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Soil and Sediment Contamination: An


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Urban vs. Marine Based Oil Pollution in


the Strait of Johor, Malaysia: A Century
Record
a b c
Mahyar Sakari , Mohamad P. Zakaria , Che A. Rahim Mohamed
d b e
, Nordin H. Lajis , Kuhan Chandru , Pourya S. Bahry , Mazlin B.
f b
Mokhtar & Azadeh Shahbazi
a
School of Science and Technology , Universiti Malaysia Sabah
(UMS) , Kota Kanabalu, Sabah, Malaysia
b
Environmental Forensics Laboratory, Faculty of Environmental
Studies , Universiti Putra Malaysia , Serdang, Selangor, Malaysia
c
Marine Ecosystem Research Center (EKOMAR), Faculty of Science
and Technology , Universiti Kebangsaan Malaysia (UKM) , Bangi,
Selangor, Malaysia
d
Laboratory of Natural Products , Institut Biosains, Universiti Putra
Malaysia , Serdang, Selangor, Malaysia
e
Department of Chemistry, Division of Science , University of
Otago , Dunedin, New Zealand
f
Institute for Environment and Development (LESTARI), Universiti
Kebangsaan Malaysia (UKM) , Bangi, Selangor, Malaysia
Published online: 15 Oct 2010.

To cite this article: Mahyar Sakari , Mohamad P. Zakaria , Che A. Rahim Mohamed , Nordin H.
Lajis , Kuhan Chandru , Pourya S. Bahry , Mazlin B. Mokhtar & Azadeh Shahbazi (2010) Urban vs.
Marine Based Oil Pollution in the Strait of Johor, Malaysia: A Century Record, Soil and Sediment
Contamination: An International Journal, 19:6, 644-666

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Soil and Sediment Contamination, 19:644–666, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1532-0383 print / 1549-7887 online
DOI: 10.1080/15320383.2010.515630

Urban vs. Marine Based Oil Pollution in the Strait


of Johor, Malaysia: A Century Record

MAHYAR SAKARI,1 MOHAMAD P. ZAKARIA,2


CHE A. RAHIM MOHAMED,3 NORDIN H. LAJIS,4
KUHAN CHANDRU,2 POURYA S. BAHRY,5
MAZLIN B. MOKHTAR,6 AND AZADEH SHAHBAZI2
1
School of Science and Technology, Universiti Malaysia Sabah (UMS), Kota
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Kanabalu, Sabah, Malaysia


2
Environmental Forensics Laboratory, Faculty of Environmental Studies,
Universiti Putra Malaysia, Serdang, Selangor, Malaysia
3
Marine Ecosystem Research Center (EKOMAR), Faculty of Science and
Technology, Universiti Kebangsaan Malaysia (UKM), Bangi, Selangor, Malaysia
4
Laboratory of Natural Products, Institut Biosains, Universiti Putra Malaysia,
Serdang, Selangor, Malaysia
5
Department of Chemistry, Division of Science, University of Otago, Dunedin,
New Zealand
6
Institute for Environment and Development (LESTARI), Universiti Kebangsaan
Malaysia (UKM), Bangi, Selangor, Malaysia

Polycyclic aromatic hydrocarbons (PAHs) constitute a class of organic pollutants in the


environment that come from combustion of organic matter and petroleum products and
from natural sources. Reconstruction of PAH history from two sedimentary cores of the
Strait of Johor in peninsular Malaysia showed predominance of urban over marine-
based sources of oil pollution. Laboratory analysis of the cores found oil pollution from
city-sourced material since 1910 and 1940 in the near-shore and offshore samples,
respectively. Using hopane as molecular biomarker of petroleum pollution, this study
found a predominance of Southeast Asian-originated oil and its derivatives. This study
concludes that crankcase oil, asphalt, street dust and urban sediments considerably
contribute to oil pollution of the study area.

Keywords gas chromatograph, hopane, Johor, Malaysia, oil pollution, PAHs

Introduction
The development of cities in the 20th century to satisfy needs related to the economy and
quality of life has been followed by various environmental problems, particularly pollution
caused by use of petroleum. Petroleum, both as a raw material and as refined products that

Address correspondence to Mahyar Sakari, School of Science and Technology, Universiti


Malaysia Sabah (UMS), 88999 Kota Kinabalu, Sabah, Malaysia. E-mail: mahyarsakari@gmail.com

