Characterization of Aromatic Hydrocarbons in Tropical Coastal Water of Sabah, Borneo

Abstract

The presence of carcinogenic compounds in the coastal waters was monitored to assess the health effects to human and the marine environment. The details on the level of hydrocarbon contamination in the coastal waters of some small islands and the port in Kota Kinabalu were provided to initiate the management and monitoring plan for ecosystem management and restoration of the target places. This paper reports the occurrences of oil and grease and 16 USEPA listed polyaromatic hydrocarbons in the selected locations of coastal waters of Sabah. A baseline reading on the oil and grease level was established using partition-gravimetric method while detection for polyaromatic hydrocarbons was studied using GC-MS. The level of oil and grease tested were all above the limit set by the Malaysian interim standards (0.04 mg/L), while the level of monitored polyaromatic hydrocarbons were still within an acceptable level. Most polyaromatic hydrocarbons monitored were detected in trace amount and many compounds were found to be below the detection limit of 0.02 μg/mL. The highest concentration of total polyaromatic hydrocarbons detected was 1.16 μg/mL, which was detected in the coastal waters of Manukan Island. Pyrene, benzo (a) anthracene and chrysene were detected in trace amounts in all locations. The levels of monitored carcinogenic hydrocarbon compounds were below the detection limit. Though detected at low levels, the presence of these elements in the coastal water is a cause for concern, hence continuous monitoring is recommended. The cumulative concentration of these compounds in molluscs and fish should be initiated to determine the accumulated level and the xenobiotic effect to humans and marine fauna. The main contributor of these pollutants was identified to originate from boating and shipping related activity in the vicinity of these area.

Full text

INTRODUCTION
Coastal environment is a vast sparsely populated wilder-
ness. These environments are susceptible to man-induced
stresses, such as pollution and climate changes. Prodigious
amount of crude oil are extracted from earth every year and
moved across the oceans and approximately 0.1 % of the total
oil extracted ends up in the marine systems each year, with
accidental spills having the most spectacular impact. Petro-
leum hydrocarbons also enter the coastal marine environment
as exhaust particulates, fuel spills, urban runoffs contaminated
with crankcase oil and the by-products of biomass combustion1,2.
Low molecular weight hydrocarbons tend to be more concen-
trated in the vapour-phase while the ones with higher molecular
weight are often associated with particulates3,4.
There are more than 600 different types of hydrocarbons
reported from petroleum products in which aromatics are the
Characterization of Aromatic Hydrocarbons in Tropical Coastal Water of Sabah, Borneo
KOGILA VANI ANNAMMALA1,*, MOHD HARUN ABDULLAH1, MAZLIN BIN MOKHTAR2, COLLIN G. JOSEPH3 and MAHYAR SAKARI1
1Environmental Science Programme, School of Science and Technology, Universiti Malaysia Sabah, Locked Bag 2073, 88999 Kota Kinabalu,
Sabah, Malaysia
2Institute for Environment and Development (LESTARI), Universiti Kebangsaan Malaysia, Selangor, 43600 UKM Bangi, Selangor, Malaysia
3Industrial Chemistry Programme, School of Science and Technology, Universiti Malaysia Sabah. Locked Bag 2073, 88999 Kota Kinabalu,
Sabah, Malaysia
*Corresponding author: Fax: +6 088 247 820; Tel: +6 088 320000 ext 5720; E-mail: a.kogilavani@gmail.com
(Received: 19 March 2012; Accepted: 14 January 2013) AJC-12692
The presence of carcinogenic compounds in the coastal waters was monitored to assess the health effects to human and the marine
environment. The details on the level of hydrocarbon contamination in the coastal waters of some small islands and the port in Kota
Kinabalu were provided to initiate the management and monitoring plan for ecosystem management and restoration of the target places.
This paper reports the occurrences of oil and grease and 16 USEPA listed polyaromatic hydrocarbons in the selected locations of coastal
waters of Sabah. A baseline reading on the oil and grease level was established using partition-gravimetric method while detection for
polyaromatic hydrocarbons was studied using GC-MS. The level of oil and grease tested were all above the limit set by the Malaysian
interim standards (0.04 mg/L), while the level of monitored polyaromatic hydrocarbons were still within an acceptable level. Most
polyaromatic hydrocarbons monitored were detected in trace amount and many compounds were found to be below the detection limit of
0.02 µg/mL. The highest concentration of total polyaromatic hydrocarbons detected was 1.16 µg/mL, which was detected in the coastal
waters of Manukan Island. Pyrene, benzo (a) anthracene and chrysene were detected in trace amounts in all locations. The levels of
monitored carcinogenic hydrocarbon compounds were below the detection limit. Though detected at low levels, the presence of these
elements in the coastal water is a cause for concern, hence continuous monitoring is recommended. The cumulative concentration of these
compounds in molluscs and fish should be initiated to determine the accumulated level and the xenobiotic effect to humans and marine
fauna. The main contributor of these pollutants was identified to originate from boating and shipping related activity in the vicinity of
these area.
Key Words: Oil and Grease, Polyaromatic hydrocarbons.
Asian Journal of Chemistry; Vol. 25, No. 7 (2013), 3773-3780
second largest group5,6. Polycyclic aromatic hydrocarbons
(PAHs) are mainly concerned pollutants in the environment
due to their toxic, mutagenic and carcinogenic properties7-9.
