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Procedia Environmental Sciences 30 (2015) 162 167

International Conference on Environmental Forensics 2015 (iENFORCE2015)

Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in

surface sediments of Kapas Island, Terengganu, Malaysia
Terence Ricky Chiua, Nurul Fathihah Mt Nanyana, Masni Mohd Alia,b*
a

School of Environmental and Natural Resource Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM
Bangi, Malaysia
b
Institute of Oceanography and Environment, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Malaysia

Abstract
Twelve surface sediment samples were taken from selected sampling points in Kapas Island, Terengganu. Soxhlet extraction with
two steps chromatography was applied to extract the PAH compounds. Collection of PAH fraction was carried out and taken for
Gas Chromatography-Mass Spectrometry (GC-MS) analysis. The concentration of individual compound ranged from 0.002 to
0.076 g/g dry weight. The highest total PAH concentration was found in S10 with 0.336 g/g dry weight while the lowest was
detected in S6 with 0.043 g/g dry weight. Molecular index using selected compound shows that Kapas Island is dominated by
pyrolytic sources. Further analysis by principle component analysis (PCA) shown that stations were divided into two distinct
groups based on their location. The total PAHs of surface sediments in Kapas Island classified as being low to moderate pollution
range.

Published
by Elsevier
B.V This
2015
2015The
TheAuthors.
Authors.
Published
by Elsevier
B.V.is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of organizing committee of Environmental Forensics Research Centre, Faculty of
Peer-review under responsibility of organizing committee of Environmental Forensics Research Centre, Faculty of Environmental Studies,
Environmental Studies, Universiti Putra Malaysia.
Universiti Putra Malaysia.
Keywords: PAHs; surface sediments; GC-MS; molecular index; Kapas Island

1.
Introduction
Massive developments in the industrial sector largely contribute to a nations economic development. Many
studies has been conducted by researchers around the world in identifying Polycyclic Aromatic Hydrocarbons
(PAHs) and Malaysia is not an exception as previous studies have been carried out to evaluate the latest status of
*Corresponding author. Tel.:+0-012-649-3598; fax:+0-03-8925-3357
Email address: [email protected]

1878-0296 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of organizing committee of Environmental Forensics Research Centre, Faculty of Environmental Studies,
Universiti Putra Malaysia.
doi:10.1016/j.proenv.2015.10.029

Terence Ricky Chiu et al. / Procedia Environmental Sciences 30 (2015) 162 167

163

PAHs in environment [1,2,3,4,5,6]. Generally, PAHs are defined as compounds consisting of two or more fused
aromatic benzene rings and is one of the most crucial types of environmental pollutants [7,8]. There are two types of
anthropogenic sources of PAHs which are pyrogenic source that originated from combustion of fossil fuel and
biomass which are expelled into the surroundings as exhaust and solid residue [9] and petrogenic source which
originated from crude and refined petroleum that are expelled to the surroundings through oil spills, off shore
exploration and natural oil seeps in open sea [10]. Pyrogenic PAHs consist of high molecular weight (HMW)
molecules with 4 to 7 fused aromatic benzene rings while petrogenic PAHs are abundant with low molecular weight
(LMW) molecules containing 2 to 3 fused aromatic benzene rings [10]. However, they give a negative impact on the
environment, particularly the marine environment. Based on findings from previous studies, the concentrations of
PAHs in sediments around Malaysia ranged from the lowest value of 0.002 g/g to the highest value of 1.689 g/g
[1,2,3,4,5,6]. Therefore, the aim of this study was to determine the distribution of PAH compounds in Kapas Island,
Malaysia by means of Gas Chromatography-Mass Spectrometry.

2.
Materials and methods

Kapas Island is an island located in the east coast of Peninsular Malaysia in the state of Terengganu (Fig. 1). In
order to collect sediment samples from the 12 sampling points (Fig.1 and Table 1) in the area surrounding the island,
a sediment grab was used and the samples were then preserved in pre-cleaned glass jar. The samples were taken
around the island based on its proximity to the jetty, resort and open sea area. All samples were frozen at 4C prior
to analysis.