644
Urban vs. Marine Based Oil Pollution 645

are used as energy sources, consists of several chemicals, such as hydrocarbon compounds
and rare ores. One component of petroleum is the polycyclic aromatic hydrocarbons (PAHs)
that belong to a group of more than 10,000 chemical compounds that consist of two or more
fused benzene rings in different arrangements (Blumer, 1976). PAHs enter into the marine
environment from different anthropogenic and natural sources (Simoneit and Mazurek,
1982; National Academy of Science, 1985). PAH compounds give reason for concern since
they are mutagenic, carcinogenic, and persistent in the environment.
Studies on related topic showed magnificent changes in sources and fluxes of PAHs
over time in the environment. Lima et al. (2003) indicated that recent increase of PAHs is
due to the increase of diesel fuel combustion and heavier vehicle traffic in Rhode Island,
USA. Several PAHs maximum peaks from the sedimentary records indicate consumption of
source materials such as petroleum products over certain periods of time (Schneider et al.,
2001). Furthermore, disordered expansion in cities demand more energy consumption and
produce higher combustion derived PAHs into the environment as was shown from 6 U.S.
metropolitan areas (Van Metre et al., 2000).
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The state of Johor ranks the second in Malaysia in terms of size, development, and
population. Since the 19th century, it has operated port activities, including marine trans-
portation to local and international destinations. However, since marine transportation plays
an important role in the economic development of the region, the use of petroleum as a
source of energy has the undesirable side-effect of releasing petroleum-related pollution
into the environment. Source identification of PAHs is a controversial subject among scien-
tists since different results are found using different techniques, such as isomer pair ratios
(Yunker, 2002), individual compound ratios (Hase and Hites, 1976), and application of
biomarkers (Volkman et al., 1997; Wang and Fingas, 2005). The source identification task
is more complicated when the combustion is responsible for derived PAHs. The combustion-
derived PAHs are subject to several effects such as physicochemical properties, chemical
oxidation, photo degradation, and biodegradation as well as type of fuel, temperature, and
the amount of oxygen (Lima et al., 2005).
Hopane is a pentacyclic triterpane, one group of molecular biomarkers derived from
microbial origins (bacteriohopentetrols) in oil reservoirs; some of them are resistant to
biodegradation (Prince et al., 1994). Hopane has been used as a biomarker for plant and
petroleum input of PAHs in aquatic sediments (Wakeham et al., 1980; Tan and Heit,
1981; Boulabassi and Saliot, 1993; Yunker and McDonald, 1995). Hopanes are commonly
found in C29 -C35 , together with two C27 species called regular steranes. Homohopanes
are the name of the hopane series in which the number of carbon arises by 30. The
hopanes are composed of three sterioisomeric series, namely 17α(H),21β(H)- Hopanes,
17β(H),21β(H)- Hopanes and 17β(H),21α(H)- Hopanes. Hopanes with αβ configuration
in C27 -C35 range are characteristics of petroleum because their greater thermodynamic
stability compares to other epimeric (ββ and βα) series. In mature samples αβ epimeric
isomers are greater, predominant over βα isomer (moretane). However ββ-isomers are
commonly found in living organisms. Ts (18α(H)-22,29,30-trisnorneohopane) and Tm
(17α(H)-22,29,30-trisnorhopane) can be sensitive indicators of thermal maturity when
capering oil or sediment samples come from the same source. Therefore hopanes having
the 17α(H), 21β(H)- stereochemistry predominate, indicating a substantial contribution
from petroleum. Thus hopane is not an environmental contaminant but exists in crude oil
and some oil products. Due to its molecular structure, it resists degradation and therefore
can be used as a source identifier of oil pollution in environmental samples (Zakaria et al.,
2002; Chandru et al., 2008).
646 M. Sakari et al.

This study aims to determine the history of polycyclic aromatic hydrocarbon pollution
in the sedimentary environment of one of the busiest straits of Malaysia (Strait of Johor)
and along the coast by its second largest city, Johor Bahru. Sediment cores were taken from
two sites, one along the Strait of Johor and the other near the Johor-Singapore Causeway
(hereafter called the Johor City site). Cores were sliced into equal intervals, which were
then dated using 210Pb. Intervals were then analyzed using a variety of extraction and
purification procedures and instrumentation. Fingerprinting using hopane as a molecular
marker as well as comparison of ratios of several specific compounds was used to identify
the sources of PAH pollution. Results of this research contribute to regional knowledge
about environmental quality in the past as well as suggesting steps for future environmental
management.

Materials and Methods


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Sample Collection
Two cores were taken along the border between Peninsular Malaysia and Singapore at the
Strait of Johor in September 2006 (Fig. 1). The study area provides fisheries, aquaculture,
and limited tourism activities. The port that operates merchant shipping activities for

Figure 1. Study area and collection sites for cores from Johor Bahru City and the Strait of Johor,
Southeast Asia.
Urban vs. Marine Based Oil Pollution 647

Malaysia is located a few kilometers to the northwest of the Strait of Johor station. Hence,
dredging is not a concern for core sampling in this study. The cores were obtained using a
stainless-steel gravity corer (i.d. 3cm), which was internally equipped with a compacted,
pre-cleaned plastic tube to prevent cross-contamination prior to slicing. The depth of the
water column was ∼4 and ∼5 m and the cores reached to 33 and 36 cm in length at the
Johor City and the Strait of Johor stations, respectively. The core was sliced at 3cm intervals
and stored at −18◦ C prior to further analysis.

Chemical Analysis of PAHs and Hopane


Authentic standards for PAHs and hopanes were purchased from Sigma Chemical Com-
pany (St. Louis, MO, US) and Chiron (Trondheim, Norway). All organic solvents such
as dichloromethane, hexane and isooctane used in the analysis were distilled in a glass
distillation system at the laboratory to get high-grade isomers of the chemicals. Analytical
processes followed those described by Zakaria et al. (2002) and Sakari et al. (2008).
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In brief, 5 g (d.w.) of the samples were dried with anhydride sodium sulfate and
placed in pre-cleaned cellulose thimbles and Soxhlet extracted for 11 hours using distilled
dichloromethane. Extracts were then each spiked with 200 µl of the surrogate internal
standards (SIS) containing 10 ppm of naphthalene-d8, anthracene-d10, chrysene-d12 and
perylene-d12. The solution was transferred onto the top of a silica gel column (i.d. 0.9 cm,
length 9 cm), which had been deactivated with 5% distilled H2 O to remove polar com-
pounds. PAHs ranging from 2 to 7 benzene rings and hopanes were obtained by elution
with 20 ml of 3:1 hexane/dichloromethane (v/v). Then, the solution was fractionated using
a fully activated silica gel column (i.d. 0.47 cm, length 18 cm).
Hopane and PAH fractions were obtained using 4 ml hexane and 14 ml 3:1 hex-
ane/dichloromethane (v/v), respectively. The PAH fraction was re-dissolved into 200 µl
isooctane containing 10 ppm of p-terphenyl-d14 as internal injection standard (IIS). The
hopane fraction was also diluted in 200 µl isooctane. Then the hopane IIS was spiked into
the solution containing 10 ppm of 17ß (H), 21ß (H)-hopane.
Instrumental analyses of PAHs and hopanes were made using a Hewlett Packard 5972A
quadruple mass spectrometer integrated with a HP5890 gas chromatograph equipped with
a J&W Scientific Durabond HP-5MS, 30 m fused silica capillary column (0.25 mm i.d. and
0.25 µm film thickness). Helium was used as the inert carrier gas at a constant pressure of
60 kg/cm2. The GC-MS operating conditions were kept at 70 eV ionization potential with
the source at 200◦ C and electron multiplier voltage at ∼1200 eV. The injection port was
maintained at 300◦ C and the samples were injected with split mode, followed by a purge 1
min after the injection. For PAH analysis, column temperature was held at 70◦ C for 2 min,
then programmed to increase at 30◦ C/min to 150◦ C, then at 4◦ C /min to 310◦ C, and held
constant for 10 minutes.
A selected ion monitoring (SIM) method was employed after a 4-min delay. PAH
concentrations were recovery-corrected using the spiked surrogates; this procedure yielded
recoveries of PAHs of 69% to 128%. For hopane analysis, column temperature was held at
50◦ C for 2 min, then programmed to increase at 6◦ C/min to 310◦ C and held for 15 minutes.
A selected ion monitoring method (m/z = 191) was employed after a delay of 4 min.
Individual PAHs and hopane compounds were quantified by comparing the integrated peak
area of the selected ion with the same peak area of the standard as well as their retention
times and spectra. The precision of the method was determined through four replicated
analyses of the heavy residual oil sample. The relative standard deviation (RSD; n = 4) of
individual PAHs identified in sample extracts was <10%.
648 M. Sakari et al.

