
123
 Environ Earth Sci

Table 4 Molecular indices of PAHs, content in surface sediments of Klang Strait

P P
Station PAHCombust PAHstoxic Phn/Ant Fla/Pyr Ant/Ant ? Phn Fla/Fla ? Pyr L/H-PAH

1 274.6 251.6 0.48 0.81 0.68 0.45 1.55

2 343.5 250.0 0.09 0.86 0.91 0.46 0.36
3 485.2 457.1 0.63 0.00 0.61 0.00 0.05
4 584.1 347.6 0.50 0.00 0.67 0.00 0.07
5 439.8 397.1 0.41 0.70 0.71 0.41 0.24
6 1,046.8 784.3 0.11 0.09 0.90 0.08 0.29
7 1,715.9 1,256.3 0.73 0.68 0.58 0.41 1.07
8 279.2 249.3 0.42 1.13 0.71 0.53 1.05
9 569.7 569.7 2.54 0.00 0.28 0.00 0.04
10 80.3 80.3 0.41 0.00 0.71 0.00 0.25
Mean 637.64 507.00 0.66 0.47 0.67 0.26 0.52
SD 467.27 331.65 0.74 0.45 0.19 0.23 0.55
Min 80.30 80.30 0.09 0.00 0.28 0.00 0.04
Max 1,715.90 1,256.30 2.54 1.13 0.91 0.53 1.55

(Table 4). Their concentrations made up an average of Table 5 Toxicity guidelines of PAH compounds for sediment
56.67 % of the total concentration of PAHs, ranging from matrices (ng/g dry weight%) and average concentrations in the sur-
35.42 to 95.83 %. These concentrations were highest in face sediments of West Port (Long et al. 1995, 2006)
stations 6 and 7, whereas at other stations toxic PAH PAHs ER-L ER-M TEL PEL
concentrations were significantly lower (Fig. 2).
Nap 160 2,100 34.6 391
Ace 44 640 5.87 128
Sediment characteristics
Acy 16 500 6.71 88.9
Flu 19 540 21.2 144
Several previous studies have recorded a significant posi-
Phe 240 1,500 86.7 544
tive correlation between PAHs and organic carbon in
Ant 853 1,100 46.9 245
sediments. In this study, the total organic carbon content of
Fla 600 5,100 113 1,494
the sediment varied from 7.55 to 15.45 lg/g and the cor-
Pyr 665 26,000 153 1,398
relation coefficient between the PAHs concentration and
BaA 261 16,000 74.8 693
total organic carbon content was 0.15, suggesting that the
Chr 384 2,800 108 846
content of total organic carbon in the sediment does not
BbF 320 1,880
appear to correlate with the PAHs concentrations. This is in
BkF 280 1,620
agreement with several previous studies (Farias et al. 2008;
BaP 430 1,600 88.8 763
Raza et al. 2013; Tam et al. 2001)where the TOC content
did not correlate with the PAH concentrations in coastal InP
sediments. Simpson et al. (1996) concluded that the cor- DibA 63.4 260 6.22 135
relation of PAHs in the sediments with TOC is only sig- BghiP 430 1,600
nificant for highly contaminated stations where the total Total PAHs 4,022 44,792 1,684 16,770
PAH concentrations were [2,000 ng/g. In this study the ERL effects range-low, ERM effects range-median, TELs threshold
sediment in all stations (except of stations 7) had total PAH effects level, PELs probable effects level
concentrations less than this value (Table 3).
Therefore, it is concluded that the concentration and
distributions of PAHs in sediments of this port are not Origin of PAHs in sediment
controlled by the TOC content.
The correlation coefficient between the PAHs concen- Anthropogenic sources of PAHs are pyrogenic and petro-
trations and fine-grained sediment content was 0.11; no genic sources. Pyrogenic PAHs mainly include high con-
correlation was observed between the PAHs concentrations centrations of HMW PAHs (Fla, Pyr, BaA, Chy, BaP, BkF,
and particle size in sediments (Table 5). InP, Bghip, and DibA) and low concentrations of alkylated

