an investigation of the levels and distribution of selected heavy

Research ArticleAn Investigation of the Levels and Distribution ofSelected Heavy Metals in Sediments and Plant Species withinthe Vicinity of Ex-Iron Mine in Bukit Besi

Ahmad A Kutty and Sarah A Al-Mahaqeri

School of Environmental and Natural Resource Sciences Universiti Kebangsaan Malaysia 43600 Bangi Selangor Malaysia

Correspondence should be addressed to Sarah A Al-Mahaqeri salmahaqeriyahoocom

Received 8 March 2016 Revised 19 May 2016 Accepted 11 July 2016

Academic Editor Yuangen Yang

Copyright copy 2016 A A Kutty and S A Al-Mahaqeri This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

An assessment of the abandoned mine impacts on the concentrations and distribution of heavy metals in surface sediments andplant species within the vicinity of an ex-iron mine in Malaysia was conducted The sequential extraction method was used toextract anthropogenic metals in sediments The results showed that metals in EFLE AR and OO fractions were higher thanambient concentrations which indicate that heavy metals have been loaded from ex-iron mining area into the surrounding aquaticenvironments The metal accumulation in the four dominant plant species grown naturally within the vicinity of Bukit Besi ex-iron mining was investigated Exceptional elevated concentrations of metal were found in plants and surface sediments Severalestablished criteria were applied to determine the hyperaccumulator plants The results revealed that Melastoma malabathricumand Pityrogramma calomelanos are classified as Fe and Al hyperaccumulators while Scirpus triqueterMelastoma malabathricumand Pityrogramma calomelanos were undoubtedly hyperaccumulator for Cd

1 Introduction

Metal contamination in abandonedmines is a global environ-mental problem which various countries around the worldare suffering from This problem ranks among the most sig-nificant environmental challenges worldwide which requiresongoing evaluation and urgent solution to overcoming thisproblem and its negative impacts [1] In general to improvethe conservation of contaminated mine areas and measurethe achievement goals on management of mine contami-nation we need access to relevant information Thereforecontamination of aquatic environments by heavy metalarising from both of mining processes either undergroundor surfacemine workings has received growing environmen-tal concern worldwide [2 3] In Malaysia several studiesrevealed that mining activities have generated considerablechemical and physical changes in their surrounding aquaticenvironments [2 4ndash6]

Bukit Besi was once an important iron mining site in theworld It was one of the worldrsquos largest iron ore producersin Southeast Asia Several recent studies have identified the

mining impacted catchments as a major source of toxicmetals discharge and other pollutants in dissolved forms Inaddition these studies have discovered that the toxic elementsare suspended in the material and are dispersed into sur-rounding river systems and floodplains in many parts of theworld [7ndash9]Therefore abandonedmining sites are defined asone of the most important sources of metal pollutants [10] Inthis regard sediments consist of a complex mixture of geo-chemical fractions which involves various physicochemicalforms of the elements Therefore the assessment of sedimentcontamination requires full knowledge of the mineral phasewith which metals are associated its physicochemical formsand strength of binding involved [6 11] The sequentialextraction technique has been developed to provide qualityinformation pertaining to the physicochemical forms pro-cesses that influence the mobilization bioavailability anddistribution of trace metals in sediments [11 12] Thus in thepresent study themodified sequential extraction technique iscarefully utilized to assess the distribution and levels of heavymetal in sediments

Hindawi Publishing CorporationJournal of ChemistryVolume 2016 Article ID 2096147 12 pageshttpdxdoiorg10115520162096147

2 Journal of Chemistry

In abandoned mining sites high concentrations of metalare found to have significant impacts on the deteriorationof the quality of the ecosystem increasing the phytotoxicityin sediments [13] Over time these impacts may cause theenhancement of nutritional deficiencies the disappearanceof the natural vegetative the decline in biological diversityand finally posing an ecological risk to the ecosystem Theeffects of these contaminants are quite varied and depend onseveral factors such as climatic changes micrometeorologicalcondition chemical form of metal sedimentsrsquo physicochem-ical characteristics and water column [14] The hazardousmetals could be transported for long distances far away fromcontamination sources via wind runoff and rainfall based onthe chemical forms of the metals either in gaseous form or(particulates) by the size of the fractions of metals [15 16]

Plants play a key role in forming a fundamental part ofthe trophic structure of aquatic ecosystems [9] Plants canbe considered as intermediate reservoirs of heavy metalsfrom the sediments water and air and are ingested by manand animal through the food chain [17] In abandoned minesites aquatic plants populations react differently to changesin the environmental factors Recent studies have indicatedthat aquatic plants have a high absorption capacity of toxicmetals through the roots or via precipitation within therhizosphere and leaves during the circulation of nutrients[18ndash21] Plants are capable of using metals through differentways such as complexing them in their sedentary naturebinding them into cell wall andor combining them toproduce certain organic acid or proteins [22]Therefore plantspecies are considered as good bioindicators in the earlystages of heavy metal pollution Additionally they can beused for monitoring the state of the aquatic ecosystem andthe changes or alterations in the aquatic environments [9]High heavy metal content in soil water sediments andorthe air is found to be the most common stress factor whichis faced by plant species naturally growing in abandonedmine sites Therefore it is imperative that plant speciesmust adapt to different environmental conditions in order tosurvive According to their adaptation strategies and heavymetals content plant species can be classified into threemain groups metal excluders indicators and accumulatorsor hyperaccumulators [23]

Hyperaccumulator plants are widely used in phytore-mediation This is due to the fact that these plants cancontain Pb Cu Co Cr and Ni gt1000 120583gg or 10000 120583ggof Fe Mn and Zn or Cd gt50 120583gg in any abovegroundtissue in their natural habitat without suffering toxic effects[23 24] Metal excluders can be defined as plants thatcan restrict translocation of heavy metals from their rootsinto their aboveground tissues These species can maintainrelatively low levels of metal concentrations in their shootsas compared with the elevated metals concentrations in theirroots [22] Indicator plants are plants which have the abilityto accumulate the metals in their aboveground tissues thusthe metals levels in the tissues reflect the metal levels in thesediments [25 26] However this type of plants dies off undercontinued uptake of heavy metals

Determination of the hyperaccumulator indicator andexclude plant species is dependent on several criteria A plant

species can be considered as a hyperaccumulator for heavymetals if it meets one of the following four strict criteria(1) the ratio of heavy metal concentrations of shoot to rootmust be higher than 1 (metal concentration in shootmetalconcentration in Root) ge1 [25] (2) (metal concentrationin rootmetal concentration in sediments or soil) gt 1 [26ndash28] (3) the hyperaccumulator plant must be 10ndash500 timesgreater than the same species growing in noncontaminatedsites [25 27] and (4) plants with Pb Cu Co Cr and Nigt1000 120583gg or 10000 120583gg of Fe Mn and Zn or Cd gt50 120583ggin any aboveground tissue in their natural habitat withoutsuffering toxic effects can be classified as hyperaccumulatorplants [25 27] According to Mganga et al [25] ldquoa plantwhich has high levels of heavy metals in the roots but withshootroot quotients less than 1 is classified as a heavy metalexcluderrdquo

Considering the above facts the overall objectives of thepresent study were (1) to assess the impact of the aban-doned mine on the accumulation and distribution of PbAl Cd and Fe in surface sediments and plant species thatare growing on a contaminated site and (2) to identifyhyperaccumulator indicator and exclude plant species usingseveral established criteria Therefore the present studycontributes to discovering the hyperaccumulator plants inex-iron mine in Bukit Besi which can be used for futurestudies on the management and decontamination of heavymetal-contaminated sediments using native plant species asdetectors and early warning in decreasing the environmentalrisk posed by mining activities