Fig.1. Sampling locations around Kapas Island

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Terence Ricky Chiu et al. / Procedia Environmental Sciences 30 (2015) 162 167
Table 1

Station
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12

Latitude (N)
05 14.162
05 13.816
05 13.356
05 12.866
05 12.356
05 12.491
05 12.710
05 13.195
05 13.409
05 13.648
05 13.790
05 13.840

Description of sampling stations around Kapas Island

Longitude (E)
103 15.679
103 16.435
103 16.547
103 16.642
103 16.470
103 15.902
103 15.681
103 15.519
103 15.564
103 15.715
103 15.861
103 15.543

Water Depth (m)

17.0
24.7
23.4
22.8
20.2
11.0
9.5
10.5
10.8
5.9
3.5
11.5

Description
Resort area
Rocky Beach with terrestrial trees
Rocky Beach with terrestrial trees
Rocky Beach with terrestrial trees
Rocky Beach with terrestrial trees
Resort area with terrestrial trees
Resort area
Jetty and resort area
Resort area
Sandy bay
Sandy bay
Sandy near resort area

Besides, PCA also has been applied in this study. Briefly, PCA is a statistical approach, which is often used to
shrink a huge dataset to produce a small set of uncorrelated factors, which can describe the most of the variance.
Mathematically, PCA can be defined with the following equation (Eq. 1) proposed by Hopke [11]:

 



 


where Xik is the ith species concentration of the kth sample; gip is the ith species concentration from the pth source; fpk
is the pth source contribution to the kth sample and eik is the error involved the analysis.
3.
PAH extraction
A total of 20 g of sediment sample from each station was taken and mixed with sodium anhydrous to eliminate
water content. The dried sample was put into a thimble extractor (30 mm x 150 mm) and extracted with
dichloromethane for about 10 h. About 250 mL of dichloromethane was put into a round bottom flask and was
heated to 60oC on a heater. After 10 hours, the extract was evaporated to near dryness by using a rotary evaporator.
The residue was later diluted with dichloromethane and was transferred into a 5 mL vial. The residue is called total
extractable lipid (TEL). The TEL extracts were divided through two stages of silica gel column chromatography.
Concentrated sample was then transferred into the silica gel column and washed with 2 mL (0.4 mL, 0.3 mL, 0.3
mL, 0.5 mL and 0.5 mL) hexane/dichloromethane (3:1) and subsequently followed by 18 mL
hexane/dichloromethane (3:1). Hydrocarbons that ranged from n-alkanes to PAHs were then collected into a conical
flask. Eluent from the first step chromatography was concentrated by the rotary evaporator and PAH fraction was
collected with 14 mL mixture of hexane/dichloromethane (3:1). The PAH fraction was labeled and stored in the
freezer until further analysis. The PAH sample was then transferred to a 1 mL vial and injected to determine the
concentration of PAH compounds.
4.
Results and discussion
4.1 Composition of PAHs
The compounds measured were benzo(ghi)perylene, phenanthrene, anthracene, naphthalene,
benzo[k]fluoranthene, chrysene and benzo[e]pyrene (Table 1). The concentration of individual compound ranged
from 0.002 to 0.076 g/g dry weight. The highest total PAH concentration was found in S10 with 0.336 g/g dry
weight while the lowest was detected in S6 with 0.043 g/g dry weight (Fig. 2). According to Malaysian
Meteorological Agency, the sampling occurs in July during which the Southwest monsoon brings wind from the
peninsular Malaysia towards South China Sea thus bringing along terrestrial particle to settle. The low concentration

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Terence Ricky Chiu et al. / Procedia Environmental Sciences 30 (2015) 162 167

of PAHs found in S8 was due the location which is slightly far from the influence of human activities. This has been
supported by Bakhtiari et al.[4] which states that low human activities contributes to low concentration of PAHs.

Fig.2. Total concentration of PAHs by stations around Kapas Island

Based on Table 2, the compound with the highest percentage was anthracene comprising 26% of all other
compounds combined, with a total concentration of 0.260 g/g dry weight. Meanwhile, the compound with the
lowest percentage was benzo(g,h,i)pyrene (8.8%), with a total concentration of 0.088 g/g dry weight. In order to
assess the current status of PAH pollution in Kapas Island, concentration of PAHs in Kapas Island were compared
with the data observed from [12], where 0-1000 ng/g of PAH in sediment is classified low to moderately contagion
while 1000-10000 ng/g is classified as being moderate to highly polluted, the concentrations value range in this
research indicated that Kapas Island was not heavily polluted compared to other parts of Malaysia.
Table 2 Concentration of individual PAHs in surface sediments of Kapas Island
Concentrations (g/g)
COMPOUNDS/STATIONS
Naphthalene