United states environmental protection agency (USEPA) listed
16 of polycyclic aromatic hydrocarbons as priority pollutant
compounds for human and the environment10-12. This paper
examines the environmental protection agency lists of the 16
polycyclic aromatic hydrocarbons hazardous compounds,
which are further divided into carcinogenic and non-carcino-
genic polycyclic aromatic hydrocarbons. The two and three
ring polycyclic aromatic hydrocarbons are non-carcinogenic,
while several four, five and six membered rings of polycyclic
aromatic hydrocarbons are carcinogenic. The four membered
ring polycyclic aromatic hydrocarbons are chrysene and benzo
(a) anthracene. The five membered ring polycyclic aromatic
hydrocarbons are benzo(a)pyrene, benzo(b)fluoranthene,
benzo(k)fluoranthene and dibenzo(a,h)anthracene. Six mem-

bered rings carcinogenic polycyclic aromatic hydro-
carbon include indeno(1,2,3-cd)pyrene. Benzo(a)pyrene is the
most potent carcinogenic among the polycyclic aromatic hy-
drocarbons13. Regulatory concerns are generally focused on
benzo(a)pyrene, total carcinogenic polycyclic aromatic
hydrocarbons (ΣPAHs) and total polycyclic aromatic hydro-
carbons (ΣPAHs), which is the main focus in this study. Benzo
(a) pyrene appears to exhibit low acute toxicity but have very
significant chronic toxicity. Single dose will not cause imme-
diate adverse effects but continuous low doses will probably
induce cancer14-18.
The international agency for research on cancer (IARC)
has characterized polycyclic aromatic hydrocarbon as carcino-
gens and classified polycyclic aromatic hydrocarbons into three
main groups which are Group 2A, Group 2B and Group 3.
Group 2A characterizes polycyclic aromatic hydrocarbons that
have probably carcinogenic impact to humans; benzo(a)-
anthracene, benzo(a)pyrene, dibenzo(a,h)anthracene. Group
2B is defined as possibly carcinogenic to humans, with maxi-
mum acceptable concentration of 200 ng/L19. polycyclic
aromatic hydrocarbons that fall in this group are fluorine,
Benzo (b) fluoranthene, benzo (k) fluoranthene, Idenol
(1,2,3cd) pyrene, finally group 3, unclassifiable with respect
to carcinogenicity in humans; phenanthrene, anthracene,
fluoranthene, pyrene, chrysene, benzo(g,h,i)prylene17,20,21.
Existence of all these compounds exceeding 20 ng/L in the
marine environment causes many problems both to the envi-
ronment and the organisms inhibiting in the ecosystem22.
According to the data provided by Malaysian Department
of Environment, Malaysia has a coastline measuring 4,675
km, inclusive of Peninsular Malaysia and the states of Sabah
and Sarawak, endowing more than 100 coastal islands whose
marine environments are generally rich in natural resources23.
This paper provides a summary on the levels of oil and grease
and polycyclic aromatic hydrocarbons, in the tropical coastal
waters of Sabah, on the island of Borneo. A total of four sites
were chosen for this study which includes three small islands
in the Tunku Abdul Rahman Park namely; Manukan, Mamutik
and Sapi Island and Kota Kinabalu main port (also known as
Jesselton port).
As mentioned, polycyclic aromatic hydrocarbons been
reported to have implications for human and ecosystem health,
analysis of spatial and temporal trends in this field are lacking
specifically in Sabah coastal area. Soh and Abdullah24 and Isobe
et al.25 studied the polycyclic aromatic hydrocarbons in Ma-
laysian mussels reported that their study areas were all heavily
polluted by petrogenic polycyclic aromatic hydro-
carbons. The location for Soh and Abdullah24, research in Sabah
was close to an oil platform, therefore the source of contami-
nation was most likely from crude oil in the area. Since oil
platforms were nowhere near this current study site, focus were
on the detecting the presence of the contaminant, level of
contamination and to suggest related actions to be taken accor-
dingly if necessary based on the significance of the concen-
tration level. Sabah's coastal and marine environment contains
many species, habitat for diverse marine flora and fauna and
other resources that could be greatly affected by oil pollution.
Tourism assists in the conservation of the environment,
but has in some cases through improper management caused
stress or destruction to the natural environment eg. Sipadan
Island, Sabah. Jakobsen etc.26 mentioned that coral reefs in
Sabah have been rapidly and adversely impacted by human
activities for decades. Further, he reported that some of the
affected area includes protected islands as the Tunku Abdul
Rahman Parks, which consists of 3 main islands namely
Manukan, Mamutik and Sapi. This research documents the
level of oil and grease and polycyclic aromatic hydrocarbons
in the waters and sediments of the coast of the selected
locations. Through a pilot study, the major source of monitored
contaminants was from local boats transporting tourists and
visitors to the islands. The only source of contaminant in
terminals and main Kota Kinabalu Port was ferries and ships
that calls at harbour. Since boating is still the main and the
only transportation to and fro the islands, the study was initially
focused on oil and grease contamination and identification of
polycyclic aromatic hydrocarbons molecular markers. This is
to detect possible contamination from incomplete combustions
and leakage related to boating activities. Active oil explorations,
drillings and operations were not present at the sampling stations
and the presence of tar-balls was also not detected.
EXPERIMENTAL
Sampling: For oil and grease analysis, samples were col-
lected using 1L glass bottles with PTFE-lined screw caps. All
samples were refrigerated and stored at 4 ºC27. Samples for
Polycyclic aromatic hydrocarbons were collected using Amber
glass with Teflon-lined caps which were cleaned according to
environmental protection agency specifications, samples were
preserved by refrigerating at 4 ºC, the liquids samples were
extracted within 7 days and the extracts were analyzed within
40 days of sampling. Liquid aqueous samples were preserved
in acidic condition (pH < 2)28,29.
Oil and grease analysis: Environmental protection
agency method 1664 was adopted for the analysis of oil
aqueous whereas partition-gravimetric method was used to
determine the concentration of oil and grease in the laboratory.
