research article marine environmental risk assessment of ......langkawi island n malacca strait (a)...

Hindawi Publishing CorporationInternational Journal of OceanographyVolume 2013 Article ID 482451 6 pageshttpdxdoiorg1011552013482451

Research ArticleMarine Environmental Risk Assessment of Sungai KilimLangkawi Malaysia Heavy Metal Enrichment Factors inSediments as Assessment Indexes

Jamil Tajam and Mohd Lias Kamal

Centre of Ocean Research Conservation amp Advances (ORCA) Division of Research Industrial LinkageCommunity Network amp Alumni Universiti Teknologi MARA 02600 Arau Perlis Malaysia

Correspondence should be addressed to Jamil Tajam jamiltajamperlisuitmedumy

Received 4 December 2012 Revised 12 February 2013 Accepted 13 May 2013

Academic Editor Heinrich Huhnerfuss

Copyright copy 2013 J Tajam and M L Kamal This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Concentrations of Cd Co Pb and Zn in riverbed sediments from six sampling stations along the Sungai Kilim LangkawiMalaysiawere determined by using the Teflon Bomb Digestion From this study the concentrations of heavy metals in riverbed sedimentswere found ranging between 610 and 887 120583gg dryweight forCo 003 and 045 120583gg dryweight forCd 598 and 749 120583gg dryweightfor Zn and 106 and 1169 120583gg dry weight for Pb From the observation these areas were polluted by domestic waste aquacultureand tourism activities For clarity enrichment factor index was used to determine the level of sediment contamination in the studyarea From this study the average EF value is a bit high for Cd (215plusmn117) followed by Zn (112plusmn009) Pb (044plusmn032) and lastlyCo (036 plusmn 004) Based on the contamination categories Cd was categorised as moderately enriched while the rest of the metalsstudied were in deficient-to-minimally enriched by the anthropogenic sources

1 IntroductionHeavy metals are one of the most poisonous and seriousgroups of pollutants due to their high toxicity abundance andease of accumulation from various plants and animals It hasbeen accepted that heavymetals can exist in the environmentderiving from a variety of natural and anthropogenic sourcesThe phenomena of erosion acidification and weatheringprocesses have brought input of these metals into the envi-ronment in a natural way According to Idris [1] the naturaloccurrence of heavymetals in aquatic environments and theirmovement through the hydrocycle in addition to the inputsfrom anthropogenic activities reflect their ubiquity and com-plexity Meanwhile human activities also contribute to theexistence of thesemetals such as industrial processes agricul-tural and aquaculture activities domestic wastes and emis-sion from vehicles [2]

Nowadays these anthropogenic heavy metals contributeto the uppermost pollution to the aquatic environment espe-cially in the sediment Sediment plays a major role in deter-mining the pollution pattern of marine ecosystem [3] Ac-cording to Singh et al [4] and Mwamburi [5] the sediments

can act as both carriers and sinks for contaminants reflectingthe history of pollutionwhile also providing a record of catch-ment inputs into the aquatic ecosystem On the other handsediment can play a significant role as a scavenger agent forheavy metals and an adsorptive sink in marine environment[6 7] Tsugonai and Yamada [8] further explained that aquat-ic sediment can act as scavengers of metals in the environ-ment due to its several sulfides organic matter iron andmanganese oxides and clays Hence the use of sediments isadvantageous to assess human impacts on the marine envi-ronment

For these reasons the assessment of pollutants in the estu-ary system of Sungai Kilim Langkawi was carried out toperform the current sediment data assessment in order toassess its level of pollution in this area Generally SungaiKilim is situated in the north-eastern region of Pulau Lang-kawi The river is located at approximately 99∘52101584080110158401015840 E and6∘251015840397510158401015840N Sungai Kilim has become one of the popularsites to be visited for its attractive ecology and features Due toits uniqueness ecotourism benefits towards many locals andtourists [8]The downstream of Sungai Kilim is characterized

2 International Journal of Oceanography

Study area

LangkawiIsland

NMalacca

Strait

(a)

6425

642

6415

641

6405

99855 9986 99865 9987 99875

St1

St2

St3

St5

St6

St4

Sampling station

(b)

Figure 1 Sampling area

by the high number of karst formations with high density ofvegetative roots covering its surface The middle stream isconnected to two small rivers or tributaries Beyond the up-stream urbanization conquered the banks where roads res-taurants and tourist jetty are developed well for tourismactivities

