research article concentrations and sources of polycyclic...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 975781 10 pageshttpdxdoiorg1011552013975781

Research ArticleConcentrations and Sources of Polycyclic AromaticHydrocarbons in the Seawater around Langkawi IslandMalaysia

Essam Nasher1 Lee Yook Heng12 Zuriati Zakaria3 and Salmijah Surif1

1 Faculty of Science and Technology Universiti Kebangsaan Malaysia Selangor 43600 Bangi Malaysia2 Southeast Asia Disaster Prevention Research Institute (SEADPRI) Universiti KebangsaanMalaysia Selangor 43600 Bangi Malaysia3Malaysia Japan International Institute of Technology Universiti Teknologi Malaysia Kuala Lumpur Malaysia

Correspondence should be addressed to Essam Nasher essam abduhyahoocom

Received 12 November 2012 Revised 28 December 2012 Accepted 10 January 2013

Academic Editor Athanasios Katsoyiannis

Copyright copy 2013 Essam Nasher et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

This paper reports the levels of polycyclic aromatic hydrocarbons (PAHs) in the water around the Island and their probable sourcesWater samples were collected from four jetties and three marine fish farms around the main Langkawi Island and analysed for18 polycyclic aromatic hydrocarbons (PAHs) in December 2010 The total PAH concentrations ranged from 61 plusmn 043 to 46plusmn 042 120583gLminus1 which exceed the maximum admissible concentrations of PAHs (020120583gLminus1) for the water standard of EuropeanUnion The calculated diagnostic benzo[a]anthracene benzo[a]anthracene + chrysene ratio of between 052 and 10 suggests thatthe sources of PAHs at the majority of the stations studied are derived primarily from pyrogenic sources from incomplete fuelcombustion of the boats and vehicle engines with lesser amounts of PAHs contributed from petrogenic sources Some stationsdisplayed mixed sources A significant positive correlation was found between total organic carbon (TOC) and the concentrationsof the high-molecular-weight PAHs (1199032 = 086 119875 lt 005) which suggests significant secondary sources of PAHs such as thosefrom atmospheric deposition

1 IntroductionThe Langkawi Archipelago in the Straits of Malacca northwest of PeninsularMalaysia consists of 104 Islands the largestand most exploited of which is Langkawi Island with an areaof 4785 km2 Targeted for ecotourism Langkawi became aduty-free island in 1987 and is protected from industrial activ-ity [1] In 2006 the Island was declared a National Geoparka year later it became an UNESCO Global Geopark [1] In2010 24million tourists visited Langkawi [1] To cater for thisincrease in tourism-related activities the local populationswelled significantly from about 40000 in 1991 to almost100000 in 2010 [2] It is envisaged that this boost in tourismindustry would significantly increase pollution in Langkawiparticularly from the boating activities which use petroleumand diesel One of the most significant polluting componentsof petroleum is polycyclic aromatic hydrocarbons (PAHs)

PAHs are a group of over 100 different compounds withfused benzene rings [3] prominent in smoke soot and

exhausts resulting from the incomplete combustion of carboncompounds such as petroleum [4]The environmentally sig-nificant PAHs are thosemolecules that contain 2 to 7 benzenerings PAHs are divided into two groups based on theirphysical chemical and biological characteristics [5] Thelower-molecular-weight PAHs for example the 2 to 3 ringsof PAHs such as naphthalenes fluorenes phenanthrenes andanthracenes have significant acute toxicity to aquatic organ-isms The high-molecular-weight (HMW) PAHs containing4 to 7 rings from chrysenes to coronenes do not cause acutetoxicity but are known to be carcinogenic [6] Sixteen PAHcompounds have been identified as priority pollutants dueto their toxic mutagenic and carcinogenic characteristics[7] Due to their low water solubility and high lipophilicityPAHs are easily and rapidly absorbed by organisms and canbe accumulated in aquatic organism or adsorbed onto thesurface of suspended matter get deposited on the sea floorand be passed onto the marine food chain

2 Journal of Chemistry

99∘40998400E 99∘45998400E 99∘50998400E 99∘55998400E

06∘25998400N

06∘20998400N

06∘15998400N

06∘10998400N

06∘25998400N

06∘20998400N

06∘15998400N

06∘10998400N

99∘40998400E 99∘45998400E 99∘50998400E 99∘55998400E

S2

S3

S1

S7S4

S5S6

S1 Sampling stationN0 3

(km)

S Kilim

Pulau Langkawi

TelagaHarbour

Kuah

LangkawiPort

P Timun

P Ular

PulanDayang Bunting

S Melaka

N

0 80(km)

100∘ 101∘ 102∘ 103∘ 104∘

8∘

7∘

6∘

5∘

4∘

3∘

2∘

8∘

7∘

6∘

5∘

4∘

3∘

2∘

100∘ 101∘ 102∘ 103∘ 104∘

Thailand

Kedah

Lang

kaw

iisl

and

PulauPinang

Malaysia

SouthChina

Sea

Straits of Malacca

Figure 1 Map showing the seven sampling stations (S1ndashS7) around Langkawi Island Malaysia

Sources of PAHs can be either petrogenic from petro-leum-related activities or pyrogenic (pyrolytic) from theincomplete combustion of diesel fuel and engine oil [8]wood coal biomass of forest grass fires waste incineratorsand fossil fuels that are used in industrial operations andpower plants [9ndash12] PAHs are also widely used in com-mercial products such as intermediaries in pharmaceuticalsagricultural products photographic products thermosettingplastics and lubricating materials

In the marine environment the pollution from PAHscan result from natural seepage or land-based sources fromriver discharges urban runoff refineries and other industrialwastewater [6] or from sea-based sources such as two-strokevessel discharge nontank vessel spills operational dischargegross atmospheric deposition and aircraft dumping [13]These possible sources of PAHs can be differentiated bytheir respective diagnostic ratios [14] A phenanthrene-to-anthracene ratio (PheAnt) of gt15 indicates that the PAHsare petrogenic whereas a ratio of lt10 shows that they arepyrolytic in origin [15]

Few studies have been done on the concentration ofhydrocarbons in the water and the sediment of LangkawiIsland Law andHii [16] reported that the hydrocarbon (poly-cyclic compounds and PAHs) concentrations in the seawaterat Pulau Payar to the south of Langkawi Island ranged from32 to 46 120583g Lminus1 which is lower than the contamination levelof hydrocarbons (50 120583g Lminus1) in the tropical sea [16] The totalPAHs in sediments collected from Langkawi Island after anoil spill accident ranged from 34 to 27 times 102 120583g kgminus1 [17]

Abdullah [18] reported a high level of total hydrocarbons inthe sediments of Langkawi Island up to 85 times 102mgkgminus1which is higher than the safety level (10 times 102mgkgminus1) [19]The high level was attributed to the oil spilled by the collisionbetween the supertanker Nagasaki Spirit and the containerOcean Blessing off of Belawan in 1992 The tar balls collectedfrom Langkawi Island had a higher PAH content (up to 47 times102 120583g gminus1) compared to most of samples collected from thewest and east coasts of Malaysia as reported by Zakaria et al[20] In fact the Langkawi Island is considered to be the thirdmost polluted coastal area by oil and grease inMalaysia whichmay lead to the increase in the levels of aliphatic and aromaticcompounds [21 22]

There is an increasing in the pressure on the fragileecosystem of Langkawi Island due to the tourism activi-ties that are being aggressively promoted by the Malaysiangovernment In particular the marine environment maybe receiving more and more loading from hydrocarbonpollutants from the increasing boating activities frommarineecotourism So far there is no reported impact study fromthe tourism sector for Langkawi Therefore the purpose ofthis study is to assess the concentration distribution andpotential sources of PAHs in Langkawi Island