2 Materials and Methods

21 Study Area Bukit Besi is an abandoned open-pit ironmine type It was one of the worldrsquos largest iron ore pro-ducers Bukit Besi is located about 85 km south of KualaTerengganu Malaysia During 1919 a team of Japanese geol-ogists discovered the iron ore at Bukit Besi then in 1923Dungun was one of the worldrsquos largest iron ore producersin Southeast Asia In the 1960s mining activities have beenstopped due to the decline in iron production Bukit Besicovers sim2400 ha of land The major minerals in this area aremagnetite quartz and goethite [2] Recently after theminingindustry has become unproductive the old structures plantsand rail tracks have been left with tailings Over time thetailings can pose a great threat to natural reserves due tolandscape changes damage to natural drainage pollutionand destruction of terrestrial and aquatic habitat ecosystemsfor decades As the iron ore of Bukit Besi became depleted inthe 1960s and 1970s themining has been stopped Dependingon the location of the catchments and distribution of the slagheaps five sampling stations were selected as described inTable 1

22 Samples Collection and Analysis For sediments surfacesediments (0ndash5 cm depth) were collected after removingplant debris and large materials Sediment samples were keptin precleaned plastic bags with tags and then sent to thesoil laboratory in the Biology Building at the UniversitiKebangsaan Malaysia (UKM) Five replicates of sediments

Journal of Chemistry 3

Table 1 The description and location of the sampling stations

Station Description Location1 Catchment downstream of the mining sites 4∘45101584021210158401015840N 103∘10101584062210158401015840E2 Leachates from the open pit mine within mine site 04∘45101584022110158401015840N 103∘10101584065210158401015840E3 Large catchment located directly downstream of old mine sites 03∘53101584059510158401015840N 103∘01101584035510158401015840E4 Stream formed by flowing ex-mine water and rainfall water 04∘45101584086710158401015840N 103∘11101584026410158401015840E5 Catchment located on a road in the ex-mine area 04∘4610158403210158401015840N 103∘10101584088910158401015840E

were selected for each station The complete samples weredried in room temperature until reaching a constant weightThe samples were then sieved to size of lt63 120583m and savedin precleaned plastic bags until analysis The measurementsof sediment characteristics (pH grain size lt 63 120583m andpercentage of organicmatter)weremade on the air-dried sed-imentsThe pHwas determined by themethods employed byDuddridge and Wainwright [29] The grain-sized lt63 120583msediments were measured according to Badri and Aston[15] and the percentage organic matter was evaluated usingmethod suggested byWalkley and Black [30] In addition thesequential extraction method was used as described by Badriand Aston [15]

For plant a total of 20 plants belonging to four familiesfour genera and four species were collected from differentstations within the vicinity of Bukit Besi Photographs weretaken for each plants species before taking the sampleOne duplicate of specimen per species was collected andplaced in plastic bags with ethanol and brought to laboratoryfor identification In the lab the plant samples have beenidentified by horticultural botanists in botanical herbariumat Universiti Kebangsaan Malaysia several books have beenused during the identification such as [31ndash33] Plant sampleswere washed with tap water to remove the sediment particlesfollowed by three times of washing twice with distilledwater and once with deionized water The samples weredried using tissue paper and then (stems roots and leaves)were separated using stainless steel scissors The separatedtissues were cut into small pieces and transferred to acid-washed petri dishes and then dried to a constant weightin an oven at 70∘C for three days Finally when samplesreached the constant weight samples were allowed to cool inthe desiccators and then pulverized using laboratory mortarto produce homogeneous tissues The metals were extractedaccording to the method of [34] The description of collectedplant species is given in Table 2

23 Quality Assurance of Heavy Metals Analysis and QualityControl Samples The standard reference materials (SRM)were used to evaluate efficiency of extraction methodsand to validate results In the present study two differenttypes of SRM were used namely Reference Material 8704Buffalo River Sediment National Institute of Standards ampTechnology and LGC7162 Certificate Reference Material(strawberry leaves) In sediments samples recoveries of thetarget elements were satisfactory and ranged from 10207to 10986 of the certified values as shown in Table 3In plants recovery of the studied elements in LGC7162Certificate ReferenceMaterial (strawberry leaves) was ranged

Table 2 The scientific name family and collection station of theplant species

Scientific name Family Collectionstation

Scirpus triqueter Torr Cyperaceae Station (5)Melastoma malabathricum L Melastomataceae Station (1)Pityrogramma calomelanos(L) Link Pteridaceae Station (4)

Blechnum orientale Linn Blechnaceae Station (4)

Table 3 Validation of extraction and analysis of standard referencesmaterials (sediments)

Element Determined values SRM values Recovery ()Pb 1531 150 1021Cd 323 294 1099Al 641 610 1051Fe 415 397 1045

Table 4 Validation of extraction and analysis of standard referencesmaterials (plants)


between 8611 and 111 from the certified value as shown inTable 4

As a precautionary exercise to avoid the contaminationduring experiments all laboratory equipment (ie glasswarepolyethylene bottles plastic containers pump tubing andplastic bags) was initially soaked in phosphate-free soaprinsed with tap water and then immersed in a solutionof 10 nitric acid (HNO

3) for 1ndash3 days It was rinsed

twice with distilled water and ended with distilled deionizedwater and then it was dried on a clean bench in dry roomtemperature Chemical solutions which were used in thecleaning stages were also of analytical reagent grade Thelaboratory equipment was permanently kept dust-free bycovering the equipment during various stages during theexperimental processes Blank samples are prepared routinelyand were used to determine any contamination that mayhave been contributed from any sample processing steps oranalytical procedure and chemical solutions


Concentrations of heavy metal in the final solution weredetermined by using inductively coupled plasma mass spec-trometry (ICP-MS) (model ELAN 9000 Perkin Elmer ICP-MS USA) ICP multielement standard solution of 1000mgLsupplied byMerck was used after dilution In order to achievehigh quality results a calibration blank and an independentcalibration verification standard were analyzed for every 20samples to confirm the calibration status of the ICP-MSMatrix interference (blank) was lt1 for all studied elementsMetal concentrations were expressed as 120583gg dry weight ofsediments and plants (leaf stem and root)

24 Calculation of Hyperaccumulation Criteria In most ofthe established criteria of identifying themetals accumulationplants it is imperative to consider the metal concentrationsin the aboveground biomass and the metal concentrations inthe sediments or soil [24] In addition both of the translo-cation factor (TF) and the enrichment factor (EF) must beevaluated to determine that a particular plant is a metalhyperaccumulatorThe enrichment factor is calculated as theratio between the plant shoot concentrations and sedimentconcentrations (metal concentration in shootmetal concen-tration in sediments or soil) by Branquinho et al [28] Thetranslocation factor can be calculated by dividing the metalconcentration in the shoot by the metal concentration in theroot (metal concentration in shootmetal concentration inRoot) According to Cheraghi et al [24] a hyperaccumulatorplant should have EF or TF gt1

25 Statistical Analysis SPSS version 210 was used to cal-culate the statistical analysis The correlation between thesediments characteristics (pH organic matter) with heavymetals concentrations at the third fraction (the oxidizable-organic fraction) was calculated using Pearsonrsquos correlationcoefficients (1199032) A one-way ANOVA was used to determinesignificance in metal concentrations differences between thesampling stations and between the plants species and meanswere compared using Tukeyrsquos test

3 Result

31 Validations of AnalyticalMethods In sediments recoveryof all of the target elements in SRM certified standardreference materials from the sediment sample (ReferenceMaterial 8704 Buffalo River Sediment National Instituteof Standards amp Technology) was ranged from 10207 to10986 from the certified value as shown in Table 3 Resultsindicate a good recovery and tested sequential extraction isappropriate to be followed

In plants to evaluate the quality of extraction methodLGC7162 Certificate Reference Material (strawberry leaves)was used A good agreement of the obtained values and thecertified values was achieved Recovery of all of the studiedelements in SRM was ranged from 8611 to 111 from thecertified value as shown in Table 4

32 Physical Properties of Sediments Thedescriptive statisticsfor sediment samples basic properties (pH OM () and

Table 5 The mean value of the selected sediments properties

Station pH Grain size lt 63 120583 () Organic matter ()1 345 plusmn 002 286 plusmn 032 156 plusmn 026

2 385 plusmn 001 261 plusmn 058 312 plusmn 118




grain size lt63 120583m ()) are shown in Table 5 The sedimentrsquospH value was extremely acidic with values ranging between345 and 385 On average the grain sizes lt63 120583mof studiedsediments from the ex-mine catchments are determined to beonly 2894The percentage of organic matter (OM) contentin the sediments at all the stations was low ranging between156 at station 1 and 312 at stations 2 and 5Themetals canbe in complex formwith insoluble organic compounds whichtherefore in effect reduces their mobility and bioavailabilityfor aquatic organisms [35]