The method is based on environmental protection agency
(EPA), which is also the current method being used in environ-
mental protection agency's survey and monitoring programs
under the clean water act. This method is applied to determine
the n-hexane extractable material (HEM) and n-hexane
extractable material that is not absorbed by silica gel (SGT-HEM)
in surface and saline waters and industrial and domestic aqueous
water. The extractable materials that may be determined in
this method are relatively non-volatile hydrocarbons, vegetable
oils, animal fats, waxes, soaps, gasses and related materials30,31.
Oil and grease is a conventional pollutant defined in the act
and is codified at CFR 401.1632.
Precision and recovery (PAR) standard was prepared with
a mixture of hexadecane/stearic acid (1:1) also known as
spiking solution which was prepared acetone at a concentration
of 4 mg/mL each. The solution was prepared by mixing 400 ±
4 mg stearic acid and 400 ± 4 mg hexadecane in a 100 mL
volumetric flask. The final weight prepared should be 40 ± 1
mg, the concentration was checked by removing 5.00 ± 0.05
mL with a volumetric pipette placed on a tared weighing pan
and evaporated to dryness in a fume hood. This precision and
recovery standard is used for determination of initial precision
3774 Annammala et al. Asian J. Chem.

and recovery and ongoing precision and recovery procedure.
This spiking solution was frequently checked for any signs of
degradation or evaporation and was replaced after 6 months
or earlier if degradation was observed.
After verifying that the pH of each sample was less than
2, the sample was prepared for extraction. Sample was poured
into a separatory funnel with 30 mL of n-hexane added to the
sample and shaken well. Then the organic phase was allowed
to separate from aqueous phase for about 10 min before
draining the aqueous layer back to the original sample
container. The solvent was evaporated by immersing the lower
end of the flask in a water bath at adjusted temperature of
70 ºC. The flasks are then cooled in the desiccators; the outside
surface was wiped to remove moisture and fingerprints prior
to be weighed.
Polycyclic aromatic hydrocarbons detection by using
GC-MS: The standard operating procedure (SOP) followed
in this study is based on the guidance as mentioned in environ-
mental protection agency Method 625 for analyzing base/
neutral and acid extractable compounds. Prior to analysis, 1 mL
of surrogate standard solution was added to both blank and
matrix spike just prior to extraction and pH adjustment. Then
internal standard were added to all samples and standards to
allow internal standard quantification, the function of internal
standard is to compensate analytical results for losses or
instrument biases over the full range GC retention times.
Approximately 1 L aliquot sample was spiked with surrogate
and serially extracted three times with 60 mL each of methylene
chloride in a 1 L separatory funnel. Water was removed from
the extract with anhydrous sodium sulphate. The dry extract
was then concentrated in volume to 1.0 to 2.0 mL with a
Kuderna-Danish concentrator and nitrogen blown-down
apparatus. The extract is exchanged into a specified solvent
with final analytical method.
The GC-MS used in this study is Hewlett-Packard Model
5980 (A or Series II) which was fitted with auto-sampler. The
column used for the Base/neutral species was a glass column
which is 1.8 m long by 2 mm I.D packed with 3 % SP-2250
on Supelco port (100/120). Meanwhile for the acid species
the column used was a glass column which is 1.8 m long by
2mm I.D. with 1 % SP-1240 DA on Supelco port (100/120
mesh). The mass spectrometer used had a mass selective
detector that was able to scan the mass range of 35 to 450 amu
every 7 sec with an ionizing potential of 70 volts in the electron
impact ionization mode. The detector and associated electronic
and software can produce a mass spectrum of decafluorotri-
phenylphosphine (DFTPP) after a 1 µL injection of GC/MS
tuning standard.
RESULTS AND DISCUSSION
The highest level of oil and grease contamination detected
was in Port Kota Kinabalu, 40.62 mg/L, followed by 23.2 mg/L
in Manukan Island. The port contained the highest oil and
grease pollution during the December sampling, similar to
results obtained by Abdullah24, but in a different location in
Peninsular Malaysia. This was due to active shipping activity
and offloading operations. It has been observed that the
concentrations of oil and grease are influenced by several
factors such as the type of oil, quantity, weathered state of the
oil and also by the prevailing climatic and tidal conditions28,33.
This explains the drastic increased in the concentration of oil
and grease in most stations when repetition sampling was
performed in February. The readings are comparatively higher
due to the tidal effect. According to the Marine Department of
Sabah, December sampling during the high tide period and
February was lower tide. Except in Port where significance
decrease was observed (8.53 mg/L), according to Tam et al.28,
and Liu et al.33, mentioned that the presence of plants and
debris in the water body may trap the oil silts together. This
explains the low concentrations of oil and grease detected in
the Port during the second sampling. During first sampling,
the location was free from rubbish and plants and was active
in shipping activities compared to the second sampling where
the water was covered with silt, rubbish and organic matters
such as leaf, tree branches and debris (Fig. 1).
In Manukan Island when significant increase in oil and
grease was observed in February (130.23 mg/L), similar drastic
increased in the nearest islands Sapi (38.40 mg/L) and
Mamutik Island (46.05) mg/L the same pattern was repeated
in December which was 23.3, 8.2 and 13.6 mg/L, respectively.