Recently quite a number of heavymetal assessment stud-ies have been reported in this area This assessment is par-ticularly carried out in order to protect and conserve the envi-ronment of the Kilim River from further contamination byanthropogenic sources Furthermore the information gath-ered from this monitoring study may also provide an aid inthe management of suitable policy for Langkawi Develop-ment Authority (LADA) to preserve the Sungai Kilim eco-system as Kilim Karst Geoforest Park

2 Methodology

21 Sample Collection and Preservation Sample collectionwas conducted in December 2009 during the northeast mon-soon season Generally Sungai Kilim Langkawi (Figure 1)is very popular for a variety of ecotourism activities anddue to this major development has been done to improvethe riverrsquos quality for providing the best services to touristsThese include eagle feeding activities (Station 3) floating res-taurants aquaculture (Station 4) yacht anchoring area (Sta-tion 4) and also boating services (Station 6) Therefore sixstations were established along the Sungai Kilim and markedusing GPS (global positioning system) (Table 1) These loca-tions were selected based on the fact that they might havebeen impacted by the nearby source of contaminationThe distance between each station was approximately 1 kmRiverbed sediment samples were collected using the VanVeen Grab where afterwards samples were placed in plasticbags which were previously immersed in 5 nitric acid fortwo to three days to prevent sample contamination The sed-iment samples were then preserved in the ice box at 4∘C tomaintain the original condition of the samples At the lab-oratory samples were dried in the oven at 105∘C for 24 hours

Table 1 The coordinates for each sampling station

Station Latitude Longitude1 06∘251015840324610158401015840N 099∘521015840064210158401015840N2 06∘251015840051410158401015840N 099∘511015840579110158401015840N3 06∘241015840577810158401015840N 099∘521015840205710158401015840N4 06∘251015840009610158401015840N 099∘511015840475810158401015840N5 06∘241015840335410158401015840N 099∘511015840561010158401015840N6 06∘241015840246610158401015840N 099∘511015840349210158401015840N

For heavy-metal analysis it was ensured that the sampleshad been completely dried before grinding the samples withmortar and pestle and sieved under 63120583msize Precautions inpreventing sample contamination were given priority Sam-ples were then stored in labelled plastic vials and kept in thedrying cabinet until lab analysis

22 Sample Digestion In this study the digestion and ana-lytical procedures were adopted and applied from those ofKamaruzzaman [9] Jamil [10] and Trimm et al [11] withlittlemodifications For this analysis 005 g of the fine powdersediment (lt63120583m) was weighed and put into a Teflon vesselAfter that 15mL of mixed acid (25 HF 3 HNO

3 3 HCl)

was added into the Teflon vessels using a single channel pi-pette 100ndash1000microlitre (120583L) of the brand CappAero whichwas ISO 9001 2000 certified This digestion method is alsoknown as the aqua regia + HF digestion method which wasalso applied by Chen and Ma [12] and Deely and Fergusson[13] Finally the Teflon Bomb jackets were screwed tightlyto prevent the appearance of silicate gel on their bodiesbefore placing the Teflon bombs into the oven for 6 hoursat 160∘C After 6 hours they were cooled down under roomtemperature where after that 30mL of acid solution com-posed of ethylenediaminetetraacetic acid (EDTA) and boricacid was added The samples were then again put into theoven at 160∘C for another 6 hoursThe clear solution obtainedwas transferred into centrifuge tubes andmeshed up to 10mLwith Mili-Q water To verify the precision of the analytical

International Journal of Oceanography 3

Table 2 Five contaminant categories based on the EF value [25]

Enrichment factor (EF) value Contamination degreelt2 Deficiency to minimal enrichment2ndash5 Moderate enrichment5ndash20 Significant enrichment20ndash40 Very high enrichmentgt40 Extremely high enrichment

procedures the sediment samples were analysed in threereplicates for each sampling point and a sample blank To con-firm analytical accuracy portions of certified reference mate-rials (SRM1646a-estuarine sediments) from the National In-stitute of Standards and Technology (NIST) were analysedwith each batch of samples The concentrations of metals(Cd Co Fe Pb and Zn) in the final digested solutions werethen analysed using the Inductively Coupled Plasma MassSpectrometer (Perkin Elmer Elan 9000)