2 Methodology

21 Study Area Water was sampled from seven stationsTelaga Harbour Kilim Jetty Porto Malai Jetty Kuah Jettyand Fish Farms I II and III in December 2010 Figure 1

Journal of Chemistry 3

Table 1 Sampling locations and associated water depths (meter)

No Station code Station name Depth Latitude (N) Longitude (E)1 S1 Kuah Jetty 3 6∘ 181015840 22910158401015840 99∘ 511015840 02010158401015840

2 S2 Kilim Jetty 1 6∘ 241015840 18410158401015840 99∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 6∘ 221015840 03610158401015840 99∘ 411015840 07010158401015840

4 S4 Porto Malai Jetty 3 6∘ 151015840 57510158401015840 99∘ 441015840 13310158401015840

5 S5 Fish Farm I 7 6∘ 131015840 12910158401015840 99∘ 461015840 07810158401015840

6 S6 Fish Farm II 8 6∘ 121015840 48010158401015840 99∘451015840 42510158401015840

7 S7 Fish Farm III 8 6∘ 161015840 39610158401015840 99∘ 481015840 15210158401015840

and Table 1 show the sampling stations with their associatedwater depths These sampling stations were chosen based ontheir unique activities Telaga Harbour is a terminal jetty forsailing boats and the yachts while Kilim Jetty and PortoMalaiJetty are both starting points for marine ecotourism activitiesincluding eagle feeding coastal bat cave exploration visitsto fish farms and trips to the limestone landscape and themangrove forests Kuah Jetty is the main terminal for ferriesfrom mainland Kuala Kedah and Penang as well as Thailandand Singapore Fish Farms I II and III are chosen to representthe many fish farms and finfish aquacultures in the coastalwater surrounding Langkawi Island that are frequented bytourists and for providing fresh seafood to the restaurants

Water samples (1 L) were collected in precleaned glassbottles at 000ndash030m from the surface They were thensealed with aluminium foil to avoid photooxidation and keptat pH asymp 20 by adding HCl (12M) to prevent degradationof the hydrocarbons [35] The samples were kept at 4∘C inice during transportation and then kept cool at minus4∘C untilanalysed During sampling several water quality parameters(temperature pH conductivity total dissolved solid andsalinity) were measured in situ using a surveyor 4a instru-ment (HACH USA)

22 Chemicals and Reagent A standard mixture of PAHsconsisting of naphthalene (Nap) 1-methylnaphthalene(1MNap) 2-methylnaphthalene (2MNap) acenaphthylene(Acy) acenaphthene (Ace) fluorene (Fl) phenanthrene(Phe) anthracene (Ant) fluoranthene (Flu) pyrene (Pyr)benz[a]anthracene (BaA) chrysene (Chr) benzo[b]fluo-ranthene (BbF) benzo[k]fluoranthene (BkF) benzo[a]py-rene (BaP) indeno[123-cd]pyrene (InP) dibenzo[ah]an-thracene (DBA) and benzo[ghi]perylene (BgP) was pur-chased from Restek Corporation USA The p-terphenyl-d14(p-Ter) (Supelco USA) was used as the surrogate internalstandard The standards were further diluted with hexane toprepare five calibration standard mixtures Dichloromethane(DCM) 119899-hexane acetone and cyclohexane which wereall of chromatographic grade in addition to HPLC-gradedistilled pentane were obtained fromMerck Germany

23 Chemical Analysis231 Sample Extraction The extraction of organic pollutantsfrom the whole seawater sample was performed according tothe US EPA method 610 [36] with slight modification andthe clean-up process following that was as described in the

EPAmethod 3630C [37] Briefly a 250mL sample was spikedwith 1mL of surrogate standard p-terphenyl-d14 (2 ng120583L)a 30mL of dichloromethane (DCM) was added The samplewas agitated in a digital shaker for 6 hrs followed by shakingin an ultrasonic bath for a further 5min to extract any organicpollutants that may have been adsorbed onto the wall of theflask The mixture was then transferred into a separationfunnel and left for 5min to separate the water from theorganic solvent layer The bottom DCM layer containing thehydrocarbons was decanted into a 250mL round-bottomedflask and the extraction was process repeated three timesThe combined extract was then allowed to mix with granuleactivated copper overnight to remove any sulphur contami-nants passed the extract through a glass column containing5 g anhydrous Na

2

SO4

(activated at 400∘C for 4 h before use)to remove any residual water and concentrated to 3mL usinga rotary evaporator Cyclohexane (10mL) was then added asan exchange solvent and the extractwas concentrated to 2mLby rotary evaporator The extract was then passed througha glass column containing 5 g activated silica gel (previouslyactivated by heating at 200∘C for 16 h before use) and 1 g ofanhydrousNa

2

SO4

The PAH fractionwas then eluted using a30mLmixture of DCM pentane (2 3 vv) and concentratedto 2mL using a rotary evaporator Hexane (10 mL) was addedas an exchange solvent [37] and it was evaporated down to2mL The extract was finally reduced to 1mL under a gentlestreamof nitrogen gas All sample extracts were kept in amberglass vials at minus4∘C until analysed within a week

The extract (1 120583L) was injected into Gas Chromatography(Agilent technologies USA) equippedwith a flame ionizationdetector (FID) [38] A fused silica TR-5MS capillary column(30mtimes 025mm id) with film thickness of 025 120583m(ThermoFisher USA) was used in the column separation High-purityhelium (999) was used as a carrier gas makeup gas andpurge gas at flow rates of 10 45 and 30mLmin respectivelyThe flow rates for the FID were 450mLmin and 45mLminfor air and hydrogen respectively The gas chromatographwas operated in splitless mode and separation was conductedwith the oven temperature programmed as follows initialsetting at 80∘C (1min hold) ramped to 180∘C at 10∘Cmin(for 2min) and finally to 320∘C at 5∘Cmin (10min hold)The injector was held at 250∘C and the FID maintainedat 350∘C Agilent Chemstation software was used to obtainthe chromatogram and for data calculations An externalstandard calibration comprising 18 PAH standards was usedto determine the identity and quantity of each componentpeak in sample chromatogram


Table 2 Concentrations of 18 PAHs in the seawater around Langkawi Island (120583gLminus1)

PAH Kuah Jetty Kilim Jetty Telaga Harbour Porto Malai Jetty Fish F I Fish F II Fish F IIINap 64 plusmn 055 31 plusmn 066 21 plusmn 012 48 plusmn 012 18 plusmn 011 25 plusmn 055 78 plusmn 016

1MNap 24 plusmn 0067 039 plusmn 0033 087 plusmn 0073 29 plusmn 015 nda nda 70 plusmn 015

2MNap 27 plusmn 0095 nda nda 064 plusmn 0069 nda nda 18 plusmn 014

Acy 13 plusmn 0063 17 plusmn 011 044 plusmn 012 14 plusmn 0023 062 plusmn 021 067 plusmn 015 41 plusmn 012

Ace 42 plusmn 016 18 plusmn 0040 049 plusmn 0022 37 plusmn 0044 046 plusmn 0040 035 plusmn 012 33 plusmn 0090

Fl 022 plusmn 0037 nda 035 plusmn 0041 nda 027 plusmn 0074 nda 046 plusmn 0028

Phe 024 plusmn 0055 055 plusmn 0018 nda 027 plusmn 0040 nda 057 plusmn 0018 037 plusmn 0055