(a)
(b)
Fig. 1. Location at Port during first (a) and second sampling (b). During
second sampling water was covered with silt, rubbish and organic
matters
During the second sampling increase in boating, scuba diving,
Vol. 25, No. 7 (2013) Characterization of Aromatic Hydrocarbons in Tropical Coastal Water of Sabah, Borneo 3775

water related sports and a lot of visitors and tourists were
noticed. Increase in activity linked in the increase in the level
of oil and grease contamination. This finding was similar as
reported by Tam et al.28. When correlation coefficient test
among pH and temperature was performed the test produced
the similar result as concluded by Burns and Codi34 and Lie
et al.33. The analysis showed that the concentration of oil and
grease concentration is positively related to the changes on
pH and temperature. Further Burns and Codi34 and Liu et al.33,
reported on negatively significant correlation with tidal effects,
which could not be achieved in this study as the data was consi-
dered as discrete. Fig. 2 shows the matrix plot relating the
positive relationship with pH and temperature the other data
is shown as discrete for tidal effects.
pH
p
H
temp
t
e
m
p
tide
tide
rainfall
rainfall
wind
wind
humidity
h
u
m
i
d
i
t
y
Observed
trend
6.64
7.39
8.52
14.34
17.67
20.95
27.93
30.93
30.96
34.07
37.65
38.40
43.23
44.42
46.05
120.21
126.74
130.23
og
Fig. 2. Matrix plot on the relationship between oil and grease contamination
and the in-situ parameters
According to the INWQS, 2003, water quality criteria for
oil and grease, for aquatic life protection is 0.04 mg/L. The
obtained data showed relatively high level of oil and grease
(Fig. 3). All of the reading obtained did not fulfil the water
quality standard for oil and grease by the Malaysian interim
water quality standard. Similar to report by the Department of
Environment of Sabah, which mentioned that fall 130 moni-
toring stations all over Sabah exceeds the limit35.
Polycyclic aromatic hydrocarbons analysis: The worst
environmental pollutants in the aquatic system are oily hydro-
carbons especially aromatic and polyaromatic compounds22.
The existence of oily compounds with an approximate concen-
tration of 0.1 µg/L in aquatic environment prevents the growth
of fish larva besides causing a generic state manner of animal.
Analysis of the sediments in the sandy soil beach of the small
islands was performed during high and low tide. Prior to the
analysis, quality analysis and quality control analysis were
conducted to ensure the quality of data produced. Among the
quality analysis and quality control was calibration checks,
method blank, matrix spikes, matrix spike duplicate and in
some case sample duplicate, GC/MS tuning standard, initial
calibration standards, continuing calibration standards (CCs),
system performance check compounds (SPCCs), calibration
Fig. 3. Summary of oil and grease concentration is all stations
check compounds (CCCs) on system check up. Apart from
that, daily calibration using DFTPP and auto tuning were
performed prior beginning the analysis.
The procedural blanks did not show any polycyclic
aromatic hydrocarbon contamination. The accuracy and
reproducibility of the polycyclic aromatic hydrocarbon
analytical method were satisfactory. The percentage recoveries
of 16 polycyclic aromatic hydrocarbons from the certified
reference standard (HS-6) ranged from 70 to 112 %. The results
were comparable with those reported by previous works such
as Nora et al.36, Zheng et al.37, also fulfilled the acceptance
criteria as guide lined by the environmental protection agency
Methods (1983) and as suggested by Burns et al.38. As shown
in Fig. 4, from the results of water samples from the small
islands; total polycyclic aromatic hydrocarbons detected in
Manukan, Sapi and Mamutik Islands are 1.12, 0.61 and 0.60
µg/mL. Naphthalene (Nap) was detected in all the three
samples, ranging from 0.18 µg/mL to 0.20 µg/mL in Sapi island
however Nap is not considered as a cancer causing substance39.
Polycyclic aromatic hydrocarbons with four rings which are
Pyrene (pyr), benzo (a) anthracene and chrysene, which areall
classified as class B2 (probable human carcinogen) weredetected
to be present in trace amounts in all these three locations.
The detected concentration in each samples vary consi-
derably from very low to below harmful limits. The concen-
trations determined from Manukan, Sapi and Manukan waters
were 0.18, 0.14 and 0.16 µg/mL for pyrene, 0.7, 0.08 and 0.06
µg/mL for benzo (a) anthracene and 0.06, 0.08 and 0.07 µg/mL
for chrysene. Comparing the three islands during the December
sampling, Manukan Island contained the highest amount of
polycyclic aromatic hydrocarbons. Mostly four ring polycyclic
aromatic hydrocarbons were detected present in each of the
locations which are pyrene, benzo(a)anthracene and chrysene.
Benzo(a)pyrene was also detected in trace amounts at all three
locations. Total polycyclic aromatic hydrocarbons detected
measures 0.10, 0.09 and 0.12 µg/mL respectively in Mamutik,
Sapi and Manukan Island however all were below the permi-
ssible polluted level (below 20-50 ng/L). Environmental
protection agency's carcinogenicity risk assessment verification
endeavour work group has classified benzo(a)pyrene as carcino-
3776 Annammala et al. Asian J. Chem.

Manukan island
Sapi island
Mamutik island
Fig. 4. Polycyclic aromatic hydrocarbons concentrations in water samples
collected in three small islands (Manukan, Sapi and Mamutik
Islands) during December sampling
genic and potential cancer causing agent in humans. Other
than water samples, sediment samples from the islands were
also collected and analyzed.
Reviewing at the sediments analysis data, results show
that most of the polycyclic aromatic hydrocarbons were not
detected or below detection limits. Only small amounts of
Acenapthane was detected in all three sample locations measu-
ring at 0.02 µg/mg in Mamutik and Sapi and 0.04 µg/mg and
Manukan. Other readings were too low which is below the
reporting limits and can be reported as < 0.02 µg/mg. This
preliminary study suggests that the occurrence on polycyclic
aromatic hydrocarbons originated from recent contamination
and not from accumulated sources. Abdullah et al.24 reported
that the presence of polycyclic aromatic hydrocarbons is low
in sandy soil sediments. These results were comparable with
the result of second sampling during low tide.