123
Environ Earth Sci
PAHs. Pyrogenic sources are from the incomplete com-
bustion of organic compounds such as fossil fuels (heating
oil, cooking, coal burning, vehicle emissions) and biomass
burning (fireplace, controlled burning; Khairy et al. 2009).
Petrogenic PAHs are abundant in low-molecular-weight
PAHs (Naf, Acy, Ace, Flr, Phn, and Ant) and alkylated
PAHs. Petrogenic PAHs involve unburned fossil fuels,
which include oil spills, and incineration of petroleum
products that have originated from coal and crude oil
sources (Beyer et al. 2010; Khairy et al. 2009; Rezayi et al.
2011).
Pyrogenic and petrogenic sources are typically distin-
guished, based on the ratios of individual PAHs, which are
identified based on molecular mass, such as Phn/Ant
(m = 178) and Fla/Pyr (m = 202). The results related to
the source identification of PAHs are summarized in
Table 4.
According to the ratio of Phn/Ant, all of the stations are
most exposed to pyrogenic sources of contamination
because the Phn/Ant ratio was below 10 at all stations,
whereas the ratio of Fla/Pyr revealed only station 8 to be
most exposed to pyrogenic sources (Fla/Pyr [ 1) and other
stations with ratios below 1.
Figure 3 reveals a clear pattern in the sources of PAHs.
Most of the investigated sediment samples presented a
mixed pattern of contamination from pyrogenic and
petrogenic origins. At the same time, just one sediment
samples (Station 8) had pyrogenic-origin PAHs. Moreover,
ratios of PAHs such as Ant/Ant ? Phn and Fla/(Fla ? Pyr)
had been applied to provide an accurate estimation of PAH
sources. The ratio of Ant/Ant ? Phn was greater than 0.1
for all stations, implying that the origin of the PAHs in the
sediments of the West Port is primarily combustion—either
wood, coal or grass combustion, or petroleum combustion.
The PAH ratio Ant/ (Ant ? Phn) was plotted against Fla/
(Fla ? Pyr) to distinguish the possible source of PAHs.
Figure 4 shows that PAHs in stations 1, 2, 5, and 7 that
originated from petroleum combustion (vehicle and crude
oil), whereas the PAHs in station 8 originated from
Fig. 3 Plots of PAH isomer pair ratios for source identification Phn/
Ant versus Fla/Pyr
Fig. 4 Plots of PAH isomer pair ratios for source identification
Ant/(Ant ? Phy) versus Flu/(Flu ? Pyr)
combustion of charcoal, coal, grass, and wood. Sedimen-
tary PAHs in stations 3, 4, 6, and 9 have primarily derived
from combustion, although petroleum-derived contamina-
tion cannot be ignored. This result implied that petrogenic
input had some contribution to the contamination of PAHs;
however, it was not a major controlling factor in distribu-
tion of PAHs within these stations.
The findings of this study demonstrate that all stations
(except station 8) were exposed to PAH contamination
from both petrogenic and pyrogenic sources. Based on this
finding, sedimentary PAHs mainly originated from com-
bustion processes and resulted from long-range atmo-
spheric transport and industry discharges, such as effluent
from cement, food, and oil factories.Moreover, the location
of West Port, which faces the Malacca Strait and Sumatra
Island, received biomass burning originating from southern
Sumatra (Raza et al. 2013). Malacca Strait is a narrow
channel of marine water located between Sumatra Island
(Indonesia) and peninsular Malaysia. This strait is vulner-
able to contamination caused by tanker operation, oil spills,
and biomass burning (Mirsadeghi et al. 2011; Pauzi
Zakaria et al. 2001). Okuda et al. (2002) indicated that the
aerosols in Peninsular Malaysia have been contaminated by
pyrogenic PAHs originating from automotive exhaust
emissions. Thus, it is expected that these atmospheric
particles, derived from pyrogenic PAHs, were transported
by air masses during the monsoon season (He et al. 2010).
More researchers have recorded that, in Peninsular
Malaysia, high levels of PAHs are derived from pyrogenic
sources and that they have originated from products of
combusted petroleum from industries and automobiles
(Krauss et al. 2005; Raza et al. 2013; Safari et al. 2010).
The results also implied that petrogenic input had a
contribution to the sedimentary PAHs in the West Port.
This study suggests that petrogenic sources of PAHs in the
West Port originate from ship and fishery boat activities as
well as from used oil spill brought to the West Port by land-
based runoff from Malacca Strait, Sumatra Island, and
residential areas near the coastline.
123

