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1. Heavymetalcontaminationofoverlyingwatersandbedsediments
of HaiheBasininChina
WenzhongTang a, YuZhao a, ChaoWang a, BaoqingShan a,n, JingguoCui b
a State KeyLaboratoryonEnvironmentalAquaticChemistry,ResearchCenterforEco-EnvironmentalSciences,ChineseAcademyofSciences,
Beijing 10085,China
b Beijing SoundEnvironmentalEngineeringCo.,Ltd.,Beijing101102,China
a rticleinfo
Article history:
Received24July2013
Receivedinrevisedform
27September2013
Accepted30September2013
Availableonline18October2013
Keywords:
Heavymetals
Haihe Basin
Contamination
Overlyingwaters
Surface sediments
a b s t r a c t
The HaiheBasinisinanareaofhighpopulationdensityandrapideconomicdevelopment,andisoneof
the mostpollutedriverbasinsinChina.Examinationofheavymetals(Cd,Co,Cr,Cu,Mn,Ni,PbandZn)in
overlyingwatersandsurfacesedimentsinriverswasconductedinthebasin'ssevenwatersheds.Cd
concentrations ofoverlyingriverwatersexceededChineseenvironmentalqualitystandardvaluesfor
surface water(40.010mg/L)at90%ofstations.Insurfaceriversediments,averageconcentrationsofCd,
Co, Cr,Cu,Mn,Ni,PbandZninthebasinwere0.364,13.4,81.9,53.3,435,27.8,20.0and256mg/kg,
respectively.Cd,ZnandCuwerethemostanthropogenicallyenrichedelements,asindicatedby
enrichment factor(EF)values41.5;EFvalueswerehighestforthesemetalsintheZiYaHe(ZYH)and
Zhang WeiHe(ZWH)watersheds.Cdinsurfaceriversedimentsshowedahighpotentialecologicalrisk
(PER) intheZYHandZWHwatersheds.ThecomprehensivePERduetoallstudiedmetalswashighat
manystations,especiallyintheZYHandZWHwatersheds.Theresultsindicatethatheavymetal
contamination intheriversoftheHaiheBasinshouldbeconsideredwhendevelopingbasinmanage-
ment strategiesforprotectingtheaquaticenvironment.
& 2013ElsevierInc.Allrightsreserved.
1. Introduction
Heavymetalcontaminationofaquaticbodiesisoneoftheenviron-
mentalproblemsthataccompanyrapideconomicdevelopmentin
bothdevelopedanddevelopingcountries(Gao andChen,2012).
Heavymetalsarewidespreadandpersistentintheenvironment,
potentiallytoxic,andcanbecomeincorporatedintofoodwebs
(Sureshetal.,2012; Taweeletal.,2013; Xiaoetal.,2012).Heavy
metals withlowsolubilityinwater,areeasilyadsorbedand
accumulated insediments(Alvarezetal.,2011; Jain etal.,2008;
Ma etal.,2013). Sedimentsinriverbedsorlakebottomstherefore
oftenrepresentamajorrepositoryforcontaminantsdischarged
into waterbodies(Ma etal.2013; Vandecasteele etal.,2004).
Heavymetalsadsorbedinsedimentscanbedesorbedbackinto
overlyingwaterundercertainconditions,causingsecondarypollution
and potentiallyhavingtoxiceffectsonorganisms(Niuetal.,2009;
Seguraetal.,2006). Moreover,theequilibriumpartitioningofmetals
at thesediment–waterinterfaceisanimportantfactorinfluencing
their biogeochemicalprocessesandbioavailability(Huoetal.,2013).
Heavymetalcontaminationofsedimentscancriticallydegrade
aquaticsystems(Suresh etal.,2012), sotheaccumulationofheavy
metal insedimentsisacauseofgrowinginterestandconcern;
environmentalproblemsduetoheavymetalpollutionofaquatic
systemshaverecentlybeenextensivelystudied(Buggy andTobin
2008; Griscom etal.,2000; Karak etal.,2013; Shi etal.,2013;
Wangetal.,2012).