Ant 027 plusmn 0056 088 plusmn 0056 nda 034 plusmn 0082 nda 032 plusmn 0019 nda

FIu 076 plusmn 0019 nda nda 086 plusmn 0020 14 plusmn 011 15 plusmn 0013 049 plusmn 0056

Pyr 053 plusmn 0037 28 plusmn 0075 nda 055 plusmn 00051 091 plusmn 0093 18 plusmn 002 17 plusmn 028

BaA 12 plusmn 0046 47 plusmn 025 040 plusmn 0025 13 plusmn 0050 19 plusmn 016 41 plusmn 023 33 plusmn 010

Chr 088 plusmn 0023 11 plusmn 0069 nda 11 plusmn 0050 080 plusmn 0046 40 plusmn 023 27 plusmn 0069

BbF nda 069 plusmn 0053 nda nda 095 plusmn 0053 nda 084 plusmn 0040

BkF nda 059 plusmn 011 nda nda 042 plusmn 0080 nda 079 plusmn 019

BaP 045 plusmn 0055 068 plusmn 0056 nda nda 11 plusmn 0028 098 plusmn 0028 091 plusmn 017

InP nda 029 plusmn 0031 nda nda 050 plusmn 013 096 plusmn 0031 nda

DBA 072 plusmn 0031 16 plusmn 013 065 plusmn 0034 096 plusmn 0068 43 plusmn 0094 51 plusmn 031 42 plusmn 019

BgP 25 plusmn 0035 44 plusmn 011 078 plusmn 0039 21 plusmn 016 25 plusmn 0071 49 plusmn 0035 64 plusmn 042

sumPAHs 25 plusmn 077 35 plusmn 089 61 plusmn 043 21 plusmn 087 18 plusmn 043 28 plusmn 18 46 plusmn 042

aNot detectable

The total organic carbon (TOC) in seawater contains dis-solved colloidal and particulate organic carbon [39] A fixedvolume of each water sample was acidified with concentratedHCL to get the pH down to le2 for removing the inorganiccarbons Concentrations of TOC were determined using thehigh-temperature combustion method using a CHNS (O)Analyser (Thermo Finnigan Italy) [40]

24 QAQC Replicate samples were analysed for each sta-tion to calculate the precision of measurements The methodblank containing the solvent and surrogate internal standardunderwent analysis to evaluate the contamination of solventsreagents and the glassware that was used The accuracy ofthe analytical procedure was examined through recoveryof spiked water after subtraction from the unspiked waterA known amount of the PAH mixture (in acetone) wasspiked into a deionized water sample and left for a few hoursbefore being similarly extracted and analysed The surrogateinternal standard (p-terphenyl-d14) was used throughout theanalytical procedure tomonitor the losses and contaminationduring the sample extraction and instrumental analysis Theaverage recovery of the 18 PAHs and p-terphenyl-d14 rangedfrom 70 to 120 with relative standard deviation (RSD)values beingmainly less than 14 whichmeet the acceptancecriteria of the EPA method [41] thereby indicating that themethod adopted from EPA is acceptable for the analysisof PAHs in the seawater samples The instrumental limitof detection (LOD) of individual PAHs was estimated tobe 3lowastS where S is the standard deviation of eight replicateanalyses of spiked water samples [42] The LOD was thenused to calculate the method detection limit (MDL) with thefollowing formula MDL = (LOD 120583gmLminus1 times final volume in

mLvolume extracted in L) [43] The MDL of the individ-ual PAHs using the present method ranged from 0010 to049 120583g Lminus1

The correlation coefficient (119903) is a measure of the ldquogood-ness of fitrdquo of the regression line to the data where (119903) mustbe greater than or equal to 099 Five PAHmixture standardswere run in theGC-FID on the same day of sample analysis toestimate the regression equations that were used to calculatethe concentration of individual PAHs in the samples All PAHregression equations gave a (119903) value of (ge099) which is anacceptable value according to the EPA method 8000B [41]

25 Statistical Analysis One-way ANOVA along withGames-Howell and post hoc multiple comparison tests wasused to evaluate the significance of the differences betweenthe total PAHs at the sampling stations using SPSS version 15for Windows Correlation Pearsonrsquos analysis was carried outto test the relationship between water quality parametersbetween individual PAHs in the water and between the totalPAHs and TOC The effect size test (119889 family) was used tomeasure the magnitude of difference between total PAHs atsampling stations small = 020 medium = 050 large = 080and very large ge 1 magnitude of the difference between twogroups [44]

3 Results and Discussion

31 Concentration of PAHs in Surface Water Table 2 showsthe concentrations of PAHs in the seawater from the sevensampling stations The total PAH concentrations vary from61 plusmn 043 120583g Lminus1 at the Telaga Harbour to 46 plusmn 042 120583g Lminus1 atthe Fish Farm III with a mean value of 26 plusmn 13 120583g Lminus1 These


Table 3 Reported PAHs concentrations (120583gLminus1) in the particulate and dissolved phase of surface seawater in different areas of the world

Locations 119873a Dissolved Particulate Whole water

(dissolved + particulate) Reference

Bay of Biscay France 18 82 times 10minus4ndash17 times 10minus3 34ndash11 times 103 34ndash11 times 103 [23]Leghorn Tyrrhenian Sea Italy 15 63 times 10minus2ndash31 055ndash75 061ndash11 [24]Yellow river delta 16 065minus034 66ndash68 times 102 66ndash68 times 102 [24]Jarzouna-Bizerte Tunisia (Mediterranean Sea) 17 (28ndash76) times 102 mdashb (28ndash76) times 102 [25]Redcar Jetty England 15 mdash mdash Ndcndash25 [26]Daliao River Estuary Bohai Sea China 16 014ndash17 023ndash14 037ndash31 [27]Gerlache Inlet Sea Antarctica 13 mdash mdash (53ndash94) times 10minus4 [28]Western Taiwan Strait China 15 0012minus0058 0010ndash0046 0022ndash010 [29]England and Wales 15 mdash mdash Ndcndash11 [26]Baltic Sea 15 mdash mdash 70 times 10minus5ndash17 times 10minus2 [30]Macao Harbour China 16 0092minus026 069ndash65 078ndash67 [31]Xiamen Harbour China 16 011ndash094 mdashb 011ndash094 [32]Jiulong River Estuary and Western Xiamen Sea China 16 70minus27 mdashb 70ndash27 [33]Singapore Island 16 0020minus85 mdashb 0020ndash85 [34]Langkawi Island Malaysia 18 mdash mdash 61ndash46 Present study

aNumber of PAHs bnot analyzed and cnot detectable

results reflect the PAH inputs from direct discharge of boatswith two-stroke engine and the deposition of fuel combustionof boats and vehicles which were clearly observed duringthe sampling The Kuah Jetty Kilim Jetty Porto Malai Jettyand Telaga Harbour which are popular jetties for touristsrecorded PAH concentrations of between 61 and 35 120583g Lminus1It is likely that boating activities especially when there isleakage of petroleum or the unscrupulous disposal of engineoil from boats and ferries [21] may contribute significantlyto the level of PAHs recorded in these locations The meanconcentration of total PAHs in the water samples of FishFarms I II and III were 18 28 and 46 120583g Lminus1 respectivelyFish Farm III (S7) recorded the highest concentration ofPAHs This could be due to it being located near the busystretch of water between themain island of Langkawiwith thesmaller Dayang Bunting Island and the numerous associatedport activities such as shipping and boating which couldcontribute to PAHs in the sediment and water Leachingprocesses and biological activity in sediment may return asmall amount of PAHs to the water column [6] McIntosh etal [45] also reported that boat engines are one of the mainsources of PAHs in fish farms