In addition, other studies have reported that various sea-
and land-based sources of contamination contribute to
increasing petrogenic pollution in the coastal waters of
western Malaysia. For example, land-based runoff and
contamination from an oil field near Sumatra Island con-
tribute to petroleum contamination in the Malacca Strait
(Mirsadeghi et al. 2011; Pauzi Zakaria et al. 2001). Pauzi
Zakaria et al. (2001) used a biomarker compound to
identify the source of tar balls off the coast of Malaysia.
They identified several petrogenic sources of contami-
nation in the western coastal waters of Malaysia, such as
accidental oil spills and tanker-derived sources in the Strait
of Malacca and crude oils originating from land-based
runoff from human activities. Additionally, they clearly
showed that the western coastal waters of Malaysia have
received approximately 30 % of their petroleum pollution
from Middle East crude oil (MECO) and South-East Asian
crude oil (SEACO), which was probably transported to
Malaysia via marine currents, tankers, and shipping dis-
charges, including ballast water and tank-washing water
(Pauzi Zakaria et al. 2001).
Ecological risk assessment
Two sets of sediment quality guidelines, including
(a) ERL/ERM and (b) the TEL/PEL (Long et al. 1995;
Macdonald et al. 1996), were applied in this study to
evaluate toxicity potential of PAHs on aquatic organisms in
surface sediments of the West Port.
Concentrations below the ERL/TEL value indicate that
adverse biological effects rarely occur and so the ERL/TEL
are considered to provide a high level of protection for
aquatic organisms. Concentrations equal to, or above, the
ERL/TEL, but below the ERM/PEL, represent a possible
adverse effects range. Lastly, concentrations equivalent to,
or above, the ERM/PEL represent adverse biological
effects frequently occur, and thus the PEL are considered
to provide a lower level of protection for aquatic organism
(Long et al. 1995).
A comparison of contamination levels with sediment
quality guidelines revealed that the concentrations of
naphthalene, acenaphthene, and benzo(g,h,i)perylene were
below their respective values (ERL/TEL) of SQGs at all of
the stations, indicating that adverse biological effects are
likely to occur only rarely due to these compounds at all of
the stations. Additionally, acenaphthylene and fluoranthene
concentrations were below the ERL/TEL values at all of
the stations except station 7.
The fluorene concentration at most of the stations
(except stations 3 and 9) suggested occasional adverse
biological effects (CERL/TEL and \ERM/PEL). The flu-
orene concentration was above the ERM/PEL level only at
station 7, indicating that adverse biological effects will
123
Environ Earth Sci
frequently occur due to fluorene at these stations. The
fluorene concentrations were below the ERL/TEL levels at
the other stations.
For phenanthrene, the levels at stations 1 and 7 were
higher than the TEL value, while at the other stations, the
levels were below the ERL/TEL levels. These results
suggest that adverse biological effects might occasionally
occur at these stations.
For anthracene, the concentrations at some of the sta-
tions (1, 2, 7, and 9) were lower than the PEL and ERM
values, while the levels at the other stations (3, 4, 5, 6, and
8) exceeded the TEL value, implying that these stations
most likely have an intermediate level of contamination.
Moreover, the PEL level was exceeded at stations 1 and 7,
indicating that adverse biological effects may occur fre-
quently at these stations. For pyrene, the levels at most of
the stations were lower than the ERL/TEL values, while
intermediate levels (CTEL) were found at the remaining
stations (4, 6, and 7).
Benzo(a)anthracene concentrations exceeded the ERM
and PEL values only at station 6, whereas the
benzo(a)anthracene levels at other stations were in the
intermediate level (CTEL or CERM), suggesting that these
stations were occasionally associated with adverse bio-
logical effects in the West Port. The chrysene concentra-
tion was below the ERL/TEL values at all of the stations
except for station 1, which contained levels higher than the
TEL values. The concentrations of benzo(b)fluoranthene
and benzo(k)fluoranthene at all of the stations were below
the ERL values, except for one station with levels greater
than the ERL values [station 8 for benzo(k)fluoranthene].
The concentration of benzo(a)pyrene at all the stations was
lower than the ERL/TEL levels; however, its concentration
at station 1 exceeded the TEL values, with occasional
adverse biological effects. Additionally, the Bap level at
stations 7 and 1 exceeded the PEL value, implying that Bap
was likely to cause frequent adverse biological effects at
these stations.
The dibenzo(a,h)anthracene concentration at all of the
stations was below the ERL and TEL levels, except at
stations 3, 6, and 9 where levels exceeded the ERL or
TEL values. Therefore, most of the individual PAHs were
likely to cause occasional or frequent adverse biological
effects in the surface sediment of some of the stations,
especially at stations 2, 6, and 7. The benzo[g,h,i]perylene
and benzo[b]fluoranthene levels were below ERL and
ERM in all stations; these individual PAHs were probably
likely to cause rare adverse effects in the surface
sediment.
Apart from these compounds, the lowest safe values
were not defined for indeno[1,2,3-c,d]pyrene. In the West
Port, indeno[1,2,3-c,d]pyrene concentrations were esti-
mated at some stations at levels that can cause mild toxic
Environ Earth Sci

