14
Hindawi Publishing Corporation e Scientific World Journal Volume 2013, Article ID 858309, 13 pages http://dx.doi.org/10.1155/2013/858309 Research Article Assessing the Ecological Risk of Polycyclic Aromatic Hydrocarbons in Sediments at Langkawi Island, Malaysia Essam Nasher, 1 Lee Yook Heng, 1,2 Zuriati Zakaria, 3 and Salmijah Surif 1 1 Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia 2 South-East Asia Disaster Prevention Research Institute (SEADPRI), Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia 3 Environment Engineering and Green Technology, Malaysia Japan International Institute of Technology, University Technologi Malaysia, 54100 Kuala Lumpur, Selangor, Malaysia Correspondence should be addressed to Essam Nasher; essam [email protected] Received 8 July 2013; Accepted 14 August 2013 Academic Editors: H. A. Alegria, A. C. Ruiz Fern´ andez, and O. Wurl Copyright © 2013 Essam Nasher et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Tourism-related activities such as the heavy use of boats for transportation are a significant source of petroleum hydrocarbons that may harm the ecosystem of Langkawi Island. e contamination and toxicity levels of polycyclic aromatic hydrocarbon (PAH) in the sediments of Langkawi were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Ten samples were collected from jetties and fish farms around the island in December 2010. A gas chromatography/flame ionization detector (GC/FID) was used to analyse the 18 PAHs. e concentration of total PAHs was found to range from 869 ± 00 to 1637 ± 20 ng g −1 with a mean concentration of 1167.00 ± 24 ng g −1 , lower than the SQG effects range-low (3442 ng g −1 ). e results indicated that PAHs may not cause acute biological damage. Diagnostic ratios and principal component analysis suggested that the PAHs were likely to originate from pyrogenic and petrogenic sources. e toxic equivalent concentrations of the PAHs ranged from 76.3 to 177 ng TEQ/g d.w., which is lower compared to similar studies. e results of mean effects range-median quotient of the PAHs were lower than 0.1, which indicate an 11% probability of toxicity effect. Hence, the sampling sites were determined to be the low-priority sites. 1. Introduction Langkawi Archipelago in the Straits of Malacca, northwest of Peninsular Malaysia, consists of 104 islands, the largest and most exploited of which is Langkawi Island with an area of 478.5 km 2 . Targeted for ecotourism, Langkawi is protected from engaging in heavy industrial activities [1]. In 2006, the island was declared a National Geopark, and in the following year, it became a UNESCO Global Geopark [2]. In 2010 alone, Langkawi was visited by 2.4 million tourists [2]. From approximately 40,000 in 1991, the local population swelled significantly to almost 100,000 in 2010 [1], mainly to cater to the increasing number of tourism-related activities. Unfortunately, the fragile ecosystem of Langkawi Island is also increasingly being threatened by these tourism activities. Among the main attractions of Langkawi are its unique geological formations accessible only by boats. Many fish farms cater to the fresh seafood restaurants that are appearing around the islands. Boating activities, which are an impor- tant tourism component in Langkawi, significantly increase petroleum and diesel pollution in the water around the island. One of the most significant polluting components of petroleum is polycyclic aromatic hydrocarbons (PAHs). PAHs are a group of over 100 different compounds with fused benzene rings [3]. Sixteen PAHs compounds are iden- tified as priority pollutants due to their toxic, mutagenic, and carcinogenic characteristics [4]. PAHs in the environment can result from petroleum and petroleum products (petro- genic) or from the incomplete or inefficient combustion of diesel fuel, engine oil, wood, coal, biomass of forest, grass fires, waste incinerators, and fossil fuels, all of which are commonly used in industrial operations and power plants (pyrogenic) [5, 6]. PAHs are also widely used in commer- cial products such as intermediaries in pharmaceuticals,

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Hindawi Publishing CorporationThe Scientific World JournalVolume 2013 Article ID 858309 13 pageshttpdxdoiorg1011552013858309

Research ArticleAssessing the Ecological Risk of Polycyclic AromaticHydrocarbons in Sediments at Langkawi Island Malaysia

Essam Nasher1 Lee Yook Heng12 Zuriati Zakaria3 and Salmijah Surif1

1 Faculty of Science and Technology Universiti Kebangsaan Malaysia 43600 Bangi Selangor Malaysia2 South-East Asia Disaster Prevention Research Institute (SEADPRI) Universiti Kebangsaan Malaysia 43600 BangiSelangor Malaysia

3 Environment Engineering and Green Technology Malaysia Japan International Institute of TechnologyUniversity Technologi Malaysia 54100 Kuala Lumpur Selangor Malaysia

Correspondence should be addressed to Essam Nasher essam abduhyahoocom

Received 8 July 2013 Accepted 14 August 2013

Academic Editors H A Alegria A C Ruiz Fernandez and O Wurl

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

Tourism-related activities such as the heavy use of boats for transportation are a significant source of petroleum hydrocarbons thatmay harm the ecosystem of Langkawi Island The contamination and toxicity levels of polycyclic aromatic hydrocarbon (PAH)in the sediments of Langkawi were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors Ten sampleswere collected from jetties and fish farms around the island in December 2010 A gas chromatographyflame ionization detector(GCFID) was used to analyse the 18 PAHs The concentration of total PAHs was found to range from 869 plusmn 00 to 1637 plusmn 20 ng gminus1with a mean concentration of 116700 plusmn 24 ng gminus1 lower than the SQG effects range-low (3442 ng gminus1) The results indicated thatPAHs may not cause acute biological damage Diagnostic ratios and principal component analysis suggested that the PAHs werelikely to originate from pyrogenic and petrogenic sources The toxic equivalent concentrations of the PAHs ranged from 763 to177 ng TEQg dw which is lower compared to similar studiesThe results of mean effects range-median quotient of the PAHs werelower than 01 which indicate an 11 probability of toxicity effect Hence the sampling sites were determined to be the low-prioritysites

1 Introduction

Langkawi Archipelago in the Straits of Malacca northwest ofPeninsular Malaysia consists of 104 islands the largest andmost exploited of which is Langkawi Island with an area of4785 km2 Targeted for ecotourism Langkawi is protectedfrom engaging in heavy industrial activities [1] In 2006 theisland was declared a National Geopark and in the followingyear it became a UNESCO Global Geopark [2] In 2010alone Langkawi was visited by 24 million tourists [2]From approximately 40000 in 1991 the local populationswelled significantly to almost 100000 in 2010 [1] mainly tocater to the increasing number of tourism-related activitiesUnfortunately the fragile ecosystem of Langkawi Island isalso increasingly being threatened by these tourism activitiesAmong the main attractions of Langkawi are its uniquegeological formations accessible only by boats Many fish

farms cater to the fresh seafood restaurants that are appearingaround the islands Boating activities which are an impor-tant tourism component in Langkawi significantly increasepetroleum and diesel pollution in the water around theisland One of the most significant polluting components ofpetroleum is polycyclic aromatic hydrocarbons (PAHs)

PAHs are a group of over 100 different compounds withfused benzene rings [3] Sixteen PAHs compounds are iden-tified as priority pollutants due to their toxic mutagenic andcarcinogenic characteristics [4] PAHs in the environmentcan result from petroleum and petroleum products (petro-genic) or from the incomplete or inefficient combustion ofdiesel fuel engine oil wood coal biomass of forest grassfires waste incinerators and fossil fuels all of which arecommonly used in industrial operations and power plants(pyrogenic) [5 6] PAHs are also widely used in commer-cial products such as intermediaries in pharmaceuticals

2 The Scientific World Journal

agricultural products photographic products thermosettingplastics and lubricating materials products that may end upcontaminating the environment

In the marine environment pollution from PAHs can bedue to natural seepage or land-based sources river dis-charges urban runoffs refineries and other industrialwastewaters [7] Sea-based sources on the other hand arefrom two-stroke vessel discharge nontank vessel spills oper-ational discharges gross atmospheric deposition and aircraftdumping [8] These various sources of PAHs can be differen-tiated by their diagnostic ratio anthracene to anthracene +phenanthrene (AntAnt+Phe) ratio of gt01 indicates that thePAHs are pyrogenic whereas a ratio of lt01 shows that theyare petrogenic in origin [9]

The ecological risk of PAHs in sediment is evaluatedbased on the effects range-low (ERL) and effects range-median (ERM) values of the effects-based sediment guideline[10] These two values establish three concentration rangesfor PAHs At concentrations ltERL biological effects rarelyoccur at concentrations geERL leERM biological effects occa-sionally occur and at concentrations gtERM negative biolog-ical effects frequently occur [11]The risk assessment of PAHsin the aquatic sediment of certain regions has been reportedin several studies [12ndash16]

To date no investigation has been conducted on theimpact of the tourism sector in Langkawi In this paper wereport the distribution composition sources and pollutionlevel of PAHs in the sediments of jetties and selected fishfarms within areas around Langkawi Island which is thefocal point of the marine tourism industry We also evaluatepotential biological toxicity and its impact on the localecosystem of the area

2 Materials and Methods

21 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]flu-oranthene (BbF) benzo[k]fluoranthene (BkF) benzo[a]pyr-ene (BaP) indeno[123-cd]pyrene (InP) dibenzo[ah]anthra-cene (DBA) and benzo[ghi]perylene (BgP) was purchasedfrom Restek Corporation USA The standard mixture wasdiluted with hexane to prepare the five calibration standardmixtures The p-terphenyl-d14 (p-Ter) (Supelco USA) wasused as the surrogate internal standard Dichloromethane(DCM) n-hexane pentane acetone and cyclohexane wereall of chromatographic grade

22 Study Area The sediment was sampled in December2010 Figure 1 and Table 1 show the ten sampling stationsaround Langkawi Island and their associated water depthsrespectively The sampling stations include Telaga HarbourKilim Jetty Porto Malai Jetty Kuah Jetty and six stationsin fish farms (I II and III) located approximately 10 km to20 km from Porto Malai Jetty These sampling stations werechosen based on their unique activities Telaga Harbor is a

terminal jetty for sailing boats and yachts while Kilim Jettyand Porto Malai Jetty are both starting points for ecotourismactivities Kuah Jetty is the main terminal for ferries frommainland Kuala Kedah and Penang as well as Thailand andSingapore 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

23 Sample Collection Stainless steel Van Veen grab samplerwas used to collect surface sediment The surface layer of theupper five centimeters was carefully taken using a stainlesssteel spatula previously cleaned with n-hexane The surfacesediments were wrapped in aluminium foil kept in plasticbags and stored in a dark place under minus4∘C until furtheranalysis A sediment sample (100 g) was taken from eachstation placed in a precleaned glass bottle and weighedbefore drying in a freeze-dryer (Labconco Lyph Lock 6Model 77530-00) Duplicate samples from each station wereused for analysis

24 Grain Size and Organic Matter Analysis Wet sedimentswere weighed accurately and dried in the freeze-dryer (Lab-conco Lyph Lock 6Model 77530-00) for 72 hThe sedimentswere carefully dispersed by mortar to keep the nature ofeach grain size They were then placed in vibratory sieveshaker (AS 300) containing a series of sieves (2 1 05 0250125 0063 and 0045mm) and agitated for 10mins Thesediments in each sieve were transferred using a metal brushto a preweighed tray and was weighed again Each grain sizefraction was taken as a percentage of the total mass of thewhole sediment Sediment grain size was classified as gravel(gt1mm) sand (1 to 0063mm) or silt and clay (lt0063mm)Sediments that contained medium fine sand and silt withsizes le025mm were used for PAHs analysis

The OM content in dry sediment was measured using themethod explained by Briggs [17] Dry sediment (2 g) fromeach station was placed in a clean preweighed porcelain dishand heated in a furnace at 550∘C for 6 h The percentageof OM was calculated based on the mass ratio of sedimentweight in the porcelain dish before and after heating

25 Total Organic Carbon TheTOC content in sediment wasmeasured as described byDahle et al [18] A sediment samplewith fixed weight was acidified using concentrated HCl tobring the pH down to le2 and remove the inorganic carbonsThe sample was then dried in an oven at 50∘C for 2 daysThe TOC content was analysed through the high temperaturecombustion method using a CHNS (O) Analyzer (ThermoFinnigan Italy)

26 Chemical Analysis Hydrocarbon pollutants wereextracted from the sediment sample according to the USEPAmethod 3540C [19] The clean-up process followed the pro-cedures described in the EPA method 3630C [20] Briefly10 g dry sediment was spiked with the surrogate standardp-terphenyl-d14 (2120583gmLminus1) and extracted into a Soxhletapparatus using 200mL GC-grade acetone DCM (v v 1 1)for 10 h The combined extract was mixed with activated

The Scientific World Journal 3

S Melaka

P Timun

P Ular

N

30

(km)

S3

S4S10

S8

S2

S9

S6S7

S5

S1

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

PulauDayangBunting

LangkawiPort

Pulau Langkawi

TelagaHarbour

KilimJetty

KuahJetty

S Sampling station

Figure 1 Map showing the ten sampling stations (S1 to S10) around Langkawi Island Malaysia

Table 1 Sampling locations and their associated water depths

Number Sampling station Station name Depth (meter) Latitude (N) Longitude (E)1 S1 Kuah Jetty 3 06∘ 181015840 22910158401015840 099∘ 511015840 02010158401015840

2 S2 Kilim Jetty 1 06∘ 241015840 18410158401015840 099∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 06∘ 221015840 03610158401015840 099∘ 411015840 07010158401015840

