Determination of total arsenic and arsenic species in drinking water, surface water, wastewater

22 Pages·2016·0.83 MB·English

by  Izabela Komorowicz

EnvironMonitAssess(2016)188:504
DOI10.1007/s10661-016-5477-y
Determination of total arsenic and arsenic species in drinking
water, surface water, wastewater, and snow
from Wielkopolska, Kujawy-Pomerania, and Lower
Silesia provinces, Poland
IzabelaKomorowicz& DanutaBarałkiewicz
Received:24March2015/Accepted:7July2016/Publishedonline:4August2016
#TheAuthor(s)2016.ThisarticleispublishedwithopenaccessatSpringerlink.com
Abstract Arsenic is a ubiquitous element which may observed.However,insnowsamplecollectedinLegni-
be found in surface water, groundwater, and drinking ca, more than 97 % of the determined concentration,
water. Inhigherconcentrations, thiselementisconsid- amountingto81±11μgL−1,wasintheformofAs(III),
eredgenotoxicandcarcinogenic;thus,itslevelmustbe themosttoxicarsenicspecies.
strictlycontrolled.Weinvestigatedtheconcentrationof
totalarsenicandarsenicspecies:As(III),As(V),MMA,
Keywords Totalarsenic.Arsenicspecies.Speciation.
DMA,andAsBindrinkingwater,surfacewater,waste-
Water.ICP-MS.HPLC/ICP-MS
water, and snow collected from the provinces of
Wielkopolska, Kujawy-Pomerania, and Lower Silesia
Abbreviations
(Poland).Thetotalarsenicwasanalyzedbyinductively
As(III) Arsenite
coupledplasmamassspectrometry(ICP-MS),andarse-
As(V) Arsenate
nicspecieswereanalyzedwithuseofhigh-performance
AsB Arsenobetaine
liquid chromatography inductively coupled plasma
CPE Cloudpointextraction
mass spectrometry (HPLC/ICP-MS). Obtained results
CRM Certifiedreferencematerial
revealed that maximum total arsenic concentration de-
DDTP Diethyldithiphosphate
termined in drinking water samples was equal to
1.01μgL−1.Thehighestconcentrationoftotalarsenic DMA Dimethylarsenicacid
insurfacewater,equalto3778μgL−1wasdetermined (dimethylarsinate)
EDTA Ethylenediaminetetraaceticacid
in Trująca Stream situated in the area affected by
ETAAS Electrothermalatomic
geogenic arsenic contamination. Total arsenic concen-
absorptionspectrometry
trationinwastewatersampleswascomparabletothose
FI-HG-AAS Flowinjection-hydride
determinedindrinkingwatersamples.However,signif-
generationatomic
icantly higher arsenic concentration, equal to
83.1±5.9μgL−1,wasfoundinasnowsamplecollected absorptionspectrometry
FI-ICPMS Flowinjectioninductively
inLegnica.As(V)waspresentinalloftheinvestigated
coupledplasmamass
samples, and in most of them, it was the sole species
spectrometry
GF-AAS Graphitefurnaceatomic
: absorptionspectrometry
I.Komorowicz (*) D.Barałkiewicz HG-AAS Hydridegenerationatomic
DepartmentofTraceElementAnalysisbySpectroscopyMethod,
absorptionspectrometry
FacultyofChemistry,AdamMickiewiczUniversityinPoznań,
89bUmultowskaStreet,61-614Poznań,Poland HG-AFS Hydridegenerationatomic
e-mail:[email protected] fluorescencespectrometry
504 Page2of22 EnvironMonitAssess(2016)188:504
HG-CT-AFS Hydridegeneration- TAs Totalarsenic
cryotrappingcoupledto TMAO Trimethylarsineoxide
atomicfluorescence USEPA USEnvironmental
spectrometry Protection
HG-CT-ICPMS Hydridegeneration- Agency
cryotrappingcoupledto WDXRF Wavelength-dispersive
inductivelycoupled X-rayfluorescence
plasmamass spectrometry
spectrometry WHO WorldHealth
HG-ICP-AES Hydridegeneration Organization
inductivelycoupled
plasmaatomic/optical
emissionspectrometry
HPLC High-performance Introduction
liquidchromatography
HPLC/ICP-MS High-performance Arsenic iswidelydistributed insurface water, ground-
liquidchromatography water,anddrinkingwater.Itsconcentrationindifferent
inductively types of water varies considerably. In some cases, it
coupledplasmamass significantly exceedsexpectedmeanvaluesforarsenic
spectrometry and maximum permissible arsenic concentration
iAs Inorganicarsenic allowed for drinkingwater, indicating a degreeof pol-
ICP-AES Inductivelycoupled lution(Fowleretal.2007).