23 Ecological Risk Assessment In this study Fe is used as thenormalizedmetal as it is an acceptable normalization elementto be used in the calculation of enrichment factor since Fe dis-tributionwas not related to other heavymetals [13] Fe usuallyhas a relatively high natural concentration and is thereforenot expected to be substantially enriched fromanthropogenicsources in estuarine sediments [14] These facts are in accor-dance with Daskalakis and OrsquoConnor [15] who proposed thatFe is associated with fine solid surfaces where its geochem-istry is similar to that ofmany tracemetals and its natural sed-iment concentration tends to be uniform Moreover a widerange of studies have used Fe and Al normalizations as analternative to grain-size normalization [16 17] The enrich-ment factors (EFs) for each metal were calculated based onthe formula following [18ndash20]

EF =(119862119904119862Fe)sample

(119862119904119862Fe)crust

(1)

Meanwhile the values for the earthrsquos crustal elementswere taken from Carmichael [21] Bodek et al [22] andRonov and Yaroshevsky [23] as published by Lide [24] Theresulting values were then referred to the contaminant cat-egories proposed by Sutherland [25] to reveal and acknowl-edge the enrichment degree of the heavy metals as illustratedby Table 2

3 Result and Discussion

For method validation certified reference material(SRM1646a) was determined as a precision check The per-centage of recoveries (119899 = 5 for each metal) for certified andmeasured concentration of thosemetals was satisfactory withthe recoveries being 8167ndash10224 Table 3 shows the recov-ery test results for SRM (1646a) analysis

From this study the heavymetal contents of the sedimentwere analysed and the results were depicted in Table 4 Thetrend of mean concentration of heavy metals in Sungai Kilim

Table 3 Recovery test results (concentration for Fe is in percentage() while other metals are in 120583gg dry weight)

Heavy metals Measured SRM Certified value Recovery ()Iron Fe 2053 plusmn 0115 2008 plusmn 0039 10224Cadmium Cd 0127 plusmn 0011 0148 plusmn 0007 8581Cobalt Co 4726 plusmn 0028 5000 9452Lead Pb 9552 plusmn 0473 117 plusmn 12 8167Zinc Zn 45389 plusmn 0698 489 plusmn 160 9282

was Fe gt Zn gt Co gt Pb gt Cd According to Table 4 theconcentration of Fe along the stations increased toward theupstream area with the average value of 4803 plusmn 0422Themaximum and minimum concentration of Fe were obtainedfrom St5 and St1 with the values 5230 and 4086 res-pectively Furthermore the highest concentration of Zn wasfound at St6 with a value of 74923120583gg dry weight whereasthe lowest concentration was found at St1 with a concentra-tion of 5981 120583gg dry weight As for Zn 66817 plusmn 4856 120583ggdry weight of Zn has been found distributed along SungaiKilim In the meantime Co and Pb displayed the highestvalue at St2 (8872 120583gg dry weight) and St4 (1169 120583gg dryweight) correspondingly Lastly Cdwas distributed unevenlyalong the river with the range value of 0026ndash0452 120583gg dryweight According to the conducted statistical analysis of 2-way ANOVA there was a significant difference between thesampling stations (119875 lt 005)

According to Rickard and Niagru [26] and Muller [27]the high concentration of heavy metals is usually not onlyinfluenced by the chemical processes but also by anthro-pogenic activities Hence these anthropogenic activities car-ried along the river plus the increase of development in thatarea are seen to have impacted the river as the domesticsewage oil spill and aquaculture and many more are con-sidered to be common sights On average Fe concentrationin Sungai Kilim was lower compared to the earthrsquos crust value(5635) It was found that Fe was more concentrated atSt5 rather than the downstream which could be possiblycaused by the weathering process of sedimentary rocks thatenter the river Williamson [28] had stated that typical levelsfor Fe in sedimentary rocks are given as limestone 033sandstone 098 shale 47 and banded iron formation28 The distribution of Fe was rather uniform along theriver decreasing towards downstream This trend suggeststhat only a small amount of Fe has been drifting downstream