4 S4 Porto Malai Jetty 3 06∘ 151015840 57510158401015840 099∘ 441015840 13310158401015840

5 S5 Fish farm I-1 11 06∘ 131015840 42910158401015840 099∘ 461015840 47810158401015840

6 S6 Fish farm I-2 11 06∘ 131015840 52910158401015840 099∘ 451015840 40810158401015840

7 S7 Fish farm I-3 11 06∘ 141015840 12910158401015840 099∘ 471015840 07810158401015840

8 S8 Fish farm II-1 10 06∘ 121015840 48010158401015840 099∘451015840 32510158401015840

9 S9 Fish farm II-2 10 06∘ 121015840 48010158401015840 099∘451015840 42510158401015840

10 S10 Fish farm III 11 06∘ 161015840 39610158401015840 099∘ 481015840 15210158401015840

copper sulphate granules and left overnight to removeany sulphur contaminants Next the extract was passedthrough a glass column that contained glass wool and thenconcentrated to 3mL using a rotary evaporator (EYELAJapan model N-1001S-W) Cyclohexane (10mL) was addedas an exchange solvent and the extract was concentrated to2mL using a rotary evaporator The extract was again passed

through a glass column containing 5 g activated silica gel(previously activated by heating at 200∘C for 16 h before use)and 1 g of anhydrous Na

2

SO4

Afterward the PAH fractionwas eluted using a 30mL mixture of DCM pentane (2 3vv) and then concentrated to 2mL using a rotary evaporatorHexane (10mL) was added as an exchange solvent [20] andevaporated down to 2mL Finallythe extract was reduced

4 The Scientific World Journal

to 1mL under a gentle stream of nitrogen gas All sampleextracts were kept in amber glass vials at minus4∘C until theywere analysed within a week

27 Instrumental Analysis Extract (1 120583L) was injected intogas chromatography (Agilent 6890 technologies USA)equipped with flame ionization detector (FID) and a fusedsilica TR-5MS capillary column (30m times 025mm id) withfilm thickness of 025 120583m (Thermo Fisher USA) High purityhelium (999) was used as a carrier gas makeup gasand purge gas at flow rates of 10 45 and 300mLminrespectively The flow rates for the FID were 450mLminand 45mLmin for air and hydrogen respectively The gaschromatograph was operated in splitless mode and separa-tion was conducted with the oven temperature programmedas follows initial setting at 80∘C (1min hold) ramped to180∘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 FIDmaintained at 350∘C Agilent Chemstation software was usedto obtain the chromatogram and for data calculations Anexternal standard calibration comprising of 18 PAH standardswas used to determine the identity and quantity of eachcomponent peak in sample chromatogram

28 Quality Assurance and Quality Control (QAQC) Repli-cate samples were analysed for all samples collected fromeach station Reagent blank and recovery procedures wereanalysed simultaneously for every five samples The reagentblank containing the surrogate standard and solvent wasanalysed to evaluate the interference and contamination ofthe solvents reagents and glassware used The accuracy ofthe analytical procedure was examined by recovering thePAHs in the standard referencematerial (SRM) 1941b (marinesediment) obtained from the National Institute of Standardsand Technology (NIST USA)

The extraction clean-up procedures and setting up ofinstrumental system were examined by spiking each realsample and reagent blank with a surrogate internal standard(p-terphenyl-d14) of a known concentration Average recov-ery of the 18 PAHs and p-terphenyl-d14 ranged from 65 to137 (Table 2) which met the 70ndash130 acceptance criteriaof the EPA method [21] The instrument limit of detectionof individual PAHs was estimated to be 3 lowast 119878 where 119878 is thestandard deviation of eight replicate analyses of blanks [22]Themethod detection limit (MDL)was calculated to be 10lowast119878The MDL values of the individual PAHs ranged from 022to 12 ng gminus1 according to the analysis method with GC-FIDThese values were within the acceptable range of EPAmethod[23]

The correlation coefficient (119903) ameasure of the ldquogoodnessof fitrdquo of the regression line to the data must be ge099 tobe acceptable for the regression equation Five PAH mixturestandards were run on the same day of the sample analysisto estimate the regression equations used to calculate theconcentration of individual PAHs in the samples All PAHregression equations obtained an 119903 value of ge099 which wasacceptable according to the EPA method 8000B [21]

One-way ANOVA Games-Howell and posthoc multiplecomparison tests were used to evaluate the significance of the

Table 2 Average recovery of 18 PAHs in marine sediment (SRM1941b)

PAHs Abbreviation Recovery plusmn SDVNaphthalene Nap 123 plusmn 14

1-Methylnaphthalene 1MNap 137 plusmn 13

2-Methylnaphthalene 2MNap 74 plusmn 6

Acenaphthylene Acy 133 plusmn 11

Acenaphthene Ace 128 plusmn 3

Fluorene Fl 99 plusmn 4

Phenanthrene Phe 94 plusmn 2

Anthracene Ant 71 plusmn 11

Fluoranthene FIu 73 plusmn 10

Pyrene Pyr 79 plusmn 4

Benzo[a]anthracene BaA 74 plusmn 8

Chrysene Chr 87 plusmn 24

Benzo[b]fluoranthene BbF 99 plusmn 16

Benzo[k]fluoranthene BkF 77 plusmn 15

Benzo[a]pyrene BaP 79 plusmn 20

Indeno[123-cd]pyrene InP 75 plusmn 11

Dibenzo[ah]anthracene DBA 106 plusmn 20

Benzo[ghi]perylene BgP 90 plusmn 32

differences between the total PAHs at the sampling stationsusing SPSS version 15 for Windows Correlation Pearsonanalysis was carried out to test the relationship betweenindividual PAHs in the sediment and between total PAHsdifferent grain size and TOCs Principal component analysis(PCA) was conducted to identify the source contributions ofPAHs

3 Results and Discussion

31 Sediment Characteristics Table 3 shows the TOC OMcontent and grain size of the sediment samples taken from10 stations around Langkawi Island TOC values ranged from066 to 317 and OM content was between 1026 and2241 in dry weight Kilim Jetty which is located at themouth of Kilim River and is covered by mangroves recordeda higher TOC content than the studied locations Kilim Jettyalso has a higher percentage of OM compared to other jettiesand harbour that have the same activities OM includes thetotal amount of organic and inorganic carbon nitrogen andphosphorus [24]The highest TOC andOMcontents at KilimJetty are expected because the jetty is amangrove area locatedat the mouth of Kilim River which receive the dischargesfrom biological productivity and high sedimentation rates[25]The lowest TOC content (066) was recorded at TelagaHarbourThe lower concentration of TOC in this stationmaybe due to the low biological productivity

The OM contents (1682ndash2241) in fish farms and inKilim Jetty (Table 3) were higher in other stations (KuahPorto Malai jetties and Telaga Harbour) indicating that feedwastage fish excretion and faecal productions from fishcages can contribute to the formation of loose and blackflocculent under the mariculture cages whichmay then cause

The Scientific World Journal 5

Table 3 TOC OM and grain size of sediments from Langkawi Island (values are in percentage)

Stations OMa TOCb Gravelc Sandc Silt + Clayc

Kuah Jetty 1194 150 535 9387 mdashKilim Jetty 1967 317 129 9810 mdashTelaga Harbour 1148 066 994 9001 015Porto Malai Jetty 1026 127 922 8972 033Fish farm I-1 1690 113 566 9322 102Fish farm I-2 1682 095 285 9622 018Fish farm I-3 2156 141 mdash 9941 021Fish farm II-1 2241 136 mdash 9890 050Fish farm II-2 2139 133 022 9909 014Fish farm III 2049 124 mdash 9975 016aOM organic matter bTOC total organic carbon cclassification of grain size sediment

the accumulation of OM [26] The high values of OM in fishfarm sediment were also found in other sites For examplethe fish farms of Corse in France have a recorded OM valuebetween 21 and 24 [27]

Based on grain size the sediments of Langkawi Islandwere mostly sandy with sand content ranging from 8972 atPorto Malai Jetty to 9975 at fish farm III (Table 3) The claycontent of these sediments was le1 Significant relationshipswere found between sediment size (le025mm) and totalorganic carbon (TOC) (119903 = 068 119875 = 003) and between thesize and organic matter (OM) content (119903 = 066 119875 = 005)of the sediment PAHs are highly hydrophobic and usuallyaccumulate in the sediment with high OM content [18]

32 Concentrations and Profile of PAHs Table 4 shows theconcentrations of PAHs in sediment from the four chosenjetties and six fish farm stations around Langkawi IslandThetotal PAH concentrations in the popular jetties for touriststhe Kuah Jetty Kilim Jetty Porto Malai Jetty and TelagaHarbour varied from 868 plusmn 85 ng gminus1 dw in the Kilim Jettyto 1637 plusmn 190 ng gminus1 dw in Telaga Harbour with a mean of1165 plusmn 235 ng gminus1 dw Total PAHs in the sediment samplesfrom the fish farm areas similarly recorded ranges of 922 plusmn170 ng gminus1 dw at fish farm I to 1432 plusmn 693 ng gminus1 dw at fishfarm III with a mean of 1143 plusmn 635 ng gminus1 dw Sedimentfrom Telaga Harbour sediment recorded the highest totalPAHs concentration of 1637 plusmn 190 ng gminus1 dw which couldbe due to the intense harbour activities of sailing boats andyachts in this popular terminal jetty Additionally the Telagasampling site is located in the sheltered part of the waterThe lowest concentration of total PAHs was found at KilimJetty at 868 plusmn 85 ng gminus1 dw which is probably due to thedilution effect of the Kilim River Kilim River crosses theforest and rural areas and is loaded with high OM that isthen deposited at the jetty The jetty has a depth of about 1to 2m and a water transparency of 080 cm This dischargemay leach the PAHs in the jetty sediment to the open seaMoreover biological activity may return a small amount ofPAH to thewater columnwhich contributes to reducingPAHlevel in the jetty [7] The PAH pollution categories adoptedby Baumard et al [28] are as follows low 0ndash100 ng gminus1

moderate 100ndash1000 ng gminus1 high 1000ndash5000 ng gminus1 and veryhigh gt5000 ng gminus1 dw On the basis of this classificationLangkawi Island can currently be considered moderately toheavily pollute with PAHs Therefore the prevailing PAHconcentration at the jetties and fish farms frequently visitedby tourists is probably the result of the fuel used in boatspassenger ferries and buses which are the important con-tributors of PAHs in this area The leakage of petroleumand the unscrupulous disposal of engine oil from boats andferries may also contribute significantly to the level of PAHsrecorded here [29 30]

To evaluate if the sediment contaminated by PAHs inLangkawi Island (868ndash1637 ng gminus1 dw) will have a toxiceffect [10] the total PAHs levels were also compared againsteffects-based guideline values such as ERL and ERM Theconcentrations of total PAHs from all the studied stationswere lower than the sediment quality guidelines (SQGs) forthe ERL of 3442 ng gminus1 and the ERM of 24290 ng gminus1 Thesefindings suggest that the sediments from these samplinglocations are not toxic to the organisms within these areas

Table 5 shows that the total PAH concentrations in thesediment of Langkawi Island were approximately lower by1 to 2 orders of magnitude than the sediments investigatedby other studies in Singapore Island the Mediterraneancoastal environment of Egypt [16] and the Naples harbourin southern Italy [32] The levels recorded here are nearlysimilar to the levels present in the sediment of Jakarta BayIndonesia [33] Jiulong River Estuary and Western XiamenSea China [34] and Tokyo Bay Japan [33] However totalPAHs in the Langkawi sediment were approximately 1 orderof magnitude higher than those detected in other countriessuch as the marine sediments in Thailand [35] Estero deUrias Estuary Mexico [36] the Gulf of Aden Yemen [37]Southwest Taiwan [38] and in Hong Kong marine fish farms[26] (Table 5) Moreover the 2006 annual report of theMalaysian Department of Environment ranked LangkawiIsland as the thirdmost polluted area by oil and grease amongthe 15 monitoring stations in the Peninsula of MalaysiaLangkawi also exceeded the water quality standard of oil andgrease by 80 [30] In general the PAHs level in the sedimentof Langkawi Island is low to moderate compared with thefindings from previous studies

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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CatalystsJournal of

Page 2: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

2 The Scientific World Journal

agricultural products photographic products thermosettingplastics and lubricating materials products that may end upcontaminating the environment

In the marine environment pollution from PAHs can bedue to natural seepage or land-based sources river dis-charges urban runoffs refineries and other industrialwastewaters [7] Sea-based sources on the other hand arefrom two-stroke vessel discharge nontank vessel spills oper-ational discharges gross atmospheric deposition and aircraftdumping [8] These various sources of PAHs can be differen-tiated by their diagnostic ratio anthracene to anthracene +phenanthrene (AntAnt+Phe) ratio of gt01 indicates that thePAHs are pyrogenic whereas a ratio of lt01 shows that theyare petrogenic in origin [9]

The ecological risk of PAHs in sediment is evaluatedbased on the effects range-low (ERL) and effects range-median (ERM) values of the effects-based sediment guideline[10] These two values establish three concentration rangesfor PAHs At concentrations ltERL biological effects rarelyoccur at concentrations geERL leERM biological effects occa-sionally occur and at concentrations gtERM negative biolog-ical effects frequently occur [11]The risk assessment of PAHsin the aquatic sediment of certain regions has been reportedin several studies [12ndash16]

To date no investigation has been conducted on theimpact of the tourism sector in Langkawi In this paper wereport the distribution composition sources and pollutionlevel of PAHs in the sediments of jetties and selected fishfarms within areas around Langkawi Island which is thefocal point of the marine tourism industry We also evaluatepotential biological toxicity and its impact on the localecosystem of the area

2 Materials and Methods

21 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]flu-oranthene (BbF) benzo[k]fluoranthene (BkF) benzo[a]pyr-ene (BaP) indeno[123-cd]pyrene (InP) dibenzo[ah]anthra-cene (DBA) and benzo[ghi]perylene (BgP) was purchasedfrom Restek Corporation USA The standard mixture wasdiluted with hexane to prepare the five calibration standardmixtures The p-terphenyl-d14 (p-Ter) (Supelco USA) wasused as the surrogate internal standard Dichloromethane(DCM) n-hexane pentane acetone and cyclohexane wereall of chromatographic grade