Comparison of data obtained during different sampling
periods: Comparing the data obtained during low tide and
hot weather conditions, it was found that the contamination
level of polycyclic aromatic hydrocarbons in the water follows
similar pattern as in February. In Manukan the first sampling
showed the presence of seven polycyclic aromatic hydrocarbon
compounds with total polycyclic aromatic hydrocarbons
(ΣPAHs) of 1.12 µg/mL, compared to only five compounds
(pyrene, benzo(a)anthracene, chrysene, benzo(a)pyrene and
traces of some amounts of naphthalene) in the second sampling.
The total polycyclic aromatic hydrocarbons (ΣPAHs) seems
to be less (0.63 µg/mL) in February, almost half of the amount
detected in December. Water related activities such as boating
but speedboat activities were observed during December
sampling and similar activity was not observed in Manukan
during the February sampling. This suggests that no recent
input of polycyclic aromatic hydrocarbons originated from
the boating activities. It also indicates that the level of polycyclic
aromatic hydrocarbons is greatly influenced by the local
activity and not from other sources. The Σpolycyclic aromatic
hydrocarbons detected in Sapi and Mamutik during the second
sampling are 0.61 µg/mL and 0.63 µg/mL respectively, some-
where similar to the concentrations reported in previous
sampling.
Similar results were observed regardless on the effect of
high tide and low tide in the water during sampling. This might
be influenced by resent rainfall and fast flushing effect that
would transfer the pollutants to other places. Thereby reducing
the influence on the dispersal of contaminants during sampling.
According to the meteorological data obtained by the Meteo-
rological Department, Kota Kinabalu reported that the mean
wind velocity on the previous and the day of sampling in
December are 1.8 m/s and 1.7 m/s. similar to the wind velocity
on February which was reported at 1.6 m/s and 1.7m/s. Other
then the similar wind speed, similar temperature and rainfall
during one day prior to sampling date were also recorded to
be almost similar. This explains on the possibility of similarity
in the obtained contaminant reading. Although similar conta-
mination and polycyclic aromatic hydrocarbons were found
in water samples, total different pattern of polycyclic aromatic
hydrocarbons contamination was recorded in the sediment
samples. Relatively higher levels of polycyclic aromatic
hydrocarbon contamination were detected during the second
sampling. In Sapi Island total polycyclic aromatic hydrocarbons
detected to was 1.18 µg/mg, whereas higher reading of total
polycyclic aromatic hydrocarbons was observed in Mamutik
which is 1.63 µg/mg. Highest level of Total polycyclic aromatic
hydrocarbons were observed in Manukan, the busiest island
compared to the rest of the two islands, Total polycyclic aromatic
hydrocarbons reading was 3.31 µg/mg. Manukan Island is very
famous for its water sports activity. Low polycyclic aromatic
hydrocarbons concentrations in the water showed that there
were no recent input or dispersed input and the sedimentation
analysis showed the accumulated occurrence of polycyclic
aromatic hydrocarbons were not severe in these islands. This
supports the suggestion from Pruell's assessment on 1986
concerning the slow release of polycyclic aromatic hydrocar-
bons from sediments39,40. Levels of hydrocarbons in seawater
tend to fluctuate throughout the year as reported by Abdullah
et al.24. Sediments containing fine particles tend to be good
accumulators of organic pollutants, presumably because of
their greater effective surface area38,41. Coarse-grained sands
and sediments made up of stones or shell on the other hand,
Nap ΣPAHsChr BaPPyr BaAAAce
PAH compounds
1.5
1.0
0.5
0
Mean concentrations
(µg/mL)
Nap ΣPAHsChr BaPPyr BaA
PAH compounds
0.8
0.6
0.4
0.2
0
Mean concentrations
(µg/mL)
Nap ΣPAHsChr BaPPyr BaA
PAH compounds
0.8
0.6
0.4
0.2
0
Mean concentrations
(µg/mL)
Vol. 25, No. 7 (2013) Characterization of Aromatic Hydrocarbons in Tropical Coastal Water of Sabah, Borneo 3777

reduce the hydrocarbon content, even though the corresponding
levels in vicinity seawater might be high. All samples in this
present study were collected from coarse-grained sands as well
as sands and shell, hence the corresponding level of polycyclic
aromatic hydrocarbons in sediment was relatively low similar
to results by Abdullah et al.24.
The dominant polycyclic aromatic hydrocarbons found
in sediment sample are naphthalene, fluorene, fluoranthene,
pyrene, benzo(a)anthracenee, chrysene, benzo (b) fluoranthene
and benzo (a) pyrene. Respectively, two to three rings polycyclic
aromatic hydrocarbon (defined as 128 < m/z > 192) dominate
in these samples, along with four to six membered rings
polycyclic aromatic hydrocarbon (defined as 202 < m/z > 292).
Total concentrations of potentially carcinogenic polycyclic
aromatic hydrocarbons (ΣCPAH), which include benzo(a)
anthracene, benzo(b)fluoranthene and benzo(a)pyrene varied
from 0.3 µg/mg in Mamutik, 0.41 µg/mg in Sapi Island and
0.53 µg/mg in Manukan Island. The influence of boating
activity amongst anthropogenic sources on sediment polycyclic
aromatic hydrocarbons pollution was quite clear.
Young19, found that fluranthene occurs widely in the
environment. The available limit fixed is for drinking water,
European community maximum acceptable concentration of
200 ng/L19. Fluoranthene is of low acute oral toxicity but no
data are available on its chronic or reproductive toxicity. It is
a potent mutant in bacterial and many mammalian in vitro test
systems, but only in the presence of metabolic activation19.