From the observation the highest Zn concentration valuewas discovered at St6 (upstream) and constantly decreasingtowards the downstream area This might be due to the batwaste from the bat cave at the upstream area Accordingto Miko et al [29] bat droppings contain a relatively highcontent of Zn thus this could justify the source of Zn in thisarea In addition Davis et al [30] showed that urban runoffmight be slightly smaller This is in agreement with Roneyet al [31] who found that Zn and its compounds are presentin the Earthrsquos crust and in most rocks certain minerals andsome carbonate sediments and as a result of weatheringeffects towards thesematerials soluble compounds of zinc areformed andmay be released to water [32] On the other hand


Table 4 Heavy metal in each station (concentration for Fe is depicted in percentage () while other metals are in 120583gg dry weight)

Heavy metals St1 St2 St3 St4 St5 St6 Average One-way ANOVACd 0288 0388 0452 0026 0201 0294 0275 plusmn 0137 119875 lt 005

lowast

Co 7989 8872 7686 6104 7761 7756 7695 plusmn 0818 119875 lt 005lowast

Fe 4086 4939 4939 4402 5230 5222 4803 plusmn 0422 119875 lt 005lowast

Pb 6508 1057 1844 1169 5571 5079 5292 plusmn 3473 119875 lt 005lowast

Zn 5981 66918 62245 68308 68697 74923 66817 plusmn 4856 119875 lt 005lowast

lowastThere are significant differences between the sampling stations

Table 5 The comparison of heavy metal concentrations in the present study with other heavy metal studies throughout Malaysia

No Area Cd Co Fe Pb Zn References(1) Sungai Kilim Langkawi 027 plusmn 014 769 plusmn 082 480 plusmn 042 529 plusmn 347 6682 plusmn 486 Present study(2) Terengganu River 09 plusmn 17 151 plusmn 74 63 plusmn 13 441 plusmn 144 656 plusmn 348 Jamil [10](3) Kemaman estuary mdash 1600 mdash mdash mdash Kamaruzzaman and Ong [40](4) Sungai Kelantan 182 plusmn 002 mdash 3860 2082 plusmn 028 1867 plusmn 056 Ahmad et al [41](5) Langkawi coastal water mdash mdash mdash 4187 plusmn 73 mdash Kamaruzzaman et al [42](6) Sungai Semenyih mdash 2095 plusmn 1297 mdash 4471 plusmn 2234 62 plusmn 3634 Muhammad et al [43](7) Kuala Perlis mdash mdash mdash 2577 5573 Yap and Pang [44](8) Kuala Kedah jetty mdash mdash mdash 2681 5321 Yap and Pang [44](9) Kuala Muda mdash mdash mdash 3192 336 Yap and Pang [44](10) Kuala Juru jetty mdash mdash mdash 3020 31739 Yap and Pang [44](11) Juru industrial drainage mdash mdash mdash 6532 48414 Yap and Pang [44](12) Earth bulk continental crust 015 25 563 14 70 Lide [24]

Monaci and Bargagli [33] have also found that the possiblesource of Zn may also be from motor oil grease phosphatefertilizers sewage sludge transmission fluid undercoatingasphalt and concrete

Meanwhile the average concentration of both Co andPb in this study area was discovered to be slightly lowerthan the earthrsquos crust value Faroon et al [34] stated thatthe primary anthropogenic sources of Co lie in phosphatefertilizers which in this study could be due to bat waste andaquaculture activities Naylor et al [35] have reported thatfish pellets also contain some cobalt elements A very highconcentration of Pb at St4 revealed that the surroundingswere heavily contaminated with leaded petrol stemmed fromoutboard boat engines from boating activities and places ofanchored yacht that were very concentrated in that particulararea compared to the other stations The contamination ofPb has been the major attention of many researchers such asLee et al [36] Alloway [37] and Monaci and Bargagli [33]where they have confirmed that leaded fuel automobile ormotor exhaust lubricating oil and grease are the possiblemajor sources of Pb

Lastly the Cd concentration for all sampling stations wasdramatically higher than that of the earthrsquos crust value exceptfor St4 From the observation the highest concentration in-dicated that themain source of heavymetal enrichment camefrom anthropogenic elements deposited directly or indirectlyby human activities such as boat cruising along the studyarea According to Miko et al [29] oil combustion from theboating activities was the main factor that influenced theincrease of Cd On the other hand Dong et al [38] stated that

human activities including discharges of municipal waste-water agriculture mining fossil fuels and industrial waste-water are a major source of Cd contamination in the marineenvironment especially in estuaries Cd however has a verylow solubility in aqueous solution It is readily adsorbed tosuspended solids where after a series of natural processesCd particles will finally sink and accumulate in sediments[39]