Heavymetalpollutioninriversinotherareasoftheworldhas
been aresearchfocusforalongtime;theReedyRiverinthe
UnitedStates(Otteretal.,2012), theHindonRiverinIndia
(Chabukdhara andNema,2012) andtheXanaesRiverinArgentina
(Harguinteguy etal.,2013) areexamplesofriversinwhichheavy
metal pollutionhasbeenexamined.InChina,heavymetalcon-
tamination ofriversedimentsdidnotattractmuchattentionfrom
researchersandgovernmentspriorto2000,withrelativelyfew
studies conducted(He etal.,1998; Ma etal.,2013; Zhaoetal.,1999).
In recentyears,industrialandminingactivitiesthatdischarge
heavymetalsthroughatmosphericemissionsoreffluent into
rivershavebeendevelopingcontinuouslyandrapidly,particularly
in theHaiheBasin.One-sixthofallarablelandsinChinahavebeen
contaminatedbyheavymetals.Tocontroltheproblemofheavy
metal contamination,inearly2011theStateCouncilofChina
approvedthe “12thNational5-yrPlanforComprehensivePreven-
tion andControlofHeavyMetalPollution”. Heavymetalpollution
has becomeanimportanttopicfortheChinesegovernmentand
the public(Ma etal.,2013). TheHaiheBasin,withanareaof
318,000km2, isoneofthemostdevelopedregionsandhasthe
Contents listsavailableat ScienceDirect
journal homepage: www.elsevier.com/locate/ecoenv
EcotoxicologyandEnvironmentalSafety
0147-6513/$-seefrontmatter & 2013ElsevierInc.Allrightsreserved.
http://dx.doi.org/10.1016/j.ecoenv.2013.09.038
Abbreviations: BSH, BeiSanHe;YDH,YongDingHe;DQH,DaQingHe;ZYH,ZiYa
He; HLG,HeiLongGang;ZWH,ZhangWeiHe;TMH,Tu-haiMa-xiaHe;EF,
enrichment factor;PER,potentialecologicalrisk;RAC,riskassessmentcode
n Corresponding author.
E-mail addresses: wztang@rcees.ac.cn (W.Tang), bqshan@rcees.ac.cn (B.Shan).
EcotoxicologyandEnvironmentalSafety98(2013)317–323

2. highest populationdensityinChina.Heavyindustrialdevelop-
ment andrapidurbanizationhavecausedsignificant pollutionof
riversinthisarea,includingheavymetalpollution.Itisimportant
to understandtheheavymetalcontaminationstatusintherivers
of alargebasin,suchastheHaiheBasin,toprovideareferencefor
the large-scalecontrolandmanagementofheavymetals.
Toassessheavymetalcontaminationandprovidebackground
information fortheHaiheBasin,Cd,Co,Cr,Cu,Mn,Ni,Pb,andZn
in overlyingriverwatersandsurfaceriversedimentswascon-
ducted inthesevenwatershedsofthebasin.Thepurposesofthis
study were(1)toinvestigateheavymetalconcentrationsinover-
lying riverwatersandsurfaceriversediments;and(2)toanalyze
their contaminationstatusthroughtheenrichmentfactor(EF),
potentialecologicalrisk(PER)andriskassessmentcode(RAC).
2. Materialsandmethods
2.1.Studyarea
The HaiheBasin,locatedmainlywithintheprovinceofHebei,includesBeijing,
Tianjin, partsofInnerMongolia,andtheprovincesofShanxi,Henan,andShandong
(Fig. 1). TheareaoftheHaiheBasinis318,000km2, anditsclimateistemperate
continental monsoon.Themeanannualprecipitationis527mm.Itisoneofseveral
majorbasinsunderthemanagementoftheMinistryofWaterResources.Heavy
industrial developmentandrapidurbanizationhavecausedsignificant pollutionto
watersinthisregion.Waterresourcesareinhighdemandandthedeteriorationofwater
qualityhashastenedtheshortageofwaterresources.Therefore,theHaiheBasinhas
attractedmuchattentionfromtheChinesegovernmentandhasbecomeoneofthemost
importantbasinsintheNational11thand12th5-yearPlanforWaterPollutionControl.
The HaiheBasinisdividedintoninemajorwatersheds:LuanHe,BeiSanHe
(BSH), YongDingHe(YDH),DaQingHe(DQH),Hai-heGan-liu,ZiYaHe(ZYH),Hei
Long Gang(HLG),ZhangWeiHe(ZWH),andTu-haiMa-xiaHe(TMH).