However limited evidence from short-term in vivo cytogenetic
and long term skin penetrating carcinogenicity studies in
rodents indicates that fluoranthene is not carcinogenic. There
is some evidence that fluoranthene may enhance the carcino-
genicity of benzo(a)pyrene but the relevance on relation to
environmental exposure and human health is unclear. Fluoranthene
is found in many combustion products. Its presence is an indicator
of less efficient or lower-temperature combustions42. While
benzo(a)pyrene is an indication that samples were exposed to
solar radiation, others sources include from automobile exhaust
fumes especially diesel engines9,37.
This polycyclic aromatic hydrocarbon distribution is in
good agreement with a petrogenic origin (combustion residues
of fossil compounds such as gasoline, kerosene, gas oil)43.
Finally, it was considered that ratio NAP/PHE is more one the
presence of fresh and un-weathered petroleum was assumed44.
In this study, NAPH/PHEN ratios ranged from 4.4 to 6 in
Manukan and Sapi Island, suggesting petrogenic sources for
polycyclic aromatic hydrocarbons in these sites. However
further monitoring and evidence is needed to support petrogenic
input prediction. The polycyclic aromatic hydrocarbon group
profile shows the predominance of two to three membered
rings polycyclic aromatic hydrocarbons in water samples while
four and six membered rings polycyclic aromatic hydrocar-
bons dominated in sediments samples. Similar to research
conducted by Abbas and Brack in 2005, on the water clarity
and influence of anthropogenic sources by weather conditions,
soil properties or easy degradation of polycyclic aromatic
hydrocarbons in soil.
Ratios between pairs of individual polycyclic aromatic
hydrocarbons have often been employed as a method of deter-
mining the most significant sources of polycyclic aromatic
hydrocarbons detected in environmental samples. In order to
characterize polycyclic aromatic hydrocarbons with respect
to specific source, Budzinki et al.45 have applied a diagnostic
elemental ratio. Yang et al.46, reported a ratio of 3 for PHE/
ANT, which indicate polycyclic aromatic hydrocarbons rising
from motor vehicle exhaust, whereas a ratio of over 50
implies major source originate from mineral oil. In this study
the PHE/ANT is 7.5 in Manukan Island and 5 in Sapi island.
Similarly, a ratio of 1 for FLT/PYR indicated polycyclic
aromatic hydrocarbon to be from combustion process and
ratio of more then one suggest of suggested origin to be petro-
leum derived as found in Mamutik and Manukan Island47,43.
Also BaA/BaP of 1 and BaP/BPE of 0.2 to 0.5 were indicative
of vehicle exhaust emission while BaP/BPE greater than one
was indicative of coal combustion. In this study the BaA/BaP
are 0.7 in Mamutik, 0.5 in Manukan and 0.9 in December, 0.6
in February for Sapi Island. This again suggests the sources
from automobile source. The PYR/BaP ratio of less than one
to 50 implied that the major source was diesel powered vehicle
as indicated in all the small islands48,49.
Determination and identification of polycyclic aromatic
hydrocarbons compounds in Port Kota Kinabalu: Water
samples from the port for both December and February sampling
are presented in Fig. 5. Low amount of total polycyclic aromatic
hydrocarbons were detected to be present during both sampling
times, at 0.53 µg/mL and 0.51 µg/mL respectively in December
and February. Although several low molecular weight polycyclic
aromatic hydrocarbons were detected, the concentrations were
very low and considered not significant. Only PYR and BaP
were detected with concentrations close to 0.1 µg/mL during
both analysis. Looking at the very low concentrations of
ΣPAHs in this location, it is safe to report that the level of
polycyclic aromatic hydrocarbons contamination in this station
is at very low level.
Hydrocarbons in water and sediment from Malaysian
waters have been determined and catalogued in previous surveys
by Phang et al.50, Law et al., etc41. Although the surveys largely
focused on areas connected with the exploration of oil and
gas reserves, several isolated studies have been conducted
along the west coast Peninsular Malaysia. Phang et al.50
reported that the levels of hydrocarbons in the range of 0.05
to 0.12 mg/L in Penang Island and 21.7 to 74.5 mg/kg in
sediment samples. Surveys in offshore waters off Sarawak in
East Malaysia recorded concentrations in range of 0.013 to
0.545 mg/L and 7.42- 1089 mg/kg for water and sediment
samples51. Hence the polycyclic aromatic hydrocarbons levels
measure in the present study appears to be in very low level,
compared to other studied locations in Peninsular Malaysia.
The level of hydrocarbon content in seawater is higher near-
coastal waters rather than in open sea24. According to the Food
and Agricultural Organization52, (FAO, 1982), seawater
containing hydrocarbon levels less than 0.0025 mg/L can be
classified as unpolluted. Unpolluted coastal sediments on the
other hand, contain hydrocarbons less than 100 mg/kg. On
these basis and also when compared to the levels in marine
water and sediments reported elsewhere in the world comparable
in terms of shipping activities, the level detected in this study
clearly shows that the coastal waters and sediments from the
study sites are in low levels (Fig. 6).
3778 Annammala et al. Asian J. Chem.

December sampling
February
Sampling
Fig. 5. Determination and identification of polycyclic aromatic
hydrocarbon compounds from water samples in KK Port
Fig. 6. Summary of total polycyclic aromatic hydrocarbons in all monitored
stations
There are two main differences in the polycyclic aromatic
hydrocarbon distributions during high tide and low tide, espe-
cially the concentration and distributions in the sediments.