The total PAH levels at the jetties harbour and fishfarms are significantly higher than the maximum admissibleconcentrations of the European Union of 020120583g Lminus1 and theEnvironmental Quality Criteria of the United States sumPAHs= 0030 120583g Lminus1 for protection of human consumers of aquaticlife [46] In addition water with total PAH concentrationsabove 10 120583g Lminus1 can be ranked as heavily contaminated byPAH pollutants [23] The total concentration of PAHs inwater at Telaga Harbour station (61120583g Lminus1) was lower than10 120583g Lminus1 but it was higher than the maximum admissibleconcentrations In asmuch as the jetties and fish farm stationsrecorded concentrations of more than 10 120583g Lminus1 (Table 2)

certain organisms especially the fish in these locations arelikely to have been exposed to rather high levels of PAHsduring their life time

The most frequently detected PAHs in the water sam-ples were naphthalene (16) acenaphthylene (6) acen-aphthene (8) benzo[a]anthracene (9) dibenzo[ah]anthracene (10) and benzo[ghi]perylene (13) The meanconcentration of individual PAHs including carcinogenicand noncarcinogenic PAHs in all samples ranged from022 to 11 120583g Lminus1 These are either within or higher than thatof the Annual Average Environmental Quality Standards(AA-EQS) of European Water Framework Directive (WFD)for individual PAHs which state that the safe range for PAHsis from 20 times 10minus2 to 24 120583g Lminus1 [47]Themean concentrationsof seven carcinogenic PAHs with high molecular weight(BaA Chr BbF BkF BaP DBA and InP) ranged from 044to 34 120583g Lminus1 with a mean of 15 120583g Lminus1 accounting for 36 oftotal PAHs in all water samples These results are higher thanthe safe limits of the EPA National Recommended WaterQuality Criteria for the protection of aquatic life and humanhealth (0020 120583g Lminus1) [46] Benzo[a]pyrene (BaA) the mostcarcinogenic pollutant of all PAHs [48] was detected in allfish farms samples with concentrations ranging from 091 to11 120583g Lminus1 (a mean of 10 120583g Lminus1) The levels were higher thanthose of the EPA National Recommended Water QualityCriteria for the protection of aquatic life (0010 120583g Lminus1) [46]which could have an adverse ecological effect in these areasparticularly for the fish

As shown inTable 3 the PAHconcentrations in thewholesurface seawater of Langkawi Island were approximately 1order of magnitude lower than water from Bay of BiscayFrance [23] and about 1 to 2 orders of magnitude lower thanwater from Jarzouna Coast Bizerte Tunisia [25] and in theYellowRiver Delta China [24] Additionally they were nearly


Table 4 Correlation coefficient between individual PAH concentrations

Nap M1Nap M2Nap Acy Ace Fl Phe Ant FIu Pyr BaA Chr BbF BkF BaP InP DBA BgP

Nap 11MNap 090lowastlowast 12MNap 088lowastlowast 066 1Acy 082lowast 091lowastlowast 052 1Ace 087lowast 067 083lowast 056 1Fl 034 054 037 041 003 1Phe 022 008 000 035 014 minus056 1Ant minus011 minus032 minus018 minus004 013 minus077lowast 069 1FIu minus015 minus021 minus005 minus028 minus018 minus024 004 minus027 1Pyr 002 minus001 minus020 039 minus010 minus036 082lowast 068 minus007 1BaA 000 minus002 minus023 036 minus017 minus037 086lowast 060 005 098lowastlowast 1Chr minus011 minus019 minus028 021 minus009 minus050 076lowast 087lowast minus032 092lowastlowast 086lowast 1BbF 004 020 minus011 047 minus014 036 minus003 minus004 minus003 050 042 033 1BkF 029 045 004 074 005 037 022 008 minus026 064 056 048 092lowastlowast 1BaP minus005 minus004 minus006 023 minus032 010 032 minus004 051 060 065 031 067 057 1InP minus057 minus059 minus053 minus040 minus067 minus046 041 017 066 044 056 029 006 minus009 065 1DBA minus010 004 minus022 020 minus044 010 030 minus026 064 044 056 009 048 040 088lowastlowast 072 1BgP 044 047 018 073 011 004 074 020 012 079lowast 084lowast 053 047 068 069 032 067 1lowastlowastCorrelation is significant at the 001 level (2 tailed) lowastCorrelation is significant at the 005 level (2 tailed)

similar to the levels presented in the dissolvedwater of JiulongRiver Estuary andWestern Xiamen Sea China [33] and waterfrom the Jetty of Redcar England [26]

However the total PAHs of Langkawi water were approx-imately 1 to 2 orders of magnitude higher than those detectedin some of the nearby water systems such as the dissolvedwater of Singapore Island [34] Daliao River Estuary in BohaiSea China [27] and Macao Harbour of China [31] (Table 4)Furthermore they were 3 to 4 orders of magnitude higherthan those found in Gerlache Inlet Sea Antarctica [28] andBaltic Sea [30] The 2006 annual report of the MalaysianDepartment of Environment ranked Langkawi Island thirdin terms of areas being polluted by oil and grease among the15 monitoring stations in Peninsula Malaysia that exceededthe water quality standard by 80 [21]

There was a significant difference (ANOVA 119875 lt 005)in the mean concentrations of total PAHs in the water fromthe fish farms the jetties and the Telaga Harbour stations(119875 = 001 119875 = 0001 resp) However there was no sig-nificant difference in the total PAHs between the fish farmsand jetties (119875 = 082) Telaga Harbour is only used as aterminal point for yachts with a lot less boating activitiesthan either the jetties or the fish farms Thus these resultssuggest that the PAH inputs in these stations could comefrom the direct discharge of petroleum products as well asthe dry and wet deposition of fuel combustion To calculatethe consistent value of differences between these stations theeffect size (119889 family) which measures the magnitude of thedifferences of mean concentrations of total PAHs betweensites was estimated for the fish farms jetties and harbourstations The 119889 values for the fish farms were 037 orders ofmagnitude higher than the seawater from the jetties and 21

orders of magnitude higher than the seawater of the harbourstation However the jetties were 35 orders of magnitudehigher than the harbour station which indicates that the fishfarms and jetties have higher orders of magnitude comparedto the harbour station

32 PAH Composition The composition pattern of PAHsby ring size for the water samples around Langkawi Islandis shown in Figure 2 The high-molecular-weight PAHs offour rings (FIu Pyr BaA and Chr) five rings (BbF BkFBaP and DBA) and six rings (InP BgP) generally accountfor 28 15 and 14 of the total PAH concentrationsrespectively The water samples of Kilim Jetty and FishFarms I and II were dominated by HMW-PAHs (4ndash6 rings)representing the range of 76ndash84 which are likely derivedfrom anthropogenic activities [49] such as incomplete fuelcombustion of the boats ships and vehicle engines Howeverthe lower-molecular-weight PAHs of two rings (1MNap2MNap and Nap) and three rings (Acy Ace Fl Phe andAnt) made up 26 and 17 of the total PAH concentrationsrespectively LMW-PAHs (2-3 rings) were the most abundantcomponents in water samples from Kuah Porto Malai Jettiesand Telaga Harbour with a range between 67 and 72 Theresults suggest a relatively recent local PAHs source whichentered into the seawater due to the inefficient two-strokeoutboard engines of most boats in Langkawi Island thatusually involve the discharge to the water of about 20 of fuelwithout burning [50] The water sample from Fish Farm IIIrepresented an approximately equal content of HMW-PAHs(46) and LMW-PAHs (54) (Figure 3) which probablyreflects both anthropogenic activities and recent local PAHsources due to the tourism boats and ships activities of