plasmaatomicemission Arsenicpollutionisaworldwideproblemmanysci-
spectrometry entists have repeatedly expressed concern about. As a
ICP-MS Inductivelycoupled result, the biological and environmental consequences
plasma of its contamination are being studied in detail. Al-
massspectrometry thoughmostresearchersfocusonthearsenicoriginating
ICP-SF-MS Inductivelycoupled from the natural sources, human activities (such as
plasmasectorfield smelting of arsenic bearing minerals, the disposal of
massspectrometry industrial waste, or burning of fossil fuels) can locally
INAA Instrumentalneutron introduce a very high contamination (Bissen and
activationanalysis Frimmel2003;Matschullat2000).
LC Liquidchromatography Issue of great importance is presence of arsenic in
LC-HGAFS Liquidchromatography groundwater used as a source of drinking water. In
hydridegenerationatomic recent years, cases of arsenic pollution have been re-
fluorescencespectrometry ported in many countries such as the USA, China,
MDL Methoddetectionlimit Bangladesh,Pakistan,Taiwan,Chile,Argentina,Japan,
MMA Monomethylarsenicacid Turkey,Thailand,Mexico,Vietnam,andIndia(Simsek
(methylarsonate) 2013;HeandCharlet2013;Sorgetal.2014;Smedley
n.d. Notdetected andKinniburgh2002;Bergetal.2001;Gammonsetal.
ORS Octopolereactionsystem 2005,Brahmanetal.2013).Duetopermanentexcessive
PAs Particulatearsenic levelofarsenic,somecountries,includingBangladesh,
SPE Solid-phaseextraction Mexico, Vietnam, and India, have considerably raised
SPE-DLLME- Solid-phaseextraction itslevelindrinkingwater.Itispresumedthataround40
SFO coupledwithdispersive millionpeopleinBangladeshliveatimmediateriskdue
liquid–liquid to arsenic pollution (Bissen and Frimmel 2003). An
microextraction analysisof20,000tube-wellwatersindicatedthatarse-
basedonthesolidification nic levels in drinking water are above the maximum
offloatingorganicdrop permissible concentration limit of 10 μg L−1 (WHO
EnvironMonitAssess(2016)188:504 Page3of22 504
2011) in case of 62 % of tube-well waters. In some of this element (Cornelis et al. 2005; Brahman et al.
places, its concentration was as high as 3700 μg L−1 2013). Although there isa vast amountof information
(Bagla and Kaiser 1996). There are also many papers onthe occurrenceand concentration of total arsenic in
reportingsimilararsenicconcentration,reachingseveral different types of water, the data on the speciation of
thousandμgL−1(Bergetal.2001;Brahmanetal.2013; arsenic are limited (Sorg et al. 2014; Haque and
Smedley et al. 2002; Farnfield et al. 2012; Gammons Johannesson 2006). The shortage of information on
et al. 2005; Aiuppa et al. 2003; Bednar et al. 2004). It the speciation of arsenic may be partially attributed to
has been estimated that as many as 60–100 million thecomplexity,cost,andtimeneededtoperformarsenic
peoplegloballymaybeatriskofexposuretoexcessive speciationanalyses(Sorgetal.2014).Nevertheless,itis
levelsofarsenic(Ngetal.2003).Sincearseniccontam- essential to develop sensitive and precise analytical
inationprovidessuchahugeprobleminmanyplacesin procedures to identify and quantify arsenic species in
theworld,itisworthtomentionthatvariousmethodsof water(Baigetal.2010;HirataandToshimitsu2005).
itseliminationfromtheaqueousenvironmentsareavail- The USEPA has elaborated a document reviewing
able.Besidesconventionalremediationtechniquessuch the science and technologies for monitoring arsenic in
asosmosis,ionexchange,orelectrodialysis,forremov- theenvironment(USEPA2004).Themethodsapproved
ingmetalormetalloidsfromwater,biosorptionischar- by USEPA include inductively coupled plasma-mass
acterizedbythesignificantdevelopmentinrecentyears spectrometry (ICP-MS), inductively coupled plasma
[Basuetal.2014;Abidetal.2016].Oneofthegreatest atomicemissionspectrometry(ICP-AES),graphitefur-
advantages of this process is material of biosorbent, naceatomicabsorption(GFAAS),andhydridegenera-
which is easy and commonly available, and inexpen- tion atomic absorption spectrometry (HGAAS), all of
sive. A lot of different agricultural and food-industry whichmaybecharacterizedbymethoddetectionlimits
biowastessuchascoconutshell,coconutcoirpith,man- (MDL) ranging from 0.5 to 50 μg L−1 (USEPA 1999;
goleaf,ricepolish,orteawastehavebeenexaminedas Ma et al. 2014). The choice of an adequate analytical
potentialbiosorbentsforAs-contaminatedwater.These method is dictated by the purpose of our analysis, the
variousapproachesarewidelydiscussedinthepaperof levelofanalyte’sconcentrationinconcretematrix,and
Shakoor et al. (2016). One of the most recent paper thetypeofcompoundinwhichanalyteispresent.The
concerns As(V) biosorption with application of food most often applied strategy is connection of HPLC
processing biowastes, more specifically orange peel separation with ICP-MS detection (Komorowicz and
biowaste. This research revealed that with use of Baralkiewicz 2014; Bednar et al. 2004; Shraim et al.