The comparison of heavy metal compositions made be-tween the study area and other places in Malaysia is availablein Table 5 The table shows the value of heavy metal con-centrations reported by previous researchers namely Kamar-uzzaman and Ong [40] Jamil [10] Ahmad et al [41] Kamar-uzzaman et al [42] Muhammad et al [43] and Yap and Pang[44] Based on Table 5 Zn concentration in the present studyarea was found to be relatively lower compared to the Juruarea and earth bulk continental crust but higher compared toother places Meanwhile the other metals obtained seemedto have lower concentrations with respect to the other placesin Malaysia

For a better estimation of anthropogenic input an enrich-ment factor (EF) was calculated for each metal by dividing itsration to the normalizing element by the same ration foundin the chosen baseline Generally throughout this study itwas found that Fe distribution was rather uniform along theriver which indicates a good stability of the metal in theriver as a whole The good stability of Fe along the riversignifies and ascertains its capability to be adopted as themostsuitable normalizing element for this study compared to othermetals particularly in this study area According to Figure 2


0

05

1

15

2

25

3

35

4

St1 St2 St3 St4 St5 St6

Enric

hmen

t fac

tor (

EF)

CdCo

PbZn

Sampling stations

Figure 2 Enrichment factors for each heavymetal in the study area

the EF value of Cd (215plusmn117) for all stations was higher than20 except for St4 and St5 This means that a significant por-tion of heavy metals was provided by anthropogenic sourcesmainly from the oil combustion from boating activitiesHowever Co (036plusmn004) Pb (044plusmn032) andZn (112plusmn009)obtainedminimal enrichment (lt20) for all stationsThe dataobtained will provide scientific evidence and may be referredto as the baseline data for a better understanding of ourestuary ecosystem In Malaysia especially in Langkawi areastudies regarding heavy-metal pollution are currently quitelimited Therefore continuous monitoring of heavy-metalpollution in this environment is definitely indispensable

4 Conclusion

From this study the overall trend of mean concentrationof heavy metals in Sungai Kilim can be concluded by thefollowing order Fe gt Zn gt Co gt Pb gt Cd However the dis-tribution of Cd in the sediment was found to be higher thanthat of the earthrsquos crust value while other metals (Co FePb and Zn) were found to be of lower values To clarifyand validate how serious the contamination level of eachmetal to the river is the enrichment factor (EF) was ap-plied According to this approach the river was moderatelyenriched by Cd The higher concentrations of Cd in thestudy area were estimated to have originated from the oilcombustion of boating activities along the study area

Acknowledgments

This research was conducted under the funding of UniversityTeknologi MARA (UiTM) through the Research ExcellenceFund The authors wish to express their gratitude to theOceanography Laboratory teammembers for their invaluableassistance and hospitality throughout the sampling period

References

[1] A M Idris ldquoCombining multivariate analysis and geochemicalapproaches for assessing heavy metal level in sediments from

Sudanese harbors along the Red Sea coastrdquoMicrochemical Jour-nal vol 90 no 2 pp 159ndash163 2008

[2] ADemirak F Yilmaz A Levent Tuna andNOzdemir ldquoHeavymetals in water sediment and tissues of Leuciscus cephalusfrom a stream in southwestern Turkeyrdquo Chemosphere vol 63no 9 pp 1451ndash1458 2006

[3] J M Casas H Rosas M Sole and C Lao ldquoHeavy metals andmetalloids in sediments from the Llobregat basin Spainrdquo Envi-ronmental Geology vol 44 no 3 pp 325ndash332 2003

[4] K P Singh D Mohan V K Singh and A Malik ldquoStudies ondistribution and fractionation of heavy metals in Gomti riversedimentsmdasha tributary of the Ganges Indiardquo Journal of Hydrol-ogy vol 312 no 1ndash4 pp 14ndash27 2005

[5] JMwamburi ldquoVariations in trace elements in bottom sedimentsof major rivers in Lake Victoriarsquos basin Kenyardquo Lakes and Res-ervoirs Research and Management vol 8 no 1 pp 5ndash13 2003