Sediments composed of high clay and silt will contain potentially
more oil or hydrocarbon than sandy sediment as is the case in
this research area, explains the low readings obtained53. It is
realized that preliminary investigation needs to be developed
further, including many more measurement in locations repre-
senting other activities. It is also probable that the chemistry
of polycyclic aromatic hydrocarbons in tropical waters, where
the ambient temperature and relative humidity are higher
coupled with abundant sunshine, may differ from that of
temperate regions. This study clearly shows that quantitative
determination of hydrocarbon is not sufficient enough to assess
the exact degree of petroleum contamination in waters and
sediments. Moreover this study managed to identify the level
of hydrocarbon is associated to petroleum contamination from
petrogenic origin. As reported by Zakaria et al.54, polycyclic
aromatic hydrocarbons provides useful additional information
in source identification of petroleum pollution, as a potent tool
for source- identification of petroleum pollution.
Conclusion
The concentrations of detected oil and grease contami-
nation are influence by several factors depending on the type,
quantity and weathered state of the oil and the prevailing
climatic and tidal condition. All the reading obtained did not
meet the water quality standard for oil and grease by the
Malaysian: interim water quality standard. Quantitative and
qualitative analyses of polycyclic aromatic hydrocarbons
molecular markers identification on tropical coastal waters and
sediments of Sabah, lead to six groups of stations distinguished
according to main origins of hydrocarbon which are all from
petroleum sources. However none observed to be derived from
pyrolitic, terrestrial or digenetic sources. The overall levels of
anthropogenic polycyclic aromatic hydrocarbons are low
compared to relevant areas in Peninsular Malaysia or other
areas worldwide and reveal a low level of polycyclic aromatic
hydrocarbons pollution.
ACKNOWLEDGEMENTS
This research was supported by the Center of Research &
Innovation, University Malaysia Sabah (Grant No.FRG0203-
SG-1/2010) and is gratefully acknowledged. The author would
also like to thank Dr Steve Hensen, En Imran, Mr Mohan,
Mrs Anitha and all team members of Anametrics (M) Sdn.
Bhd,Shah Alam for assistance with the polycyclic aromatic
hydrocarbons analysis. Special thanks to Ms Nurulain Rahmat
and Ms Khuneswari Gopal Pillay for their enormous help
during sampling and analysis.
REFERENCES
1. D. Thomas, Principles of Water Quality. Academy Press Inc. Florida
(1984).
2. S. Payal, Annual Edition Environment 02/03. L.A. John, McGraw-
Hill Publications. United States, edn. 21 (2002).
3. K. Ravindra, E. Wauters and R. Van Grieken, Sci. Total Environ., 396,
100 (2008).
4. Y. Wang, P.-H. Li, H.-L. Li, X.-H. Liu and W.-X. Wang, Atmos. Res..
95, 1 (2010).
5. I. William, Environmental Chemistry, John Wiley & Sons, U.K. (2001).
6. W. Stumm, Chemistry of the Solid-Water Interface; Process at the
Mineral Water and Particle-Water Interface in Natural System, John
Wiley & Sons, New York (1992).
7. International Agency for Research on Canser (IARC), Polynuclear
Aromatic Compounds, Part 1; Chemical, Environmental and Experi-
mental Data, 32 (95-129) (1983).
8. A. Negri, K. Burns, S. Boyle, D. Brinkman and N. Webster, Environ.
Pollut., 143, 456 (2006).
9. C.D. Simpson, W.R. Cullen, T.Y.T He, M. Ikonomou and K.J. Reimer,
Chemosphere, 49, 315 (2002).
10. United States Environmental Protection Agency (USEPA), 1995.
Method 1664; N-Hexane Extractable Material (HEM) and Silica Gel
Treated N-Hexane Extractable Material (SGT-HEM) by Extraction and
Gravimetry (Oil and Grease and Total petroleum Hydrocarbons). EPA-
821-B-94-004b, April 1995. www.doe.gov.my, 29/09/2007.
Nap ΣPAHsChr BaPPyr BaA
PAH compounds
0.6
0.4
0.2
0
Mean concentrations
(µg/mL)
Nap
A
Ace
F
Pyr
BaA
Chr
BaP
ΣPAHs
PAH compounds
0.6
0.5
0.4
0.3
0.2
0.1
0
Mean concentrations
(µg/mL)
Dec Water Dec Sediment
Feb Water Feb Sediment
Vol. 25, No. 7 (2013) Characterization of Aromatic Hydrocarbons in Tropical Coastal Water of Sabah, Borneo 3779

11. A.D. Geiselbrecht, R.P. Herwig, J.W. Deming and J.T. Stanley, Appl.
Environ. Microbiol., 62, 3344 (1996).
12. United States Environmental Protection Agency (USEPA), Test plan
for Tall Oil and Related Substances. May (2001).
13. J.M. Rebecca, E.A. Sabine and B.H. Barbara, Appl. Environ. Microbiol.,
68, 2858 (2002).
14. P. O'neil, Environmental Chemistry, Chapman and Hall, London, edn
2 (1993).
15. W.K. Chung and G.M. King, Appl. Environ. Microbiol., 67, 5585 (2001).
16. R.B.J. Peachey, Marine Pollut. Bull., 46, 1365 (2003).
17. A. Masih and A. Taneja, Chemosphere, 65, 449 (2006).
18. K.K. Lie, S. Meier and P.A. Olsvok, Comp. Biochem. Physiol. Part C:
Toxicol. Pharmacol., 150, 141 (2009).
19. W. Young, Fluranthene in Drinking Water and its Effects on Human
Health. Foundation for Water Research.Report No FR0276 (1992).
20. The International Agency for Research on Cancer (IARC), IARC Mono-
graphs on the Evaluation of the Carcinogenic Risk of Chemicals to
Humans; Polynuclear Aromatic Compounds, Chemical, Environment
and Experimental Data, Part 1, 32 (1998).
21. Wei Wang, Min-Juan Huang, Yuan Kang, Hong-Sheng Wang, Anna
O.W. Lung, Kwai Ching Cheung and Ming Hung Wong, Sci. The Total
Environ. (2011) (in Press).