22 Study Area The sediment was sampled in December2010 Figure 1 and Table 1 show the ten sampling stationsaround Langkawi Island and their associated water depthsrespectively The sampling stations include Telaga HarbourKilim Jetty Porto Malai Jetty Kuah Jetty and six stationsin fish farms (I II and III) located approximately 10 km to20 km from Porto Malai Jetty These sampling stations werechosen based on their unique activities Telaga Harbor is a

terminal jetty for sailing boats and yachts while Kilim Jettyand Porto Malai Jetty are both starting points for ecotourismactivities Kuah Jetty is the main terminal for ferries frommainland Kuala Kedah and Penang as well as Thailand andSingapore 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

23 Sample Collection Stainless steel Van Veen grab samplerwas used to collect surface sediment The surface layer of theupper five centimeters was carefully taken using a stainlesssteel spatula previously cleaned with n-hexane The surfacesediments were wrapped in aluminium foil kept in plasticbags and stored in a dark place under minus4∘C until furtheranalysis A sediment sample (100 g) was taken from eachstation placed in a precleaned glass bottle and weighedbefore drying in a freeze-dryer (Labconco Lyph Lock 6Model 77530-00) Duplicate samples from each station wereused for analysis

24 Grain Size and Organic Matter Analysis Wet sedimentswere weighed accurately and dried in the freeze-dryer (Lab-conco Lyph Lock 6Model 77530-00) for 72 hThe sedimentswere carefully dispersed by mortar to keep the nature ofeach grain size They were then placed in vibratory sieveshaker (AS 300) containing a series of sieves (2 1 05 0250125 0063 and 0045mm) and agitated for 10mins Thesediments in each sieve were transferred using a metal brushto a preweighed tray and was weighed again Each grain sizefraction was taken as a percentage of the total mass of thewhole sediment Sediment grain size was classified as gravel(gt1mm) sand (1 to 0063mm) or silt and clay (lt0063mm)Sediments that contained medium fine sand and silt withsizes le025mm were used for PAHs analysis

The OM content in dry sediment was measured using themethod explained by Briggs [17] Dry sediment (2 g) fromeach station was placed in a clean preweighed porcelain dishand heated in a furnace at 550∘C for 6 h The percentageof OM was calculated based on the mass ratio of sedimentweight in the porcelain dish before and after heating

25 Total Organic Carbon TheTOC content in sediment wasmeasured as described byDahle et al [18] A sediment samplewith fixed weight was acidified using concentrated HCl tobring the pH down to le2 and remove the inorganic carbonsThe sample was then dried in an oven at 50∘C for 2 daysThe TOC content was analysed through the high temperaturecombustion method using a CHNS (O) Analyzer (ThermoFinnigan Italy)

26 Chemical Analysis Hydrocarbon pollutants wereextracted from the sediment sample according to the USEPAmethod 3540C [19] The clean-up process followed the pro-cedures described in the EPA method 3630C [20] Briefly10 g dry sediment was spiked with the surrogate standardp-terphenyl-d14 (2120583gmLminus1) and extracted into a Soxhletapparatus using 200mL GC-grade acetone DCM (v v 1 1)for 10 h The combined extract was mixed with activated

The Scientific World Journal 3

S Melaka

P Timun

P Ular

N

30

(km)

S3

S4S10

S8

S2

S9

S6S7

S5

S1

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

PulauDayangBunting

LangkawiPort

Pulau Langkawi

TelagaHarbour

KilimJetty

KuahJetty

S Sampling station

Figure 1 Map showing the ten sampling stations (S1 to S10) around Langkawi Island Malaysia

Table 1 Sampling locations and their associated water depths

Number Sampling station Station name Depth (meter) Latitude (N) Longitude (E)1 S1 Kuah Jetty 3 06∘ 181015840 22910158401015840 099∘ 511015840 02010158401015840

2 S2 Kilim Jetty 1 06∘ 241015840 18410158401015840 099∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 06∘ 221015840 03610158401015840 099∘ 411015840 07010158401015840

4 S4 Porto Malai Jetty 3 06∘ 151015840 57510158401015840 099∘ 441015840 13310158401015840

5 S5 Fish farm I-1 11 06∘ 131015840 42910158401015840 099∘ 461015840 47810158401015840

6 S6 Fish farm I-2 11 06∘ 131015840 52910158401015840 099∘ 451015840 40810158401015840

7 S7 Fish farm I-3 11 06∘ 141015840 12910158401015840 099∘ 471015840 07810158401015840

8 S8 Fish farm II-1 10 06∘ 121015840 48010158401015840 099∘451015840 32510158401015840

9 S9 Fish farm II-2 10 06∘ 121015840 48010158401015840 099∘451015840 42510158401015840

10 S10 Fish farm III 11 06∘ 161015840 39610158401015840 099∘ 481015840 15210158401015840

copper sulphate granules and left overnight to removeany sulphur contaminants Next the extract was passedthrough a glass column that contained glass wool and thenconcentrated to 3mL using a rotary evaporator (EYELAJapan model N-1001S-W) Cyclohexane (10mL) was addedas an exchange solvent and the extract was concentrated to2mL using a rotary evaporator The extract was again passed

through a glass column containing 5 g activated silica gel(previously activated by heating at 200∘C for 16 h before use)and 1 g of anhydrous Na

2

SO4

Afterward the PAH fractionwas eluted using a 30mL mixture of DCM pentane (2 3vv) and then concentrated to 2mL using a rotary evaporatorHexane (10mL) was added as an exchange solvent [20] andevaporated down to 2mL Finallythe extract was reduced

4 The Scientific World Journal

to 1mL under a gentle stream of nitrogen gas All sampleextracts were kept in amber glass vials at minus4∘C until theywere analysed within a week

27 Instrumental Analysis Extract (1 120583L) was injected intogas chromatography (Agilent 6890 technologies USA)equipped with flame ionization detector (FID) and a fusedsilica TR-5MS capillary column (30m times 025mm id) withfilm thickness of 025 120583m (Thermo Fisher USA) High purityhelium (999) was used as a carrier gas makeup gasand purge gas at flow rates of 10 45 and 300mLminrespectively The flow rates for the FID were 450mLminand 45mLmin for air and hydrogen respectively The gaschromatograph was operated in splitless mode and separa-tion was conducted with the oven temperature programmedas follows initial setting at 80∘C (1min hold) ramped to180∘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 FIDmaintained at 350∘C Agilent Chemstation software was usedto obtain the chromatogram and for data calculations Anexternal standard calibration comprising of 18 PAH standardswas used to determine the identity and quantity of eachcomponent peak in sample chromatogram

28 Quality Assurance and Quality Control (QAQC) Repli-cate samples were analysed for all samples collected fromeach station Reagent blank and recovery procedures wereanalysed simultaneously for every five samples The reagentblank containing the surrogate standard and solvent wasanalysed to evaluate the interference and contamination ofthe solvents reagents and glassware used The accuracy ofthe analytical procedure was examined by recovering thePAHs in the standard referencematerial (SRM) 1941b (marinesediment) obtained from the National Institute of Standardsand Technology (NIST USA)

The extraction clean-up procedures and setting up ofinstrumental system were examined by spiking each realsample and reagent blank with a surrogate internal standard(p-terphenyl-d14) of a known concentration Average recov-ery of the 18 PAHs and p-terphenyl-d14 ranged from 65 to137 (Table 2) which met the 70ndash130 acceptance criteriaof the EPA method [21] The instrument limit of detectionof individual PAHs was estimated to be 3 lowast 119878 where 119878 is thestandard deviation of eight replicate analyses of blanks [22]Themethod detection limit (MDL)was calculated to be 10lowast119878The MDL values of the individual PAHs ranged from 022to 12 ng gminus1 according to the analysis method with GC-FIDThese values were within the acceptable range of EPAmethod[23]

The correlation coefficient (119903) ameasure of the ldquogoodnessof fitrdquo of the regression line to the data must be ge099 tobe acceptable for the regression equation Five PAH mixturestandards were run on the same day of the sample analysisto estimate the regression equations used to calculate theconcentration of individual PAHs in the samples All PAHregression equations obtained an 119903 value of ge099 which wasacceptable according to the EPA method 8000B [21]

One-way ANOVA Games-Howell and posthoc multiplecomparison tests were used to evaluate the significance of the

Table 2 Average recovery of 18 PAHs in marine sediment (SRM1941b)

PAHs Abbreviation Recovery plusmn SDVNaphthalene Nap 123 plusmn 14

1-Methylnaphthalene 1MNap 137 plusmn 13

2-Methylnaphthalene 2MNap 74 plusmn 6

Acenaphthylene Acy 133 plusmn 11

Acenaphthene Ace 128 plusmn 3

Fluorene Fl 99 plusmn 4

Phenanthrene Phe 94 plusmn 2

Anthracene Ant 71 plusmn 11

Fluoranthene FIu 73 plusmn 10

Pyrene Pyr 79 plusmn 4

Benzo[a]anthracene BaA 74 plusmn 8

Chrysene Chr 87 plusmn 24

Benzo[b]fluoranthene BbF 99 plusmn 16

Benzo[k]fluoranthene BkF 77 plusmn 15

Benzo[a]pyrene BaP 79 plusmn 20

Indeno[123-cd]pyrene InP 75 plusmn 11

Dibenzo[ah]anthracene DBA 106 plusmn 20

Benzo[ghi]perylene BgP 90 plusmn 32

differences between the total PAHs at the sampling stationsusing SPSS version 15 for Windows Correlation Pearsonanalysis was carried out to test the relationship betweenindividual PAHs in the sediment and between total PAHsdifferent grain size and TOCs Principal component analysis(PCA) was conducted to identify the source contributions ofPAHs

3 Results and Discussion

31 Sediment Characteristics Table 3 shows the TOC OMcontent and grain size of the sediment samples taken from10 stations around Langkawi Island TOC values ranged from066 to 317 and OM content was between 1026 and2241 in dry weight Kilim Jetty which is located at themouth of Kilim River and is covered by mangroves recordeda higher TOC content than the studied locations Kilim Jettyalso has a higher percentage of OM compared to other jettiesand harbour that have the same activities OM includes thetotal amount of organic and inorganic carbon nitrogen andphosphorus [24]The highest TOC andOMcontents at KilimJetty are expected because the jetty is amangrove area locatedat the mouth of Kilim River which receive the dischargesfrom biological productivity and high sedimentation rates[25]The lowest TOC content (066) was recorded at TelagaHarbourThe lower concentration of TOC in this stationmaybe due to the low biological productivity

The OM contents (1682ndash2241) in fish farms and inKilim Jetty (Table 3) were higher in other stations (KuahPorto Malai jetties and Telaga Harbour) indicating that feedwastage fish excretion and faecal productions from fishcages can contribute to the formation of loose and blackflocculent under the mariculture cages whichmay then cause

The Scientific World Journal 5

Table 3 TOC OM and grain size of sediments from Langkawi Island (values are in percentage)

Stations OMa TOCb Gravelc Sandc Silt + Clayc

Kuah Jetty 1194 150 535 9387 mdashKilim Jetty 1967 317 129 9810 mdashTelaga Harbour 1148 066 994 9001 015Porto Malai Jetty 1026 127 922 8972 033Fish farm I-1 1690 113 566 9322 102Fish farm I-2 1682 095 285 9622 018Fish farm I-3 2156 141 mdash 9941 021Fish farm II-1 2241 136 mdash 9890 050Fish farm II-2 2139 133 022 9909 014Fish farm III 2049 124 mdash 9975 016aOM organic matter bTOC total organic carbon cclassification of grain size sediment

the accumulation of OM [26] The high values of OM in fishfarm sediment were also found in other sites For examplethe fish farms of Corse in France have a recorded OM valuebetween 21 and 24 [27]

Based on grain size the sediments of Langkawi Islandwere mostly sandy with sand content ranging from 8972 atPorto Malai Jetty to 9975 at fish farm III (Table 3) The claycontent of these sediments was le1 Significant relationshipswere found between sediment size (le025mm) and totalorganic carbon (TOC) (119903 = 068 119875 = 003) and between thesize and organic matter (OM) content (119903 = 066 119875 = 005)of the sediment PAHs are highly hydrophobic and usuallyaccumulate in the sediment with high OM content [18]

32 Concentrations and Profile of PAHs Table 4 shows theconcentrations of PAHs in sediment from the four chosenjetties and six fish farm stations around Langkawi IslandThetotal PAH concentrations in the popular jetties for touriststhe Kuah Jetty Kilim Jetty Porto Malai Jetty and TelagaHarbour varied from 868 plusmn 85 ng gminus1 dw in the Kilim Jettyto 1637 plusmn 190 ng gminus1 dw in Telaga Harbour with a mean of1165 plusmn 235 ng gminus1 dw Total PAHs in the sediment samplesfrom the fish farm areas similarly recorded ranges of 922 plusmn170 ng gminus1 dw at fish farm I to 1432 plusmn 693 ng gminus1 dw at fishfarm III with a mean of 1143 plusmn 635 ng gminus1 dw Sedimentfrom Telaga Harbour sediment recorded the highest totalPAHs concentration of 1637 plusmn 190 ng gminus1 dw which couldbe due to the intense harbour activities of sailing boats andyachts in this popular terminal jetty Additionally the Telagasampling site is located in the sheltered part of the waterThe lowest concentration of total PAHs was found at KilimJetty at 868 plusmn 85 ng gminus1 dw which is probably due to thedilution effect of the Kilim River Kilim River crosses theforest and rural areas and is loaded with high OM that isthen deposited at the jetty The jetty has a depth of about 1to 2m and a water transparency of 080 cm This dischargemay leach the PAHs in the jetty sediment to the open seaMoreover biological activity may return a small amount ofPAH to thewater columnwhich contributes to reducingPAHlevel in the jetty [7] The PAH pollution categories adoptedby Baumard et al [28] are as follows low 0ndash100 ng gminus1

moderate 100ndash1000 ng gminus1 high 1000ndash5000 ng gminus1 and veryhigh gt5000 ng gminus1 dw On the basis of this classificationLangkawi Island can currently be considered moderately toheavily pollute with PAHs Therefore the prevailing PAHconcentration at the jetties and fish farms frequently visitedby tourists is probably the result of the fuel used in boatspassenger ferries and buses which are the important con-tributors of PAHs in this area The leakage of petroleumand the unscrupulous disposal of engine oil from boats andferries may also contribute significantly to the level of PAHsrecorded here [29 30]