Sediment Core Dating


The method for sediment dating has been described by Mohamed et al. (2006). However,
other methods such as application of 137Cs are accurate but this was not considered where
Malaysia shows a negligible amount of 137Cs in the environment. Thus, in brief, for the
conducted method 2 g of each sediment interval was dried in an oven at 50◦ C overnight,
sieved at 60 mesh (≤250 µm), and kept dry for analysis. An aliquot of 0.3 g of each
sediment layer sample (homogenized) was placed in a 50-ml beaker. One ml (25 ppm)
PbSO4 solution was added as extraction carrier. Twenty ml of HCl (8 M) was added to
the sample, which was then left for 2 h on a hot plate at 60◦ C for digestion. Digested
material was filtered with Whatman glass microfiber filter (≤0.45 µm porosity) to separate
solid residuals. Then the solution was left on the hot plate to obtain a yellowish-brown
colored paste. Thirty ml HClO4 was added to the paste and prepared for ion-exchange resin
column chromatography by gradually adding 200 ml HCl (1 M) to dilute the samples in the
column. The Pb was extracted from the column and dried until a white paste formed. Fifty
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ml HNO3 (1 M) was added to the paste and left on the hotplate for 1–2 minutes and then
cooled to room temperature. A few drops of concentrated H2 SO4 were added to get the
precipitated PbSO4 . Then the obtained Pb was filtered and placed on ProspecTM and taken
to the instrumental analysis using a machine called Gross β-spectrometry from Tennelec
Inc. (Model: LB5100). According to the counted β–emissions (from 210Pb), the following
equation (1) was used to determine the sedimentation rate and the age of each layer (Theng
et al., 2003).

A = A0 e−λ (z/s) (1)

where

A is the activity of 210Pb of the sediment in the laboratory (cpm/g)


A0 is the activity of 210Pb of the sediment in the date of sampling (cpm/g)
is the half-life of 210Pb
z is the depth of the sediment
s is the sedimentation rate

Results and Discussion

Reconstruction of Sedimentary Record


The sedimentation records were reconstructed using the counts of the 210Pb radioactivity.
The activity of 210Pb declined along the core to the deeper layers.
In the uppermost 10 cm of the cores, the number of radio nuclides is usually affected
by bioturbation processes of organisms (Mohamed et al., 2006). Therefore, we excluded
these uppermost layers with bioturbation from age determination.
Furthermore, some sediment layers in the remaining core showed irregular and excess
activities (humps) of 210Pb. These humps of 210Pb activity appear as a result of 210Pb input
from non-atmospheric sources. Hence, the age determinations of cores also exclude layers
with humps (Fig. 2a, b).
Based on the data in Figures 2A and 2B and using Equation (1), the sedimentation
rates were calculated. In addition, the age of each sedimentary interval was determined.
Urban vs. Marine Based Oil Pollution 649
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Figure 2. The 210Pb clean activities along the cores from (a) Johor City and (b) Strait of Johor.

Historical Record of PAHs in Johor City


The total PAH (TPAH) concentration demonstrated a general decline since World War II
(Table 1). A sudden drop of TPAHs was observed in the layers of the sedimentary core that
were laid down almost a decade after Singapore’s independence in 1958. Singapore has
been showing phenomenal economic growth since the 1970s, with more economic activity
than Johor Bahru in Malaysia (Fig. 3). Specific PAH compounds in the core from the Johor
City station revealed high concentrations of parent PAHs such as phenanthrene, anthracene,
pyrene, benzo(k)fluoranthene, benzo(e)pyrene, and benzo(a)pyrene.
An abundance of parent and high molecular weight (HMW) PAHs usually indicates
petroleum combustion (i.e. a pyrogenic source) and biomass burning. Increases of either
parent or HMW PAHs are followed by a decline in the ratios of methyl phenanthrenes to
phenanthrene (MP/P) and a ratio of low molecular weight (LMW) to HMW PAH (L/H) to
less than unity. (However, an exception exists for use of these ratios for the examination
of crude oil from Venezuela.) This pattern was observed in the core intervals dating since
the 1970s in the Johor City core (R2 = 0.582; Sig = 0.006; p < 0.05 for HMW). Most
petrogenic PAHs show high abundance of LMW, higher L/H ratio, and MP/P between 2 to
6 (Takada et al., 1991). In this station, the results from L/H ratio (average, 1.42) with MP/P
values ranging from 0.72 to 2.45 (average∼1.67) indicate a wide range of sources from a
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Table 1

