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ContentslistsavailableatScienceDirect
Ecological
 
Indicators
Heavy
 
metals
 
distribution,
 
risk
 
assessment
 
and
 
water
 
qualitycharacterization
 
by
 
water
 
quality
 
index
 
of 
 
the
 
River
 
Soan,
 
Pakistan
Summiya
 
Nazeer
a
,
 
Muhammad
 
Zaffar
 
Hashmi
b
,
 
Riffat
 
Naseem
 
Malik
a
,
a
EnvironmentalBiologyandEcotoxicologyLaboratory,DepartmentofEnvironmentalSciences,FacultyofBiologicalSciences,Quaid-i-AzamUniversity,Islamabad,PO45320,Pakistan
b
DepartmentofEnvironmentalEngineering,CollegeofEnvironmentalandResourceScience,ZhejiangUniversity,Hangzhou310029,People’sRepublicof China
a
 
r
 
t
 
i
 
c
 
le
 
i
 
n
 
f
 
o
 Articlehistory:
Received14October2013Receivedinrevisedform6March2014Accepted12March2014
Keywords:
SedimentsandwaterEnrichmentfactorGeo-accumulationindexWQIHeavymetals
a
 
b
 
s
 
t
 
r
 
a
 
c
 
t
Distribution
 
of 
 
heavy
 
metals,
 
nutrients
 
and
 
some
 
physico-chemical
 
variables
 
were
 
studied
 
in
 
water,suspended
 
and
 
bed
 
sediment
 
samples
 
along
 
River
 
Soan
 
and
 
its
 
tributaries
 
during
 
pre-
 
and
 
post-monsoonseasons.
 
Nutrient
 
loading
 
in
 
water
 
samples
 
were
 
relatively
 
high
 
during
 
pre-monsoon
 
season
 
while
 
metalconcentrations
 
were
 
found
 
to
 
be
 
high
 
during
 
post-monsoon
 
season.
 
Water
 
quality
 
as
 
determined
 
bywater
 
quality
 
index
 
(WQI)
 
was
 
found
 
to
 
be
 
relatively
 
better
 
during
 
the
 
pre-monsoon
 
season.
 
Ni,
 
PbandCdconcentrations
 
were
 
found
 
to
 
be
 
higher
 
than
 
recommended
 
for
 
water
 
use
 
for
 
domestic
 
or
 
aquaticlife.
 
Metal
 
concentrations
 
were
 
relatively
 
high
 
in
 
the
 
suspended
 
sediment
 
samples
 
as
 
compared
 
to
 
thebed
 
sediment
 
samples.
 
geo
 results
 
indicated
 
that
 
bed
 
and
 
suspended
 
sediment
 
samples
 
were
 
moderatelycontaminated
 
with
 
Cd
 
while
 
Ni,
 
Cu
 
and
 
Cr
 
showed
 
moderate
 
contamination
 
inthe
 
suspended
 
sedimentsamples.
 
Further,
 
results
 
indicated
 
that
 
contamination
 
sources
 
in
 
the
 
bed
 
(Cd,
 
Znand
 
Pb)
 
and
 
suspended(Cd,
 
Zn,
 
Ni,
 
Cu
 
and
 
Cr)
 
sediment
 
samples
 
were
 
from
 
natural
 
processes
 
and
 
anthropogenic
 
activities.According
 
to
 
the
 
classification
 
carried
 
out
 
on
 
the
 
basis
 
of 
 
EF,
 
the
 
bed
 
sediment
 
samples
 
were
 
significantlycontaminated
 
with
 
Cdand
 
moderately
 
contaminated
 
with
 
Pb
 
and
 
Zn.
 
While
 
Cd,
 
Pb,
 
Ni,
 
Cu
 
and
 
Cr
 
showedsignificant
 
contamination
 
and
 
Zn
 
showed
 
moderate
 
contamination
 
in
 
the
 
suspended
 
sediment
 
samples.Potential
 
risk
 
index
 
revealed
 
moderate
 
ecological
 
risk
 
in
 
the
 
suspended
 
sediment
 
samples
 
of 
 
urban
 
areas.The
 
results
 
suggested
 
that
 
Cd,
 
Zn
 
and
 
Pb
 
threats
 
to
 
aquatic
 
ecosystem
 
should
 
not
 
be
 
ignored.©
 
2014
 
Elsevier
 
Ltd.
 