To evaluate if the sediment contaminated by PAHs inLangkawi Island (868ndash1637 ng gminus1 dw) will have a toxiceffect [10] the total PAHs levels were also compared againsteffects-based guideline values such as ERL and ERM Theconcentrations of total PAHs from all the studied stationswere lower than the sediment quality guidelines (SQGs) forthe ERL of 3442 ng gminus1 and the ERM of 24290 ng gminus1 Thesefindings suggest that the sediments from these samplinglocations are not toxic to the organisms within these areas

Table 5 shows that the total PAH concentrations in thesediment of Langkawi Island were approximately lower by1 to 2 orders of magnitude than the sediments investigatedby other studies in Singapore Island the Mediterraneancoastal environment of Egypt [16] and the Naples harbourin southern Italy [32] The levels recorded here are nearlysimilar to the levels present in the sediment of Jakarta BayIndonesia [33] Jiulong River Estuary and Western XiamenSea China [34] and Tokyo Bay Japan [33] However totalPAHs in the Langkawi sediment were approximately 1 orderof magnitude higher than those detected in other countriessuch as the marine sediments in Thailand [35] Estero deUrias Estuary Mexico [36] the Gulf of Aden Yemen [37]Southwest Taiwan [38] and in Hong Kong marine fish farms[26] (Table 5) Moreover the 2006 annual report of theMalaysian Department of Environment ranked LangkawiIsland as the thirdmost polluted area by oil and grease amongthe 15 monitoring stations in the Peninsula of MalaysiaLangkawi also exceeded the water quality standard of oil andgrease by 80 [30] In general the PAHs level in the sedimentof Langkawi Island is low to moderate compared with thefindings from previous studies

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

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CatalystsJournal of

Page 3: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 3

S Melaka

P Timun

P Ular

N

30

(km)

S3

S4S10

S8

S2

S9

S6S7

S5

S1

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

99∘40998400 E 99∘45998400 E 99∘55998400 E99∘50998400 E

06∘25998400 N

06∘20998400 N

06∘10998400 N

06∘15998400 N

PulauDayangBunting

LangkawiPort

Pulau Langkawi

TelagaHarbour

KilimJetty

KuahJetty

S Sampling station

Figure 1 Map showing the ten sampling stations (S1 to S10) around Langkawi Island Malaysia

Table 1 Sampling locations and their associated water depths

Number Sampling station Station name Depth (meter) Latitude (N) Longitude (E)1 S1 Kuah Jetty 3 06∘ 181015840 22910158401015840 099∘ 511015840 02010158401015840

2 S2 Kilim Jetty 1 06∘ 241015840 18410158401015840 099∘ 511015840 31010158401015840

3 S3 Telaga Harbour 3 06∘ 221015840 03610158401015840 099∘ 411015840 07010158401015840

4 S4 Porto Malai Jetty 3 06∘ 151015840 57510158401015840 099∘ 441015840 13310158401015840

5 S5 Fish farm I-1 11 06∘ 131015840 42910158401015840 099∘ 461015840 47810158401015840

6 S6 Fish farm I-2 11 06∘ 131015840 52910158401015840 099∘ 451015840 40810158401015840

7 S7 Fish farm I-3 11 06∘ 141015840 12910158401015840 099∘ 471015840 07810158401015840

8 S8 Fish farm II-1 10 06∘ 121015840 48010158401015840 099∘451015840 32510158401015840

9 S9 Fish farm II-2 10 06∘ 121015840 48010158401015840 099∘451015840 42510158401015840

10 S10 Fish farm III 11 06∘ 161015840 39610158401015840 099∘ 481015840 15210158401015840

copper sulphate granules and left overnight to removeany sulphur contaminants Next the extract was passedthrough a glass column that contained glass wool and thenconcentrated to 3mL using a rotary evaporator (EYELAJapan model N-1001S-W) Cyclohexane (10mL) was addedas an exchange solvent and the extract was concentrated to2mL using a rotary evaporator The extract was again passed

through a glass column containing 5 g activated silica gel(previously activated by heating at 200∘C for 16 h before use)and 1 g of anhydrous Na

2

SO4

Afterward the PAH fractionwas eluted using a 30mL mixture of DCM pentane (2 3vv) and then concentrated to 2mL using a rotary evaporatorHexane (10mL) was added as an exchange solvent [20] andevaporated down to 2mL Finallythe extract was reduced

4 The Scientific World Journal

to 1mL under a gentle stream of nitrogen gas All sampleextracts were kept in amber glass vials at minus4∘C until theywere analysed within a week

27 Instrumental Analysis Extract (1 120583L) was injected intogas chromatography (Agilent 6890 technologies USA)equipped with flame ionization detector (FID) and a fusedsilica TR-5MS capillary column (30m times 025mm id) withfilm thickness of 025 120583m (Thermo Fisher USA) High purityhelium (999) was used as a carrier gas makeup gasand purge gas at flow rates of 10 45 and 300mLminrespectively The flow rates for the FID were 450mLminand 45mLmin for air and hydrogen respectively The gaschromatograph was operated in splitless mode and separa-tion was conducted with the oven temperature programmedas follows initial setting at 80∘C (1min hold) ramped to180∘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 FIDmaintained at 350∘C Agilent Chemstation software was usedto obtain the chromatogram and for data calculations Anexternal standard calibration comprising of 18 PAH standardswas used to determine the identity and quantity of eachcomponent peak in sample chromatogram

28 Quality Assurance and Quality Control (QAQC) Repli-cate samples were analysed for all samples collected fromeach station Reagent blank and recovery procedures wereanalysed simultaneously for every five samples The reagentblank containing the surrogate standard and solvent wasanalysed to evaluate the interference and contamination ofthe solvents reagents and glassware used The accuracy ofthe analytical procedure was examined by recovering thePAHs in the standard referencematerial (SRM) 1941b (marinesediment) obtained from the National Institute of Standardsand Technology (NIST USA)

The extraction clean-up procedures and setting up ofinstrumental system were examined by spiking each realsample and reagent blank with a surrogate internal standard(p-terphenyl-d14) of a known concentration Average recov-ery of the 18 PAHs and p-terphenyl-d14 ranged from 65 to137 (Table 2) which met the 70ndash130 acceptance criteriaof the EPA method [21] The instrument limit of detectionof individual PAHs was estimated to be 3 lowast 119878 where 119878 is thestandard deviation of eight replicate analyses of blanks [22]Themethod detection limit (MDL)was calculated to be 10lowast119878The MDL values of the individual PAHs ranged from 022to 12 ng gminus1 according to the analysis method with GC-FIDThese values were within the acceptable range of EPAmethod[23]

The correlation coefficient (119903) ameasure of the ldquogoodnessof fitrdquo of the regression line to the data must be ge099 tobe acceptable for the regression equation Five PAH mixturestandards were run on the same day of the sample analysisto estimate the regression equations used to calculate theconcentration of individual PAHs in the samples All PAHregression equations obtained an 119903 value of ge099 which wasacceptable according to the EPA method 8000B [21]

One-way ANOVA Games-Howell and posthoc multiplecomparison tests were used to evaluate the significance of the

Table 2 Average recovery of 18 PAHs in marine sediment (SRM1941b)

PAHs Abbreviation Recovery plusmn SDVNaphthalene Nap 123 plusmn 14

1-Methylnaphthalene 1MNap 137 plusmn 13

2-Methylnaphthalene 2MNap 74 plusmn 6

Acenaphthylene Acy 133 plusmn 11

Acenaphthene Ace 128 plusmn 3

Fluorene Fl 99 plusmn 4

Phenanthrene Phe 94 plusmn 2

Anthracene Ant 71 plusmn 11

Fluoranthene FIu 73 plusmn 10

Pyrene Pyr 79 plusmn 4

Benzo[a]anthracene BaA 74 plusmn 8

Chrysene Chr 87 plusmn 24

Benzo[b]fluoranthene BbF 99 plusmn 16

Benzo[k]fluoranthene BkF 77 plusmn 15

Benzo[a]pyrene BaP 79 plusmn 20

Indeno[123-cd]pyrene InP 75 plusmn 11

Dibenzo[ah]anthracene DBA 106 plusmn 20

Benzo[ghi]perylene BgP 90 plusmn 32

differences between the total PAHs at the sampling stationsusing SPSS version 15 for Windows Correlation Pearsonanalysis was carried out to test the relationship betweenindividual PAHs in the sediment and between total PAHsdifferent grain size and TOCs Principal component analysis(PCA) was conducted to identify the source contributions ofPAHs

3 Results and Discussion

31 Sediment Characteristics Table 3 shows the TOC OMcontent and grain size of the sediment samples taken from10 stations around Langkawi Island TOC values ranged from066 to 317 and OM content was between 1026 and2241 in dry weight Kilim Jetty which is located at themouth of Kilim River and is covered by mangroves recordeda higher TOC content than the studied locations Kilim Jettyalso has a higher percentage of OM compared to other jettiesand harbour that have the same activities OM includes thetotal amount of organic and inorganic carbon nitrogen andphosphorus [24]The highest TOC andOMcontents at KilimJetty are expected because the jetty is amangrove area locatedat the mouth of Kilim River which receive the dischargesfrom biological productivity and high sedimentation rates[25]The lowest TOC content (066) was recorded at TelagaHarbourThe lower concentration of TOC in this stationmaybe due to the low biological productivity

The OM contents (1682ndash2241) in fish farms and inKilim Jetty (Table 3) were higher in other stations (KuahPorto Malai jetties and Telaga Harbour) indicating that feedwastage fish excretion and faecal productions from fishcages can contribute to the formation of loose and blackflocculent under the mariculture cages whichmay then cause

The Scientific World Journal 5

Table 3 TOC OM and grain size of sediments from Langkawi Island (values are in percentage)

Stations OMa TOCb Gravelc Sandc Silt + Clayc

Kuah Jetty 1194 150 535 9387 mdashKilim Jetty 1967 317 129 9810 mdashTelaga Harbour 1148 066 994 9001 015Porto Malai Jetty 1026 127 922 8972 033Fish farm I-1 1690 113 566 9322 102Fish farm I-2 1682 095 285 9622 018Fish farm I-3 2156 141 mdash 9941 021Fish farm II-1 2241 136 mdash 9890 050Fish farm II-2 2139 133 022 9909 014Fish farm III 2049 124 mdash 9975 016aOM organic matter bTOC total organic carbon cclassification of grain size sediment

the accumulation of OM [26] The high values of OM in fishfarm sediment were also found in other sites For examplethe fish farms of Corse in France have a recorded OM valuebetween 21 and 24 [27]

Based on grain size the sediments of Langkawi Islandwere mostly sandy with sand content ranging from 8972 atPorto Malai Jetty to 9975 at fish farm III (Table 3) The claycontent of these sediments was le1 Significant relationshipswere found between sediment size (le025mm) and totalorganic carbon (TOC) (119903 = 068 119875 = 003) and between thesize and organic matter (OM) content (119903 = 066 119875 = 005)of the sediment PAHs are highly hydrophobic and usuallyaccumulate in the sediment with high OM content [18]

32 Concentrations and Profile of PAHs Table 4 shows theconcentrations of PAHs in sediment from the four chosenjetties and six fish farm stations around Langkawi IslandThetotal PAH concentrations in the popular jetties for touriststhe Kuah Jetty Kilim Jetty Porto Malai Jetty and TelagaHarbour varied from 868 plusmn 85 ng gminus1 dw in the Kilim Jettyto 1637 plusmn 190 ng gminus1 dw in Telaga Harbour with a mean of1165 plusmn 235 ng gminus1 dw Total PAHs in the sediment samplesfrom the fish farm areas similarly recorded ranges of 922 plusmn170 ng gminus1 dw at fish farm I to 1432 plusmn 693 ng gminus1 dw at fishfarm III with a mean of 1143 plusmn 635 ng gminus1 dw Sedimentfrom Telaga Harbour sediment recorded the highest totalPAHs concentration of 1637 plusmn 190 ng gminus1 dw which couldbe due to the intense harbour activities of sailing boats andyachts in this popular terminal jetty Additionally the Telagasampling site is located in the sheltered part of the waterThe lowest concentration of total PAHs was found at KilimJetty at 868 plusmn 85 ng gminus1 dw which is probably due to thedilution effect of the Kilim River Kilim River crosses theforest and rural areas and is loaded with high OM that isthen deposited at the jetty The jetty has a depth of about 1to 2m and a water transparency of 080 cm This dischargemay leach the PAHs in the jetty sediment to the open seaMoreover biological activity may return a small amount ofPAH to thewater columnwhich contributes to reducingPAHlevel in the jetty [7] The PAH pollution categories adoptedby Baumard et al [28] are as follows low 0ndash100 ng gminus1

moderate 100ndash1000 ng gminus1 high 1000ndash5000 ng gminus1 and veryhigh gt5000 ng gminus1 dw On the basis of this classificationLangkawi Island can currently be considered moderately toheavily pollute with PAHs Therefore the prevailing PAHconcentration at the jetties and fish farms frequently visitedby tourists is probably the result of the fuel used in boatspassenger ferries and buses which are the important con-tributors of PAHs in this area The leakage of petroleumand the unscrupulous disposal of engine oil from boats andferries may also contribute significantly to the level of PAHsrecorded here [29 30]