650
a) PAH composition, concentration and relative ratio in the Johor City sedimentary core
Concentration (ng/g
PAHs Compounds Name d. w.)
Dibenzothiophene 25.24 12.00 49.80 11.21 57.47 27.06 11.22 27.11 2.41 0.69 10.50
(DBT)
Phenanthrene (Ph) 43.93 18.48 81.37 24.54 136.90 54.63 33.58 69.58 24.52 5.13 50.61
Anthracene (An) 36.86 14.76 66.88 19.24 112.64 48.34 26.61 33.77 1.86 1.22 9.61
3-Methylphenanthrene 27.70 11.32 50.44 14.26 77.84 30.67 17.30 17.67 4.71 2.06 9.82
(3-MP)
2-Methylphenanthrene 21.02 8.53 37.37 8.21 38.79 15.63 10.28 22.90 6.22 2.62 13.57
(2-MP)
2-Methylanthracene 12.49 4.88 18.18 8.68 41.75 18.32 12.20 12.76 1.12 0.57 2.23
(2-MA)
9-Methylphenanthrene 37.08 15.10 67.23 16.11 87.93 25.58 15.31 18.47 3.48 1.91 7.24
(9-MP)
1-Methylphenanthrene 21.78 9.30 40.79 8.71 50.87 18.98 11.18 13.56 3.13 1.57 6.65
(1-MP)
Fluoranthene (Fl) 2.82 11.28 5.04 3.95 16.47 4.91 4.15 4.44 0.57 0.41 1.14
Pyrene (Py) 54.14 21.94 9.85 64.48 294.70 107.36 80.27 104.56 11.67 6.32 18.12
1-Methyl Pyrene 26.35 11.00 4.95 25.49 10.26 45.72 30.66 43.90 2.77 1.10 3.69
(1-Mpy)
Chrysene (Chry) 24.42 3.63 41.43 31.26 21.58 46.72 33.94 46.92 2.23 1.81 3.53
Benzo (a) anthracene 21.86 80.27 35.58 27.82 15.93 40.25 35.16 44.69 2.03 1.69 3.22
(BaA)
Benzo (k) fluoranthene 70.06 247.52 113.82 102.10 50.67 136.41 130.07 144.78 7.13 5.63 10.07
(BkF)
Benzo (e) 21.07 71.41 3.49 32.42 16.15 40.97 40.25 44.96 1.96 1.65 2.96
acephenanthrylene
(BeAc)
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Benzo (e) pyrene (BeP) 82.98 287.82 13.88 11.91 57.73 162.25 152.99 179.57 9.37 6.79 12.78
Benzo (a) pyrene (BaP) 41.80 145.86 7.01 63.19 33.98 85.68 80.58 91.34 3.93 3.46 6.20
Dibenzo (a,h) anthracene 8.93 30.32 1.55 5.14 7.86 25.78 0.00 0.00 0.00 0.00 0.00
(DahA)
Sediment age (year) 1874–1885 1886–1897 1898–1909 1910–1921 1922–1933 1934–1945 1946–1957 1958–1969 1970–1981 1982–1993 1994–2005
a
Total PAHs (ng/g d.w.) 580.51 1005.40 648.67 478.73 1129.52 935.25 725.76 920.98 89.11 44.64 171.95
b
LMW PAHs (ng/g d. w.) 283.06 127.58 426.95 179.39 915.37 351.48 222.11 324.82 59.68 22.51 129.49
c
HMW PAHs (ng/g d. w.) 297.45 877.82 221.71 299.34 214.14 583.77 503.65 596.16 29.42 22.13 42.46
d
L/H PAHs 0.95 0.15 1.93 0.60 4.27 0.60 0.44 0.54 2.03 1.02 3.05
e
MP/P 2.45 2.39 2.41 1.93 1.87 1.66 1.61 1.04 0.72 1.59 0.74
f
TOC mg/g 131.83 126.79 128.30 117.51 120.41 128.30 62.76 148.48 103.47 96.98 119.54
g
Total PAHs/TOC 4.40 7.93 5.06 4.07 9.38 7.29 11.56 6.20 0.86 0.46 1.44
(ng/mg)
h
Ph/An 1.19 1.25 1.22 1.28 1.22 1.13 1.26 2.06 13.15 4.20 5.27
i
Fl/Py 0.05 0.51 0.51 0.06 0.06 0.05 0.05 0.04 0.05 0.07 0.06
j
Fl/(Fl+Py) 0.05 0.34 0.34 0.06 0.05 0.04 0.05 0.04 0.05 0.06 0.06
k
BeP/(BaP+BeP) 0.67 0.66 0.66 0.16 0.63 0.65 0.66 0.66 0.70 0.66 0.67
m
BaA/(BaA+Chry) 0.47 0.96 0.46 0.47 0.42 0.46 0.51 0.49 0.48 0.48 0.48
a
Total PAHs: sum of 18 PAHs ranging from Dibenzothiophene to Dibenzo (a,h) anthracene; bLMW PAHs: sum of PAHs ranging from Dibenzothiophene to
Pyrene; cHMW PAHs: sum of PAHs ranging from 1-methyl pyrene to Dibenzo (a,h) anthracene; dL/H PAHs: ratio of LMW over HMW PAHs; eMP/P: ratio of
sum of 3-Methylphenanthrene, 2-Methylphenanthrene, 9-Methylphenanthrene and 1-Methylphenanthrene to Phenanthrene; fTOC: Total Organic Carbon; gTotal
PAHs/TOC: ratio of Total PAHs over TOC; hRatio of Phenanthrene to Anthracene; iRatio of Fluoranthene to Pyrene;jFl/(Fl+Py), Ratio of Fluoranthene over
sum of Fluoranthene and Pyrene; kBeP/(BeP+BaP): ratio of Benzo(e)pyrene over sum of Benzo(e)pyrene and Benzo(a)pyrene; mBaA/(BaA+Chry): ratio of
Benzo(a)anthracene over sum of Benzo(a)anthracene and Chrysene. ∗ Sediment age (year): was calculated using method described in “Materials and Methods”
section.
b) Chronological features of the Johor City core

Core length Surface Pb clean Deep Pb clean Sedimentation Core age


Core Name (cm) activity (cpm)a activity (cpm) rate (cm/y) (y)
Johor City 33 0.94 0.37 0.25 127
a 210
Clean Activity (cpm), activity of the lead ( Pb) excluding the lead activities from other sources based on Count Per Minute.