[6] A Tessier and P G C Campbell ldquoPartitioning of trace metalsin sediments relationships with bioavailabilityrdquo Hydrobiologiavol 149 no 1 pp 43ndash52 1987

[7] N W Chan ldquoProtecting and conserving our natural heritagepotentials threats and challenges of Langkawi Geoparkrdquo in Pro-ceedings of the International Conference World Civic ForumSeoul South Korea May 2009

[8] S Tsugonai andM Yamada ldquo226Ra in Bering sea sediment andits application as a geochronometerrdquo Geochemical Journal vol13 pp 231ndash238 1980

[9] B Y Kamaruzzaman Geochemistry or the marine sediments Itspaleoceanographic significance [PhD thesis] Hokkaido Univer-sity 1999

[10] T Jamil Physicochemical and sediment characteristics of the bot-tom sediment of Terengganu River Terengganu Malaysia [MSthesis] Kolej Universiti Sains dan Teknologi Malaysia 2006

[11] D L TrimmHH Beiro and S J Parker ldquoComparison of diges-tion techniques in analyses for total metals in marine sedi-mentsrdquo Bulletin of Environmental Contamination and Toxicol-ogy vol 60 no 3 pp 425ndash432 1998

[12] M Chen and L Q Ma ldquoComparison of three aqua regia diges-tion methods for twenty Florida soilsrdquo Soil Science Society ofAmerica Journal vol 65 no 2 pp 491ndash499 2001

[13] J M Deely and J E Fergusson ldquoHeavy metal and organicmatter concentrations and distributions in dated sediments ofa small estuary adjacent to a small urban areardquo The Science ofthe Total Environment vol 153 no 1-2 pp 97ndash111 1994

[14] L F Niencheski H L Windom and R Smith ldquoDistribution ofparticulate tracemetal in Patos Lagoon estuary (Brazil)rdquoMarinePollution Bulletin vol 28 no 2 pp 96ndash102 1994

[15] K D Daskalakis and T P OrsquoConnor ldquoNormalization and ele-mental sediment contamination in the coastal United StatesrdquoEnvironmental Science and Technology vol 29 no 2 pp 470ndash477 1995

[16] V T Breslin and S A Sanudo-Wilhelmy ldquoHigh spatial resolu-tion sampling of metals in the sediment and water column inPort Jefferson Harbor New Yorkrdquo Estuaries vol 22 no 3 pp669ndash680 1999

[17] H L Windom S J Schropp F D Calder et al ldquoNatural tracemetal concentrations in estuarine and coastal marine sedimentsof the Southeastern United Statesrdquo Environmental Science andTechnology vol 23 no 3 pp 314ndash320 1989

[18] S Covelli and G Fontolan ldquoApplication of a normalization pro-cedure in determining regional geochemical baselinesrdquo Envi-ronmental Geology vol 30 no 1-2 pp 34ndash45 1997


[19] V Simeonov D L Massart G Andreev and S Tsakovski ldquoAs-sessment of metal pollution based on multivariate statisticalmodeling of ldquohot spotrdquo sediments from the Black Seardquo Chemo-sphere vol 41 no 9 pp 1411ndash1417 2000

[20] L Zhang X Ye H Feng et al ldquoHeavy metal contamination inwestern Xiamen Bay sediments and its vicinity ChinardquoMarinePollution Bulletin vol 54 no 7 pp 974ndash982 2007

[21] R S CarmichaelCRCPractical Handbook of Physical Propertiesof Rocks and Minerals CRC Press Boca Raton Fla USA 1989

[22] I Bodek W J Lyman W F Reehl and D H Rosenblatt Envi-ronmental Inorganic Chemistry Pergamon Press NewYork NYUSA 1988

[23] A B Ronov andAA Yaroshevsky ldquoEarthrsquos crust geochemistryrdquoin Encyclopedia of Geochemistry and Environmental Sciences RW Fairbridge Ed Van Nostrand New York NY USA 1969

[24] D R LideCRCHandbook of Chemistry and Physics CRCPressBoca Raton Fla USA 85th edition 2005

[25] R A Sutherland ldquoBed sediment-associated trace metals in anurban stream Oahu Hawaiirdquo Environmental Geology vol 39no 6 pp 611ndash627 2000