33 HeavyMetal Concentrations in Plants and Sediments Themean concentration and percentages of Pb Al Cd and Fein the surface sediments form five different stations of theBukit Besi are presented in Table 6 The analytical results ofthe present study showed that the sequence of heavy metallevels in plants was similar to those in sediments howeversome element concentrations were higher in sediments ascompared with those reported in plant species Althoughthere are differences in exposure and uptake processes of eachplant species the mean concentrations of heavy metal in theevaluated plants species tend to decrease as the distance awayfrom the ex-mining area along the flow direction increasesThe toxic levels of Fe were found in leaves of all the analyzedplant samples

The mean concentrations of heavy metal in differentparts (leaves stem shoot and root) of plants species aredemonstrated in Table 7 The obtained results showed thatdependent on the most common criteria almost all of thestudied plant species were able to grow on sediments withelevated heavy metal concentrations In the present studyfour different plant species were evaluated against a numberof heavy metals namely iron aluminium cadmium andlead based metals on the several established criteria Table 9summarizes the results of translocation factor (TF) andenrichment factor (EF) for plant species growing aroundex-iron mine The results demonstrated that S triqueterM malabathricum P calomelanos and B orientale wereclassified as good bioindicators plant species for Fe and Al

4 Discussion

41 Heavy Metal Concentrations and Distributions in Sedi-ments In general the sedimentrsquos pH value plays a major rolein the controllingactivities and transfer of heavy metal insediments Meanwhile the pH values of sediments at all ofthe sampling sites were acidic which prevented most of theaquatic herbaceous plants from growing [17] According to


Table 6Themean concentration (120583gg) and percentages () of PbAl Cd and Fe in the surface sediments from five different stationsof the Bukit Besi ex-mine catchments

Element (EFLE) (AR) (OO) (119877) NonresistantStation 1

FeMean 1980 1423 2459 9850

373SD 122 100 578 972Ratio (126) (906) (157) (627)

AlMean 521 551 1021 3034

271SD 254 271 193 903Ratio (125) (133) (245) (729)

CdMean 005 002 002 012

411SD 000 000 000 000Ratio (235) (913) (840) (590)

PbMean 020 020 055 136

66SD 001 001 001 217Ratio (14) (14) (38) (934)

Station 2Fe

Mean 381 251 4044 10163297SD 342 403 402 628

Ratio (003) (17) (280) (703)Al

Mean 056 400 1495 3034336SD 024 030 140 809

Ratio (001) (088) (327) (664)Cd

Mean 001 002 01 02333SD 000 001 000 032

Ratio (41) (599) (232) (668)Pb

Mean 008 17 092 138163SD 000 004 090 144

Ratio (048) (102) (559) (837)Station 3

FeMean 244 653 2425 10612

239SD 477 344 115 305Ratio (175) (468) (174) (762)

AlMean 208 776 2244 3034

436SD 308 079 251 325Ratio (039) (144) (417) (564)

CdMean 004 003 004 002

849SD 000 000 000 000Ratio (346) (212) (290) (151)

PbMean 005 029 054 148

561SD 001 000 004 051Ratio (035) (184) (343) (944)

Table 6 Continued


FeMean 287 320 3511 13624

220SD 17 694 375 844Ratio (002) (183) (201) (780)

AlMean 085 443 2637 3034

469SD 026 069 907 325Ratio (002) (078) (461) (531)

CdMean 002 002 005 012

441SD 000 000 000 000Ratio (831) (101) (257) (560)

PbMean 007 134 119 81

243SD 000 002 040 11Ratio (068) (125) (111) (757)

Station 5FeMean 232 324 3503 5701

403SD 294 343 429 108Ratio (024) (34) (367) (597)

AlMean 675 462 2170 3034

423SD 048 072 324 432Ratio (013) (088) (413) (577)

CdMean 001 001 005 02

314SD 000 001 005 001Ratio (607) (488) (205) (686)

PbMean 002 011 153 143

105SD 001 001 001 11Ratio (014) (071) (961) (896)

Peng et al [35] a low pH increases the competition betweenH+ and the dissolved metals for binding sites (OHminus ClminusCO3

2minus S2minus and SO4

2minus) with low pH dissolving metal-carbonate complexes releasing more free metal ions into thewater column In general the low pH values are a majorindictor for formation of acid mine drainage (AMD) atBukit Besi On average the grain sizes lt63 120583m of studiedsediments from the ex-mine catchments are determined to beonly 289 Numerous studies reported that great quantitiesof metals are associated with very fine-grained particles ofsediments such as clay lt2 120583m and lt63 120583m [12 35] Thiscondition is due to these particles having larger surface areato volume ratio than coarse particles

The background values of metal in sediments are notavailable to the public therefore the comparison with theaverage concentrations in the earthrsquos crust [17] can be used todetermine the potentially toxic or anomalous concentrationsThe comparison study proved that the total heavy metals inthe sediments of the Bukit Besi ex-mine were higher than theconcentration of metals in natural earth crust as introduced


Table 7 Heavy metals concentrations in different plant species collected from within Bukit Besi ex-mine

Plant Fe (120583gg) Al (120583gg) Pb (120583gg) Cd (120583gg)S triqueter

Leaves 696 plusmn 132 200 plusmn 360 395 plusmn 001 028 plusmn 000

Stem 6664 plusmn 116 419 plusmn 904 400 plusmn 008 046 plusmn 001

Shoot 7360 619 796 074Root 8010 plusmn 101 378 plusmn 958 979 plusmn 013 028 plusmn 001

Sediments 9551 5257 160 022M malabathricum

Flower 356 plusmn 055 139 plusmn 011 lowastBDL 014 plusmn 000




Sediments 15711 4162 1459 019P calomelanos




Sediments 17457 5717 107 021B orientale




Sediments 17457 5717 107 021lowastBDL below detection limits of ICP-MS

by Kabata-Pendias [17] In finer detailed explication Al isfound to be present in the earthrsquos crust at an approximationof 8 Fe is occurring at approximately 5 with the averagecontent of Cd in the earthrsquos crust being found to be 01 120583ggand Pb is reported to be approximately at 15 120583gg [17] Thepresent study results indicated that the highest heavy metalsconcentrations are found to be associatedwith labile fractions(EFLE AR and OO) at the stations within the mine siteThe elevated metal concentrations associated with sedimentsof Bukit Besi are likely the best evidence of mining-inducedinfluence on the sediments and aquatic environments Inaddition the presence of high content of metals in sedimentsis indicating that these metals are continuously disperseddownstream from the tailings by clastic movement throughwind and water In this regard the sediments of the ex-mine areas of Bukit Besi are extremely polluted with elevatedconcentrations of metals due to heavily anthropogenic metalloads into the catchments from the ex-iron mines Thisconstitutes direct health hazards to aquatic life and humanhealth in case of using the water of these catchments fordrinking or cooking

411 Easily Freely Leachable or Exchangeable (EFLE) Thisfraction is used to extract easily freely leachable andexchangeable ions that are weakly bound to the sedimentsand can be released into water by changes in the pH value or

ionic competition [11 15] The analytical results showed thatFe was found to be the highest accumulation in the presentfraction followed by Al Pb and Cd The concentrations ofFe in EFLE fraction were found to be ranging from 287to 1980 120583gg in stations 4 and 1 respectively with meanpercentage of 293 of the total metals In general theanalytical results proved that the presence of Fe Al Cdand Pb in high concentrations in EFLE fraction indicatesthe occurrence of high anthropogenic loading from themining sites into the surrounding aquatic environmentsIkenaka et al [36] studied heavy metal levels in sedimentsof lake sediments in Zambia and reported that due to themining activities the increase in metal pollution in Zambiais still ongoing Yacoub et al [11] reported that the highcontent of Zn Ni Cu and Cd in EFLE fraction indicated asignificant threat for the aquatic environment In additionhigh concentrations of Cu Zn and Fe in EFLE fraction werefound in sediments of catchments around Sungai Lembingabandoned tin mine in a study by Ahmad and Sarah [6]