charged orange peel, it was possible to remove 98 % 2002;Dengetal.2009;Jabłońska-Czaplaetal.2014)or
of As(V) from the solution containing 200 mg L−1 of AFSdetection(Yuetal.2014;Gongetal.2006;Keller
As(V)using4gL−1ofbiosorbent[Abidetal.2016]. etal.2014;Fariasetal.2015).CouplingofHGsystem
Inmostaquifers,bio-geointeractionsprobablydom- toAAS(Bergetal.2001;Affumetal.2015);ICP-MS
inateasthesourceofarsenic.Interactionofarsenicwith (Musiletal.2014),ASF(Aiuppaetal.2003;Dengetal.
organic and mineral colloids can elevate its concentra- 2009; Musil et al. 2014), or ICP-AES (Smedley et al.
tion(HeandCharlet2013).Arseniccanexistinwaterin 2002) is also quite popular. There are either reports
severalorganicandinorganicforms.Speciationofarse- about application of SPE system used for separation
nicdependsonpH,salinity,aciddissociationconstantat purposes before detection by WDXRF, ICP-MS,
logarithmicscale(pK ),andredoxpotential(Sugáretal. DLLME-SFO, GF-AAS, and ETAAS (Brahman et al.
a
2013).Thetoxicityofarseniccompoundsdecreasesin 2013;Baigetal.2010;Shamsipuretal.2014;Pengetal.
the following order: arsines > inorganic arsenites > 2015;Hagiwaraetal.2015).
organictrivalentcompounds(arsenooxides)>inorganic Although a variety of analytical techniques have
arsenates>organicpentavalentcompounds>arsonium beenalreadyappliedforarsenicspeciesdetermination,
compounds>elementalarsenic(Adriano2001;Fowler as mentioned, HPLC separation which is followed by
1983; Mandal and Suzuki 2002). Arsenobetaine and ICP-MS or HG-AFS undeniably belong to the most
arsenocholineareconsideredasnontoxic(Komorowicz often used hyphenated techniques. ICP-MS technique
andBarałkiewicz2011). is mostcommonly applied for speciation analysis, and
Itiswellknownthattoxicologicalandenvironmental this tendency is expected to continue to grow as the
impactofarsenicstrictlydependsonthechemicalform required instrumentation becomes more widely
504 Page4of22 EnvironMonitAssess(2016)188:504
available. Said method provides reliable quantitative Kaczawa River Kaczawa is the left-bank tributary of
data for arsenic species at environmentally relevant Odra River. Water supply point of drinking water for
levels in diverse matrices (Ma et al. 2014) as well as thecityofLegnicaissituatedontheKaczawaRiver,in
othersignificantadvantages.Theseincludetheexcellent Smokowice.UppercourseoftheKaczawaRiverflows
separating power of HPLC, associated with a high de- through farmlands; its lower and middle course flows
greeofelementspecificityandverylowdetectionlimits throughindustrially-agriculturalareas,whichmakesthe
of the ICP-MS technique. HPLC/ICP-MS can detect riverexposedtoimpuritiesflowingfromthefarmlands
arsenicininorganicandorganicformswithhighpreci- and cultivated fields. Supplies of the Kaczawa River
sion. Additionally, this systemistotally integratedand may also be a great source of contamination (RRIEP
automated (Liévremont et al. 2009; Tomlinson et al. 2006).
1995).