[26] D T Rickard and J O Niagru ldquoAqueous environmental chem-istry of leadrdquo in The Biochemistry of Lead in the EnvironmentPart A Ecological Cycles pp 219ndash284 Elsevier AmsterdamTheNetherlands 1978

[27] F L L Muller ldquoColloidsolution partitioning of metal-selectiveorganic ligands and its relevance to Cu Pb and Cd cycling inthe firth of Clyderdquo Estuarine Coastal and Shelf Science vol 46no 3 pp 419ndash437 1998

[28] M A Williamson ldquoIronrdquo in Encyclopedia of Geochemistry CP Marshall and R W Fairbridge Eds pp 348ndash353 KluwerAcademic Dordrecht Germany 1999

[29] S Miko M Kuhta and S Kapelj ldquoEnvironmental baseline geo-chemistry of sediments and percolating waters in the ModricCave CroatiardquoActa Carsologica vol 31 no 1 pp 135ndash149 2002

[30] A P Davis M Shokouhian and S Ni ldquoLoading estimates oflead copper cadmium and zinc in urban runoff from specificsourcesrdquo Chemosphere vol 44 no 5 pp 997ndash1009 2001

[31] N Roney V Cassandra M Williams M Osier and S J Pai-koff Toxicological Profile for Zinc US Department Of HealthAnd Human Services Public Health Service Agency for ToxicSubstances and Disease Registry 2005

[32] NAS ldquoInorganic solutesrdquo in Drinking Water and Health vol 1pp 205ndash229 National Academy of Sciences National AcademyPress Washington DC USA 1977

[33] F Monaci and R Bargagli ldquoBarium and other trace metals asindicators of vehicle emissionsrdquo Water Air and Soil Pollutionvol 100 no 1-2 pp 89ndash98 1997

[34] O M Faroon H Abadin S Keith et al Toxicological Profilefor Cobalt US Department of Health and Human ServicesPublic Health Service Agency for Toxic Substances and DiseaseRegistry 2004

[35] S J Naylor R D Moccia and G M Durant ldquoThe chemicalcomposition of settleable solid fish waste (Manure) from com-mercial rainbow trout farms in Ontario Canadardquo North Amer-ican Journal of Aquaculture vol 61 no 1 pp 21ndash26 1999

[36] D S Lee J A Garland and A A Fox ldquoAtmospheric concentra-tions of trace elements in urban areas of the United KingdomrdquoAtmospheric Environment vol 28 no 16 pp 2691ndash2713 1994

[37] B J Alloway Heavy Metals in Soils Blackie Academic and Pro-fessional Glasgow UK 2nd edition 1995

[38] C D Dong C F ChenM S Ko and CW Chen ldquoEnrichmentaccumulation and ecological risk evaluation of cadmium in thesurface sediments of Jen-Gen River Estuary Taiwanrdquo Interna-tional Journal of Chemical Engineering and Applications vol 3no 6 pp 370ndash373 2012

[39] C W Chen C F Chen and C D Dong ldquoContamination andpotential ecological risk of mercury in sediments of KaohsiungRiver mouth Taiwanrdquo International Journal of EnvironmentalScience and Development vol 3 pp 66ndash71 2012

[40] Y Kamaruzzaman andM C Ong ldquoGeochemical proxy of somechemical elements in sediments of kemaman river Estuary Ter-engganu Malaysiardquo Sains Malaysiana vol 38 no 5 pp 631ndash636 2009

[41] A K Ahmad I Mushrifah and M Shuhaimi-Othman ldquoWaterquality and heavy metal concentrations in sediment of SungaiKelantan Kelantan Malaysia a baseline studyrdquo Sains Malay-siana vol 38 no 4 pp 435ndash442 2009

[42] B Y Kamaruzzaman N T Shuhada B Akbar et al ldquoSpatialconcentrations of lead and copper in bottom sediments ofLangkawi Coastal Area Malaysiardquo Research Journal of Environ-mental Sciences vol 5 pp 179ndash186 2011

[43] B G Muhammad N A S Wan and I Mohd ldquoSebaran logamberat dalam lembangan sungai semenyihrdquo in Proceedings of theRegional Symposium on Environment and Natural Resourcesvol 1 pp 595ndash602 Kuala Lumpur Malaysia April 2002