The high percentage of Fe Al Cd and Pb associated withEFLE fraction would suggest that a considerable amount ofFe Al Cd and Pb is becoming easily available for aquaticuptake following lowering of pH As a summary associationof Fe Al Cd and Pb with EFLE fraction is likely thebest example of mining-induced influence in the Bukit Besisediments The results of present study were higher than


those reported by [37] in which the authors studied theheavy metals concentrations in sediment of the Ngwenyairon ore mine quarry dam and reported that the metalsconcentrations in EFLE were 227120583gg for Fe 0253 120583gg forPb and 0318 120583gg for Cd

412 Acid-Reducible (AR) Fraction Hydroxylamine chloride(pH 2) (025M) is usually used in AR fraction as a reagent torelease metals from manganese iron oxides and hydroxideand possibly with carbonates too [15]TheAR fraction is usedto extractmetals contained in iron andmanganese oxides andhydroxides which can be released under reducing conditions[11 12] In AR fraction the metal concentrations were in theorder of Fe Al Pb and Cd Fe concentrations were rangingfrom 251 to 1423120583gg in stations 2 and 1 respectively with amean percentage of 414 of the total metals According toNemati et al [38] under acidic conditions the iron mobilityenhances

In addition Al and Pb were also found in high con-centrations Al concentrations ranged from 443 to 776120583ggin stations 4 and 3 respectively and Pb concentrationsranged from 017 to 111 120583gg in stations 2 and 5 respec-tively These results are in agreement with those reportedby Yacoub et al [11] Furthermore [39] studied the heavymetals concentrations in the former tin mining catchmentand reported that Pb was dominant in the RR followed byreducible fraction The high abundance of Fe Al Pb and Cdin AR fraction is caused by the adsorption of these metalsby the Fe-Mn colloids [40 41] This result is at par withthe findings reported by [41] that analyzed river sedimentsamples ofNomiRiver Tokyo JapanThedischarged effluentsfrom inactivated iron mine may be one of the factors forthe increased metals concentrations in Bukit Besi sedimentsOne-way ANOVA analysis showed that there are significantvariations between the stations in concentrations of Fe AlPb and Cd in AR EFLE and OO fractions This is mostlikely due to the fact that the adsorption and coprecipitationmechanisms of metals are sensitive to changes in redoxpotential rendering them moderately mobile and affectingtheir relative concentration as well as the degree of theoccurrence of AMD phenomenon and location of stationfrom the tailings

413 Oxidizable-Organic (OO) Fraction According to Tor-res and Auleda [42] organic matter has been recognizedas the main electron donor in the system thus the OOfraction is used to extract the oxidizable metals that arenot easily released into the water [11] In oxidizable-organicfraction H

2O2has been widely used as a reagent to extract

metals bounded onto organic matter due to H2O2being

considered as a strong oxidant to recover the organicallybound fraction From the present study it was noted that allmetals were found in high concentrations in OO fractionFe was the highest accumulation found in OO fractionfollowed by Al Pb and Cd Fe concentrations ranged from2425 to 4044 120583gg at stations 3 and 2 respectively whichrepresent 236 of the total metals Al concentrations werefound to be high and ranged from 1021 to 2637120583gg atstations 1 and 4 respectively with a mean percentage of

373 of the total metals These findings were in agreementwith those reported by Ahmad and Sarah [6] In addition[39] reported that the sediments of the former tin miningcatchment Bestari Jaya have been polluted by arsenic (88)chromium (129) copper (174) lead (195) zinc (149)and tin (338) Metals in the present fraction are notconsidered mobile or freely available as they are thoughtto be associated with stable high molecular weight humicsubstances that slowly release only small amounts of metals[41]

The relationship between heavy metal concentrations atoxidizable-organic fraction and the sedimentrsquos pH value andOM were determined The result shows that there are sig-nificant positive linear correlations between concentrationsof Fe Cd Al and Pb in oxidizable-organic fraction andOM and the pH value of the sediments From the resultthe correlation data reflect that OM and the pH valuepossess a high ability to absorb Fe Al Pb and Cd in thesurface sediments of Bukit Besi ex-mine The comparison ofnonresistance (anthropogenic) and resistance of all studiedelements in surface sediments of Bukit Besi ex-mine catch-ments is tabulated in Table 6 Percentage of heavy metalconcentrations in the labile fractions (EFLE AR and OO) insediments is shown in Figure 1 Due to the fact that fraction119877would overshadow the bioavailable part which is of interestit has been left out in Figure 1

42 Heavy Metal Concentrations in Plant Species The meanconcentrations of heavymetal in different parts (leaves stemshoot and root) of plants species are presented in Table 7 andFigure 2 The different characteristics of sediment samplesdetermined the ability of plant species to grow The highaccumulation of metals in the surface water and sedimentsdisabled growth of various plant species on the catchmentsThe results showed that all the investigated plant species havedifferent metal-enrichment capabilities The extent of metalaccumulation in the evaluated plant species differs by speciesorgan and metals Similar observation was reported by [43]Higher metals contents were observed to decrease in theorder of root gt stem gt leaves of most of the plants samplesexcept for Fe and Al concentrations in M malabathricumof which the leaves were found to contain the highestconcentrations of Fe and Al followed by the stem root andflowers The root of P calomelanos had the highest Fe level of27683plusmn788 120583gg while the lowest Fe valuewas recorded inMmalabathricum flower and root with the values of 356 plusmn 055and 224 plusmn 508 120583gg respectively

The analytical results showed that the levels of Fe in theleaves of all plants species evaluated were found to havehigher toxic levels of Fe in leaves which was suggested byKabata-Pendias [17] in Table 8 The results of the presentstudy were highly compared by [18] which were ranged from780 to 1560120583gg for Fe in different types of vegetables grownnear sewage water area The levels of Al found were followedby levels of Fe the highest level of Al was 48843 plusmn 000 120583ggwhich was detected in the leaves of M malabathricum andin the shoots with value of 55271120583gg whereas the leastvalues of Al (139 plusmn 617 and 139 plusmn 011 120583gg) were foundin the stem of B orientale and flowers of M malabathricum


Fe Al Cd PbStation 1

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(a)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(b)


EFLE ()AR ()OO ()

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

(c)


0

20

40

60

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100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(d)


Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

0

20

40

60

80

100

EFLE ()AR ()OO ()

(e)Figure 1 Percentage of heavy metal concentrations in the labile fractions (EFLE AR and OO) in sediments

respectively According to Watanabe and Osaki [44] Mmalabathricum are woody plants which have high capacity toaccumulate elevated concentrations of Al over 10000 120583gg intheir leaves as monomeric Al and Al-oxalate complexes Thisphenomenon is attributed toM malabathricum having highcapacity for retention of Al in root symplasts rather than highAl uptake rate into the symplasts

Reference [17] reported that Al is a common and essentialelement for plants and that accumulators species are plants

that contain more than 1000 120583gg of Al in their tissuesResults of the present study reported that only M mala-bathricum and P calomelanos exhibit Al concentrations intheir tissues of more than the normal ranges introduced byKabata-Pendias [17] Regarding Pb the highest value 979 plusmn013 120583gg was estimated in the root of S triqueter and thelowest value 065plusmn001 120583gg was found inMmalabathricumleaves Therefore Pb concentrations in all of the evaluatedplant species were found to be still within the normal range as


05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)

S triqueter Mmalabathricum

Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)

Figure 2 The mean concentrations of heavy metal in different parts (leaves stem shoot and root) of plants species

Table 8 Normal excessive and toxic values of metals inmature leaftissue and vegetation generalized for various species (120583gg)

Element Sufficient ornormal values

Excessive ortoxic values

Tolerable incrop plant

Cd 005ndash02 5ndash30 005ndash05Pb 5ndash10 30ndash300 05ndash10Fe 45ndash200 200ndash500 100

Table 9 Translocation factor (TF) and enrichment factor (EF) forplant species growing around ex-iron mine