Table 6 Ecological risk calculated for individual PAHs surface sediment of different station
Stations Nap Acy Ace Flr Phn Ant Fla Pyr BeA Chy BbF BkF BaP DibA BghiP PELq

1 0.00 0.00 0.00 0.19 0.23 1.09 0.01 0.01 0.29 0.00 0.00 0.03 0.00 0.00 0.00 0.12
2 0.01 0.00 0.01 0.27 0.01 0.29 0.01 0.01 0.07 0.00 0.00 0.00 0.16 0.00 0.04 0.06
3 0.00 0.00 0.00 0.05 0.01 0.03 0.00 0.02 0.28 0.23 0.00 0.00 0.00 0.50 0.00 0.08
4 0.00 0.00 0.00 0.16 0.01 0.04 0.00 0.17 0.40 0.00 0.00 0.00 0.00 0.00 0.00 0.05
5 0.00 0.00 0.01 0.34 0.03 0.15 0.01 0.02 0.04 0.00 0.00 0.23 0.00 0.00 0.00 0.06
6 0.01 0.00 0.01 0.28 0.05 0.95 0.01 0.24 1.12 0.00 0.00 0.00 0.00 0.05 0.00 0.18
7 0.04 7.26 0.12 4.31 0.41 1.26 0.11 0.17 0.56 0.00 0.01 0.02 1.08 0.00 0.03 1.03
8 0.01 0.00 0.00 0.23 0.14 0.74 0.01 0.01 0.21 0.00 0.01 0.00 0.08 0.00 0.00 0.10
9 0.01 0.00 0.00 0.06 0.02 0.02 0.00 0.00 0.11 0.00 0.01 0.00 0.00 0.96 0.00 0.08
10 0.00 0.00 0.00 0.09 0.00 0.02 0.00 0.00 0.08 0.00 0.01 0.00 0.00 0.00 0.00 0.01
Mean 0.02 0.33 0.01 0.50 0.08 0.41 0.01 0.08 0.42 0.05 0.03 0.01 0.21 0.18 0.00 0.16