2.2. Samplecollectionandanalysis
Surface sedimentswerecollectedfromJulytoNovember2009at117stationsin
the BSH,YDH,DQH,ZYH,HLG,ZWHandTMHwatersheds(Fig. 1) usinghand-held
PVC corerswithadiameterof80mmandalengthof150cm.Threesediment
columns weretakenatrandomfromeachstation,andtheupper0–10cmof
sediment wasmanuallycollectedwithaplasticspoon.Inthelaboratory,the
samples (n¼351)wereair-driedthentransferredtoanoventodryat40 1C, then
groundandpassedthrougha100-meshsievepriortoanalysis.Theoverlyingwater
samples (n¼351)werecollectedateachstationsimultaneously.Thewatersamples
were filteredusingMilliporemembrane filters with0.45 mm pores,thenstoredin
polystyrenebottlesandpreservedwithconcentratednitricacid(ARgrade)at
pHo2 priortoheavymetalanalysis.
For totalheavymetalanalysis,sedimentsamples(0.100g)weredigestedwitha
5:l mixtureofhydrofluoric: perchloricacid(Tessieretal.,1979) inamicrowavein
Teflon vessels(MarsxPress,CEM);thedigestionconditionsarepresentedin Table
S1. ThegeochemicalfractionationofheavymetalswasdeterminedusingtheBCR
three-stepsequentialextractionprocedure(Nemati etal.,2011). Thismethod
providestheexchangeable(sedimentsolution,carbonates,exchangeablemetals),
reducible (oxidesFe/Mn),oxidizable(organicmatterandsulfides), andresidual
(remaining,non-silicateboundmetals)fractionsofheavymetalsinsediments.All
of theabovesolutionsandtheoverlyingwatersampleswerestoredat4 1C priorto
analysis.TheconcentrationsofCd,Co,Cr,Cu,Mn,Ni,Pb,Zn,andAlweremeasured
byinductivelycoupledplasma-massspectrometry(ICP-MS)(7500a,Agilent,USA)
(detectionlimit0.015–0.120 mg/L) andinductivelycoupledplasmaopticalemission
spectrometer(ICP-OES)(Optima2000DV,PerkinElmer,USA)(detectionlimit
0.001–0.030 mg/L).Laboratoryqualitycontrolconsistedoftheanalysisofsediment
referencematerial(GBW07302a,China)andtriplicatesamples.Recoveriesvaried
but allfellwithintherangeof90–95%, andtheprecisionwasunder5%relative
standard deviation(RSD).Theresultsofallindicesweretheaverageofthethree
parallel samplesofsedimentsandoverlyingwater,respectively.
2.3. Enrichmentfactor
Toobtaininformationaboutthesourcesandtemporalvariationofmetalcon-
taminants,theEFsofheavymetalsinriversedimentswerecalculatedusingthe
equationfrom Zhang andShan,(2008)
EF ¼ ½CnðsampleÞ=CAlðsampleÞ =½BnðbaselineÞ=BAlðbaselineÞ ð1Þ
where Cn is metalcontentinthesediments, Bn is thebackgroundconcentrationof
the metal, CAl is theAlconcentrationinthesediments,and BAl is thebackground
concentrationofAl.Inthisstudy,thesoilbackgroundvaluesoftheHaiheBasin
wereadoptedasthebaselinevalues(China NationalEnvironmentalMonitoring
Center (CNEMC),1990).
2.4. Potentialecologicalrisk
The PERindexwasusedtoassessthedegreeofcontaminationofheavymetals
in thesediments.TheequationsforcalculatingthePERindexwereproposedby
Guo etal.(2010) and areasfollows:
Ei
r ¼ Ti
r Ci
f ¼ Ti
r ðCi
s n Ci
nÞ ð2Þ
RI ¼ Σ n
i ¼ 1
Ei
r
ð3Þ
where Ci
s is thecontentoftheelementinsamples, Ci
n is thereferencevalueofthe
element, Ci
f is thesingleelementpollutionfactor, Ei
r is thePERindexofanindividual
element, and Ti
r is thebiologicaltoxicityfactorofanindividualelement,whichare
defined asCd¼30, Cr¼2, Co¼Cu¼Ni¼Pb¼5, Mn¼Zn¼1 (Guo etal.,2010;
Hakanson, 1980). RIisthecomprehensivePERindex,whichisthesumof Ei
r.