Plant Species (Fe) (Al) (Pb) (Cd)(TF) (EF) (TF) (EF) (TF) (EF) (TF) (EF)

S triqueter 092 077 164 012 081 050 268 338M malabathricum 790 011 2852 1328 148 019 393 144P calomelanos 040 064 078 035 056 047 131 151B orientale 022 008 053 005 078 037 134 039

shown in Table 8 Reference [45] reported Pb concentrationin root of Calotropis procera which was collected from theheavy traffic area site as 2 120583gg

The highest value of Cd with the value of 046 plusmn 001 120583ggwas determined in stem of S triqueter while the lowest value

004 plusmn 000 120583gg was recorded in the stem and leaves of Borientale According to [17 46] ldquothe normal concentrationof Cd in leaf tissue ranges between 005ndash02 120583gg and theexcessive or toxic values range from 5ndash10 up to 30mggrdquoThus Cd concentrations in all of the evaluated plants werefound to be within the normal rangeThe high concentrationof Cd was between 885 and 1825 120583gg in Conyza canadensiswhich was found to be growing on Mn Mine Tailings andranged from 275 to 275120583gg in Poa pratensis [10] Inaddition [22] determined theCd concentrations in 30 speciescollected ore mines centers in the Gafsa-Metlaoui Basin(GMB) in Tunisia The Cd levels were ranged from 011 to82 120583gg and the highest Cd concentrations were reported inthe leaves of Anthemis Stiparum According to Kumar et al[47] the aquatic plant uptakes metals either by root systemor by leaves or by both ways One-way ANOVA test showedthat significant differences existed between the leaves stemand roots (119901 lt 005)

As a main result it was found that some of the plantspecies could grow as colonies on the contaminated waterand sediments Plant species under natural conditions canpotentially uptake and accumulate some metals ions in levelsexceeding the metals in the surrounding medium [22] Theresults would give an indication that consuming the metalscontaminated leaves by herbivores for a reasonable length oftime could be a link to exposure in humans which may pose


Translocation factor (TF)

0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)

Enrichment factor (EF)

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)

Figure 3 Translocation factor (TF) and enrichment factor (EF) for investigated plant species

a health risk According to [24 48] Al Fe and Pb could betoxic to various plant species in concentrations gt 100 500and 300 120583gg respectively thus in the present study most ofplants species have heavy metals contents which are higherthan the toxic levels of Al and Fe

43 Identification of Tolerant and Hyperaccumulator Plantsin Study Area Considering the hyperaccumulator plantsdefinition of [23 24] the shoot of M malabathricum andP calomelanos reveals metal concentrations higher than10000 120583gg of Fe with value of 1766 and 11141 120583gg respec-tively In addition to this only M malabathricum had TFgt1 Considering the hyperaccumulator plants definition of[25 27] the authors proposed that the hyperaccumulatorplant must contain contaminants 10ndash500 times greater thanthe same species growing in noncontaminated sitesHoweverin the present study the difficulty and lack of findingsderived from other locations Thus the normal values ofmetals in mature leaf tissues and vegetation generalized forvarious species (120583gg) introduced by Kabata-Pendias [17]were used to compare the results with the species growingin noncontaminated sites In this regard the concentrationsof Fe in M malabathricum and P calomelanos were higherthan those found in normal plants M malabathricum andP calomelanos had values of 393 and 248 times greater thanthe normal range of Fe 45 120583gg as introduced by Kabata-Pendias [17] According to the results M malabathricummet three criteria for Fe hyperaccumulation therefore it wasundoubtedly Fe hyperaccumulators while P calomelanosmetonly two criteria for Fe hyperaccumulation

Regarding Al Kabata-Pendias [17] reported that Al isa common and essential element for plants Accumulatorspecies are plants that contain more than 1000 120583gg of Alin their tissues According to the results Al concentrationswere found to be higher than 1000 120583gg inM malabathricumand P calomelanos shoot with values of 55271 and 2019 120583ggrespectively Therefore both of the species are considered asAl accumulators species On the other hand the results alsoshow that only M malabathricum had TF and EF gt1 for AlThis signifies thatM malabathricum was undoubtedly an Al

hyperaccumulator because it met three of the criteria for Alaccumulators

On the other side S triqueterM malabathricum and Pcalomelanos had TF and EF gt1 for Cd while B orientale hadonly TF gt1 for CdTherefore S triqueterM malabathricumand P calomelanos have met two of the criteria thus thesespecies were undoubtedly identified as hyperaccumulator forCd In the case of Pb only M malabathricum had TF gt1as shown in Figure 3 According to [49] hyperaccumulationof lead is particularly rare because of the low solubilitycharacteristic of most Pb compounds ldquoA tolerant species isone that can grow on soil with concentrations of a partic-ular element that are toxic to most other plantsrdquo [22 24]Therefore the field study results indicated that S triqueterM malabathricum P calomelanos and B orientale were themost dominant plants species which are found to be naturallygrowing on extraordinarily contaminated sediments Thusthese plant species could be classified as hypertolerant to FeAl Pb and Cd metals found in the Bukit Besi ex-mine areas[10]

The results of the present study showed that B orientalewas identified in this study as iron and Al excluder StriqueterM malabathricum P calomelanos and B orientalewere classified as good bioindicators plant species for Feand Al The present study also classified S triqueter Mmalabathricum and P calomelanos as Cd indictors It isimportant to note that plant species are classified into threemain groups metal excluders indicators and accumulatorswhich must be subject to several stringent standards This isbecause some of the plant species are potentially classified ashyperaccumulators or excluders during their early stages ofmetal uptake

5 Conclusions

The results of this investigation revealed that heavy metallevels in surface sediments of ex-mining catchments areextremely hazardous The analytical results of the presentstudy showed that the sequence of heavy metal levels inplants was similar to those reported in sediments however


some element concentrations were higher in sediments ascompared with those in plant species Although there aredifferences in exposure and uptake processes of each plantspecies in the present study the mean concentrations ofheavy metals in the evaluated plants species tend to decreaseas the distance away from the ex-mining area along the flowdirection increasesThe toxic levels of Fe were found in leavesof all analyzed plant samples The obtained results showedthat dependent on the most common criteria almost all ofthe studied plant species were able to grow on sediments andwater with elevated heavy metal concentrations They werealso able to accumulate extraordinarily high concentrationsof metals such as Fe and Al In the present study S triqueterM malabathricum P calomelanos and B orientale wereclassified as good bioindicators plant species for Fe andAl Therefore they are beneficial for carrying out phytore-mediation of contaminated sediments and water and forrevegetation initiatives around the Bukit Besi ex-iron minesite However through this study it is ascertained that thereis an urgent need for future studies on the agronomicalrequirements tracing elements bioaccumulation

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

The authors would like to express their deepest appreciationto Universiti Kebangsaan Malaysia for the FRGS12013ST03UKM023(STWN) grant and toThamarUniversity forfinancial support

References

[1] A K Ahmad and A Sarah ldquoConcentrations of heavymetal (FeMn Al Ni Ba Cd Pb AND Cr) in different fish species col-lected from wang mengkuang ex-tin mine caverdquo Asian Journalof Science and Technology (AJST) vol 07 no 02 pp 2460ndash24682016

[2] B Panahi A R Norhan and a E T Mohamad ldquoPossible reme-diation plan to mitigate acid mine drainage at an ex-ironmine in Dungun Terengganu Malaysiardquo in Proceedings of theInternational Conference and Exhibition on the RehabilitationRestoration and Transformation of Mining Land MalaysianChamber of Mines Sunway Pyramid Convention Centre SJanuary 2010

[3] A Ahmad and A Sarah ldquoHuman health risk assessmentof heavy metals in fish species collected from catchmentsof former tin miningrdquo International Journal of Research Studiesin Science Engineering and Technology vol 2 no 4 pp 9ndash212015

[4] M A Ashraf M J Maah and I B Yusoff ldquoStudy of waterquality and heavy metals in soil amp water of ex-mining areaBestari Jaya peninsularMalaysiardquo International Journal of Basicamp Applied Sciences vol 10 no 3 pp 7ndash27 2011