All
 
rights
 
reserved.
1.Introduction
Aquaticecosystemshavebeenaffectedbyvarioustypesofcon-taminationsroundtheglobeintherecentfewyears.Tracemetalsareoneofthemostcommonpollutantswhichhaveseverelydete-rioratedtheaquaticecosystems(Alietal.,2013).Theirreleasein aquaticecosystemistriggeredbybothnaturalandanthropogenicprocesses(Zhangetal.,2009).Oncereleasedintotherivers,they may
 
geteitherdissolvedtoformionsorcomplexes,suspendedasparticulatematterorsettleddownasbedsediments(Tunaetal.,2007).Tracemetalsmay
 
causeseriousecologicalthreatthroughbioaccumulationifgetachancetoenterfoodchain(Seguraetal.,2006).Increaseinconcentrationoftoxicmetalsbeyondtoxiclim-itsresultsinlossofwaterqualitymakingwaterunfitfordrinking,
Correspondingauthor.Tel.:+925190643017.
E-mailaddress:
irrigation,aquacultureandrecreationalpurposes(Zhangetal.,2009).Restorationandconservationofsurfacewaterresourcesisthusnecessaryforthesakeoftheirinevitableroleinsustainingbothaquaticandterrestriallife.Suspendedandbedsedimentsareconsideredasmostsensitiveindicatoroftracemetalsastheyactassinkformetalsduetotheirabilitytoabsorbdissolvedmetalsandcanactasnon-pointsourceoftracemetalbyreleasingthemtowatercolumnwhenunder-goesphysico-chemicalchanges(Karbassietal.,2008;SharmaandSubramanian,2010).Assessmentofbedsedimentsqualityisoftenconsideredasmostcrucialindetermininganthropogenicinputof tracemetalsinaquaticecosystemsduetotheirlongresidencetimehencecapableofreflectinghistoryofpollutioninaquaticecosys-tems(Tunaetal.,2007).Howevertemporalvariationsinmetals couldbebetterevaluatedbyanalyzingmetalsindissolvedandsuspendedforms.Aneffectivewatermanagementprogramshouldthereforebebasedontheevaluationofdistributionoftracemetalsamongdifferentphasesinanaquaticenvironment(Davideetal.,2003).
http://dx.doi.org/10.1016/j.ecolind.2014.03.0101470-160X/©2014ElsevierLtd.Allrightsreserved.
 
S.Nazeeretal./EcologicalIndicators43(2014)262–270
263
CurrentstudyisbasedonthedistributionoftracemetalsindissolvedandsedimentsinbothsuspendedandsettledformsinRiverSoanwhichdrainsoneofthehighlyurbanizedcatchmentsofPakistan.Nutrientenrichmentduetohugesewageinfluxfromurbanareasandotherphysico-chemicalfactorsaffectingthedistri-butionoftracemetalsinwaterandbedsedimentshavealsobeendiscussedwiththeaimtoidentifythepotentialsourcesoftracemetalsinriverineecosystemofRiverSoan.
2.Materialsandmethods
 2.1.Studyarea
Studyareaexhibitsdiverselithologicalfeaturesbasedmainlyonlimestone,shale,continentalsandstonesandclaybelongtoeocene,mioceneepoch,plioceneandlowerpliestoceneages.SurficialunitsofgeologywereformedduringPlioceneandHoloceneagesandarecomposedofLeiconglomerateschieflycomposedoflimestoneandPotoharclaycomposedofquartz,feldspar,kaoliniteandillitewhileterracealluvium,alluviumandwindblownsilt,floodplain,fanandstreamchannelalluviumaresomeothergeologicalsurficialunits.RiverSoanhasitsorigininlowerHimalayanfoothillsanddrainsoneoffivemajorphysicaldivisionsofPakistan,thePotoharPlateau.Studyareaextendedfrom71
45
to73
35
ineastand32
45
to33
55
innorth(Fig.1).RiverKurang,RiverLingandNallahLei arethemaintributariesofRiverSoan.RiverSoanultimatelyjoinsRiverIndusnearMakhadvillage,DistrictAttockaftertraversingthroughcapitalcityofIslamabadandthreedistrictslocatedinnorthofPunjabprovincewhichincludeRawalpindi,ChakwalandAttock.
 2.2.Samplingandanalysis
Waterandsedimentsampleswerecollectedfrom18samp-linglocatedontheRiveranditstributariesduringpre-monsoon(April–May)andpost-monsoonseason(September–October)in2008(Fig.1).Watersampleswerecollectedfrom25cmdepth whereapplicableusinggrabmethod.Differentparametersliketemperature,pH,DO,TDS,electricalconductivityandsalinitywererecordedinthefieldusingportableHydrolabSurveyor(MS5SurveyorHachEnvironmental)andturbiditywas
 