[44] C K Yap and B H Pang ldquoAssessment of Cu Pb and Zn con-tamination in sediment of north western Peninsular Malaysiaby using sediment quality values and different geochemical in-dicesrdquo Environmental Monitoring and Assessment vol 183 no1ndash4 pp 23ndash39 2011

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Geological ResearchJournal of


Geology Advances in


Study area

LangkawiIsland

NMalacca

Strait

(a)

6425

642

6415

641

6405

99855 9986 99865 9987 99875

St1

St2

St3

St5

St6

St4

Sampling station

(b)

Figure 1 Sampling area

by the high number of karst formations with high density ofvegetative roots covering its surface The middle stream isconnected to two small rivers or tributaries Beyond the up-stream urbanization conquered the banks where roads res-taurants and tourist jetty are developed well for tourismactivities

Recently quite a number of heavymetal assessment stud-ies have been reported in this area This assessment is par-ticularly carried out in order to protect and conserve the envi-ronment of the Kilim River from further contamination byanthropogenic sources Furthermore the information gath-ered from this monitoring study may also provide an aid inthe management of suitable policy for Langkawi Develop-ment Authority (LADA) to preserve the Sungai Kilim eco-system as Kilim Karst Geoforest Park

2 Methodology

21 Sample Collection and Preservation Sample collectionwas conducted in December 2009 during the northeast mon-soon season Generally Sungai Kilim Langkawi (Figure 1)is very popular for a variety of ecotourism activities anddue to this major development has been done to improvethe riverrsquos quality for providing the best services to touristsThese include eagle feeding activities (Station 3) floating res-taurants aquaculture (Station 4) yacht anchoring area (Sta-tion 4) and also boating services (Station 6) Therefore sixstations were established along the Sungai Kilim and markedusing GPS (global positioning system) (Table 1) These loca-tions were selected based on the fact that they might havebeen impacted by the nearby source of contaminationThe distance between each station was approximately 1 kmRiverbed sediment samples were collected using the VanVeen Grab where afterwards samples were placed in plasticbags which were previously immersed in 5 nitric acid fortwo to three days to prevent sample contamination The sed-iment samples were then preserved in the ice box at 4∘C tomaintain the original condition of the samples At the lab-oratory samples were dried in the oven at 105∘C for 24 hours

Table 1 The coordinates for each sampling station

Station Latitude Longitude1 06∘251015840324610158401015840N 099∘521015840064210158401015840N2 06∘251015840051410158401015840N 099∘511015840579110158401015840N3 06∘241015840577810158401015840N 099∘521015840205710158401015840N4 06∘251015840009610158401015840N 099∘511015840475810158401015840N5 06∘241015840335410158401015840N 099∘511015840561010158401015840N6 06∘241015840246610158401015840N 099∘511015840349210158401015840N

For heavy-metal analysis it was ensured that the sampleshad been completely dried before grinding the samples withmortar and pestle and sieved under 63120583msize Precautions inpreventing sample contamination were given priority Sam-ples were then stored in labelled plastic vials and kept in thedrying cabinet until lab analysis

22 Sample Digestion In this study the digestion and ana-lytical procedures were adopted and applied from those ofKamaruzzaman [9] Jamil [10] and Trimm et al [11] withlittlemodifications For this analysis 005 g of the fine powdersediment (lt63120583m) was weighed and put into a Teflon vesselAfter that 15mL of mixed acid (25 HF 3 HNO

3 3 HCl)

was added into the Teflon vessels using a single channel pi-pette 100ndash1000microlitre (120583L) of the brand CappAero whichwas ISO 9001 2000 certified This digestion method is alsoknown as the aqua regia + HF digestion method which wasalso applied by Chen and Ma [12] and Deely and Fergusson[13] Finally the Teflon Bomb jackets were screwed tightlyto prevent the appearance of silicate gel on their bodiesbefore placing the Teflon bombs into the oven for 6 hoursat 160∘C After 6 hours they were cooled down under roomtemperature where after that 30mL of acid solution com-posed of ethylenediaminetetraacetic acid (EDTA) and boricacid was added The samples were then again put into theoven at 160∘C for another 6 hoursThe clear solution obtainedwas transferred into centrifuge tubes andmeshed up to 10mLwith Mili-Q water To verify the precision of the analytical






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