S1

S2

S3

S4

S5

S6

S7

S8

S9

S10

S11

S12

0.017

0.018

0.019

0.018

0.017

0.016

0.012

0.004

0.004

0.018

0.014

0.016

Phenanthrene

0.019

0.026

0.018

0.020

0.022

0.008

0.007

0.006

0.016

0.023

0.015

0.015

Anthracene

0.028

0.035

0.026

n.d

0.028

0.017

0.026

0.009

0.018

0.028

0.026

0.019

Chrysene

0.014

0.018

n.d

n.d

n.d

n.d

0.004

n.d

n.d

0.065

n.d

0.005

n.d

0.006

0.006

0.002

0.003

0.002

0.005

n.d

0.005

0.076

0.005

0.006

Benzo (a) pyrene

0.008

0.008

0.008

0.003

0.005

n.d

0.015

n.d

0.008

0.068

0.007

n.d

Benzo (g,h,i) pyrene

0.004

n.d

0.007

0.007

n.d

n.d

n.d

n.d

0.007

0.058

n.d

0.005

Benzo (k) fluoranthene

Total PAHs

0.090

0.111

0.084

0.050

0.075

0.043

0.069

0.019

0.058

0.336

0.067

0.066

Total LMW PAHs

0.047

0.061

0.044

0.020

0.050

0.025

0.033

0.015

0.034

0.051

0.041

0.034

Total HMW PAHs

0.026

0.032

0.021

0.012

0.008

0.005

0.024

0.000

0.020

0.304

0.012

0.016

Penantherene/Anthracene

0.679

0.743

0.692

0.000

0.786

0.471

0.269

0.667

0.889

0.821

0.577

0.789

LMW/HMW

1.808

1.906

2.095

1.667

6.250

5.000

1.375

0.000

1.700

0.168

3.417

2.125

TOC (%)
2.340
0.910
0.620
0.520
*LMW : Low Molecular Weight; HMW : High Molecular Weight
*TOC : Total Organic Carbon
*n.d : Not Detected

2.110

6.440

7.496

6.990

9.100

8.770

9.480

10.210

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4.2 Molecular ratio index

For phenanthrene /anthracene molecular index, all the sampling stations indicated that the main source type was
pyrolytic (Table 2). For Low Molecular Weight (LMR)/High Molecular Weight (HMR) index, the only station that
obtained values of less than 1 (petrogenic) was S10 while the rest attained values of more than 1(pyrolytic) (Table
2). This means that all the sampling stations in Kapas Island were based on pyrolytic source type of sediment. This
shows that Kapas Island was dominated by pyrolitic sources such as fossil fuel combustion, vehicle engine
combustion, waste combustion, open wood combustion and charcoal combustion.
4.3 Multivariate statistical analysis
Principle Component Analysis (PCA) was also carried out in this study. The purpose of principal component
analysis (PCA) is to perform the total variation of PAHs data with minimum number of the factor loadings. This
type of analysis has been proven to be able to increase the weight of the significant factor loadings by the varimax
rotation in PCA and thus reduce the weight of the non-significant ones [13]. The PCA of sampling locations is
reported in Fig. 3 which shows the loadings of the variable. The first two components, which are PC1 (54.1%) and
PC2 (25.8%), accounted for 79.9% of the total of the variance. As can be seen from Fig. 3, it is clear that the
sampling stations were divided into two distinct groups.

Fig. 3. The loadings of first two components of sampling stations of Kapas Island

The first group comprises 9 sampling locations that were loaded negatively in PC1, namely S3, S4, S5, S6, S7,
S8, S9, S11 and S12 while the second group consist of 3 sampling locations were loaded positively, namely S1, S2
and S10. Apart from that, there are 7 sampling locations that were loaded positively in PC2 and these are S6, S7, S8,
S9, S10, S11 and S12, while the other sampling locations, namely S1, S2, S3, S4 and S5 were loaded negatively in
PC2. While the two are grouped into two large groups together, there was one station that was loaded far away from
the others, which was loaded positively in both PC1 and PC2. The first group (S6, S7, S8, S9, S11, S12) is grouped
together because of the location of these stations which was within the inner area, located between the mainland of
Peninsular Malaysia and the island itself. The second group (S1, S2, S3, S4, S5) is grouped together because of the
location of these stations which was in the outer open sea of the island, facing South China Sea.
5. Conclusion
The value measured of the concentrations in this study shows that Kapas Island was not heavily polluted. Based on
the molecular index calculations, some concentrations ratios were considered between the PAHs it was likely to
imply pyrolysis processes as the most probable source of contamination. The basic and statistical method analysis
used in this study provided worthy and better understanding of organic matter composition and its sources.

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167

Acknowledgements
The authors gratefully acknowledge the support provided by the Science Fund grant No. 04-01-02-SF0698 and
Universiti Kebangsaan Malaysia (UKM). The authors also would like to thank Mr. Haris Hafizal for technical
support.
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