measuredwith2100Pturbidmeter(HACH).Allsamplesweretransportedinbottlespre-washedwithHNO
3
,bottleswerestorediniceboxesconservedat4
C.Watersampleswereanalyzedfordiffer-entanalysisinlaboratory.AnalysesconductedinlabwereCO
2
elimination(titrationmethod),alkalinity(acid–basetitrometry),chlorides(silver-nitratetitrometry),CODkits(HACHspectrometricmethodology),totalphosphorous(alkalinepersulphatedigestion),totalnitrogen(alkalinepersulphatedigestion),orthophosphates(ammoniummolybdatemethod),nitrate-nitrogen(phenoldisul-phonicmethod),ammonia-nitrogen(phenatemethod),sulphates(bariumchloridemethod)asdescribedpreviously(AllenandHansen,1996).WatersampleswerefilteredthroughWhatmanfilterpaperforestimationofdissolvedmetalsandacidifiedwithnitricacidtoadjustpH<2inordertopreservesamples(Sadeghietal.,2012).WatersampleswererunonfastsequentialAtomicabsorptionspectrometerforanalysisofdissolvedmetals.SuspendedsedimentsampleswerecollectedbyfilteringthewatersamplesthroughWhatmanfilterspaper(Sadeghietal.,2012).Metalswereextractedfromsuspendedsedimentsamplesusingmicrowaveassisteddigestionoffilterpaperscarriedoutusing13.5mL 
 
ofHNO
3
 and4.5mL 
 
HClandadjustingtemperatureat180
±
5
Cwhilepowerof1200Wwasprovidedduringdiges-tion.Digestedsampleswerefilteredandvolumewasadjustedwithdistilledwaterupto50mL.Surfacesedimentsampleswerecollectedattheplaceswherewaterflowwas
 
lowandtransportedtothelabinprecleanedpoly-thenebags(Sutharetal.,2009).Sampleswereair-dried,ground, sievedthrough2mmsizedsievetoremovedebris,stonesandothercoarsestructuresandstoredincleanedpolythenebags.Sampleswereanalyzedforparticlesizeasdescribedpreviously(PalmerandTroeh,1977)andtexturalclassesweredeterminedbyusingtexturaltriangle.Tyurin’smethod(NIKOLSKII,1964)was
 
usedtodetermineOMinsedimentsamples.Solutionofsedimentsampleswaspreparedinaratioof1:10todeterminesoilpHusingportablepHmeter(Milwaukee,modelSM802).AcidextractionusingH
2
SO
4
wascarriedoutinordertoextractorthophosphatesfromthesedi-mentsampleswhilecoppersulphateextractionwas
 
carriedoutfornitrateextractionfromsediments.Ammoniummolybdatemethodwasusedfordeterminationoforthophosphateswhilephenoldisul-phonicmethodwas
 
usedforthedeterminationofnitrates.Foraciddigestion,9
±
0.1mL 
 
concentratednitricacidand3
±
0.1mL 
 
ofconcentratedhydrochloricacidwereaddedto0.5gofthesedimentsamplesplacedinTeflontubes.Rateofchangeintemperaturewasadjustedto220
±
5
Cand1200Wofpowerwasprovided.DigestedsampleswerecooleddownandfilteredthroughWhatmanfilterpaperno.42anddilutedupto50mL.
 