Kuah

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Kilim

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

60

50

40

30

20

10

0

Com

posit

ion

()

2 rings3 rings4 rings

5 rings6 rings

Figure 2 Composition pattern () of PAHs by the number of rings2-3-4-5- and 6-ring PAH

0

10

20

30

40

50

60

Kuah

Jetty

Kilim

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

sumLMWsumHMWsumTPAHs

Con

cent

ratio

n (120583

gLminus1)

Figure 3 The total of HMW LMW and PAHs concentrations(120583g Lminus1) in seawater from different sampling stations

Langkawi port that are located in front of this farm Theresults of the paired samples 119905-test of LMW to HMW-PAHs show no significant difference between the LMW- andHMW-PAHs in the water of Langkawi Island (119875 = 054)suggesting the importance of both LMW- and HMW-PAHinputs in the water of Langkawi

For individual PAHs the highest concentrationmeasuredin the seawater samples was chrysene (11120583g Lminus1) at KilimJetty This high concentration of chrysene is perhaps dueto its very low solubility in water that permits it to be

adsorbed onto the surface of suspended matter and its highresistance to degradation The study reported by Wang etal [51] found that the level of chrysene did not significantlychange after 12 years of oil spill which reflects the resistanceof chrysene in aquatic environment and its high increasecompared to others Benzo[ghi]perylene (BgP) a compoundthat has the fingerprint of a combustion engine and whichis more abundant in soot [10] was found to have the secondhighest mean concentration for individual PAHs (34120583g Lminus1)in the water samples of Langkawi Island A study by Omaret al [49] also supported the phenomenon of BgP emissioncoming from engines The study mentioned that the highestabundance of BgP was recorded in the urban aerosols ofKuala LumpurMalaysia and that incomplete fuel combustionwas its source Therefore the amount of BgP measuredin this study was most probably related to the incompletefuel combustion of the boats and vehicle engines that wereextensively used in the Island

The total organic carbon (TOC) of seawater representsthe content of dissolved and particulate organic matter (incarbonaceous form) The mean concentration of TOC inseawater for all stations studied ranged from 0030 to 18A positive significant correlation between the TOC contentand total concentrations of HMW-PAHs (1199032 = 083 119875 lt005) in the whole seawater was observed Due to theirhigh hydrophobic nature PAHs tend to get adsorbed ontothe surface of suspended matter Such a correlation is anindication that the high molecular weight of PAHs deter-mined from the seawater samples is from secondary sourcessuch as the atmospheric deposition of soot particles that arecharacterized byHMW-PAHs [52] which are probably due tothe fuel combustion of tourism boats ships fishing ships andvehicles This correlation is similar to that found in DaliaoRiver Estuary water of Liaodong Bay Bohai Sea China [27]

33 Identification of PAH Sources The difficulty in identi-fying the PAH sources relies on many factors The possiblecoexistence ofmany origins of pollutants and the transforma-tion process that PAHs can undergo before or after depositionto sediment [53] The correlation factor values approach anddiagnostic ratios can be used to identify the possible sourcesof PAHs The correlation factor value is a statistical approachthat is used depending on the fact that each pollution sourceproduces a characteristic PAH pattern which means thatit can be applied to assess the linear dependence of theindividual PAHs Therefore the correlation factor betweenthe water concentrations for all the individual PAHs cangive an idea of whether they all originate from the sameor different sources Table 4 shows the correlation betweenthe individual PAHs There is a positive correlation amongthe LMW PAHs (052 lt 1199032 lt 091) except Fl Phe Antand among the HMW PAHs (006 lt 1199032 lt 098) exceptFlu and BkF The weaker correlations between LMW PAHscompared to the HMW PAHs support that their sourcesare dissimilar and imply that there are probably at least twosources of PAHs petrogenic andpyrogenic Correspondinglythese results were in agreement with the findings by Itoh etal [54] The strongest relationships among the LMW PAHs


Table 5 Diagnostic PAH ratios in seawater and their possiblesources

Station BaABaA + Chra PheAntb LMWHMWc

Kuah Jetty 057 087 25Kilim Jetty 031 062 032Telaga Harbour 10 NCd 23Porto Malai Jetty 055 080 21Fish F I 070 NCd 021Fish F II 050 18 019Fish F III 055 NCd 12Mean 060 11 13Petrogenic sources lt020 gt15 gt1Pyrogenic sources gt035 lt10 lt1

abenzo[a]anthracene to benzo[a]anthracene plus chrysene ratiobphenanthrene to anthracene ratio clower-molecular-weight PAHs to high-molecular-weight PAHs ratio dnot calculated due to the concentration ofone of ratio variables being undetectable

was between M1Nap and Acy (1199032 = 091 119875 lt 001) whileamong HMW PAHs it was between Pyr with BaA (1199032 = 098119875 lt 001) The significant correlation between the LMWPAHs and HMWPAHs was between Phe and Pyr (1199032 = 082)BaA (1199032 = 086) and Chr (1199032 = 076) and between Ant andChr (1199032 = 087) Thus the strong correlation of these PAHsmay suggest that they originated from a common source thatis widely distributed in the investigated location

As mentioned above there were at least two sources ofPAHs To elucidate the details of PAH sources in the watersamples diagnostic ratios were applied which are a usefultool to distinguish the petrogenic and pyrogenic sourcesof PAH in different media of the environment dependingon their physical chemical properties and stability againstphotolysis [55] The petrogenic source is a result of the directinput from petroleum and its products while the pyrogenicsources are a result of incomplete combustion of fossil fuels(ie exhausts of vehicles) [10 11]

Various PAH congener ratios that display the best poten-tial to distinguish between the petrogenic and pyrogenicsources and the most consistently quantifiable compoundsin the majority of these samples were selected as indicationfor example the ratios of (PheAnt) and (BaABaA + Chr)[15 55] Table 5 shows the diagnostic ratios of some PAHcompounds The ratios of PheAnt which are lower than10 are seen as characteristic of the combustion processeswhereas values higher than 10 indicate petroleum input ordiagenetic [56] The ratios of PheAnt found in this studywhich were between 062 and 18 (mean 11) suggest thatthe PAHs are from combustion sources Possible contributingsources in the Island are from incomplete fuel combustion ofthe boats and vehicle engines

In addition the ratio (BaABaA + Chr) of lt020 usuallyimplies petrogenic origin 020ndash035 indicates mixed petro-genic and pyrogenic origin while gt035 indicates pyrogenicorigin [55] Hence the values of this ratio from the seawatersamples ranged from 052 to 10 (mean = 060) (Table 5)Theywere above 035 for all samples with the exception of thewater

samples fromKilim Station (ratio = 034) whichmight reflectmixed inputs from the direct discharge of two-stroke engineboats and the deposition of fuel combustion of boats andvehicles

The calculated ratios for the LMWHMW for all stationswere between 032 and 25 (mean 13) which suggests thatthe sources of PAHs were both pyrogenic (ratio of lt1) andpetrogenic (ratio ofgt1) [53] Some stations such asKuah Jettyand Telaga Harbour derived their PAHs from both sources(Table 5)