22. F. Yazdanparasr, Nouri and A. Rabbani, Int. J. Environ. Sci. Technol.,
1, 215 (2004).
23. Michael Wong, Sipadan Borneo's Underwater Paradise.Odyssey Pub-
lishing. Singapore (1991).
24. A.R. Abdullah, N.M. Tahir and L.K. Wei, Bull. Environ. Contaminat.
Toxicol., 53, 618 (1994).
25. T. Isobe, H. Takada, M. Kanai, S. Tsutsumi, K.O. Isobe, R.
Boonyatumanond and M.P. Zakaria, Environ. Monit. Assess., 135, 423
(2007).
26. F. Jakobsen, N. Hartstein, J. Franchisse and T. Golingi, Ocean Coastal
Manage, 50, 84 (2007).
27. D. Cataldo, J.C. Colombo, D. Boltovskoy, C. Bilos and P. Landoni,
Environ. Pollut., 112, 379 (2001).
28. N.F.Y. Tam, Y.W. Teressa and Y.S. Wong, Marine Pollut. Bull., 51, 1092
(2005).
29. C.L. Gou, H.W. Zhou, Y.S. Wong and N.F.Y. Tam, Marine Pollut. Bull.,
51, 1054 (2005).
30. Environmental Protection Agency, Environmental Protection Agency,
Methods for Chemical Analysis of Water and Wastes, 3rd Ed. Environ-
mental Protection Agency, Environmental Monitoring System Labo-
ratory-Cincinnati (EMSL-Ci), Cincinnati, Ohio. EPA-600/4-79-020,
Method 413.1 (1983).
31. American Public Health Association, Standard Methods for the Ex-
amination of Water and Wastewater, 18th Ed. APHA. Washington.
Method 5520B and Method 5520F (1992).
32. American Chemical Society, Safety in Academic Chemistry
Laboratoties, 3rd Ed. Committee on Chemical Safety (1979).
33. Liu Ying, Ling Chen, Qing-hui Huang, Wei-Ying Li, Yin-Jian Tang
and Jian-Fu Zhao, Sci. Total Environ., 407, 2931 (2009).
34. K.A. Burns and S. Codi, Mangrove and Salt Marshes, 2, 63 (1998).
35. Jabatan Alam Sekitar, Malaysia Marine Oil Spills. JAS, Sabah (2007).
36. F.Y. Nora, T. Tam, W.Y. Wong and Y.S. Wong, Marine Pollut. Bull., 51,
1092 (2005).
37. M. Zheng, M. Fang, F. Wang and K.L. To, Atmosph. Chem., 34, 2691
(2000).
38. K.A. Burns, J.P. Villanueve, V.C. Anderlini and S.W. Fowler, Marine
Pollut. Bull., 13, 240 (1982).
39. J.M. Ayotamuno, R.N. Okparanma and F. Amadi, Afr. J. Environ. Sci.
Technol., 54, 262 (2006).
40. R. D'Adamo, S. Pelosi, P. Trotta and G. Sansone, Bioaccumulation
and Biomagnifications of Polycyclic Aromatic Hydrocarbons in Aquatic
Organisms. Department of Environment, Ministry of Natural Resources
and Environment Malaysia (1997).
41. A.T. Law, N.A. Shazili, R. Yaacob, L.H. Chark, M.N. Saadon and L.
Shamsuddin, Coastal oceanographic studies in the Straits if Malacca
and South Cjina Sea: In port Dickson coastal waters. Conference on
the intensification of research in priority areas,Deceber 1991. Penang,
Malaysia, p. 12 (1991).
42. Y.M.J. Nasr, Omar, Tan Chin Mon, N.A. Rahman and A. Radzi, Sci.
Total Environ., 369, 76 (2006).
43. G. Mille, M. Guiliano, L. Asia, L. Malleret and N. Jalaluddin, Chemo-
sphere, 64, 1062 (2006).
44. S. Dahle, V. Savinov, G. Matishov, A. Evenset and K. Naes, Sci. Total
Environ., 306, 57 (2003).
45. H. Budzinki, I. Jones, J. Bellocq, C. Pierand and P. Garrigue, Mar.
Vhem., 58, 85 (1997).
46. S.S. Yang, H.L. Chang, and C.B. Wei, J. Biomass Energy Soc. China,
10, 147 (1991).
47. M.B. Yunker, S.M. Backus, E.G. Pannatier, D.S. Jeffries, R.W.
Macdonald, Estuary Coast Shelf Sci., 55, 1 (2002).
48. A.A. Olajire and W. Brack, Sci. Total Environ., 340, 123 (2005).
49. N.Y. Omar, R. Abas, K.A. Ketuly and N.M. Tahir, Atmos. Environ.,
36, 247 (2002).
50. S. Phang, T.K. Hwang and T.T. Ang, Hydrocarbon Content in the
Coastal Water Along the East Coast of Peninsular Malaysia. Coastal
Resources of East Coast Peninsular Malaysia, An Assessment in Rela-
tion to Potential Oil Spills. University Sains Malaysia Publication
(1984).
51. A.T. Law and S. Libi, Occational Publications, 4, 53 (1988).
52. Food and Agricultural Organization (FAO), The review of the health
of the oceans. FAO/ IMCO/ Unesco/ WMO/ IAEA/ Unep Joint Group
of Experts on Scientific Aspects of Marine Pollution (Gesamp). Rep
Stud Gesamp, 15, 108 (1982).
53. A. Pauzi, Environ. Monit. Assess., 44, 443 (1997).
54. M.P. Zakaria, T. Okuda and H. Takada, Marine Pollut. Bull., 42, 1357
(2007).
3780 Annammala et al. Asian J. Chem.