Con-centrationofmetalswas
 
determinedthroughcalibrationcurveof standardsolutionsusingAtomicAbsorptionSpectrometry(Vari-anceFSS-240).
 2.3.Waterqualityindex(WQI)
Waterqualityindex(WQI)was
 
developedonthebasisofAlbertaRiverWaterQualityIndex(AlbertaWQI
 
2007)andGuidelineCom-plianceIndex(GCI)(Kotze,2008)usingfollowingequations. WQI
 
=
100
 
21
 +
22
 +
23
1
.
732
 (1)where
1
=
NumberofwatervariablesthatdonotmeetobjectiveTotalnumberofwatervaribles
×
100
(2)
2
=
NumberoftestthatdonotmeetobjectiveTotalnumberoftests
×
100(3)
3
=
 nse0
.
01nse
+
0
.
01
 (4)wherense(normalizedsumofexcursions)
=
ni
=
1
departurenumberoftests (5)Here,departureisthenumberoftimesbywhichanindividualconcentrationisgreaterthanorlessthantheobjective(referencevalue).Ifthetestvaluedoesnotexceedobjectivethendeparturewillbecalculatedas:departure
i
 =
Failedtest
i
Objective
 j
1(6)Ifthetestvaluedoesnotfallbelowobjectivethendeparturewillbecalculatedas:departure
i
 =
 Objective
 j
Failedtest
i
1(7)WQI
 
scorewasscaledfrom0to100whereas,eachsitewasclassifiedintooneoffivequalityclasses,e.g.excellent(>80),good(60–80),fair(40–60)andpoor(<40).Potentialriskindex(RI)reflectsthecollectiveeffectsofdiffer-entpollutantsinthesedimentsandquantitativelymeasurethe
 
264
S.Nazeeretal./EcologicalIndicators43(2014)262–270
Fig.1.
Map
 
ofthestudyareaillustratingthelocationsofsamplingsitesalongRiverSoananditstributaries.
ecologicalriskcausedbydifferentpollutants(Hakanson,1980).MethodologyproposedbyHakanson(1980)wasfollowedtoassess potentialecologicalriskofdifferentheavymetalinbedandsus-pendedsediments.Calculationofcontaminationfactor(
 f 
)isthefirststeptowardtheestimationofRI.Followingistheequationtomeasure
 f 
 f 
 =
n
b
where
n
 istheconcentrationofmetalninthesedimentsand
b
 isthepreindustrialbackgroundconcentrationadoptedfromHakanson(1980)ofthatmetalinthesediments.Contaminationcausedbyheavymetalsinsuspendedandbedsedimentsareassessedbygeoaccumulationindex(
geo
geo
 =
log2
 
n
1
.
5
B
n
where
n
 istheconcentrationofmetalninthesediment,
B
n
 isthegeochemicalbackgroundconcentrationofmetal
n
,factor1.5isusedforpossiblelithologicalvariationsinthebackgroundvaluebasedonShalevaluereportedpreviously(TurekianandWedepohl,1961).Enrichmentfactorwasusedtoinvestigatethedegreeofcontam-inationandpossibleinputofmetalsfromanthropogenicsources(Erginetal.,1991).EF
=
(M/Fe)Sample(M/Fe)ShalevaluewhereEF,enrichmentfactor,(M/Fe)sampleistheratioofparticularmetaltoironconcentrationinthesample,(M/Fe)shalevalueistheratioofparticularmetaltoironconcentrationintheearthcrust.Basedonthe
 f 
 measuredfromaboveequationandtoxicresponsefactor(
)adoptedfromHakanson(1980)orparticular metalconcentrationinthesediments,ecologicalriskfactor(
)iscalculatedusingfollowingequation.
 =
 f 
 ·
Finally,theriskindex(RI)iscalculatedsummingtheecologicalfactorscalculatedforeachheavymetal.RI
=
3.Resultsanddiscussion
 3.1.Physico-chemistryofwaterofRiverSoan
Physico-chemicalvariationsofSoanRiverwateralongspatio-temporalscalesisdescribedinTable1.Heavymetals,TP,TNand

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