To evaluate if the sediment contaminated by PAHs inLangkawi Island (868ndash1637 ng gminus1 dw) will have a toxiceffect [10] the total PAHs levels were also compared againsteffects-based guideline values such as ERL and ERM Theconcentrations of total PAHs from all the studied stationswere lower than the sediment quality guidelines (SQGs) forthe ERL of 3442 ng gminus1 and the ERM of 24290 ng gminus1 Thesefindings suggest that the sediments from these samplinglocations are not toxic to the organisms within these areas

Table 5 shows that the total PAH concentrations in thesediment of Langkawi Island were approximately lower by1 to 2 orders of magnitude than the sediments investigatedby other studies in Singapore Island the Mediterraneancoastal environment of Egypt [16] and the Naples harbourin southern Italy [32] The levels recorded here are nearlysimilar to the levels present in the sediment of Jakarta BayIndonesia [33] Jiulong River Estuary and Western XiamenSea China [34] and Tokyo Bay Japan [33] However totalPAHs in the Langkawi sediment were approximately 1 orderof magnitude higher than those detected in other countriessuch as the marine sediments in Thailand [35] Estero deUrias Estuary Mexico [36] the Gulf of Aden Yemen [37]Southwest Taiwan [38] and in Hong Kong marine fish farms[26] (Table 5) Moreover the 2006 annual report of theMalaysian Department of Environment ranked LangkawiIsland as the thirdmost polluted area by oil and grease amongthe 15 monitoring stations in the Peninsula of MalaysiaLangkawi also exceeded the water quality standard of oil andgrease by 80 [30] In general the PAHs level in the sedimentof Langkawi Island is low to moderate compared with thefindings from previous studies

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

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CatalystsJournal of

Page 4: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

4 The Scientific World Journal

to 1mL under a gentle stream of nitrogen gas All sampleextracts were kept in amber glass vials at minus4∘C until theywere analysed within a week

27 Instrumental Analysis Extract (1 120583L) was injected intogas chromatography (Agilent 6890 technologies USA)equipped with flame ionization detector (FID) and a fusedsilica TR-5MS capillary column (30m times 025mm id) withfilm thickness of 025 120583m (Thermo Fisher USA) High purityhelium (999) was used as a carrier gas makeup gasand purge gas at flow rates of 10 45 and 300mLminrespectively The flow rates for the FID were 450mLminand 45mLmin for air and hydrogen respectively The gaschromatograph was operated in splitless mode and separa-tion was conducted with the oven temperature programmedas follows initial setting at 80∘C (1min hold) ramped to180∘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 FIDmaintained at 350∘C Agilent Chemstation software was usedto obtain the chromatogram and for data calculations Anexternal standard calibration comprising of 18 PAH standardswas used to determine the identity and quantity of eachcomponent peak in sample chromatogram

28 Quality Assurance and Quality Control (QAQC) Repli-cate samples were analysed for all samples collected fromeach station Reagent blank and recovery procedures wereanalysed simultaneously for every five samples The reagentblank containing the surrogate standard and solvent wasanalysed to evaluate the interference and contamination ofthe solvents reagents and glassware used The accuracy ofthe analytical procedure was examined by recovering thePAHs in the standard referencematerial (SRM) 1941b (marinesediment) obtained from the National Institute of Standardsand Technology (NIST USA)

The extraction clean-up procedures and setting up ofinstrumental system were examined by spiking each realsample and reagent blank with a surrogate internal standard(p-terphenyl-d14) of a known concentration Average recov-ery of the 18 PAHs and p-terphenyl-d14 ranged from 65 to137 (Table 2) which met the 70ndash130 acceptance criteriaof the EPA method [21] The instrument limit of detectionof individual PAHs was estimated to be 3 lowast 119878 where 119878 is thestandard deviation of eight replicate analyses of blanks [22]Themethod detection limit (MDL)was calculated to be 10lowast119878The MDL values of the individual PAHs ranged from 022to 12 ng gminus1 according to the analysis method with GC-FIDThese values were within the acceptable range of EPAmethod[23]

The correlation coefficient (119903) ameasure of the ldquogoodnessof fitrdquo of the regression line to the data must be ge099 tobe acceptable for the regression equation Five PAH mixturestandards were run on the same day of the sample analysisto estimate the regression equations used to calculate theconcentration of individual PAHs in the samples All PAHregression equations obtained an 119903 value of ge099 which wasacceptable according to the EPA method 8000B [21]

One-way ANOVA Games-Howell and posthoc multiplecomparison tests were used to evaluate the significance of the

Table 2 Average recovery of 18 PAHs in marine sediment (SRM1941b)

PAHs Abbreviation Recovery plusmn SDVNaphthalene Nap 123 plusmn 14

1-Methylnaphthalene 1MNap 137 plusmn 13

2-Methylnaphthalene 2MNap 74 plusmn 6

Acenaphthylene Acy 133 plusmn 11

Acenaphthene Ace 128 plusmn 3

Fluorene Fl 99 plusmn 4

Phenanthrene Phe 94 plusmn 2

Anthracene Ant 71 plusmn 11

Fluoranthene FIu 73 plusmn 10

Pyrene Pyr 79 plusmn 4

Benzo[a]anthracene BaA 74 plusmn 8

Chrysene Chr 87 plusmn 24

Benzo[b]fluoranthene BbF 99 plusmn 16

Benzo[k]fluoranthene BkF 77 plusmn 15

Benzo[a]pyrene BaP 79 plusmn 20

Indeno[123-cd]pyrene InP 75 plusmn 11

Dibenzo[ah]anthracene DBA 106 plusmn 20

Benzo[ghi]perylene BgP 90 plusmn 32

differences between the total PAHs at the sampling stationsusing SPSS version 15 for Windows Correlation Pearsonanalysis was carried out to test the relationship betweenindividual PAHs in the sediment and between total PAHsdifferent grain size and TOCs Principal component analysis(PCA) was conducted to identify the source contributions ofPAHs

3 Results and Discussion

31 Sediment Characteristics Table 3 shows the TOC OMcontent and grain size of the sediment samples taken from10 stations around Langkawi Island TOC values ranged from066 to 317 and OM content was between 1026 and2241 in dry weight Kilim Jetty which is located at themouth of Kilim River and is covered by mangroves recordeda higher TOC content than the studied locations Kilim Jettyalso has a higher percentage of OM compared to other jettiesand harbour that have the same activities OM includes thetotal amount of organic and inorganic carbon nitrogen andphosphorus [24]The highest TOC andOMcontents at KilimJetty are expected because the jetty is amangrove area locatedat the mouth of Kilim River which receive the dischargesfrom biological productivity and high sedimentation rates[25]The lowest TOC content (066) was recorded at TelagaHarbourThe lower concentration of TOC in this stationmaybe due to the low biological productivity

The OM contents (1682ndash2241) in fish farms and inKilim Jetty (Table 3) were higher in other stations (KuahPorto Malai jetties and Telaga Harbour) indicating that feedwastage fish excretion and faecal productions from fishcages can contribute to the formation of loose and blackflocculent under the mariculture cages whichmay then cause

The Scientific World Journal 5

Table 3 TOC OM and grain size of sediments from Langkawi Island (values are in percentage)

Stations OMa TOCb Gravelc Sandc Silt + Clayc

Kuah Jetty 1194 150 535 9387 mdashKilim Jetty 1967 317 129 9810 mdashTelaga Harbour 1148 066 994 9001 015Porto Malai Jetty 1026 127 922 8972 033Fish farm I-1 1690 113 566 9322 102Fish farm I-2 1682 095 285 9622 018Fish farm I-3 2156 141 mdash 9941 021Fish farm II-1 2241 136 mdash 9890 050Fish farm II-2 2139 133 022 9909 014Fish farm III 2049 124 mdash 9975 016aOM organic matter bTOC total organic carbon cclassification of grain size sediment

the accumulation of OM [26] The high values of OM in fishfarm sediment were also found in other sites For examplethe fish farms of Corse in France have a recorded OM valuebetween 21 and 24 [27]

Based on grain size the sediments of Langkawi Islandwere mostly sandy with sand content ranging from 8972 atPorto Malai Jetty to 9975 at fish farm III (Table 3) The claycontent of these sediments was le1 Significant relationshipswere found between sediment size (le025mm) and totalorganic carbon (TOC) (119903 = 068 119875 = 003) and between thesize and organic matter (OM) content (119903 = 066 119875 = 005)of the sediment PAHs are highly hydrophobic and usuallyaccumulate in the sediment with high OM content [18]

32 Concentrations and Profile of PAHs Table 4 shows theconcentrations of PAHs in sediment from the four chosenjetties and six fish farm stations around Langkawi IslandThetotal PAH concentrations in the popular jetties for touriststhe Kuah Jetty Kilim Jetty Porto Malai Jetty and TelagaHarbour varied from 868 plusmn 85 ng gminus1 dw in the Kilim Jettyto 1637 plusmn 190 ng gminus1 dw in Telaga Harbour with a mean of1165 plusmn 235 ng gminus1 dw Total PAHs in the sediment samplesfrom the fish farm areas similarly recorded ranges of 922 plusmn170 ng gminus1 dw at fish farm I to 1432 plusmn 693 ng gminus1 dw at fishfarm III with a mean of 1143 plusmn 635 ng gminus1 dw Sedimentfrom Telaga Harbour sediment recorded the highest totalPAHs concentration of 1637 plusmn 190 ng gminus1 dw which couldbe due to the intense harbour activities of sailing boats andyachts in this popular terminal jetty Additionally the Telagasampling site is located in the sheltered part of the waterThe lowest concentration of total PAHs was found at KilimJetty at 868 plusmn 85 ng gminus1 dw which is probably due to thedilution effect of the Kilim River Kilim River crosses theforest and rural areas and is loaded with high OM that isthen deposited at the jetty The jetty has a depth of about 1to 2m and a water transparency of 080 cm This dischargemay leach the PAHs in the jetty sediment to the open seaMoreover biological activity may return a small amount ofPAH to thewater columnwhich contributes to reducingPAHlevel in the jetty [7] The PAH pollution categories adoptedby Baumard et al [28] are as follows low 0ndash100 ng gminus1

moderate 100ndash1000 ng gminus1 high 1000ndash5000 ng gminus1 and veryhigh gt5000 ng gminus1 dw On the basis of this classificationLangkawi Island can currently be considered moderately toheavily pollute with PAHs Therefore the prevailing PAHconcentration at the jetties and fish farms frequently visitedby tourists is probably the result of the fuel used in boatspassenger ferries and buses which are the important con-tributors of PAHs in this area The leakage of petroleumand the unscrupulous disposal of engine oil from boats andferries may also contribute significantly to the level of PAHsrecorded here [29 30]

To evaluate if the sediment contaminated by PAHs inLangkawi Island (868ndash1637 ng gminus1 dw) will have a toxiceffect [10] the total PAHs levels were also compared againsteffects-based guideline values such as ERL and ERM Theconcentrations of total PAHs from all the studied stationswere lower than the sediment quality guidelines (SQGs) forthe ERL of 3442 ng gminus1 and the ERM of 24290 ng gminus1 Thesefindings suggest that the sediments from these samplinglocations are not toxic to the organisms within these areas

Table 5 shows that the total PAH concentrations in thesediment of Langkawi Island were approximately lower by1 to 2 orders of magnitude than the sediments investigatedby other studies in Singapore Island the Mediterraneancoastal environment of Egypt [16] and the Naples harbourin southern Italy [32] The levels recorded here are nearlysimilar to the levels present in the sediment of Jakarta BayIndonesia [33] Jiulong River Estuary and Western XiamenSea China [34] and Tokyo Bay Japan [33] However totalPAHs in the Langkawi sediment were approximately 1 orderof magnitude higher than those detected in other countriessuch as the marine sediments in Thailand [35] Estero deUrias Estuary Mexico [36] the Gulf of Aden Yemen [37]Southwest Taiwan [38] and in Hong Kong marine fish farms[26] (Table 5) Moreover the 2006 annual report of theMalaysian Department of Environment ranked LangkawiIsland as the thirdmost polluted area by oil and grease amongthe 15 monitoring stations in the Peninsula of MalaysiaLangkawi also exceeded the water quality standard of oil andgrease by 80 [30] In general the PAHs level in the sedimentof Langkawi Island is low to moderate compared with thefindings from previous studies

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

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Carbohydrate Chemistry

International Journal of

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Journal of

Chemistry

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Advances in

Physical Chemistry

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

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Theoretical ChemistryJournal of

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Analytical ChemistryInternational Journal of

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Journal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 5: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 5

Table 3 TOC OM and grain size of sediments from Langkawi Island (values are in percentage)

Stations OMa TOCb Gravelc Sandc Silt + Clayc

Kuah Jetty 1194 150 535 9387 mdashKilim Jetty 1967 317 129 9810 mdashTelaga Harbour 1148 066 994 9001 015Porto Malai Jetty 1026 127 922 8972 033Fish farm I-1 1690 113 566 9322 102Fish farm I-2 1682 095 285 9622 018Fish farm I-3 2156 141 mdash 9941 021Fish farm II-1 2241 136 mdash 9890 050Fish farm II-2 2139 133 022 9909 014Fish farm III 2049 124 mdash 9975 016aOM organic matter bTOC total organic carbon cclassification of grain size sediment

the accumulation of OM [26] The high values of OM in fishfarm sediment were also found in other sites For examplethe fish farms of Corse in France have a recorded OM valuebetween 21 and 24 [27]