effects, but will not cause serious biological effects in the

sedimentary environment in the West Port.
Referring to Table 3, the mean total PAHs concentration
in the West Port sediments at the nine sampling stations is
910 ng/g, which is lower than the ERL and TEL values,
which correspond to 4,022 and 1,684 ng/g, respectively.
Likewise, concentrations of total PAHs at station 7 were
higher than the TEL value, while at the other stations, the
concentrations were below the ERL/TEL levels. These
results suggest that adverse biological effects might occa-
sionally occur at station 7.
The results obtained from the ecological risk assessment
of PAHs in the surface sediments of West Port are sum-
marized in Table 6. These results were arranged, based on
the concentration of PAHs measured at ten stations.
Fig. 5 Cluster analysis to classify stations based on adverse biolog-
In general, the risk assessment revealed that total PAHs
ical effect of PAHs in surface sediment
are likely to cause slight toxic effects on the biological
communities at stations 1 and 6 because these stations
showed 0.1 \ PELq \ 0.5. Additionally, moderately toxic The present study shows that the sediment is slightly
effects were shown for station 7 (0.5 \ PELq \ 1.5); polluted with PAHs (PELq = 0.16). According to the
however, the rest of the stations rarely showed toxic effects above discussion, it may be concluded that PAHs are not a
due to PAH exposure in surface sediments. Cluster analysis primary pollution concern in the Klang Strait, and that only
showed a better view of PAH contaminations and classified station 7 can be considered as vulnerable in the West Port.
the stations into three groups, with station 13 completely In this research, our hypothesis was defined, based on
separate from the other stations and stations 1 and 6 the serious threat posed by petroleum contamination to the
arranged in the same group (cluster B) with the same range West Port because of rapid development related to marine
of toxic effects (0.1 \ PELq \ 0.5). The other stations are transportation, urbanization, industrialization, and motor-
arranged in cluster A (Fig. 5). Based on a comparison with izations along the shore. Moreover, in 1997, a collision
the sediment quality guidelines, contamination factors for between two tankers in the straits of Singapore caused
individual PAHs such as Nap, Ace, Phn, Fla, Pyr, Chy, 25,000 tons of heavy fuels oil to be released into the marine
BbF, BkF, and BghiP were lower than 1 at all stations. This environment, of which 700 tons of oil were released into
implies that these PAHs rarely have adverse effects on the the Malacca Strait, negatively affecting the coastal area of
biological community; only Acy, Flr, Ant, BaA, BaP, and the Klang Strait (Krauss et al. 2005; Raza et al. 2013;
DibA were associated with adverse biological effects at Safari et al. 2010).
stations 1 (cement outlet), 7(container terminal in the West According to the present study, this hypothesis was
Port), and 6 (around the mangrove forest in the West Port). rejected because, at most of the stations, the average PAH