However this generally suggests that PAHs can be largelyattributed to combustionwith a contribution frompetrogenicsources Distinguishing the sources of PAHs by the diagnosticratios chosen could reveal the inputs of the pyrogenic mate-rial Moreover the diminution of the level of high-molecular-weight PAHs compared to low-molecular-weight PAHs insome stations can also reflect a lesser amount contributed bypetrogenic sources due to the direct discharge of unburnedfuel of the two-stroke engine boats

34 Correlation between the PAH Levels and the Physicochem-ical Characteristics of Water Physicochemical properties ofthe sea water (TDS temperature conductivity pH salinityand dissolved oxygen) and their relationship to the PAHconcentrations were measured (see Supplementary MaterialS1 available online at httpdxdoiorg1011552013975781)The mean temperature of the seawater for all stations studiedranged from 286 to 292∘C with a conductivity 49 to51 120583 S cmminus1 total dissolved solid (TDS) 298 to 305mg Lminus1pH from 73 to 80 salinity from 302 to 303 and dissolvedoxygen from 40 to 58mg Lminus1 Generally these levels ofwater parameters in the sampling stations were in the goodrange for water quality guidelines of the European WaterFramework Directive (WFD) The dissolved oxygen levelsin the seawater surrounding the fish farms were lower thanthe equilibrium value of 64mg Lminus1 [57] but were sufficientlyhigh for fish aquaculture activities These observations indi-cate that the seawater bodies around Langkawi Island arewithin the normal range Moreover possible relationshipanalysis among water quality parameters was carried out Asignificant positive correlation was noticed between TDS andconductivity (1199032 = 097 119875 lt 0001) and between TDS andsalinity (1199032 = 061) This correlation reflects that seawater hasthe same type and nature of dissolved cations and anionsThere is a good positive correlation between temperatureand LMW-PAHs (1199032 = 074) suggesting that temperaturehas an effect on the aqueous solubility of PAHs as highertemperatures cause more PAHs to be soluble in the water [6]

4 Conclusion

The concentrations of PAHs in water samples collected fromjetties and the tourism fish farms were approximately two tothree orders of magnitude higher than those in the harbourThis implies that all the samples exceeded the maximumadmissible concentrations of PAHs (020120583g Lminus1) accordingto the water standard of the European Union and maycause toxicity to certain exposed organisms The significant


correlation between TOC and the high molecular weight ofPAHs (1199032 = 083 119875 lt 005) indicate the importance ofsecondary sources of PAHs (eg combustion-derived PAH)the diagnostic PAH ratios indicate that PAHs can be largelyattributed to pyrogenic (pyrolytic) sources with a lesseramount contributed by petrogenic source which is possiblydue to the nonburning fuel discharge of the inefficient two-stroke engines of Langkawi boats Some stations displayedmixed sources

Acknowledgments

This work was financially supported by Grants nos UKM-ST-06-FRGS0245-2010 and UKM-OUP-PLW-11-482010 andGrant UKM-Arus Perdana on Langkawi Geopark Herewithall the authors declare and acknowledge that this paper isoriginal and has been written by the stated authors who areall aware of its content and approve its submissionThis paperhas not been published previously nor is under considerationfor publication elsewhere No conflict of interests exists

References

[1] LADA Langkawi Development Authority Report 2011[2] N Samat ldquoAssessing land use land cover changes in Langkawi

island towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 pp 48ndash57 2010

[3] M C Wei and J F Jen ldquoDetermination of polycyclic aro-matic hydrocarbons in aqueous samples by microwave assistedheadspace solid-phase microextraction and gas chromatogra-phyflame ionization detectionrdquoTalanta vol 72 no 4 pp 1269ndash1274 2007

[4] A Katsoyiannis A J Sweetman and K C Jones ldquoPAHmolec-ular diagnostic ratios applied to atmospheric sources a criticalevaluation using two decades of source inventory and airconcentration data from the UKrdquo Environmental Science andTechnology vol 45 no 20 pp 8897ndash8906 2011

[5] E Martinez M Gros S Lacorte and D Barcelo ldquoSimplifiedprocedures for the analysis of polycyclic aromatic hydrocarbonsin water sediments andmusselsrdquo Journal of Chromatography Avol 1047 no 2 pp 181ndash188 2004

[6] J M Neff Polycyclic Aromatic Hydrocarbons in the AquaticEnvironment Sources Fates and Biological Effects AppliedScience Publishers 1979

[7] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[8] M Szewczynska M Posniak and E Dobrzynska ldquoStudy onindividual PAHs content in ultrafine particles from solid frac-tions of diesel and biodiesel exhaust fumesrdquo Journal of Chem-istry vol 2013 Article ID 528471 10 pages 2013

[9] M W Ashraf S I H Taqvi A R Solangi and U A QureshildquoDistribution and risk assessment of polycyclic aromatic hydro-carbons in vegetables grown in Pakistanrdquo Journal of Chemistryvol 2013 Article ID 873959 5 pages 2013

[10] R Boonyatumanond M Murakami G Wattayakorn A Togoand H Takada ldquoSources of polycyclic aromatic hydrocarbons(PAHs) in street dust in a tropical Asian mega-city Bangkok

Thailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

[11] E Y Zeng and C L Vista ldquoOrganic pollutants in the coastalenvironment off San Diego California 1 Source identificationand assessment by compositional indices of polycyclic aromatichydrocarbonsrdquo Environmental Toxicology and Chemistry vol16 no 2 pp 179ndash188 1997

[12] E Caylak ldquoHealth risk assessment for trace metals polycyclicaromatic hydrocarbons and trihalomethanes in drinking waterof Cankiri Turkeyrdquo Journal of Chemistry vol 9 no 4 pp 1976ndash1991 2012

[13] NRC National ReSearch Council Oil in the Sea III InputsFates and Effectsed National Academies Press WashingtonDC USA 2003

[14] A Katsoyiannis E Terzi and Q Y Cai ldquoOn the use of PAHmolecular diagnostic ratios in sewage sludge for the under-standing of the PAH sources Is this use appropriaterdquo Chemo-sphere vol 69 no 8 pp 1337ndash1339 2007

[15] Z Zhang J Huang G Yu and H Hong ldquoOccurrence of PAHsPCBs and organochlorine pesticides in the Tonghui River ofBeijing Chinardquo Environmental Pollution vol 130 no 2 pp249ndash261 2004

[16] A T Law and Y S Hii ldquoStatus impacts and mitigation ofhydrocarbon pollution in the Malaysian seasrdquo Aquatic Ecosys-tem Health and Management vol 9 no 2 pp 147ndash158 2006

[17] M S Ibrahim Z Din andN Abdullah ldquoExtent of hydrocarbonpollution in Langkawi A study on PAH pollution after themajor oil spill in 1992rdquoMalaysian Journal of Analytical Sciencesvol 2 pp 115ndash122 1996

[18] M P Abdullah ldquoHydrocarbon pollution in the sediment ofsome Malaysian coastal areasrdquo Environmental Monitoring andAssessment vol 44 no 1ndash3 pp 443ndash454 1997

[19] P L Bishop Marine Pollution and Its Control McGraw-HillBook Company New York NY USA 1983

[20] M P Zakaria T Okuda and H Takada ldquoPolycyclic aromatichydrocarbon (PAHs) and hopanes in stranded tar-balls on thecoasts of Peninsular Malaysia applications of biomarkers foridentifying sources of oil pollutionrdquo Marine Pollution Bulletinvol 42 no 12 pp 1357ndash1366 2001

[21] DOEMalaysia Environmental Quality Report 2005 2006[22] S L Tong S H Goh A R Abdulah N M Tahir and C