Based on grain size the sediments of Langkawi Islandwere mostly sandy with sand content ranging from 8972 atPorto Malai Jetty to 9975 at fish farm III (Table 3) The claycontent of these sediments was le1 Significant relationshipswere found between sediment size (le025mm) and totalorganic carbon (TOC) (119903 = 068 119875 = 003) and between thesize and organic matter (OM) content (119903 = 066 119875 = 005)of the sediment PAHs are highly hydrophobic and usuallyaccumulate in the sediment with high OM content [18]

32 Concentrations and Profile of PAHs Table 4 shows theconcentrations of PAHs in sediment from the four chosenjetties and six fish farm stations around Langkawi IslandThetotal PAH concentrations in the popular jetties for touriststhe Kuah Jetty Kilim Jetty Porto Malai Jetty and TelagaHarbour varied from 868 plusmn 85 ng gminus1 dw in the Kilim Jettyto 1637 plusmn 190 ng gminus1 dw in Telaga Harbour with a mean of1165 plusmn 235 ng gminus1 dw Total PAHs in the sediment samplesfrom the fish farm areas similarly recorded ranges of 922 plusmn170 ng gminus1 dw at fish farm I to 1432 plusmn 693 ng gminus1 dw at fishfarm III with a mean of 1143 plusmn 635 ng gminus1 dw Sedimentfrom Telaga Harbour sediment recorded the highest totalPAHs concentration of 1637 plusmn 190 ng gminus1 dw which couldbe due to the intense harbour activities of sailing boats andyachts in this popular terminal jetty Additionally the Telagasampling site is located in the sheltered part of the waterThe lowest concentration of total PAHs was found at KilimJetty at 868 plusmn 85 ng gminus1 dw which is probably due to thedilution effect of the Kilim River Kilim River crosses theforest and rural areas and is loaded with high OM that isthen deposited at the jetty The jetty has a depth of about 1to 2m and a water transparency of 080 cm This dischargemay leach the PAHs in the jetty sediment to the open seaMoreover biological activity may return a small amount ofPAH to thewater columnwhich contributes to reducingPAHlevel in the jetty [7] The PAH pollution categories adoptedby Baumard et al [28] are as follows low 0ndash100 ng gminus1

moderate 100ndash1000 ng gminus1 high 1000ndash5000 ng gminus1 and veryhigh gt5000 ng gminus1 dw On the basis of this classificationLangkawi Island can currently be considered moderately toheavily pollute with PAHs Therefore the prevailing PAHconcentration at the jetties and fish farms frequently visitedby tourists is probably the result of the fuel used in boatspassenger ferries and buses which are the important con-tributors of PAHs in this area The leakage of petroleumand the unscrupulous disposal of engine oil from boats andferries may also contribute significantly to the level of PAHsrecorded here [29 30]

To evaluate if the sediment contaminated by PAHs inLangkawi Island (868ndash1637 ng gminus1 dw) will have a toxiceffect [10] the total PAHs levels were also compared againsteffects-based guideline values such as ERL and ERM Theconcentrations of total PAHs from all the studied stationswere lower than the sediment quality guidelines (SQGs) forthe ERL of 3442 ng gminus1 and the ERM of 24290 ng gminus1 Thesefindings suggest that the sediments from these samplinglocations are not toxic to the organisms within these areas

Table 5 shows that the total PAH concentrations in thesediment of Langkawi Island were approximately lower by1 to 2 orders of magnitude than the sediments investigatedby other studies in Singapore Island the Mediterraneancoastal environment of Egypt [16] and the Naples harbourin southern Italy [32] The levels recorded here are nearlysimilar to the levels present in the sediment of Jakarta BayIndonesia [33] Jiulong River Estuary and Western XiamenSea China [34] and Tokyo Bay Japan [33] However totalPAHs in the Langkawi sediment were approximately 1 orderof magnitude higher than those detected in other countriessuch as the marine sediments in Thailand [35] Estero deUrias Estuary Mexico [36] the Gulf of Aden Yemen [37]Southwest Taiwan [38] and in Hong Kong marine fish farms[26] (Table 5) Moreover the 2006 annual report of theMalaysian Department of Environment ranked LangkawiIsland as the thirdmost polluted area by oil and grease amongthe 15 monitoring stations in the Peninsula of MalaysiaLangkawi also exceeded the water quality standard of oil andgrease by 80 [30] In general the PAHs level in the sedimentof Langkawi Island is low to moderate compared with thefindings from previous studies

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

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[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

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Page 6: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

6 The Scientific World Journal

Table4Con

centratio

nsof

18PA

Hsinsedimento

fLangkaw

iIsla

nd(nggminus1 )(m

eanplusmnSD

)

PAH

Kuah

Jetty

Kilim

Jetty

Telaga

Harbo

urPo

rtoMalaiJetty

Fish

FI-1

Fish

FI-2

Fish

FI-3

Fish

FII-1

Fish

FII-2

Fish

FIII

Nap

72plusmn16

169plusmn66

325plusmn3

164plusmn59

362plusmn141

164plusmn20

293plusmn42

269plusmn140

110plusmn39

151plusmn99

1MNap

65plusmn0

12plusmn4

94plusmn10

65plusmn5

63plusmn42

44plusmn18

19plusmn10

81plusmn44

31plusmn10

47plusmn20

2MNap

53plusmn0

2plusmn1

70plusmn20

32plusmn9

26plusmn17

86plusmn36

13plusmn3

49plusmn6

37plusmn4

44plusmn19

Acy

16plusmn19

21plusmn18

159plusmn26

66plusmn10

16plusmn16

36plusmn22

13plusmn3

39plusmn0

35plusmn20

38plusmn9

Ace

20plusmn7

30plusmn5

242plusmn154

259plusmn121

17plusmn4

17plusmn7

31plusmn9

32plusmn9

15plusmn13

26plusmn14

Fl8plusmn5

6plusmn1

12plusmn3

10plusmn3

16plusmn17

21plusmn23

4plusmn0

8plusmn4

3plusmn3

37plusmn45

Phe

39plusmn5

40plusmn7

52plusmn3

19plusmn1

65plusmn23

25plusmn3

64plusmn5

64plusmn15

39plusmn6

44plusmn2

Ant

60plusmn14

17plusmn13

10plusmn3

23plusmn1

24plusmn1

27plusmn12

29plusmn10

7plusmn0

7plusmn7

36plusmn37

FIu

54plusmn15

33plusmn6

79plusmn2

40plusmn13

36plusmn11

23plusmn1

35plusmn1

391

41plusmn21

33plusmn6

Pyr

94plusmn1

43plusmn9

81plusmn21

71plusmn7

57plusmn3

82plusmn31

65plusmn3

73plusmn1

66plusmn32

162plusmn88

BaA

44plusmn1

139plusmn7

145plusmn31

94plusmn16

29plusmn12

21plusmn3

30plusmn2

17plusmn1

112plusmn16

28plusmn14

Chr

260plusmn12

49plusmn35

162plusmn17

116plusmn13

26plusmn10

231plusmn70

33plusmn15

218plusmn23

230plusmn117

455plusmn247

BbF

31plusmn8

63plusmn15

21plusmn16

38plusmn3

61plusmn55

18plusmn7

21plusmn21

21plusmn0

60plusmn40

34plusmn17

BkF

49plusmn3

64plusmn24

49plusmn10

68plusmn43

58plusmn60

39plusmn36

31plusmn21

40plusmn0

76plusmn43

53plusmn11

BaP

21plusmn1

55plusmn16

43plusmn23

42plusmn32

46plusmn15

18plusmn3

38plusmn6

24plusmn1

48plusmn36

29plusmn11

InP

60plusmn4

9plusmn5

5plusmn8

38plusmn0

32plusmn4

112plusmn58

77plusmn55

32plusmn7

122plusmn19

32plusmn1

DBA

47plusmn1

43plusmn11

16plusmn7

18plusmn5

18plusmn12

136plusmn39

82plusmn74

38plusmn7

97plusmn53

39plusmn11

BgP

82plusmn0

73plusmn25

72plusmn20

52plusmn36

22plusmn5

131plusmn68

44plusmn21

77plusmn10

48plusmn32

143plusmn86

sum18PA

Hs1074plusmn19

868plusmn85

1637plusmn190

1213plusmn248

974plusmn961231plusmn376922plusmn1701129plusmn1921176plusmn2421432plusmn693

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

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Journal of

Chemistry

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Advances in

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

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Theoretical ChemistryJournal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 7: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 7

Table 5 PAH concentrations (ng gminus1 dw) in sediments from various marine sites in the world

Locations Na Concentrations ReferenceLangat Estuary-Malaysia 17 322ndash2480 [46]East coast of Malaysia 17 260ndash590 [59]Singapore Island 15 15220ndash82410 [31]Egypt-Mediterranean sea 39 135ndash22600 [16]Naples harbour southern Italy 16 9ndash31774 [32]Gulf of Fos area France Mediterranean sea 13 34ndash2700 [60]Tokyo Bay Japan 26 1372ndash1615 [33]Italian marine protected areas (MPA) 16 071ndash1550 [61]Jakarta Bay Indonesia 26 257ndash1511 [33]Jiulong River Estuary and Western Xiamen Sea China 16 59ndash1177 [34]Marine sediments in Thailand 15 6ndash228 [35]Estero de Urias Estuary Mexico 12 27ndash418 [36]Italy Mediterranean sea 16 40ndash679 [62]Gulf of Aden Yemen 46 22ndash604 [37]Southwest Taiwan 28 15ndash907 [38]Hong Kong (fish farms) 16 123ndash947 [26]Langkawi Island Malaysia 18 868ndash1637 Present studyaNumber of PAHs

The dominant PAH compounds found in the sedi-ment samples include naphthalene from two-ring PAHs(208 ng gminus1) and chrysene from four-ring PAHs (178 ng gminus1)with a content percentage of 18 and 15 of the total PAHsin all stations respectively Compared to the SQGs for ERLand ERM the amount of naphthalene was higher than theERL (160 ng gminus1) and lower than the ERM (2100 ng gminus1) theseresults indicate that the probability of a negative toxic effectis lower than 50 The amount of chrysene was also lowerthanERL (384 ng gminus1) which suggests that the probability of anegative toxic effect is lower than 10The high abundance ofnaphthalene is probably caused by a fresh input of fuel due toboat activities related to tourismThe inefficiency of the two-stroke outboard engines of most Langkawi boats causes themto discharge unburned fuel directly to the water column thiscould be the reason for the high concentration of LMW-PAHs especially naphthalene [39] This finding correspondswith the findings of Tam et al [4] who found a high levelof naphthalene in the sediment of mangrove swamps inHong Kong Moreover the abundance of chrysene is dueto their very low solubility in water and high resistance todegradation Wang et al [40] arrived at the same conclusionwhen the level of chrysene in the sediment was not degradedeven 12 years after an oil spill

Benzo[ghi]perylene (BgP) a compound with the finger-print of a combustion engine and is abundant in soot [6] wasfound in sediment samples from the island This compoundhas the fourth highest mean concentration for individualPAH (744 ng gminus1) which is lower than the value indicated inthe SQGs-ERL (85 ng gminus1) The most probable source of BgPis the burning of fossil fuels (eg gasoline and diesel) of boatsand vehicle engines commonly used in the island A studyby Omar et al [41] also supported the emission of BgP fromengines The study mentioned that the highest abundance of

BgP was recorded in the urban aerosols of Kuala LumpurMalaysiaThe source of these aerosols was the incomplete fuelcombustion

Benzo[a]pyrene (BaP) is considered as the most haz-ardous of the seven carcinogenic PAHs [42] An effectivemarker of pollution by PAHs was detected in all sedimentsamples from the jetties and fish farms where the concentra-tions ranged from 18 to 55 ng gminus1 (mean of 364 ng gminus1) whichare lower than the ERL and ERM SQGs of 430 ng gminus1 and1600 ng gminus1 respectively These results show that organismsespecially fish in these locations are in safe condition at theisland

The relationship between the PAH concentration andthe physicochemical characteristics of the sediment sampleswas analyzed The results show no significant and negativecorrelation between the concentration of total PAHs and theconcentrations of TOC andOM(119903 = minus058 119903 = minus035)Thesepoor correlations are probably due to the differences in inputsof PAHs TOC and OM [43] Simpson et al [44] suggestedthat the strong correlation between total PAHs and TOC ismostly significant for highly contaminated sites when thetotal PAH concentration is greater than 2000 ng gminus1 whichcan explain the weak correlations in this study These resultsare in agreement with the results of other studies such as Zhuet al [43] and Ouyang et al [45]

33 PAH Composition The composition pattern of PAHs byring size in the sediment samples around Langkawi Islandis shown in Figure 2 On average the high molecular weightPAHswith four rings (FIu Pyr BaA andChr) five rings (BbFBkF BaP and DBA) and six rings (InP BgP) account for 3115 and 11 of the total PAH concentrations respectivelyHowever the lower molecular weight PAHs with two rings(1MNap 2MNap andNap) and three rings (Acy Ace Fl Phe

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

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Journal of

Chemistry

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Advances in

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

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Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

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Quantum Chemistry

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ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 8: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

8 The Scientific World Journal

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Relat

ive d

istrib

utio

n (

)

50

40

30

20

10

0

6 rings5 rings

4 rings3 rings2 rings

Figure 2 Relative distribution () of 2- 3- 4- 5- and 6-ring PAHsin the sediment samples of Langkawi Island

0102030405060708090

()

sumLMW (2-3 rings)sumHMW (4ndash6 rings)