123

concentration was significantly lower than the guideline-
specific values and rarely reached a level likely to cause
adverse biological effects. More studies have recorded a
significant decline in PAH discharges around the near-
shore zone of the west coastal area of Malaysia between
2000 and 2007. Several reasons have been described for the
subsequent decline of the concentrations of petroleum
hydrocarbons from 2000–2007, including the establishment
of an integrated management program, meteorological
conditions, and weathering (Krauss et al. 2005; Raza et al.
2013; Safari et al. 2010).
In 1996, several integrated management programs such
as MARPOL 1997, CLC convention, UNCLOS IN 1996,
and OPRC 1990 were established, and responsible orga-
nizations (the weather forecast department, maritime
department, DOE, Navy, Coastal Guards, emergency
response, and NGOs) contributed to solve the environ-
mental problems in Malaysia’s marine environments (Yap
2005). For example, urban management defined an inte-
grated approach to prevent oil derivatives from entering
marine and coastal waters. Similarly, the DOE and other
organizations needed to take part in wastewater treatment
and runoff control. These regulations focused on strategies
that were based on international agreements to prevent and
control petroleum and chemical contaminants from ships,
platform draining, and industrial inputs (Pauzi Zakaria
et al. 2001).
The weathering process can greatly deplete PAH con-
centrations in a marine environment. In the list of com-
positional indices of PAHs, presented in Table 4, the
L/H–PAH ratio is accepted as a practical method for
assessing weathering, based on the differences between
the low molecular weight and high molecular weight of
PAH compounds. These results show that the concentra-
tion of high-molecular-weight PAHs is significantly
greater than that of low-molecular-weight PAHs in most
stations, and the L/H-PAH ratio was below 1 at most of
the stations and above 1 only at stations 1, 7, and 8. In
general, a low ratio of L/H–PAHs is probably due to the
high resistance of the high-molecular-weight PAHs to
microbial degradation, which is consistent with other
studies. Such a low ratio could also be due to the high
solubility and volatility of the low-molecular-weight
PAHs, which would lead to their depletion (Chandru et al.
2008; Pauzi Zakaria et al. 2001; Rocher et al. 2004).
Likewise, there is also evidence of a greater depletion of
low-molecular-weight PAHs by the weathering process,
which was clearly indicated by Pauzi Zakaria et al.
(2001). His results revealed that the tar-ball samples from
western Malaysia coastal waters had undergone significant
weathering because their L/H-PAH ratios were much
lower (0.23–1.48) than the ratios of crude oil samples
(8–44 for SEACO and 12.13–20.3 for MECO) (Pauzi
123
Environ Earth Sci
Zakaria et al. 2001). In the present study, this ratio ranged
from 0.02 to 2.61, which was significantly lower than that
of the crude oil in this region. Thus, this result revealed
that the PAHs compounds from Klang Strait coastal
waters have undergone weathering, which is the cause of
decline in PAHs concentration.
Additional research has indicated that meteorological
conditions play a major role in controlling PAH concen-
trations over spatial and temporal scales, and a significant
negative linear relationships were found between wind
speed, temperature, and PAH concentration because
atmospheric turbulence causes a dilution of contaminant
concentrations and speeds the weathering process, espe-
cially if the wind speed is greater than 5.8 km/h and the
temperature is greater than 20 °C (Guitart et al. 2010;
Montuori and Triassi 2012; Rocher et al. 2004; Tan et al.
2006). Thus, the higher temperature (approximately 30 °C)
in the West Port (as a tropical area) may increase the
depletion of PAHs.
Conclusion
Ecological assessment of PAHs compounds in this study
was highlighted via two main problems: the first problem
was related to the scarcity of information on the PAHs
concentrations in sediments of the West Port, and there-
fore no background or updated databases were available.
The second problem was related to the biological effects
and guidelines, as no SQGs were available for the coastal
waters of Malaysia. In spite of these limitations, the
adopted approach in the present study highlighted that no
toxic biological effects were associated with the exposure
to PAHs levels in the West Port, and only areas around
the terminal container (station 7) are moderately polluted.
Source analysis showed that the PAHs in the West Port
sediments are dominated by HMW PAHs as well as being
influenced both by pyrogenic and petrogenic sources.
Pyrogenic input appears to be a main source of PAHs in
the West Port. The pyrogenic sources of PAHs include
particulate PAHs resulting from combustion activities,
which are brought by long-range atmospheric transports
and industry discharges, such as effluents from cement,
food, and oil factories.This study also revealed that pe-
trogenic sources had some contribution to the sedimentary
PAHs; however, it was not a major controlling factor in
distribution of PAHs within the West Port. Petrogenic
sources originate from shipping activities, tanker opera-
tion, and urban runoff. This paper represents a baseline
study for future studies, which may include the whole of
Malaysia estuary and coastal water to promote knowledge
of the distribution of PAHs in coastal and estuary
ecosystem.
Environ Earth Sci
Acknowledgments The authors’ gratitude goes to the support of the
University Malaya Research Grant (UMRG) with Project Number
RG174/12SUS and University Malaya Postgraduate Research Grant
(PPP).
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