651
652 M. Sakari et al.
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Figure 3. Total PAHs concentration from Johor City core in historical perspective.

mixture of both pyrogenic and petrogenic (i.e. from uncombusted oil) sources in the cores
sampled at the Johor City station (Figure 4).
The statistical results showed that all alkylated Phenanthrene (3,2,9 and 1 MP) have
been highly correlated with Ph (r > 0.901, sig = 0.000, p < 0.05) since World War II,
indicative that the Ph and its methyl derivatives are derived primarily from petroleum,
as distinct from the pre-WWII measurements, which showed a lower correlation (Okuda
et al., 2002), indicating that the Ph and its methyl derivatives derive from non-petroleum
sources. The fact that this low correlation found for earlier intervals indicates biogenic
sources should make us cautious in accepting at face value the findings of other methods
that indicate petrogenic sources for those intervals.
The concentration of total organic carbon (TOC) in this core is elevated in comparison
with that of other countries such as Japan and the United States (Moriwaki et al., 2005)
due to climate and environmental conditions at the equator. The Johor region frequently
experiences floods caused by its high water table and almost daily heavy rain, consequently
flushing off the washed-away materials, including organic contents, into the marine en-
vironment. It has been noted that heavy rain and flooding can affect the distribution and
re-distribution of the pollutants in the soil and detritus runoff in the marine and terrestrial
environments (Ikenaka et al., 2005; Moriwaki et al., 2005).

Historical Record of PAHs at the Strait of Johor Station


The core from the Strait of Johor in general demonstrated lower concentrations of TPAHs
compared with samples from the Johor City core. The trend was for increasing TPAHs
from the 1930s on, but over the last 30 years the TPAH has dropped to half the maximum
measured level ( Tables 2a and 2b and Fig. 5).
Urban vs. Marine Based Oil Pollution 653
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Figure 4. MP/P and L/H ratios changes of Johor City core in historical perspective.

The Strait of Johor sampling station is located a few kilometers away from the in-
ternational shipping lane connecting the Straits of Malacca to the South China Sea. It is
also adjacent to the southeastern port of Johor, which contributes the pollution expected of
port activities, particularly those that are petroleum-based, as confirmed by analysis of the
specific PAH compounds in this core that indicates higher concentrations of phenanthrene
and its alkyl-substitutes. The data from specific compound analysis, together with values
from MP/P and L/H ratios, revealed petrogenic input of PAHs with MP/P ratio range from
0.90 to 3.08 with average value of around 1.52 (Fig. 6).
As in the Johor City core, rapid decline of TPAHs in cores from the Strait of Johor
station was found to have occurred after the rapid development of Singapore and the
subsequent shift of marine traffic away from Johor in the 1970s. The highest concentration
of PAHs with a value of 521 ng/g d. w. was observed for a decade after WWII. During
this era compounds such as dibenzothiophene (DBT) were present in higher concentration
(229.60 ng/g d. w.) than that of any other PAH compound. DBT is confirmed to be abundant
in the crude oil and petroleum products released into the marine environment.
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654
Table 2
a) PAH composition, concentration and relative compound ratio in the sedimentary core from the Strait of Johor core
Concentration (ng/g
PAHs Compounds Name d.w.)
Dibenzothiophene (DBT) 4.36 3.96 26.27 20.21 228.36 172.49 229.60 14.84 14.73 21.63 32.06 27.05
Phenanthrene (Ph) 114.41 150.77 19.41 12.89 85.09 85.50 92.05 23.90 43.55 78.46 33.11 18.94
Anthracene (An) 7.79 8.55 5.05 3.01 13.94 3.01 31.91 19.41 13.68 13.77 0.00 0.00
3-Methylphenanthrene 43.68 38.22 8.96 4.81 18.61 21.04 22.83 15.51 88.21 22.61 11.11 8.36
(3-MP)
2-Methylphenanthrene 52.69 52.56 10.56 5.68 24.68 29.65 30.51 14.55 18.50 21.74 13.72 9.37
(2-MP)
2-Methylanthracene 8.43 7.28 1.05 1.01 3.18 3.06 2.97 1.67 7.54 2.21 1.84 0.50
(2-MA)
9-Methylphenanthrene 32.80 27.74 9.30 5.37 19.24 18.64 20.64 14.81 16.06 14.35 12.15 8.09
(9-MP)
1-Methylphenanthrene 29.29 26.12 7.50 4.10 14.26 16.50 17.71 13.28 11.39 12.09 9.55 6.46
(1-MP)
Fluoranthene (Fl) 0.36 0.22 0.11 0.16 0.16 0.16 0.38 1.29 0.28 0.30 0.17 0.25
Pyrene (Py) 8.02 3.32 2.61 9.92 2.08 2.96 20.46 73.58 6.93 13.54 3.34 11.72
1-Methyl Pyrene (1-Mpy) 0.50 0.49 0.18 0.16 0.55 3.58 2.69 0.57 4.10 0.81 0.42 0.40
Chrysene (Chry) 0.51 0.56 0.00 0.00 0.00 0.00 0.00 2.62 6.69 2.53 0.00 0.73
Benzo (a) anthracene 0.28 0.51 0.00 0.00 0.00 0.00 0.00 0.00 0.35 0.00 0.00 0.73
(BaA)
Benzo (k) fluoranthene 0.38 0.16 0.30 0.21 0.00 2.64 20.00 3.85 11.71 4.50 2.71 2.62
(BkF)
Benzo (e) 0.13 0.00 0.11 0.05 0.23 1.41 0.00 0.82 3.22 1.36 0.87 0.00
acephenanthrylene
(BeAc)
Benzo (e) pyrene (BeP) 0.84 1.03 0.47 0.77 0.47 2.56 14.75 11.55 36.07 8.76 3.89 3.32
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Benzo (a) pyrene (BaP) 0.17 0.19 0.18 0.23 0.15 0.49 14.65 3.03 3.61 2.90 1.71 1.06
Dibenzo (a,h) anthracene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(DahA)
Sediment age (year) 1886–1895 1896–1905 1906–1915 1916–1925 1926–1935 1936–1945 1946–1955 1956–1965 1966–1975 1976–1985 1986–1995 1996–2005
a
Total PAHs (ng/g d.w.) 304.64 321.69 92.06 68.58 411.00 363.70 521.15 215.28 286.63 221.57 126.65 99.60
b
LMW PAHs (ng/g d. w.) 301.83 318.75 90.83 67.17 409.60 353.02 469.06 192.85 220.87 200.71 117.05 90.74
c
HMW PAHs (ng/g d. w.) 2.81 2.94 1.23 1.41 1.40 10.68 52.09 22.44 65.75 20.86 9.59 8.86
d
L/H PAHs 107.31 108.39 73.57 47.71 291.92 33.05 9.01 8.60 3.36 9.62 12.20 10.24
e
MP/P 1.38 0.96 1.87 1.55 0.90 1.00 1.00 2.43 3.08 0.90 1.41 1.70
f
TOC mg/g 45.18 47.61 89.03 30.97 29.17 32.13 25.98 29.98 26.33 30.56 30.27 29.69
g
Total PAHs/TOC (ng/mg) 6.74 6.76 1.03 2.21 14.09 11.32 20.06 7.18 10.89 7.25 4.18 3.35
h
Ph/An 14.69 17.63 3.84 4.28 6.10 28.42 2.88 1.23 3.18 5.70 NA NA
i
Fl/Py 0.05 0.07 0.04 0.02 0.08 0.05 0.02 0.02 0.04 0.02 0.05 0.02
j
Fl/(Fl+Py) 0.04 0.06 0.04 0.02 0.07 0.05 0.02 0.02 0.04 0.02 0.05 0.02
k
BeP/(BaP+BeP) 0.83 0.84 0.72 0.77 0.76 0.84 0.50 0.79 0.91 0.75 0.69 0.76
m
BaA/(BaA+Chry) 0.35 0.48 NA NA NA NA NA 0.00 0.05 0.00 NA 0.50