Fish

FII

I

Fish

FII

-2

Fish

FII

-1

Fish

FI-

3

Fish

FI-

2

Fish

FI-

1

Port

Mal

aiJe

tty

Tela

ga H

arbo

ur

Kilim

Jetty

Kuah

Jetty

Figure 3 Relative percentages () of sumLMW and sumHMW in thesediment of different sampling stations

Ant) comprised 26 and 17 of the total PAH concentrationsin the sediment respectively Sediment samples from theKilim and Kuah jetties and fish farms I-1 II-2 and IIIwere dominated by HMW-PAH (4 to 6 rings) (Figure 3)representing a range of 658 to 765 The lower molecularweight LMW-PAHs (2 to 3 rings) were the most abundantcomponents in the sediment sample of Telaga Harbour (59)and fish farm I-1 (605) Sediment sample from PortoMalaithe fish farms I-3 and II-1 represented approximately anequal content of HMW-PAH and LMW-PAH (Figure 3) Theresults indicate that the high content of HMW fractions may

be due to lower water solubility less volatility and higherpersistence of the HMW compared with the LMW in anaquatic environment [46] The major source of HMW-PAHsin this area is also probably anthropogenic activities [47]such as the incomplete fuel combustion of boats and vehicleengines as well as the unscrupulous disposal of engine oilfrom boats and ferries [30] However the high abundanceof LMW-PAHs in some stations suggests relatively recentlocal PAH sources that entered the seawater [48] due tothe inefficient two-stroke outboard engines of most boats inLangkawi Island These engines usually discharge about 20of unburned fuel directly into the water column [48] Theresults of the paired sample 119905-test which is used to display thedifference between the means of two groups of the LMW toHMW-PAHs show a significant difference between themeansof LMW andHMW-PAHs in Langkawi Island sediment (119875 =0021) and the correlation coefficient between LMW andHMW-PAHs was insignificant and negative (119903 = minus0316)suggesting different inputs for both LMW and HMW PAHsin the sediment of Langkawi

34 Identification of PAH Sources Diagnostic ratios andprincipal component analysis (PCA) are used to explain thedetails regarding the sources of PAHs sources in sedimentsamples [49ndash51]

341 Diagnostic Ratios Diagnostic ratios are used to dis-tinguish the sources petrogenic and pyrogenic of PAH indifferent environment media depending on their physicaland chemical properties and stability against photolysis [51]Several PAHdiagnostic ratios have been selected as indicatorsthat have the most potential to distinguish between petro-genic and pyrogenic sources and are the most consistentlyquantifiable compounds in the majority of these samplesThis includes the ratios of AntAnt+Phe BaABaA+Chrand LMW-PAH to HMW-PAH [9 51 52] Table 6 showsthe diagnostic ratios of several PAH compounds and theirpossible sourcesThe ratio of AntAnt+Phe of gt01 indicates adominance of heavy fuel combustion whereas a ratio of lt01suggests petroleum sources [9] In our study the values of theAntAnt+Phe ratio were between 010 and 061 (mean 034)which suggests that the PAHs are from a combustion sourceA possible contribution source of PAH in the island is the fuelcombustion of boats and vehicle engines that are transportedto sea by direct dry and wet deposition from the atmosphereand rainwater runoff [53]

In addition a BaABaA+Chr ratio of lt02 usually impliesa petrogenic origin 02 to 035 indicates a mixed petrogenicand pyrogenic origin and gt035 indicates pyrogenic origin[51] The values of this ratio from the sediment samplesranged from 006 to 074 (mean = 034) (Table 6) Kuah Jettyfish farm I and Fish farm III showed petrogenic inputs whilethe Kilim and Proto Malai jetties Telaga Harbour fish farmI-1 and fish farm I-3 indicate a strong pyrogenic origin Fishfarm II-2 represented a mixture of petrogenic and pyrogenicinputs which may might come from direct discharge of two-stroke engine boats and the deposition of fuel combustionfromboats and vehiclesTheLMWHMWratiowas relatively

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

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Carbohydrate Chemistry

International Journal of

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Journal of

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Advances in

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

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Chromatography Research International

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Applied ChemistryJournal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 9: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 9

Table 6 Diagnostic PAH ratios in the sediment and their possible sources

BaABaA + Chrya AnAn + Phb LMWHMWc

Kuah Jetty 014 Petr 061 Pyr 045 PyrKilim Jetty 074 Pyr 029 Pyr 052 PyrTelaga Harbour 047 Pyr 016 Pyr 143 PyrPorto Malai Jetty 045 Pyr 055 Pyr 111 PyrFish FI-1 053 Pyr 027 Pyr 153 PyrFish FI-2 008 Petr 052 Pyr 052 PyrFish FI-3 047 Pyr 031 Pyr 102 PyrFish FII-1 007 Petr 010 Pyr 093 PyrFish FII-2 033 Petr + Pyr 015 Pyr 031 PyrFish FIII 006 Petr 045 Pyr 042 PyrMean 034 034 082Petrogenic S lt02 lt01 gt1Pyrogenic S gt035 gt01 lt1aBenzo[a]anthracene to benzo[a]anthracene plus chrysene banthracene to anthracene plus phenanthrene ratio cPAHs with low molecular weight to PAHswith high molecular weight Petr petrogenic Pyr pyrogenic

low for most sites le1 suggesting a pyrogenic origin of PAHsat these sites 031ndash153

However these ratios generally suggest that PAHs canbe largely attributed to the fuel combustion of petrogenicorigin Distinguishing the sources of PAH depends on thechosen diagnostic ratios which can reveal pyrogenicmaterialinputs Moreover the decrease in HMW-PAHs compared tothe LMW-PAHs in some stations can also reflect a lessercontribution by petrogenic sources due to the direct dischargeof unburned fuel from two-stroke engine boats

342 Principal Component Analysis PCA is a statistical toolthat resets large data and allows the easy visualisation ofsimilarities and differences between data sets [49] PCAresults were characterised by five principal components (PC1to PC5) accounting for 218 195 174 118 and117 of the total variance respectively (Table 7) Loadingscores higher than 03 are considered meaningful PC1has significant positive loadings for fluorene anthracenechrysene pyrene and benzo[ghi]perylene which have pyro-genic fingerprint These are usually the result of the com-plete and incomplete combustion of petroleum productsPC2 has loads of alkylated naphthalene acenaphthyleneacenaphthene fluoranthene and benz[a]anthracene Basedon this composition PC2 is essentially the petrogeniccomponents with low-temperature pyrogenic sources suchas boats and ships engines PC3 is predominantly com-posed of benzo[b]fluoranthene benzo[k]fluoranthene andbenzo[a]pyrene which are similar to the PAH compositionsof engine emission [54] PC4 had significant positive load-ings for indeno[123-cd]pyrene and dibenzo[ah]anthracenewhich could be attributed to pyrogenic sources such as gaso-line engines lubrication oil and used motor oils PC5 hadpositive loadings for phenanthrene and naphthalene whichreflected petrogenic components that could be attributed tothe direct discharge of two-stroke boat engines The resultsof the PAH source distribution indicated that the majorsources of all PAHs were petrogenic inputs such as the direct

Table 7 Rotated component loadings of the principal components(PCs) for PAH composition in the sediment of Langkawi Island

PAHs PC1 PC2 PC3 PC4 PC5Naphthalene mdash mdash mdash 0871-Methylnaphthalene mdash 055 mdash mdash 0352-Methylnaphthalene 033 049 mdash 049 mdashAcenaphthylene mdash 097 mdash mdash mdashAcenaphthene mdash 082 mdash mdash mdashFluorene 087 mdash mdash mdash mdashPhenanthrene mdash mdash mdash 090Anthracene 062 mdash mdash mdash mdashFluoranthene mdash 077 mdash mdash mdashPyrene 096 mdash mdash mdashBenzo[a]anthracene mdash 061 039 mdash mdashChrysene 089 mdash mdash mdash mdashBenzo[b]fluoranthene mdash mdash 091 mdash mdashBenzo[k]fluoranthene mdash mdash 086 mdash mdashBenzo[a]pyrene mdash mdash 090 mdash mdashIndeno[123-cd]pyrene mdash mdash mdash 087 mdashDibenzo[ah]anthracene mdash mdash mdash 086 mdashBenzo[ghi]perylene 086 mdash mdash mdashExplained variance () 218 195 174 118 117Rotation method Varimax with Kaiser Normalizationmdash PCA loading values lower than 03 are not presented

discharge of two-stroke engine boats and pyrogenic inputssuch as the deposition of complete and burning of fossil fuelfrom boats ferries ships and vehicles

35 Sediment Potential Toxicity Based on Carcinogenic PAHs(CPAHs) The toxicity assessment of Langkawi sediment wascarried out according to the total concentration of sevenpotentially carcinogenic PAHs including BaA Chr BbF BkFBaP DBA and InP [12] The sum concentrations of the sevenCPAHs ranged from 2704 to 7443 ng gminus1 dw with a mean

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

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Advances in

Physical Chemistry

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Analytical Methods in Chemistry

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Theoretical ChemistryJournal of

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Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

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Journal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 10: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

10 The Scientific World Journal

Table 8 Concentration of carcinogenic PAHs (ng gminus1 dry wt) and total toxic BaP equivalent (total TEQ ngTEQ gminus1 dry wt) in sedimentsfrom different locations around the world data show range

Location 119899 sumCPAHs sumTEQ carc ReferenceBarents Sea Russia 7 864ndash63 18ndash300 [55]Kaohsiung Harbor Taiwan 7 256ndash8067 55ndash1964 [12]Meiliang Bay China 5 621ndash2737 94ndash856 [13]Sediment quality guidelines (ERL) 7 1373 mdash [10]Sediment quality guidelines (ERM) 7 8410 mdash [10]Langkawi Island Malaysia 7 270ndash744 763ndash1746 Present study

concentration of 4751 plusmn 635 ng gminus1 dw representing 275 to633 of the total PAHs in the sediment of Langkawi IslandThese results are lower than the SQGs of CPAHs an ERL of1373 ng gminus1 and an ERM of 8410 ng gminus1 [10]

Among all known potentially carcinogenic PAHs BaPis the only PAH for which toxicological data are sufficientto derive a carcinogenic potency factor [54] The potentialtoxicity of sediment was assessed by calculating the total toxicBaP equivalent (TEQ carc) for all carcinogenic PAHs usingthe following equation [12 55]

Total TEQ carc = sum119894

119862119894

times TEF119894 carc (1)

where119862119894

is the concentration of individual carcinogenic PAH(ng gminus1 dw) and TEF119894 carc (toxic equivalency factors) isthe toxic factor of carcinogenic PAHs relative to BaP TheUS Environmental Protection Agency [56] established theTEFs for each CPAHs 01 for BaA 0001 for Chr 01 forBbF 001 for BkF 1 for BaP 01 for IP and 1 for DBA TotalTEQ carc calculated for all samples investigated in this studyranged from 763 to 1746 ng TEQ gminus1 dw with a meanconcentration of 107 plusmn 24 ng TEQ gminus1 dw (Table 8 Figure 4)Theprobable sources of these compoundswere the burning offossil fuels of the boats ships and vehicle engines extensivelyused in the island In comparison with the published studiesTEQ carc values were lower in the sediment of LangkawiIsland than those of other areas reported in other studiessuch as the sediment from the Barents Sea in Guba pechengaRussia [55] Meiliang Bay in Taihu Lake China [13] andKaohsiung Harbor in Taiwan [12] The contribution of eachcarcinogenic PAH and the average values of relative contentsto the total TEQ carc varied according to the following orderDBA (458) BaP (386) BaA (65) InP (46) BbF(38) BkF (05) and Chr (02)

36 Potential EcosystemRisk Assessment To assess the poten-tial toxicity influence of Langkawi Island sediment on thesurrounding sea organisms and their ecosystem PAH levelsin the sediment of the island were compared with thesediment toxicity screening guideline of the US NationalOceanic and Atmospheric Administration which includetwo target values ERL and ERM [10]

Table 9 shows the concentration ranges of individual PAHfor all stations Some have concentrations lower than theERL values and others have concentrations higher than theERL As shown in Table 9 all individual PAH concentrations

StationsS10S9S8S7S6S5S4S3S2S1

Relat

ive c

onte

nt (

)

120

100

80

60

40

20

0

DBAInPBaP

BkFBbFChrBaA

Figure 4 Relative contents of toxic BaP of potentially carcinogenicPAHs in sediments from the ten stations of Langkawi Island

were below the ERM which indicates that no high negativetoxic effect can occur in this area However several individualPAHs in some sites were above ERL and below ERM Whichwere occasionally caused negative toxic effects with a rangeof 10ndash50 on the surrounding sea organisms and theirecosystem For example at station S1 (Ace) S2 and S5 (NapAce) S3 (Nap 1MNap Acy Ace) S4 (Nap Acy Ace) S6 (NapAce Fl DBA BgP) S7 (Nap Ace DBA) S8 (Ace) S9 (DBA)and S10 (Ace Fl Chr BgP)

In addition another approach that can be used to evaluatethe possible biological effects or toxicity of PAHs in sedimentis the mean ERM quotient (m-ERM-q)This approach calcu-lates the mean quotients for all PAHs according to the for-mula suggested by Long and MacDonald [57] m-ERM-q =sum(119862119894

ERM119894)119899 where 119862119894

is the concentration of PAH ERM119894is the ERM value for the same target of PAH and 119899 is

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 11: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 11

Table 9 Concentration ranges of PAHs in sediment from Langkawi Island and toxicity guidelines

SQG ng gminus1 PAH concentration ng gminus1dw (s) Stations (S)ERL ERM MIN MAX S lt ERL ERL lt S lt ERM Name of S lt ERM S OF gt ERM