W Wang ldquoASEAN marine water quality criteria for oil andgreaserdquo Marine Environment Division Water quality man-agement Bureau Pollution control department ASEAN-CANADA Cooperative programme on Marine Science 1999

[23] J Tronczynski C Munschy K Heas-Moisan et al ldquoContami-nation of the Bay of Biscay by polycyclic aromatic hydrocarbons(PAHs) following the TV ldquoErikardquo oil spillrdquo Aquatic LivingResources vol 17 no 3 pp 243ndash259 2004

[24] L Wang Z Yang J Niu and J Wang ldquoCharacterizationecological risk assessment and source diagnostics of polycyclicaromatic hydrocarbons in water column of the Yellow RiverDelta one of the most plenty biodiversity zones in the worldrdquoJournal of Hazardous Materials vol 169 no 1ndash3 pp 460ndash4652009

[25] I Zrafi-Nouira Z Khedir-Ghenim R Bahri I Cheraeif MRouabhia and D Saidane-Mosbahi ldquoHydrocarbons in seawa-ter and water extract of Jarzouna-Bizerte coastal of Tunisia(Mediterranean Sea) petroleum origin investigation aroundrefinery rejection placerdquoWater Air and Soil Pollution vol 202no 1ndash4 pp 19ndash31 2009


[26] R J Law V J Dawes R J Woodhead and P MatthiessenldquoPolycyclic aromatic hydrocarbons (PAH) in seawater aroundEngland and Walesrdquo Marine Pollution Bulletin vol 34 no 5pp 306ndash322 1997

[27] B Men M He L Tan C Lin and X Quan ldquoDistributions ofpolycyclic aromatic hydrocarbons in the Daliao River Estuaryof Liaodong Bay Bohai Sea (China)rdquoMarine Pollution Bulletinvol 58 no 6 pp 818ndash826 2009

[28] A M Stortini T Martellini M Del Bubba L Lepri GCapodaglio and A Cincinelli ldquon-Alkanes PAHs and surfac-tants in the sea surface microlayer and sea water samples of theGerlache Inlet sea (Antarctica)rdquoMicrochemical Journal vol 92no 1 pp 37ndash43 2009

[29] Y L Wu X H Wang Y Y Li and H S Hong ldquoOccurrence ofpolycyclic aromatic hydrocarbons (PAHs) in seawater from theWestern Taiwan Strait Chinardquo Marine Pollution Bulletin vol63 no 5-12 pp 459ndash463 2011

[30] G Witt ldquoOccurrence and transport of polycyclic aromatichydrocarbons in the water bodies of the Baltic Seardquo MarineChemistry vol 79 no 2 pp 49ndash66 2002

[31] X Luo B Mai Q Yang J Fu G Sheng and Z WangldquoPolycyclic aromatic hydrocarbons (PAHs) and organochlorinepesticides in water columns from the Pearl River and theMacao harbor in the Pearl River Delta in South ChinardquoMarinePollution Bulletin vol 48 no 11-12 pp 1102ndash1115 2004

[32] J L Zhou H Hong Z Zhang K Maskaoui and W ChenldquoMulti-phase distribution of organicmicropollutants inXiamenHarbour Chinardquo Water Research vol 34 no 7 pp 2132ndash21502000

[33] K Maskaoui J L Zhou H S Hong and Z L Zhang ldquoCon-tamination by polycyclic aromatic hydrocarbons in the JiulongRiver Estuary andWestern Xiamen Sea Chinardquo EnvironmentalPollution vol 118 no 1 pp 109ndash122 2002

[34] K K Chee M K Wong and H K Lee ldquoDetermination ofpolycyclic aromatic hydrocarbons in sea water using solid-phase microextractionrdquo International Journal of EnvironmentalStudies vol 56 no 5 pp 689ndash701 1999

[35] S K Kim D S Lee W J Shim U H Yim and Y S ShinldquoInterrelationship of pyrogenic polycyclic aromatic hydrocar-bon (PAH) contamination in different environmental mediardquoSensors vol 9 no 12 pp 9582ndash9602 2009

[36] USEPA EPA-Method 610 Polynuclear Aromatic Hydrocarbons2010

[37] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[38] USEPA EPA-method 8100 Polycyclic Aromatic Hydrocarbons

1986[39] L Guo T Tanaka D Wang N Tanaka and A Murata ldquoDistri-

butions speciation and stable isotope composition of organicmatter in the southeastern Bering Seardquo Marine Chemistry vol91 no 1-4 pp 211ndash226 2004

[40] Guo Laodong C H Coleman Jnr and P H Santschi ldquoThedistribution of colloidal and dissolved organic carbon in theGulf of MexicordquoMarine Chemistry vol 45 no 1-2 pp 105ndash1191994

[41] USEPA EPA Method 8000B Determinative ChromatographicSeparations 1996

[42] R K Smith Handbook of Environmental Analysis Geniumpublishing 1999

[43] J RM Ross andD R Oros ldquoPolycyclic aromatic hydrocarbonsin the San Francisco Estuary water column sources spatialdistributions and temporal trends (1993ndash2001)rdquo Chemospherevol 57 no 8 pp 909ndash920 2004

[44] J Cohen Statistical Power Taylor and Francis Group 2ndedition 1988

[45] A D McIntosh L Webster P J Hayes and C F Moffat ldquoThesource and fate of polycyclic aromatic hydrocarbons (PAHs) insediment and water from Loch Levenrdquo FRSMarine LaboratoryAberdeen Report 02 2 2002

[46] EPA Environmental Protection Agency United States NationalRecommended Water Quality Criteria 2009

[47] F Werres P Balsaa and T C Schmidt ldquoTotal concentrationanalysis of polycylic aromatic hydrocarbons in aqueous sampleswith high suspended particulate matter contentrdquo Journal ofChromatography A vol 1216 no 12 pp 2235ndash2240 2009

[48] H S Wang P Liang Y Kang et al ldquoEnrichment of polycyclicaromatic hydrocarbons (PAHs) in mariculture sediments ofHong Kongrdquo Environmental Pollution vol 158 no 10 pp 3298ndash3308 2010

[49] N Y M J Omar M R B Abas N A Rahman N M TahirA I Rushdi and B R T Simoneit ldquoLevels and distributionsof organic source tracers in air and roadside dust particles ofKuala Lumpur Malaysiardquo Environmental Geology vol 52 no 8pp 1485ndash1500 2007

[50] T D Mosisch and A H Arthington ldquoPolycyclic aromatichydrocarbon residues in the sediments of a dune lake as a resultof power boatingrdquo Lakes and Reservoirs vol 6 no 1 pp 21ndash322001

[51] ZWangM Fingas andG Sergy ldquoChemical characterization ofcrude oil residues from an arctic beach byGCMS andGCFIDrdquoEnvironmental Science and Technology vol 29 no 10 pp 2622ndash2631 1995

[52] C H Vane I Harrison and A W Kim ldquoPolycyclic aromatichydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) insediments from the Mersey Estuary UKrdquo Science of the TotalEnvironment vol 374 no 1 pp 112ndash126 2007

[53] H H Soclo P Garrigues and M Ewald ldquoOrigin of polycyclicaromatic hydrocarbons (PAHs) in coastal marine sedimentscase studies in Cotonou (Benin) and Aquitaine (France) AreasrdquoMarine Pollution Bulletin vol 40 no 5 pp 387ndash396 2000