[5] H Takaijudin S A K S A Tajuddin A M Hashim and SIshak ldquoMonitoring stormwater quality of potential ex-miningponds international conference on environmental science and

technology IPCBEErdquo in Proceedings of the International Con-ference on Environmental Science and Technology (IPCBEE rsquo12)vol 30 Singapore 2012

[6] A K Ahmad and A Sarah ldquoAssessment of abandoned mineimpacts on concentrations and distribution of heavy metalsin surface sediments of catchments around sungai lembingabandoned tin minerdquo Iranica Journal of Energy amp Environmentvol 5 no 4 pp 453ndash460 2014

[7] S F L Lynch L C Batty and P Byrne ldquoEnvironmental riskof metal mining contaminated river bank sediment at redox-transitional zonesrdquoMinerals vol 4 no 1 pp 52ndash73 2014

[8] F Y AlshaebiW ZW Yaacob A R Samsudin and E AlsabahildquoRisk assessment at abandoned tin mine in Sungai LembingPahang Malaysiardquo The Electronic Journal of Geotechnical Engi-neering vol 14 pp 1ndash9 2009

[9] C A Harguinteguy A F Cirelli and M L Pignata ldquoHeavymetal accumulation in leaves of aquatic plant Stuckenia fil-iformis and its relationship with sediment and water in theSuquıa river (Argentina)rdquo Microchemical Journal vol 114 pp111ndash118 2014

[10] Y-G Liu H-Z Zhang G-M Zeng B-R Huang and X LildquoHeavy metal accumulation in plants on Mn mine tailingsrdquoPedosphere vol 16 no 1 pp 131ndash136 2006

[11] C Yacoub A Perez-Foguet and N Miralles ldquoTrace metalcontent of sediments close to mine sites in the Andean regionrdquoThe Scientific World Journal vol 2012 Article ID 732519 12pages 2012

[12] AA Idriss andAKAhmad ldquoHeavymetal concentrations (CuCd and Pb) in sediments in the Juru River Penang MalaysiardquoJournal of Biological Sciences vol 12 no 7 pp 376ndash384 2012

[13] F Armah S Obiri D Yawson A Pappoe and B Akoto ldquoMin-ing and heavy metal pollution assessment of aquatic environ-ments in Tarkwa (Ghana) usingmultivariate statistical analysisrdquoJournal of Environmental Statistics vol 1 no 4 2010

[14] M A M Abdallah ldquoChemical speciation and contaminationassessment of Pb and V by sequential extraction in surfacesediment off Nile Delta Egyptrdquo Arabian Journal of Chemistry2012

[15] M A Badri and S R Aston ldquoObservations on heavy metalgeochemical associations in polluted and non-polluted estuar-ine sedimentsrdquo Environmental Pollution Series B Chemical andPhysical vol 6 no 3 pp 181ndash193 1983

[16] A K Ahmad and M Shuhaimi-Othman ldquoHeavy metal con-centrations in sediments and fishes from Lake Chini PahangMalaysiardquo Journal of Biological Sciences vol 10 no 2 pp 93ndash100 2010

[17] A Kabata-Pendias Trace Elements in Soils and Plants CRCPress Boca Raton Fla USA 2011

[18] W Ahmed A Ahmed A AhmadM A Randhawa R Ahmadand N Khalid ldquoHeavy metal contamination in vegetablesgrown in Rawalpindi Pakistanrdquo Journal of the Chemical Societyof Pakistan vol 34 no 4 pp 914ndash919 2012

[19] M Keshtegar A R AkbariMoghaddam M Rostami and SJahantigh ldquoInvestigation of plants purification capability of Pbon two cultivars of vetch plants(VignaRadiata) in contaminatedsoilsrdquo International Research Journal of Applied and BasicSciences vol 7 no 13 pp 983ndash987 2013

[20] F Gakwerere An Investigation of the Level of Selected TraceMetals in Plant Species Within the Vicinity of Tantalum Min-ing Area in Gatumba Ngororero District Rwanda Univer-sity of South Africa Pretoria South Africa 2013 httphdlhandlenet105008834


[21] R A Olowu G O Adewuyi O J Onipede O A Lawal andO M Sunday ldquoConcentration of Heavy Metals in Root Stemand Leaves of Acalypha indica and Panicum maximum jacqfromThreeMajor Dumpsites in IbadanMetropolis SouthWestNigeriardquoAmerican Journal of Chemistry vol 5 no 1 pp 40ndash482015

[22] I Galfati E Bilal A B Sassi H Abdallah and A ZaıerldquoAccumulation of heavy metals in native plants growing nearthe phosphate treatment industry Tunisiardquo Carpathian Journalof Earth and Environmental Sciences vol 6 no 2 pp 85ndash1002011

[23] A Baker and R Brooks ldquoTerrestrial higher plants which hyper-accumulate metallic elements A review of their distributionecology and phytochemistryrdquo Biorecovery vol 1 no 2 pp 81ndash126 1989

[24] M Cheraghi B Lorestani and N Yousefi ldquoIntroduction ofhyperaccumulator plants with phytoremediation potential of aleadndashzinc mine in IranrdquoWorld Academy of Science Engineeringand Technology vol 77 pp 163ndash168 2011

[25] N Mganga M Manoko and Z Rulangaranga ldquoClassificationof plants according to their heavy metal content around NorthMara Gold Mine Tanzania implication for phytoremediationrdquoTanzania Journal of Science vol 37 no 1 pp 109ndash119 2011

[26] S P McGrath and F-J Zhao ldquoPhytoextraction of metals andmetalloids from contaminated soilsrdquo Current Opinion in Bio-technology vol 14 no 3 pp 277ndash282 2003

[27] Z Yanqun L Yuan C Jianjun CHaiyanQ Li andC SchvartzldquoHyperaccumulation of Pb Zn and Cd in herbaceous grownon lead-zinc mining area in Yunnan Chinardquo EnvironmentInternational vol 31 no 5 pp 755ndash762 2005

[28] C Branquinho H C Serrano M J Pinto and M A Martins-Loucao ldquoRevisiting the plant hyperaccumulation criteria to rareplants and earth abundant elementsrdquo Environmental Pollutionvol 146 no 2 pp 437ndash443 2007

[29] J E Duddridge and M Wainwright ldquoHeavy metals in riversediments-calculation ofmetal adsorptionmaxima using Lang-muir and Freundlich isothermsrdquo Environmental PollutionSeries B Chemical and Physical vol 2 no 5 pp 387ndash397 1981

[30] A Walkley and I A Black ldquoAn examination of the degtjareffmethod for determining soil organic matter and a proposedmodification of the chromic acid titrationmethodrdquo Soil Sciencevol 37 no 1 pp 29ndash38 1934

[31] A Piggott andC J Piggott Ferns ofMalaysia in Colour TropicalPress 1988

[32] K Meyer ldquoRevision of the Southeast Asian genus Melastoma(Melastomataceae)rdquo Blumea vol 46 no 2 pp 351ndash398 2001

[33] A A Beetle ldquoStudies in the Genus Scirpus L VI The SectionSchoenoplectus pallardquo American Journal of Botany vol 30 no6 pp 395ndash401 1943

[34] S Williams Official Methods of Analysis of the Association ofOfficial Analytical Chemists AOAC 1984

[35] J-F Peng Y-H Song P Yuan X-Y Cui and G-L Qiu ldquoTheremediation of heavy metals contaminated sedimentrdquo Journalof Hazardous Materials vol 161 no 2-3 pp 633ndash640 2009

[36] Y Ikenaka S M Nakayama K Muzandu et al ldquoHeavy metalcontamination of soil and sediment in ZambiardquoAfrican Journalof Environmental Science and Technology vol 4 no 11 pp 729ndash739 2010

[37] C L Dlamini A O Fadiran and J M Thwala ldquoA study ofenvironmental assessment of acid mine drainage in NgwenyaSwazilandrdquo Journal of Environmental Protection vol 4 no 11pp 20ndash26 2013

[38] K Nemati N K A Bakar and M R Abas ldquoInvestigation ofheavy metals mobility in shrimp aquaculture sludgemdashcompar-ison of two sequential extraction proceduresrdquo MicrochemicalJournal vol 91 no 2 pp 227ndash231 2009