See Table 1 for definitions of “a” to “m”


b) Chronological features of the core from the Strait of Johor
Core length Surface Pb clean Deep Pb clean Sedimentation Core age
Core Name (cm) activity (cpm)a activity (cpm) rate (cm/y) (y)
Johor Strait 36 0.35 0.27 0.3 117
a 210
Clean Activity (cpm), activity of the lead ( Pb) excluding the lead activities from other sources based on Count Per Minute

655
656 M. Sakari et al.
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Figure 5. Concentrations of total PAHs from the Strait of Johor core by historical periods.

Figure 6. MP/P and L/H values in the core collected from Strait of Johor.
Urban vs. Marine Based Oil Pollution 657

The amount of TOC in this core fluctuated between 44.80 to 82.10 mg/g
(average∼56.10 mg/g), except during the period between 1906 and 1915, when TOC
was higher (153 mg/g). This irregular change of TOC can indicate flood events that bring
more organic content from terrestrial sources than usual. PAH compounds depend on TOC
for transport (Baker et al., 1986). However, although higher amounts of TOC usually carry
more PAHs, this study showed inconsistent relationships between levels of PAHs and levels
of TOC (r = −0.320). When TOC was high, we found both high and low PAH levels, but
when TOC was low, we found only low levels of PAHs. This finding is consistent with
reports of other investigators (Pereira et al., 1999; Boulabassi and Saliot, 1993).

Predominance of Urban Source Oil Pollution


An MP/P ratio reflects hydrocarbon origins: it is higher for coal combustion sources
(MP/P∼6) than for petroleum-based sources (Lee et al., 1977; Takada et al., 1990, 1991).
In the analysis of the core from the Strait of Johor, the MP/P ratio ranged from 0.90 to 3.08
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with an average value of around 1.52 (Fig. 6), indicating petrogenic sources of PAHs. The
MP/P values for the Johor City core, ranging from 0.63 to 1.11 with average of around 0.87
(Fig. 4), indicate a mixture of petrogenic and pyrogenic PAHs.
Our findings provide evidence that both Johor City and Strait of Johor cores had PAHs
derived from locations adjacent to the sampling stations. Figures 7a and b show various
ratios applied to determine sources of PAHs in the cores. The Fl/Py ratios show values below
unity, which indicates that the PAHs have their source close to the city center (Gschwend
and Hites, 1981; Helfrich and Armstrong, 1986). Since Johor Bahru is the second largest
city of Malaysia in population, it is assumed that the station near the urban area would bear
the impact of urban pollution. Similarly, the Ph/An ratio for the Johor City core with a value
of 3.02 and that of the Strait of Johor station with a value of 8.80 indicate that the source of
PAH production is closer to the Johor City station. However, the Ph/An ratio for samples
from the Strait of Johor station for the periods of 1896–1905 and 1936–1945 exceeded 15,
possibly due to non-petroleum sources (Yunker and McDonald, 1995; Quiroz et al., 2005).
From a historical perspective, the Johor City core indicated that combustion processes
were the predominant source of PAHS in the past, while more recently PAH input has
a petrogenic signature, either from combustion or petroleum product release, as revealed
by the increasing Ph/An ratios (1.13 in the past to 13.15 for recent input). Evidence of
vehicular emission, especially from diesel combustion, was predominant in the sediment
layers (Yang et al., 1998; Rogge et al., 1993). The Johor cores indicated an insignificant
contribution from forest fire, coal combustion, and biomass burning along the sediment
cores, where Fl/(Fl+Py) values do not exceed 0.5 (Yunker et al., 2002).
It could be expected that this predominance of petrogenic sources is at least partly
explained by the 127 oil spill incidents since 1976, as reported by the Malaysian Marine
Department (2003), due to heavy oil tanker traffic in the Straits of Malacca. In this research,
however, in neither station was found the signature of either isomer pair ratio or hopane
that would indicate an oil spill. It is concluded that the marine environment of the studied
area has not been affected by oil spill incidents since the late 19th century.