The objective of this study was to determine total TrującaStream TheNysaKłodzkaRiveristhelargest
arsenic and arsenic species concentration in drinking river of the Kłodzko Basin, and it starts in the Lower
water, surface water, wastewater, and snow samples Silesia province. Nysa Kłodzka River enters Lower
collected from Wielkopolska, Kujawy-Pomerania, and Silesiaprovincebelowaconfluencepointwithanoutlet
Lower Silesia provinces located in Poland. The last of the Trująca Stream and above the Otmuchowski
mentioned province is the As-affected area known for Reservoir.TheNysaKłodzkaRiverinitsuppercourse
geogeniccontaminationwiththiselement. flowsthroughmountainousareas,functioningmainlyas
atouristarea.Theriveranditssuppliescollectthewater
from nature preservation areas as well as from farm
Experimental areas. There are industrial plants working in the river
catchmentarea(RRIEP2006).
Samplingsites
Samples were collected in the area of Poland from Snow
provinces of Wielkopolska, Kujawy-Pomerania, and
LowerSilesia.Samplecollectionlocationsarepresented Snow samples were collected in the city of Legnica
indetailonthesamplingmapofstudyarea(Fig.1).One situated in the Lower Silesia province and in the city
sampleateachsamplingpointwascollected.Intotal,23 of Poznań situated in the Wielkopolska province. The
samples of drinking water, surface water, wastewater, LowerSilesiaprovinceisanarearecognizedassignif-
and snow were submitted to analysis, three replicate icantly richer in arsenic in comparison to other prov-
measurementsofeachweremade. inces.During its history, a goldminewas operating in
ZłotyStokCity(LowerSilesia).Apartfromgoldmin-
Drinkingwaterandwastewater ing, mine also produced an arsenic trioxide from the
local ore (www.kopalniazlota.pl/pl/historia/historia-
Drinkingwaterandwastewatersampleswerecollected kopalni-zlota). Aforementioned sample was collected
from places located in three different provinces of Po- near the copper smelter and the refinery located near
land:Wielkopolska,Kujawy-Pomerania,andLowerSi- cityofLegnica.Secondsampleofsnow,collectedfrom
lesia.Sampleswerecollectedatpointsofwaterintake, thecenterofPoznań,maybetreatedasacontrolsample.
fromwatertreatmentstationsormunicipalsewagetreat- Samplecollectionandpreparation.
mentplants. All samples were collected in polyethylene bottles
previously cleaned with metal-free detergent, rinsed
Surfacewater with deionized water, then soaked in 5 % nitric acid
for 24 h and finally rinsed once again with deionized
SurfacewatersampleswerecollectedfromLowerSile- water. After collection, samples were promptly
siaprovince,whichistheregiondefinitelymuchricher transportedinacool-boxtothelaboratory.Totalarsenic
in arsenic than Wielkopolska or Kujawy-Pomerania. and arsenic species determination were followed by
Samples were taken from the Kaczawa River and the waterqualityparameter’sinvestigation(pH,conductiv-
TrującaStreamfromfewdifferentlocations. ity, COD, BOD, TOC) and determination of major
EnvironMonitAssess(2016)188:504 Page5of22 504
Inowrocław
Kujawy-
Pomerania
province
Wągrowiec
Szamotuły Wielkopolska
POLAND
province
Koziegłowy
Gniezno
Poznań
Jarocin
Krotoszyn
Lower
Silesia
province
Złotoryja drinking water
Legnica
Wojcieszów Górny
surface water
Kaczawa River
Świerzawa wastewater
Wałbrzych
Złoty Stok snow
Trująca Stream
Fig.1 Samplingmapofstudyarea
inorganicions(Ca2+,Mg2+,Na+,K+,Cl−,SO2−,PO3−, samplemelted,thewaterwhicharosefromthemelting
4 4
NO−) concentration. Results regarding water quality snowwassampled.