[54] N Itoh S Tamamura T Sato and M Kumagai ldquoElucidationof polycyclic aromatic hydrocarbon sources in the sinkingparticles in Lake Biwa Japanrdquo Limnology vol 11 no 3 pp 241ndash250 2010

[55] M B Yunker R W Macdonald R Vingarzan R H MitchellD Goyette and S Sylvestre ldquoPAHs in the Fraser River basin acritical appraisal of PAH ratios as indicators of PAH source andcompositionrdquoOrganic Geochemistry vol 33 no 4 pp 489ndash5152002

[56] P Baumard H Budzinski P Garrigues J C Sorbe T Burgeotand J Bellocq ldquoConcentrations of PAHs (polycyclic aromatichydrocarbons) in various marine organisms in relation to thosein sediments and to trophic levelrdquoMarine Pollution Bulletin vol36 no 12 pp 951ndash960 1998

[57] K Booij M T Hillebrand R F Nolting and J V OoijenldquoNutrients trace metals and organic contaminants in BantenBay Indonesiardquo Marine Pollution Bulletin vol 42 no 11 pp1187ndash1190 2001

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


99∘40998400E 99∘45998400E 99∘50998400E 99∘55998400E

06∘25998400N

06∘20998400N

06∘15998400N

06∘10998400N

06∘25998400N

06∘20998400N

06∘15998400N

06∘10998400N

99∘40998400E 99∘45998400E 99∘50998400E 99∘55998400E

S2

S3

S1

S7S4

S5S6

S1 Sampling stationN0 3

(km)

S Kilim

Pulau Langkawi

TelagaHarbour

Kuah

LangkawiPort

P Timun

P Ular

PulanDayang Bunting

S Melaka

N

0 80(km)

100∘ 101∘ 102∘ 103∘ 104∘

8∘

7∘

6∘

5∘

4∘

3∘

2∘

8∘

7∘

6∘

5∘

4∘

3∘

2∘

100∘ 101∘ 102∘ 103∘ 104∘

Thailand

Kedah

Lang

kaw

iisl

and

PulauPinang

Malaysia

SouthChina

Sea

Straits of Malacca

Figure 1 Map showing the seven sampling stations (S1ndashS7) around Langkawi Island Malaysia

Sources of PAHs can be either petrogenic from petro-leum-related activities or pyrogenic (pyrolytic) from theincomplete combustion of diesel fuel and engine oil [8]wood coal biomass of forest grass fires waste incineratorsand fossil fuels that are used in industrial operations andpower plants [9ndash12] PAHs are also widely used in com-mercial products such as intermediaries in pharmaceuticalsagricultural products photographic products thermosettingplastics and lubricating materials

In the marine environment the pollution from PAHscan result from natural seepage or land-based sources fromriver discharges urban runoff refineries and other industrialwastewater [6] or from sea-based sources such as two-strokevessel discharge nontank vessel spills operational dischargegross atmospheric deposition and aircraft dumping [13]These possible sources of PAHs can be differentiated bytheir respective diagnostic ratios [14] A phenanthrene-to-anthracene ratio (PheAnt) of gt15 indicates that the PAHsare petrogenic whereas a ratio of lt10 shows that they arepyrolytic in origin [15]

Few studies have been done on the concentration ofhydrocarbons in the water and the sediment of LangkawiIsland Law andHii [16] reported that the hydrocarbon (poly-cyclic compounds and PAHs) concentrations in the seawaterat Pulau Payar to the south of Langkawi Island ranged from32 to 46 120583g Lminus1 which is lower than the contamination levelof hydrocarbons (50 120583g Lminus1) in the tropical sea [16] The totalPAHs in sediments collected from Langkawi Island after anoil spill accident ranged from 34 to 27 times 102 120583g kgminus1 [17]

Abdullah [18] reported a high level of total hydrocarbons inthe sediments of Langkawi Island up to 85 times 102mgkgminus1which is higher than the safety level (10 times 102mgkgminus1) [19]The high level was attributed to the oil spilled by the collisionbetween the supertanker Nagasaki Spirit and the containerOcean Blessing off of Belawan in 1992 The tar balls collectedfrom Langkawi Island had a higher PAH content (up to 47 times102 120583g gminus1) compared to most of samples collected from thewest and east coasts of Malaysia as reported by Zakaria et al[20] In fact the Langkawi Island is considered to be the thirdmost polluted coastal area by oil and grease inMalaysia whichmay lead to the increase in the levels of aliphatic and aromaticcompounds [21 22]

There is an increasing in the pressure on the fragileecosystem of Langkawi Island due to the tourism activi-ties that are being aggressively promoted by the Malaysiangovernment In particular the marine environment maybe receiving more and more loading from hydrocarbonpollutants from the increasing boating activities frommarineecotourism So far there is no reported impact study fromthe tourism sector for Langkawi Therefore the purpose ofthis study is to assess the concentration distribution andpotential sources of PAHs in Langkawi Island

2 Methodology

21 Study Area Water was sampled from seven stationsTelaga Harbour Kilim Jetty Porto Malai Jetty Kuah Jettyand Fish Farms I II and III in December 2010 Figure 1




2 S2 Kilim Jetty 1 6∘ 241015840 18410158401015840 99∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 6∘ 221015840 03610158401015840 99∘ 411015840 07010158401015840


5 S5 Fish Farm I 7 6∘ 131015840 12910158401015840 99∘ 461015840 07810158401015840

6 S6 Fish Farm II 8 6∘ 121015840 48010158401015840 99∘451015840 42510158401015840

7 S7 Fish Farm III 8 6∘ 161015840 39610158401015840 99∘ 481015840 15210158401015840






2

SO4


2

SO4
























aNot detectable





























Kuah

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Kilim

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

60

50

40

30

20

10

0

Com

posit

ion

()


5 rings6 rings


0

10

20

30

40

50

60

Kuah

Jetty

Kilim

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I


Con

cent

ratio

n (120583

gLminus1)




















4 Conclusion




Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




2 S2 Kilim Jetty 1 6∘ 241015840 18410158401015840 99∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 6∘ 221015840 03610158401015840 99∘ 411015840 07010158401015840


5 S5 Fish Farm I 7 6∘ 131015840 12910158401015840 99∘ 461015840 07810158401015840

6 S6 Fish Farm II 8 6∘ 121015840 48010158401015840 99∘451015840 42510158401015840

7 S7 Fish Farm III 8 6∘ 161015840 39610158401015840 99∘ 481015840 15210158401015840






2

SO4


2

SO4
























aNot detectable





























Kuah

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Kilim

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

60

50

40

30

20

10

0

Com

posit

ion

()


5 rings6 rings


0

10

20

30

40

50

60

Kuah

Jetty

Kilim

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I


Con

cent

ratio

n (120583

gLminus1)




















4 Conclusion




Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






















aNot detectable





























Kuah

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Kilim

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

60

50

40

30

20

10

0

Com

posit

ion

()


5 rings6 rings


0

10

20

30

40

50

60

Kuah

Jetty

Kilim

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I


Con

cent

ratio

n (120583

gLminus1)




















4 Conclusion




Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






















Kuah

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Kilim

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I

60

50

40

30

20

10

0

Com

posit

ion

()


5 rings6 rings


0

10

20

30

40

50

60

Kuah

Jetty

Kilim

Jetty

Tela

ga H

arbo

ur

Port

o M

alai

Jetty

Fish

Far

m I

Fish

Far

m II

Fish

Far

m II

I


Con

cent

ratio

n (120583

gLminus1)




















4 Conclusion




Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














4 Conclusion




Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Acknowledgments


References





































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of











































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

research article concentrations and sources of polycyclic...

Documents