Hopane Composition: Oil Contaminated City Materials


The relative composition of individual compounds of pentacyclic triterpanes (hopane) has
recently been applied for identification of the source of petroleum pollution (Chandru
et al., 2008; Wang and Stout, 2007; Zakaria et al., 2002). Table 3 shows the findings for
658 M. Sakari et al.
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Figure 7. Various ratios that were applied to determine sources of PAHs in the collected cores; a)
Johor City and b) Strait of Johor.

hopane composition of both cores in this study. The ratio of 17α-22,29,30-trisnorhopane


to 18α-22,29,30-trisnorhopane (Tm/Ts) ratio; like hopane composition, a source indicator
for petroleum) for the Johor City station revealed a wide range of sources such as street
dust, asphalt, fresh and used crankcase oil materials with the average of 0.78 (Fig. 8).
This ratio was not applicable for the core collected from the Strait of Johor station due to
mathematical error.
Table 4 compares the results of this study with other crude oil signatures such as
those from Norway, Alaska, and California, whose ratio of 17α(H),21β(H)-30-norhopane
over 17α,21β(H)-hopane (C29 /C30 ) values ranged from zero to 1.52 (Wang and Stout,
2007; Zakaria et al., 2002). Note that while the signature of oil from Norway (Troll) has
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Table 3
Pentacyclic triterpanes (hopane) relative compound ratio in the studied cores: (a) Johor City and (b) Strait of Johor

(a)

Johor City 1898–1909 1910–1921 1922–1933 1934–1945 1946–1957 1958–1969 1970–1981 1982–1993 1994–2005
a
C31–35 /C30 7.60 0.00 16.06 14.89 31.96 11.65 39.14 13.64 12.78
b
C29 /C30 NA 1.10 1.10 1.10 1.10 1.15 1.18 1.03 1.01
c
Tm/Ts NA NA 0.63 0.49 0.74 0.53 1.38 0.88 0.55

a
Ratio of sum 17α,21β(H)-C31 homohopane to 17α,21β(H)-C35 homohopane relative to 17α,21β(H)-hopane; bRatio of 17α(H),21β(H)-30-norhopane over
17α,21β(H)-hopane; cRatio of 17α-22,29,30-trisnorhopane relative to 18α-22,29,30-trisnorhopane.
NA, not available either from GC-MS or from calculations
(b)

Johor Strait 1896–1905 1906–1915 1916–1925 1926–1935 1936–1945 1946–1955 1956–1965 1966–1975 1976–1985 1986–1995 1996–2005
a
C31–35 /C30 0.00 0.00 23.42 50.65 45.94 4.05 47.56 36.77 50.82 140.67 21.67
b
C29 /C30 0.00 0.23 0.09 0.19 0.00 1.52 0.95 0.89 Na 0.83 0.91
c
Tm/Ts NA NA NA NA NA 0.00 NA NA 1.88 NA NA
See Table 3 (a) for definitions of “a” to “c”

659
660 M. Sakari et al.
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Figure 8. Source identification of PAHs in marine sedimentary record using Tm/Ts ratio of Johor
City.

been reported from tar-ball samples collected from the east coast of peninsular Malaysia
(Chandru et al., 2008), we found no evidence of Norway oil as a source in the Strait of
Johor.
Analysis of cores from both the Johor City and the Strait of Johor stations showed
a predominance of South East Asian petroleum products, which are the main content of
several intermediate materials such as asphalt and lubricating oils, presumably washed off
by frequent rainfall and flash flooding (Ikenaka et al., 2005).

Origins of Middle Eastern and Southeast Asian Oil since the 1910s
One of the instruments that have been applied to the identification of oil from non-petroleum
sources is the C29 /C30 ratio. In this study the C29 /C30 ratio was applied in combination with
the MP/P ratio to distinguish petroleum from non-petroleum pollution. The results of
cross-plot analysis are shown in Figure 9a and 9b.
These cross plot graphs show that the Johor City core has been receiving petroleum
pollution since 1910. This is consistent with the history of oil usage and transportation
in Southeast Asia. While the MP/P ratio for the Johor City core indicates a petrogenic
signature before 1910, C29 /C30 ratio does not agree, indicating the possibility of forest fire
and biogenic derived PAHs as sources.
The C29 /C30 ratio obtained in this study shows that the Straits of Johor core has been
receiving most of its petroleum-based pollution from petroleum products from Southeast
Asia since 1946. The Middle East oil signature was only observed once, in the core sample
for 1946 to 1955. Similarly, in the Johor City core, no signature was found for oil from
Alaska, California, and Norway (Troll).
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Table 4
List of reference materials and samples, their molecular marker indices of C29 /C30 and Tm/Ts in this and several other studies
a b
Reference Material Type of Materials Area of Origin C29 /C30 Tm/Ts Reference
Arabian Light Crude Oil Middle East and Persian 2.01 2.31 Zakaria et al. (2001)
Gulf
Umm Shaif Crude Oil Middle East and Persian 1.56 0.76 Zakaria et al. (2001)
Gulf
Marban Crude Oil Middle East and Persian 1.41 0.35 Zakaria et al. (2001)
Gulf
Labuan Crude Oil Southeast 0.98 2.20 Zakaria et al. (2001)
Asia—Malaysia
Miri Crude Oil Southeast 0.85 1.49 Zakaria et al. (2001)
Asia—Malaysia
Tapis Crude Oil Southeast 1.16 1.43 Zakaria et al. (2001)
Asia—Malaysia
Sumatra oil Crude Oil Southeast 0.85 0.52 Zakaria et al. (2001)
Asia—Indonesia
Norway Troll oil Crude Oil Norway 0.45 1.46 Wang and Stout (2007)
Alaska oil Crude Oil Alaska—USA 0.62 1.56 Wang and Stout (2007)
California oil Crude Oil California—USA 0.64 6.60 Wang and Stout (2007)
Petronas Fresh Crankcase Oil Kuala Lumpur, Malaysia 1.52 0.70 Zakaria et al. (2002)
Brithish Petroleum Fresh Crankcase Oil Kuala Lumpur, Malaysia 1.32 1.00 Zakaria et al. (2002)
Petronas Gas Station Used Crankcase Oil Kuala Lumpur, Malaysia 2.04 0.92 Zakaria et al. (2002)
Malaysian Street Dust 1 Street Dust Kuala Lumpur, Malaysia 1.64 1.12 Zakaria et al. (2002)
Malaysian Street Dust 2 Street Dust Kuala Lumpur, Malaysia 1.62 1.41 Zakaria et al. (2002)
Malaysian Street Dust 3 Street Dust Kuala Lumpur, Malaysia 1.57 1.33 Zakaria et al. (2002)
Asphalt 1 Asphalt Kuala Lumpur, Malaysia 1.66 1.58 Zakaria et al. (2002)
(Continued on next page)