Nap 160 2100 72 362 3 7 S2 S3 S4 S5 S6 S7 S8 mdash1MNap 85 800 12 94 9 1 S3 mdash2MNap 70 670 2 86 10 mdash mdashAcy 44 640 13 159 8 2 S3 S4 mdashAce 16 500 15 259 1 9 S1 S2 S3 S4 S5 S6 S7 S8 S10 mdashFl 19 540 3 21 8 2 S6 S10 mdashPhe 240 1500 19 65 10 mdash mdashAnt 85 1100 7 60 10 mdash mdashFIu 600 5100 23 79 10 mdash mdashPyr 665 2600 43 162 10 mdash mdashBaA 260 1600 17 145 10 mdash mdashChr 380 2800 26 455 9 1 S10 mdashBbF mdash mdash 18 63 mdash mdash mdashBkF mdash mdash 31 76 mdash mdash mdashBaP 430 2800 18 55 10 mdash mdashInP 240 950 5 112 10 mdash mdashDBA 63 260 16 136 7 3 S6 S7 S9 mdashBgP 85 330 22 143 8 2 S6 S10 mdashsumPAHs 3442 24290 362 2532SQGs sediment quality guidelines ERL effect range-low ERM effect range-median

the number of PAH As mentioned in Long et al [58] m-ERM-q can be categorised into four levels according to theirprobability of toxicity le01 indicates an 11 probability oftoxicity 011 to 05 indicates a 30 probability of toxicity 051to 15 indicates a 46probability of toxicity andgt15 indicatesa 75 probability of toxicity Moreover the probabilitypercentage of toxicity in these four categories can be usedto classify the sampling sites as low medium-low medium-high and high-priority sites respectively According to thesecategories and classifications the m-ERM-q values of thesediment from each site in Langkawi Island ranged from 004to 010 with a mean value of 007The results of this study canbe ranked under the first category where the value is less than01 with an 11 probability of toxicity They are also classifiedas low-priority sites

4 Conclusion

PAHs were detected in all surface sediment samples collectedfrom four jetties and three marine fish farms around themain Langkawi Island Concentrations of total PAHs variedfrom 869 to 1637 ng gminus1 dw with a mean concentrationof 1167 ng gminus1 dw Concentrations did not exceed the SQGERL (3442 ng gminus1) indicating the absence of acute biologicaleffects The possible source of PAHs in the majority ofsediment samples from Langkawi Island is pyrogenic such asfrom incomplete and complete petroleum combustion fromboats ships and vehicle engines In other areas the sourcescould be petrogenic such as from nonburnt fuel discharge oftwo-stroke engine boats The results of potential toxicity and

biological effect assessment show that the surface sedimentsfrom Langkawi Island have low contamination and a lowprobability of toxic pollution

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

References

[1] N Samat ldquoAssessing land use land cover changes in langkawiisland towards sustainable urban livingrdquo Malaysian Journal ofEnvironmental Management vol 11 no 1 2010

[2] LADA Langkawi Development Authority Report 2011[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] 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

[5] 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 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 12: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

12 The Scientific World Journal

[6] 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 BangkokThailandrdquo Science of the Total Environment vol 384 no 1ndash3 pp420ndash432 2007

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

[8] National Research Council Oil in the Sea III Inputs Fates andEffects National Academies PressWashington DCUSA 2003

[9] 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

[10] E R Long D D Macdonald S L Smith and F D CalderldquoIncidence of adverse biological effects within ranges of chem-ical concentrations in marine and estuarine sedimentsrdquo Envi-ronmental Management vol 19 no 1 pp 81ndash97 1995

[11] C F Chen CW Chen C DDong andCM Kao ldquoAssessmentof toxicity of polycyclic aromatic hydrocarbons in sediments ofKaohsiung Harbor Taiwanrdquo Science of the Total EnvironmentIn press

[12] C-W Chen and C-F Chen ldquoDistribution origin and potentialtoxicological significance of polycyclic aromatic hydrocarbons(PAHs) in sediments of Kaohsiung Harbor Taiwanrdquo MarinePollution Bulletin vol 63 no 5ndash12 pp 417ndash423 2011

[13] M Qiao C Wang S Huang D Wang and Z Wang ldquoCom-position sources and potential toxicological significance ofPAHs in the surface sediments of the Meiliang Bay Taihu LakeChinardquo Environment International vol 32 no 1 pp 28ndash332006

[14] B T Sany A Salleh M Hajjartabar and G M TehranildquoEcological risk assessment of poly aromatic hydrocarbons inthe west port Malaysiardquo International Proceedings of ChemicalBiological amp Environmenta vol 33 p 130 2012

[15] N Montero M J Belzunce-Segarra I Menchaca et al ldquoInte-grative sediment assessment at atlantic spanish harbours bymeans of chemical and ecotoxicological toolsrdquo EnvironmentalMonitoring and Assessment vol 185 no 2 pp 1305ndash1318 2013

[16] A O Barakat A Mostafa T L Wade S T Sweet and N B ElSayed ldquoDistribution and characteristics of PAHs in sedimentsfrom the Mediterranean coastal environment of EgyptrdquoMarinePollution Bulletin vol 62 no 9 pp 1969ndash1978 2011

[17] D Briggs Soils Sources and Methods in Geography Butter-worths London UK 1977

[18] S Dahle V M Savinov G G Matishov A Evenset and KNaeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) in bottomsediments of the Kara Sea shelf Gulf of Ob and Yenisei BayrdquoScience of the Total Environment vol 306 no 1ndash3 pp 57ndash712003

[19] USEPAMethods 3540C Soxhlet Extraction 1996[20] USEPA EPA-Method 3630C Silica Gel Cleanup 1996[21] USEPA EPA Method 8000B Determinative Chromatographic

Separations 1996[22] R K Smith Handbook of Environmental Analysis Genium

1999[23] US-EPA United States Environmental Protection Agency

Method 610 Polynuclear Aromatic Hydrocarbons 2010[24] E S Carol E E Kruse and E L Tavani ldquoPhysicochemical

characterization of sediments from the coastal wetland ofSamborombon Bay Argentinardquo Journal of South AmericanEarth Sciences vol 34 pp 26ndash32 2012

[25] V Ramaswamy B Gaye P V Shirodkar et al ldquoDistributionand sources of organic carbon nitrogen and their isotopicsignatures in sediments from the ayeyarwady (irrawaddy)continental shelf northern Andaman Seardquo Marine Chemistryvol 111 no 3-4 pp 137ndash150 2008

[26] 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

[27] G Cancemi G De Falco and G Pergent ldquoEffects of organicmatter input fromafish farming facility on a posidonia oceanicameadowrdquo Estuarine Coastal and Shelf Science vol 56 no 5-6pp 961ndash968 2003

[28] 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

[29] E Nasher L Yook Heng Z Zakaria and S Surif ldquoConcen-trations and sources of polycyclic aromatic hydrocarbons inthe seawater around Langkawi Island Malaysiardquo Journal ofChemistry vol 2013 Article ID 975781 10 pages 2013

[30] DOEMalaysia Environmental Quality Report 2005 2006[31] C Basheer J P Obbard and H K Lee ldquoPersistent organic

pollutants in Singaporersquos coastal marine environment Part IIsedimentsrdquo Water Air and Soil Pollution vol 149 no 1ndash4 pp315ndash325 2003

[32] M SprovieriM L Feo L Prevedello et al ldquoHeavymetals poly-cyclic aromatic hydrocarbons and polychlorinated biphenylsin surface sediments of the naples harbour (southern Italy)rdquoChemosphere vol 67 no 5 pp 998ndash1009 2007

[33] R Rinawati T Koike H Koike et al ldquoDistribution sourceidentification and historical trends of organic micropollutantsin coastal sediment in Jakarta Bay Indonesiardquo Journal ofHazardous Materials vol 217-218 pp 208ndash216 2012

[34] 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

[35] R Boonyatumanond G Wattayakorn A Togo and H TakadaldquoDistribution and origins of polycyclic aromatic hydrocarbons(PAHs) in riverine estuarine and marine sediments in Thai-landrdquo Marine Pollution Bulletin vol 52 no 8 pp 942ndash9562006

[36] F M Jaward H A Alegria J G Galindo Reyes and A HoareldquoLevels of PAHs in the waters sediments and shrimps of Esterode Urias an estuary in Mexico and their toxicological effectsrdquoThe Scientific World Journal vol 2012 Article ID 687034 9pages 2012

[37] A R Mostafa T L Wade S T Sweet A K A Al-Alimi andA O Barakat ldquoDistribution and characteristics of polycyclicaromatic hydrocarbons (PAHs) in sediments of Hadhramoutcoastal area Gulf of Aden Yemenrdquo Journal of Marine Systemsvol 78 no 1 pp 1ndash8 2009

[38] J-J Jiang C-L Lee M-D Fang and J T Liu ldquoPolycyclic aro-matic hydrocarbons in coastal sediments of southwest Taiwanan appraisal of diagnostic ratios in source recognitionrdquoMarinePollution Bulletin vol 58 no 5 pp 752ndash760 2009

[39] 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

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 13: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

The Scientific World Journal 13

[40] 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

[41] 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

[42] H-SWang Z Cheng P Liang et al ldquoCharacterization of PAHsin surface sediments of aquaculture farms around the PearlRiver Deltardquo Ecotoxicology and Environmental Safety vol 73no 5 pp 900ndash906 2010

[43] L Zhu Y Chen and R Zhou ldquoDistribution of polycyclicaromatic hydrocarbons in water sediment and soil in drinkingwater resource of Zhejiang Province Chinardquo Journal of Haz-ardous Materials vol 150 no 2 pp 308ndash316 2008

[44] C D Simpson A A Mosi W R Cullen and K J ReimerldquoComposition and distribution of polycyclic aromatic hydro-carbon contamination in surficial marine sediments fromKitimat Harbor Canadardquo Science of the Total Environment vol181 no 3 pp 265ndash278 1996

[45] Y Ouyang J E Zhang and L-T Ou ldquoTemporal and spatialdistributions of sediment total organic carbon in an estuaryriverrdquo Journal of Environmental Quality vol 35 no 1 pp 93ndash100 2006

[46] M P Zakaria and A A Mahat Distribution of PolycyclicAromatic Hydrocarbon (PAHs) in Sediments in the LangatEstuary 2006

[47] R M Dickhut E A Canuel K E Gustafson et al ldquoAutomotivesources of carcinogenic polycyclic aromatic hydrocarbons asso-ciated with particulate matter in the Chesapeake Bay regionrdquoEnvironmental Science and Technology vol 34 no 21 pp 4635ndash4640 2000

[48] 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

[49] W Guo M He Z Yang C Lin X Quan and H WangldquoDistribution of polycyclic aromatic hydrocarbons in watersuspended particulate matter and sediment from Daliao Riverwatershed ChinardquoChemosphere vol 68 no 1 pp 93ndash104 2007

[50] N Qin X Z Kong Y Zhu et al ldquoDistributions sourcesand backward trajectories of atmospheric polycyclic aromatichydrocarbons at Lake Small Baiyangdian Northern ChinardquoTheScientific World Journal vol 2012 Article ID 416321 13 pages2012

[51] 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

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

[53] L Lim O Wurl S Karuppiah and J P Obbard ldquoAtmosphericwet deposition of PAHs to the sea-surface microlayerrdquo MarinePollution Bulletin vol 54 no 8 pp 1212ndash1219 2007

[54] C A Peters C D Knightes andD G Brown ldquoLong-term com-position dynamics of PAH-containing NAPLs and implications

for risk assessmentrdquo Environmental Science and Technology vol33 no 24 pp 4499ndash4507 1999

[55] V M Savinov T N Savinova G G Matishov S Dahle andK Naeligs ldquoPolycyclic aromatic hydrocarbons (PAHs) and organ-ochlorines (OCs) in bottom sediments of the Guba PechengaBarents Sea Russiardquo Science of the Total Environment vol 306no 1ndash3 pp 39ndash56 2003

[56] US-EPA Provisional Guidance For Quantitative Risk Assessmentof Polycyclic Aromatic Hydrocarbons EPA600R089 Officeof Research and Development US Environmental ProtectionAgency Washington DC USA 1993

[57] E R Long and D D MacDonald ldquoRecommended uses ofempirically derived sediment quality guidelines formarine andestuarine ecosystemsrdquo Human and Ecological Risk Assessmentvol 4 no 5 pp 1019ndash1039 1998

[58] E R Long D D MacDonald C G Severn and C B HongldquoClassifying probabilities of acute toxicity in marine sedimentswith empirically derived sediment quality guidelinesrdquo Environ-mental Toxicology and Chemistry vol 19 no 10 pp 2598ndash26012000

[59] M S Elias A b Khalik Wood and Z Hashim ldquoPolycyclic aro-matic hydrocarbon (PAH) contamination in the sediments ofEast Coast Peninsular Malaysiardquo Malaysian Journal of Analyti-cal Sciences vol 11 no 1 pp 70ndash75 2007

[60] G Mille L Asia M Guiliano L Malleret and P DoumenqldquoHydrocarbons in coastal sediments from the Mediterraneansea (Gulf of Fos area France)rdquo Marine Pollution Bulletin vol54 no 5 pp 566ndash575 2007

[61] G Perra K Pozo C Guerranti et al ldquoLevels and spatialdistribution of polycyclic aromatic hydrocarbons (PAHs) insuperficial sediment from 15 Italian marine protected areas(MPA)rdquo Marine Pollution Bulletin vol 62 no 4 pp 874ndash8772011

[62] P Montuori and M Triassi ldquoPolycyclic aromatic hydrocarbonsloads into the Mediterranean Sea estimate of Sarno Riverinputsrdquo Marine Pollution Bulletin vol 64 no 3 pp 512ndash5202012

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 14: Research Article Assessing the Ecological Risk of ...downloads.hindawi.com/journals/tswj/2013/858309.pdf · Kilim Jetty, Porto Malai Jetty, Kuah Jetty, and six stations in sh farms

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of