TableS2 shows thefactorstandardofdifferentlevels.
2.5. Riskassessmentcode
The RACwasusedtoassesstheheavymetalcontentofthesedimentsfroma
regulatoryperspectiveinthisstudy.TheRACassessesthepotentialreleaseofheavy
metals insolutionbycalculatingthepercentageofmetalsoccurringinexchange-
able fractioninthestudiedsediments(Singh etal.,2005).
3. Resultsanddiscussion
3.1.Heavymetalconcentrationsinoverlyingriverwaters
The heavymetalconcentrationsinoverlyingriverwatersofthe
HaiheBasinaregivenin TableS3. AverageconcentrationsofCd,Cr,Cu,
Mn, Ni,PbandZnintheentirebasinwere0.028,0.062,0.079,0.162,
0.056,0.069and0.058mg/L,respectively.Concentrationsofallmetals,
exceptCd,werelowerthanthestandardvaluesoftheenvironmental
qualitystandardsforChinesesurfacewater(China2002).Incontrast, Fig. 1. Map showingthesedimentsamplingstationsintheriversoftheHaiheBasin.
W.Tangetal./EcotoxicologyandEnvironmentalSafety98(2013)317–323 318

3. high Cdconcentrations(40.010mg/L)wereobservedatmostsites,
exceededtheenvironmentalqualitystandardat90%ofstationsand
werehighestintheBSH,ZYHandZWHwatersheds.Theseresults
indicatethatCdpollutionhasbecomeamajorenvironmentalproblem
in theriversoftheHaiheBasin.
3.2. Heavymetalcontentofsurfaceriversediments
Fig. 2 showsheavymetalconcentrationsofsurfaceriver
sediments intheHaiheBasin.AverageconcentrationsofCd,Co,
Cr,Cu,Mn,Ni,PbandZnacrossthebasinwere0.364,13.4,81.9,
53.3, 435,27.8,20.0and256mg/kg,respectively.AverageCd
concentrations werehighestinthesurfaceriversedimentsof
ZYH (0.704mg/kg)andZWH(0.587mg/kg).AverageCr,CuandPb
concentrations werehighestinthesurfaceriversedimentsofthe
ZYH watershed(201,114and43.0mg/kg,respectively).AverageZn
concentrations werehighestinsurfaceriversedimentsoftheYDH,
ZYH andZWHwatersheds(327,580and269mg/kg,respectively).
There wasnoapparentspatialvariabilityinaverageCo,Mn,andNi
concentrations inthesurfaceriversedimentsofthesevenwater-
sheds. Inaddition,Alconcentrationsofthestudiedsediments
rangedfrom47.9g/kgto81.2g/kg.Highlevelsofmetalsinthe
surface riversedimentsoftheZYHandZWHwatershedsimplied
that asubstantialincreaseinanthropogenicmetalloadinghas
occurredinthesetworegions,assuggestedby Sondi etal.(2008).
The inter-elementrelationshipscanprovideinformation
regardingheavymetalsources(Dragovicetal.,2008); therefore,
the Spearmancorrelationcoefficients oftheheavymetalswere
analyzed(TableS4). Theresultsrevealedthattheheavymetals
(Cd, Cr,PbandZn)(Co,MnandNi)werepositivelycorrelated
Fig. 2. Concentrations ofheavymetalsinsurfaceriversedimentsoftheHaiheBasin(mg/kg).
W.Tangetal./EcotoxicologyandEnvironmentalSafety98(2013)317–323 319

4. among themselves(pr0.01),andthattherewasalsoapositive
correlation (pr0.01)betweenCuandtheothermetals,exceptCd,
Co andMn.Inaddition,asignificant positivecorrelation(pr0.05)
wasobservedbetweenCdandCu,CoandCr,CrandNi,NiandPb,
and NiandZn.Theseresultsindicatethatthemetalsinthe
analyzedsedimentshaddifferentoriginsorcontrollingfactors.