661
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662
Table 4
List of reference materials and samples, their molecular marker indices of C29 /C30 and Tm/Ts in this and several other studies (Continued)
a b
Reference Material Type of Materials Area of Origin C29 /C30 Tm/Ts Reference
Asphalt 2 Asphalt Kuala Lumpur, Malaysia 1.66 2.04 Zakaria et al. (2002)
Sediment Marine Surface Sediment Klang Stuary, Malaysia 1.61–1.67 0.81–0.92 Zakaria et al. (2002)
Sediment Marine Surface Sediment Klang Coast (inshore), 1.69–1.79 0.93–1.33 Zakaria et al. (2002)
Malaysia
Sediment Marine Surface Sediment Straits of Malacca 1.35–1.73 1.07–2.35 Zakaria et al. (2002)
(offshore), Malaysia
Sediment River Surface Sediment Johor Bahru, Malaysia 1.41 0.82 Zakaria et al. (2002)
Sediment Marine Surface Sediment Kim Kim Estuar, Johor, na na Zakaria et al. (2002)
Malaysia
Sediment River Surface Sediment Muar, Johor Bahru, na na Zakaria et al. (2002)
Malaysia
Sediment deposited before Marine Core Sediment Johor City, Johor, na 0.55–0.88 Present Study (2008)
1910 Malaysia
Sediment deposited after Marine Core Sediment Johor City, Johor, 1.01–1.18 0.49–1.38 Present Study (2008)
1910 Malaysia
Sediment deposited before Marine Core Sediment Johor Straits, na na Present Study (2008)
1946 Malaysia-Singapore
border
Sediment deposited after Marine Core Sediment Johor Straits, 0.12–1.20 na Present Study (2008)
1946 Malaysia-Singapore
border
Please see Table 3(a) for definitions of C29 /C30 , Tm/Ts ratios.
Urban vs. Marine Based Oil Pollution 663
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Figure 9. Differentiation between petroleum and non-petroleum origin PAHs plotting C29 /C30
against MP/P for cores from (a) Johor City and (b) Strait of Johor.
664 M. Sakari et al.

Implications of the Study and Future Research


We found several eras that represent high and low measured levels of PAHs in the study
area. This observation shows how historical events such as war, industrialization, and
development of the adjacent urban areas can affect the trend of petroleum input to the
environment. While some of these events are not predictable or preventable, precautionary
steps would help lower PAH pollution effects on the environment. Steps like expansion of
the wastewater collection network and treatment for the city of Johor Baharu would reduce
the amount of polluted materials, including dust and organic materials, from the city run-off
that are exposed to petroleum-sourced pollution.
Besides the city run-off, other activities such as aquaculture in the Strait of Johor
generate high levels of organic carbon (OC). To prevent production of OC, this study
suggests precautionary steps such as effective environmental control for the usage of
fertilizers and chemicals. Additional and future research would expand the scope of this
research by studying sediment cores for other persistent organic pollutants of environmental
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concern, such as PCBs and DDTs. These scientific investigations can be followed by
carrying out short/long-term monitoring plans in the study area. This suggestion will be
applicable to other parts of peninsular Malaysia, including the developing East Coast and
Eastern Malaysia.
As we found inconsistency in source identification among petroleum and non-
petroleum sources of PAHs across determination methods, we recommend a reliable method
such as stable isotope analysis for source identification of PAHs.

Conclusion
This research found that petroleum pollution started a century ago in the Johor region. High
PAH concentrations were observed in the core intervals corresponding to the WWII and
postwar periods, but have been declining in the last 30 years, probably due to the formation
of Singapore as an independent, economically prosperous country, causing oil traffic to
shift from Johor to Singapore. We found evidence to conclude that the studied area has
been receiving PAHs from various sources such as street dust, urban sediment, asphalt, and
fresh and used crankcase oil.
City-sourced materials that are carried by lateral transport of rivers, channels, streams
and urban collection systems demonstrated greater concentration of PAHs in Johor City
core station than in the core collected from the Strait of Johor. The core from Strait of
Johor showed not only lower concentrations of PAHs but also is fingerprinted as having
long-range transported input to the study area.
This is unlikely to stop the pollution input in the study area but there are several
potential possibilities either to minimize the levels of the PAH production or to control the
intermediate carrying materials such as dust and organic matters.

Acknowledgement
The authors thank the Malaysian Institute of Nuclear Technology (MINT) and Marine
Ecosystem Research Center at Universiti Kebangsaan Malaysia (UKM) for their valu-
able help in the instrumentation of aging procedures. Universiti Putra Malaysia (UPM)
is acknowledged for providing laboratory facilities. The illustrations and artwork were
technically edited by Mr. Seyed Yashar Bani Hashem from the Faculty of Information Sci-
ence and Technology, Universiti Kebangsaan Malaysia. The authors appreciate technical
Urban vs. Marine Based Oil Pollution 665

and editorial comments from Mrs. Alena Sanusi, who provided close observation on our
manuscript during the revision. This study was supported by the Science Fund from the
Ministry of Science, Technology and Innovation (MOSTI), Malaysia.

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