[39] M A Ashraf M J Maah and I Yusoff ldquoSpeciation of heavymetals in the sediments of former tin mining catchmentrdquo Ira-nian Journal of Science and Technology Transaction A Sciencevol 36 no 2 pp 163ndash180 2012

[40] M Sanjay D Amit and S Mukherjee ldquoApplications of adsorp-tion process for treatment of landfill leachaterdquo Journal ofEnvironmental Research and Development vol 8 no 2 p 3652013

[41] S Sharmin H Zakir and N Shikazono ldquoFractionation profileand mobility pattern of trace metals in sediments of NomirdquoJournal of Soil Science and Environmental Management vol 1no 1 pp 1ndash14 2010

[42] E Torres and M Auleda ldquoA sequential extraction procedurefor sediments affected by acid mine drainagerdquo Journal ofGeochemical Exploration vol 128 pp 35ndash41 2013

[43] J Nouri N Khorasani B Lorestani M Karami A H Has-sani and N Yousefi ldquoAccumulation of heavy metals in soiland uptake by plant species with phytoremediation potentialrdquoEnvironmental Earth Sciences vol 59 no 2 pp 315ndash323 2009

[44] T Watanabe and M Osaki ldquoRole of organic acids in aluminumaccumulation and plant growth inMelastoma malabathricumrdquoTree Physiology vol 22 no 11 pp 785ndash792 2002

[45] J Barthwal S Nair and P Kakkar ldquoHeavy metal accumulationin medicinal plants collected from environmentally differentsitesrdquo Biomedical and Environmental Sciences vol 21 no 4 pp319ndash324 2008

[46] F A Solıs-Domınguez M C Gonzalez-Chavez R Carrillo-Gonzalez and R Rodrıguez-Vazquez ldquoAccumulation andlocalization of cadmium in Echinochloa polystachya grownwithin a hydroponic systemrdquo Journal of Hazardous Materialsvol 141 no 3 pp 630ndash636 2007

[47] I N Kumar P R Sajish R N Kumar G Basil and V Shai-lendra ldquoAn assessment of the accumulation potential of Pb Znand Cd by Avicennia marina (Forssk) Vierh in VamleshwarMangroves Gujarat Indiardquo Notulae Scientia Biologicae vol 3no 1 pp 36ndash40 2011

[48] I Pais and J B Jones JrThe Handbook of Trace Elements CRCPress Boca Raton Fla USA 1997

[49] P Rotkittikhun M Kruatrachue R Chaiyarat et al ldquoUptakeand accumulation of lead by plants from the BoNgam leadminearea in Thailandrdquo Environmental Pollution vol 144 no 2 pp681ndash688 2006

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


In abandoned mining sites high concentrations of metalare found to have significant impacts on the deteriorationof the quality of the ecosystem increasing the phytotoxicityin sediments [13] Over time these impacts may cause theenhancement of nutritional deficiencies the disappearanceof the natural vegetative the decline in biological diversityand finally posing an ecological risk to the ecosystem Theeffects of these contaminants are quite varied and depend onseveral factors such as climatic changes micrometeorologicalcondition chemical form of metal sedimentsrsquo physicochem-ical characteristics and water column [14] The hazardousmetals could be transported for long distances far away fromcontamination sources via wind runoff and rainfall based onthe chemical forms of the metals either in gaseous form or(particulates) by the size of the fractions of metals [15 16]

Plants play a key role in forming a fundamental part ofthe trophic structure of aquatic ecosystems [9] Plants canbe considered as intermediate reservoirs of heavy metalsfrom the sediments water and air and are ingested by manand animal through the food chain [17] In abandoned minesites aquatic plants populations react differently to changesin the environmental factors Recent studies have indicatedthat aquatic plants have a high absorption capacity of toxicmetals through the roots or via precipitation within therhizosphere and leaves during the circulation of nutrients[18ndash21] Plants are capable of using metals through differentways such as complexing them in their sedentary naturebinding them into cell wall andor combining them toproduce certain organic acid or proteins [22]Therefore plantspecies are considered as good bioindicators in the earlystages of heavy metal pollution Additionally they can beused for monitoring the state of the aquatic ecosystem andthe changes or alterations in the aquatic environments [9]High heavy metal content in soil water sediments andorthe air is found to be the most common stress factor whichis faced by plant species naturally growing in abandonedmine sites Therefore it is imperative that plant speciesmust adapt to different environmental conditions in order tosurvive According to their adaptation strategies and heavymetals content plant species can be classified into threemain groups metal excluders indicators and accumulatorsor hyperaccumulators [23]

Hyperaccumulator plants are widely used in phytore-mediation This is due to the fact that these plants cancontain Pb Cu Co Cr and Ni gt1000 120583gg or 10000 120583ggof Fe Mn and Zn or Cd gt50 120583gg in any abovegroundtissue in their natural habitat without suffering toxic effects[23 24] Metal excluders can be defined as plants thatcan restrict translocation of heavy metals from their rootsinto their aboveground tissues These species can maintainrelatively low levels of metal concentrations in their shootsas compared with the elevated metals concentrations in theirroots [22] Indicator plants are plants which have the abilityto accumulate the metals in their aboveground tissues thusthe metals levels in the tissues reflect the metal levels in thesediments [25 26] However this type of plants dies off undercontinued uptake of heavy metals

Determination of the hyperaccumulator indicator andexclude plant species is dependent on several criteria A plant

species can be considered as a hyperaccumulator for heavymetals if it meets one of the following four strict criteria(1) the ratio of heavy metal concentrations of shoot to rootmust be higher than 1 (metal concentration in shootmetalconcentration in Root) ge1 [25] (2) (metal concentrationin rootmetal concentration in sediments or soil) gt 1 [26ndash28] (3) the hyperaccumulator plant must be 10ndash500 timesgreater than the same species growing in noncontaminatedsites [25 27] and (4) plants with Pb Cu Co Cr and Nigt1000 120583gg or 10000 120583gg of Fe Mn and Zn or Cd gt50 120583ggin any aboveground tissue in their natural habitat withoutsuffering toxic effects can be classified as hyperaccumulatorplants [25 27] According to Mganga et al [25] ldquoa plantwhich has high levels of heavy metals in the roots but withshootroot quotients less than 1 is classified as a heavy metalexcluderrdquo

Considering the above facts the overall objectives of thepresent study were (1) to assess the impact of the aban-doned mine on the accumulation and distribution of PbAl Cd and Fe in surface sediments and plant species thatare growing on a contaminated site and (2) to identifyhyperaccumulator indicator and exclude plant species usingseveral established criteria Therefore the present studycontributes to discovering the hyperaccumulator plants inex-iron mine in Bukit Besi which can be used for futurestudies on the management and decontamination of heavymetal-contaminated sediments using native plant species asdetectors and early warning in decreasing the environmentalrisk posed by mining activities

2 Materials and Methods

21 Study Area Bukit Besi is an abandoned open-pit ironmine type It was one of the worldrsquos largest iron ore pro-ducers Bukit Besi is located about 85 km south of KualaTerengganu Malaysia During 1919 a team of Japanese geol-ogists discovered the iron ore at Bukit Besi then in 1923Dungun was one of the worldrsquos largest iron ore producersin Southeast Asia In the 1960s mining activities have beenstopped due to the decline in iron production Bukit Besicovers sim2400 ha of land The major minerals in this area aremagnetite quartz and goethite [2] Recently after theminingindustry has become unproductive the old structures plantsand rail tracks have been left with tailings Over time thetailings can pose a great threat to natural reserves due tolandscape changes damage to natural drainage pollutionand destruction of terrestrial and aquatic habitat ecosystemsfor decades As the iron ore of Bukit Besi became depleted inthe 1960s and 1970s themining has been stopped Dependingon the location of the catchments and distribution of the slagheaps five sampling stations were selected as described inTable 1

22 Samples Collection and Analysis For sediments surfacesediments (0ndash5 cm depth) were collected after removingplant debris and large materials Sediment samples were keptin precleaned plastic bags with tags and then sent to thesoil laboratory in the Biology Building at the UniversitiKebangsaan Malaysia (UKM) Five replicates of sediments