3.3. Heavymetalcontaminationinsurfaceriversediments
3.3.1.Enrichmentfactor
Enrichment factorisanormalizationtechniquewidelyusedto
separatemetalsderivedfromnaturalsourcesintheenviron-
mentfromthoseassociatedwithanthropogenicactivities(Gao and
Chen, 2012). Tofurtherevaluateanthropogenicinfluences on
heavymetalsinthesurfaceriversedimentsoftheHaiheBasin,
the EFforeachmetalwascalculatedandisshownin Fig. 3. The
mean EFwashighestforCd(4.47)indicatingthehighestdegreeof
anthropogeniccontaminationofthismetal,followedbyZn(3.71),
Cu (2.50),Cr(1.34),Co(1.10),Ni(1.05),Pb(1.02),andMn(0.76).
The spatialdistributionpatternofEFvaluesofthemetalsexam-
ined wassimilartothatoftheircontents.
An EFvalueofapproximately1suggeststhatagivenmetalmay
originateentirelyfromnaturalsources,suchascrustalmaterialsor
naturalweatheringprocesses(Zhang andLiu,2002). Aslight
positivedeviationofanEFvaluefromunitymaynotnecessarily
arise fromanthropogenicactivities;itmayalsobecausedby
Fig. 3. EF valuesforheavymetalsinsurfaceriversedimentsoftheHaiheBasin.
W.Tangetal./EcotoxicologyandEnvironmentalSafety98(2013)317–323 320

5. natural variationintheelementalcompositionbetweenstudied
sediments andreferencesoilsusedintheEFcalculation(Gao and
Chen, 2012). Therefore,anEFvaluebetween0.5and1.5suggests
that themetalmaybeentirelyfromcrustalmaterialsornatural
weathering processes.However,anEFgreaterthan1.5suggests
that asignificant portionofthemetaloriginatedfromanthropo-
genic processes(Feng etal.,2004). IntheHaiheBasin,Cd,Znand
Cu werepositivelycorrelatedamongthemselves(TableS4) and
werethemostanthropogenicallyenrichedelementsinthesurface
riversediments;potentialanthropogenicsourcesincludemining,
leather industryactivities,andagriculturalfertilization.Themean
EF valuesofCr,Co,Ni,PbandMnwerealllessthan1.5,indicating
that thesemetalswerederivedfromthenaturalsources,suchas
underlyinggeologicalmaterial.Withtheexceptionofsediments
from theTMHwatershed,themeanEFvaluesforCdwereall
greaterthan1.5inthesurfaceriversediments,andwereparticu-
larlyhighintheZYH(8.34)andZWH(8.07)watersheds.Themean
EF valuesofZnandCuwerealsogreaterinZYHandZWH(Fig. 3).
These resultsindicatecontaminationoftheHaiheBasinwithCd,
Zn andCu,whichisconsistentwithotherstudies(Chabukdhara
and Nema,2012; Quinton andCatt,2007; Tangetal.,2010); theEF
valuesobtainedmaybeusefulindicatorsoftheroleofanthro-
pogenicprocessesintheirdistribution.
3.3.2. Potentialecologicalrisk
Potentialecologicalriskrepresentsthesensitivityofthebiolo-
gical communitytoagivensubstanceandillustratestheriskposed
by contamination(Suresh etal.,2012; Yi etal.,2011). Calculated
PER indexesofanindividualelement(Ei
r) arepresentedin Table
S5, andthecomprehensivePERs(RI)areshownin Fig. 4. Inthe
Haihe Basin,allelementsshowedlowPER,withtheexceptionof
Cd. The Ei
r valuesofCdrangedfrom33.8to240,withanaverageof
119inthesurfaceriversedimentsofsevenwatersheds,indicating
high CdcontaminationofthesedimentsintheriversoftheHaihe
Basin (Nemati etal.,2011), whichisconsistentwiththeresults
obtained fromtheoverlyingwatersamples.ThePERofCdwaslow
in theTMHwatershed,moderateintheDQHwatershed,consider-
able intheBSH,YDHandHLGwatersheds,andhighintheZYH
andZWHwatersheds,respectively.IntheZYHandZWHwatersheds,
30.0% and19.0%ofsampleshadveryhighPER.ThemeanRIvaluesof
the surfaceriversedimentswere117,141,91.2,302,125,231,and
57.1inBSH,YDH,DQH,ZYH,HLG,ZWHandTMHwatersheds,
km
Da Qing He
Hai-he Gan-liu
Bei Luan He San He Yong Ding He
Zhang Wei He
Zi YaHe
River
150
Watershed boundary
Basin boundary
150-300
300-600
≥ 600
Fig. 4. PER indexesofheavymetalsinsurfaceriversedimentsintheHaiheBasin.
W.Tangetal./EcotoxicologyandEnvironmentalSafety98(2013)317–323 321

6. respectively,withanoverallaverageof152.Asshownin TableS2,
there weremanystationsintheriversoftheHaiheBasinwithhigh
PER, whichweremainlylocatedintheZYHandZWHwatersheds
(Fig. 4). Thismaybeduetominingandindustrialdevelopmentin
the twowatersheds,andthedistributionplotsofRIcouldbe
useful inidentifyingthestationsthatneedthemostattention.
Tofurtherexamineheavymetalcontaminationinsurfaceriver
sediments oftheHaiheBasin,thespeciationofCd,Cr,Cu,Ni,Pb
and ZninsamplesfromZYHwatershed(RI4300)wasinvesti-
gated.Theresultsofthesequentialextractionareshownin Fig. 5.
Cr,Cu,NiandPboccurpredominantlyintheresidualfraction,
representinganaverageof58%,48%,74%and61%ofthetotal
metal contents,respectively.Incontrast,morethan30%ofthe
totalCdandZncontentswereobservedintheexchangeable
fraction.Thehighproportionofmetalsintheexchangeable
fractionisindicativeofanthropogenicpollutionandisinaccor-
dance withtheresultsofsimilarstudiescarriedoutonsites
affectedbyheavymetalpollutionindifferentrivers,includingthe
LouroRiver(Spain)(Filgueiras etal.,2004), theDanubeRiver(Relić
et al.,2005) andtheRiverPo(Italy)(Farkasetal.,2007). The
classification ofRACisasfollows:proportionofametaloccurring
in theexchangeablefraction o1%, norisk;1–10%,lowrisk;11–
30%, mediumrisk;31–50%, highrisk;andZ75%, veryhighrisk
(Singh etal.,2005). Accordingtotheclassification, therisk
associatedwithCdandZninthesedimentsofZYHwatershed
(RI4300)washigh,whichcorroboratetheresultsoftheEFand
PER index.Sedimentcontaminantsmaymoveintothefoodchain,
particularlyifthecontaminantsoccurinbioavailableforms.Cd
andZncanaccumulateinrelativelylargeamountsinplantswithout
anyapparenteffects,whichcouldcausehumanhealthproblems
(Lambertetal.,2007; Zhao etal.,2007).Therefore,itisimportant
that heavymetalcontaminants,especiallyCd,intheriversedimentsof
theHaiheBasincontinuetobecarefullymonitored.
4. Conclusion
An examinationofheavymetalcontaminationinoverlying
watersandsurfacesedimentswasconductedintheriversofseven
watershedsintheHaiheBasin.HighCdconcentrationsinover-
lying waters,especiallyintheriversoftheBSH,ZYHandZWH
watershedswereobserved,whileCdconcentrationsinsurface
sediments werehighestinriversoftheZYHandZWHwatersheds.
As indicatedbyEFvalues,Cd,Zn,andCuwerethemostanthro-
pogenicallyenrichedelementsinthesurfaceriversedimentsof
theHaiheBasin,whileCr,Co,Ni,PbandMnwerederivedfromnatural
sourcesinmostrivers.CdhadlowPERintheTMHwatershed,
moderatePERintheDQHwatershed,considerablePERintheBSH,
YDHandHLGwatersheds,andhighPERintheZYHandZWH
watersheds.ManystationsintheriversoftheHaiheBasinwerefound
tohavehighPER;thesesitesweremainlydistributedintheZYHand
ZWH watersheds,whichmaybeduetominingandrapidindustrial
development.Thisinformationcould beusefulinthedevelopmentof
effectivemanagementstrategiestocontrolheavymetalpollutionin
theriversoftheHaiheBasin.
Acknowledgments
This researchwassupportedbytheNationalNaturalScience
FoundationofChina(No.21107126),andtheNationalWater
Pollution ControlProgram(No.2012ZX07203-006).
Appendix A.Supplementarymaterials
Supplementarydataassociatedwiththisarticlecanbefoundinthe
onlineversionat http://dx.doi.org/10.1016/j.ecoenv.2013.09.038.
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