3 Result













4 Discussion





FeMean 1980 1423 2459 9850

373SD 122 100 578 972Ratio (126) (906) (157) (627)

AlMean 521 551 1021 3034

271SD 254 271 193 903Ratio (125) (133) (245) (729)

CdMean 005 002 002 012

411SD 000 000 000 000Ratio (235) (913) (840) (590)

PbMean 020 020 055 136

66SD 001 001 001 217Ratio (14) (14) (38) (934)

Station 2Fe

Mean 381 251 4044 10163297SD 342 403 402 628

Ratio (003) (17) (280) (703)Al

Mean 056 400 1495 3034336SD 024 030 140 809

Ratio (001) (088) (327) (664)Cd

Mean 001 002 01 02333SD 000 001 000 032

Ratio (41) (599) (232) (668)Pb

Mean 008 17 092 138163SD 000 004 090 144

Ratio (048) (102) (559) (837)Station 3

FeMean 244 653 2425 10612

239SD 477 344 115 305Ratio (175) (468) (174) (762)

AlMean 208 776 2244 3034

436SD 308 079 251 325Ratio (039) (144) (417) (564)

CdMean 004 003 004 002

849SD 000 000 000 000Ratio (346) (212) (290) (151)

PbMean 005 029 054 148

561SD 001 000 004 051Ratio (035) (184) (343) (944)

Table 6 Continued


FeMean 287 320 3511 13624

220SD 17 694 375 844Ratio (002) (183) (201) (780)

AlMean 085 443 2637 3034

469SD 026 069 907 325Ratio (002) (078) (461) (531)

CdMean 002 002 005 012

441SD 000 000 000 000Ratio (831) (101) (257) (560)

PbMean 007 134 119 81

243SD 000 002 040 11Ratio (068) (125) (111) (757)

Station 5FeMean 232 324 3503 5701

403SD 294 343 429 108Ratio (024) (34) (367) (597)

AlMean 675 462 2170 3034

423SD 048 072 324 432Ratio (013) (088) (413) (577)

CdMean 001 001 005 02

314SD 000 001 005 001Ratio (607) (488) (205) (686)

PbMean 002 011 153 143

105SD 001 001 001 11Ratio (014) (071) (961) (896)











































0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(a)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(b)


EFLE ()AR ()OO ()

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

(c)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(d)


Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

0

20

40

60

80

100

EFLE ()AR ()OO ()






05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)
















0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of























3 Result













4 Discussion





FeMean 1980 1423 2459 9850

373SD 122 100 578 972Ratio (126) (906) (157) (627)

AlMean 521 551 1021 3034

271SD 254 271 193 903Ratio (125) (133) (245) (729)

CdMean 005 002 002 012

411SD 000 000 000 000Ratio (235) (913) (840) (590)

PbMean 020 020 055 136

66SD 001 001 001 217Ratio (14) (14) (38) (934)

Station 2Fe

Mean 381 251 4044 10163297SD 342 403 402 628

Ratio (003) (17) (280) (703)Al

Mean 056 400 1495 3034336SD 024 030 140 809

Ratio (001) (088) (327) (664)Cd

Mean 001 002 01 02333SD 000 001 000 032

Ratio (41) (599) (232) (668)Pb

Mean 008 17 092 138163SD 000 004 090 144

Ratio (048) (102) (559) (837)Station 3

FeMean 244 653 2425 10612

239SD 477 344 115 305Ratio (175) (468) (174) (762)

AlMean 208 776 2244 3034

436SD 308 079 251 325Ratio (039) (144) (417) (564)

CdMean 004 003 004 002

849SD 000 000 000 000Ratio (346) (212) (290) (151)

PbMean 005 029 054 148

561SD 001 000 004 051Ratio (035) (184) (343) (944)

Table 6 Continued


FeMean 287 320 3511 13624

220SD 17 694 375 844Ratio (002) (183) (201) (780)

AlMean 085 443 2637 3034

469SD 026 069 907 325Ratio (002) (078) (461) (531)

CdMean 002 002 005 012

441SD 000 000 000 000Ratio (831) (101) (257) (560)

PbMean 007 134 119 81

243SD 000 002 040 11Ratio (068) (125) (111) (757)

Station 5FeMean 232 324 3503 5701

403SD 294 343 429 108Ratio (024) (34) (367) (597)

AlMean 675 462 2170 3034

423SD 048 072 324 432Ratio (013) (088) (413) (577)

CdMean 001 001 005 02

314SD 000 001 005 001Ratio (607) (488) (205) (686)

PbMean 002 011 153 143

105SD 001 001 001 11Ratio (014) (071) (961) (896)











































0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(a)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(b)


EFLE ()AR ()OO ()

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

(c)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(d)


Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

0

20

40

60

80

100

EFLE ()AR ()OO ()






05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)
















0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




FeMean 1980 1423 2459 9850

373SD 122 100 578 972Ratio (126) (906) (157) (627)

AlMean 521 551 1021 3034

271SD 254 271 193 903Ratio (125) (133) (245) (729)

CdMean 005 002 002 012

411SD 000 000 000 000Ratio (235) (913) (840) (590)

PbMean 020 020 055 136

66SD 001 001 001 217Ratio (14) (14) (38) (934)

Station 2Fe

Mean 381 251 4044 10163297SD 342 403 402 628

Ratio (003) (17) (280) (703)Al

Mean 056 400 1495 3034336SD 024 030 140 809

Ratio (001) (088) (327) (664)Cd

Mean 001 002 01 02333SD 000 001 000 032

Ratio (41) (599) (232) (668)Pb

Mean 008 17 092 138163SD 000 004 090 144

Ratio (048) (102) (559) (837)Station 3

FeMean 244 653 2425 10612

239SD 477 344 115 305Ratio (175) (468) (174) (762)

AlMean 208 776 2244 3034

436SD 308 079 251 325Ratio (039) (144) (417) (564)

CdMean 004 003 004 002

849SD 000 000 000 000Ratio (346) (212) (290) (151)

PbMean 005 029 054 148

561SD 001 000 004 051Ratio (035) (184) (343) (944)

Table 6 Continued


FeMean 287 320 3511 13624

220SD 17 694 375 844Ratio (002) (183) (201) (780)

AlMean 085 443 2637 3034

469SD 026 069 907 325Ratio (002) (078) (461) (531)

CdMean 002 002 005 012

441SD 000 000 000 000Ratio (831) (101) (257) (560)

PbMean 007 134 119 81

243SD 000 002 040 11Ratio (068) (125) (111) (757)

Station 5FeMean 232 324 3503 5701

403SD 294 343 429 108Ratio (024) (34) (367) (597)

AlMean 675 462 2170 3034

423SD 048 072 324 432Ratio (013) (088) (413) (577)

CdMean 001 001 005 02

314SD 000 001 005 001Ratio (607) (488) (205) (686)

PbMean 002 011 153 143

105SD 001 001 001 11Ratio (014) (071) (961) (896)











































0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(a)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(b)


EFLE ()AR ()OO ()

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

(c)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(d)


Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

0

20

40

60

80

100

EFLE ()AR ()OO ()






05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)
















0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







































0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(a)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(b)


EFLE ()AR ()OO ()

0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

(c)


0

20

40

60

80

100

Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

EFLE ()AR ()OO ()

(d)


Rela

tive o

f bio

avai

labl

efr

actio

ns (

)

0

20

40

60

80

100

EFLE ()AR ()OO ()






05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)
















0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


05000

1000015000200002500030000

Fe co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(a)

0100002000030000400005000060000

Al c

once

ntra

tion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot

(b)

0

2

4

6

8

10

12

Pb co

ncen

trat

ion

(120583g

g)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(c)

00102030405060708

Cd

conc

entr

atio

n (120583

gg)


Pcalomelanos

B orientale

Plant species

LeavesStem

ShootRoot(d)
















0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



0

5

10

15

20

25

30

(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale

(a)


(Fe)(Al)

(Pb)(Cd)


Pcalomelanos

B orientale02468

101214

(b)








5 Conclusions




Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Competing Interests


Acknowledgments


References





























































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

an investigation of the levels and distribution of selected heavy

Documents