3
parametersand basic anions and cations werepartially
providedbywatertreatmentstationsormunicipalsew- Instrumentation
age treatment plants, from where some of the samples
had been collected. For measurements aiming at the ELAN DRC II ICP-MS (PerkinElmerSCIEX, Ontario,
determination of total arsenic concentration, samples Canada)wasusedfortotalarsenicdeterminationaswell
wereacidifiedwith125μLofnitricacid(suprapurnitric as for arsenic species determination. In case of specia-
acidof65%(v/v))oneach125mLofsample.However, tionanalysis,ICP-MSwashyphenatedwithHPLCsys-
forarsenicspeciationanalysissampleswereimmediate- tem.Tocollectthedata,ionsofarsenicatmasstocharge
lyfrozenand thawedjustbeforethe analysis. Samples ratio(m/z+)75weremonitored.HPLCsystemconsisted
werethenfilteredthroughsyringefilterswithaporesize ofaPerkinElmerSeries200HPLCPump,PerkinElmer
of0.45μm.Thesnowsamples(LowerSilesiaprovince Series 225 HPLC Autosampler and a Perkin Elmer
andWielkopolskaprovince)werecollectedtothepoly- Series 200 Column Oven. Autosampler was equipped
ethylenebottleswithuseofpolyethylenespatula.They withaPeltierCoolingTrayinordertokeepthesample
weretakenfromthesurfaceand2cmdeepintothesnow temperature equal to4 °C. The anion exchangeHPLC
layer,sonotonlythedarklayeroftheatmosphericdust columnPRP-X100(4.6×150mm)wasusedforarsenic
butalsocleansnowunderneathwascollected.Afterthe speciesseparation.Thecolumnwaspackedwith5μm
504 Page6of22 EnvironMonitAssess(2016)188:504
particles of styrene divinylbenzene copolymer with Total arsenic concentration was determined accord-
trimethylammoniumexchangesitesinPEEKhardware ingtoISO17294–2(2003)standard;however,concen-
(Hamilton Company, Bonaduz, Switzerland). Applied tration of arsenic species was determined according to
columnenabledtoseparatefivearsenicspeciesin7min methodologydevelopedandfullyvalidatedinourlab-
usingoptimizedHPLCconditions.Arsenicspecieselut- oratory(KomorowiczandBaralkiewicz2014).
ed in the following order:AsB, As(III),DMA, MMA,
andAs(V). Reagents
TheoutletoftheHPLCcolumnwasconnectedviaa
switch, directly to the nebulizer of the ICP mass spec- Chemicalsandreagentsusedfortotalarsenicsolutions
trometer.ThedatawerecollectedusingChromerasoft- and arsenic species (inorganic: arsenite (As(III)), and
ware(PerkinElmerSCIEX,Ontario,Canada).Operating arsenate (As(V)); organic: arsenobetaine (AsB),
conditions and optimal values of HPLC and ICP-MS monomethylarsenic acid (MMA), and dimethylarsenic
parametersarepresentedinTable1. acid(DMA))solutionspreparation,saltsusedformobile
phasepreparation,buffersolution,reagentsusedforpH
adjustment,aswellasotherchemicalsusedthroughout
the experiment, were described in details in the previ-
Table1 OperatingconditionsforHPLCandICP-MSsystems
ously published work (Komorowicz and Baralkiewicz
Parameter Setting 2014).Particularsteps of bothanalyticalprocedures—
for total arsenic determination and for arsenic species
HPLC determination—arepresentedontheFig.2intheform
Instrument PESeries200HPLCPump, ofdiagram.
PESeries225HPLC
AutosamplerandPESeries
Figuresofmerit
200ColumnOven
Column HamiltonPRP-X100
Alotofinformationinthescientificfieldismadeonthe
Elution Isocratic
basisofanalyticalmeasurements.Ensuringthatobtain-
Mobilephase Ammoniumdihydrogen
phosphate,ammonium edanalyticalresultsarereliableisextremelyimportant
nitrate therefore the process of quality control is a significant
Concentrationofmobilephase 0.01mol step of each analytical procedure (Konieczka and
pH 9.2±0.1 Namieśnik 2010). In our work, the analytical proce-
Flowrate 1.0mLmin−1 dures,for totalarsenic determination byICP-MS tech-
Injectionvolume 75μL niqueandarsenicspeciesdeterminationbyHPLC/ICP-
Columntemperature 25°C MStechnique,werecharacterizedbythefollowingpa-
ICP-MS rameters:selectivity,linearity,limitofdetection,limitof
Instrument PESciexELAN6100DRCII quantification,precision,andtrueness.Traceabilitywas
RFpower 1250W assured by analysis of certified reference material and
Nebulizergasflow 0.95Lmin−1 analysisofspikedsamples,fortotalarsenicandarsenic
Auxiliarygasflow 1.375Lmin−1 species, respectively. Measurement uncertainty of the
Plasmagasflow 14.5Lmin−1 analytical result for total arsenic and for each arsenic
specieswasassessedbythemodelingapproachaccord-
Samplerandskimmercones Pt
ing to the Guide to the Expression of Uncertainty of
Lensvoltage 9.75V
Measurement (GUM 1993; Konieczka and Namieśnik
Detectormode Dual(pulsecountingand
analogmode) 2010). Validation parameters together with uncertainty
Datacollectionmode 75As+ for total arsenic and arsenic species are presented in
Scanmode Peakhopping Table2.
Dwelltime 250ms
Total arsenic Total arsenic concentration was deter-
Sweeps 1
mined with ICP-MS technique according to validated
Reading 2362
methodology described in ISO 17294–2 (2003)
EnvironMonitAssess(2016)188:504 Page7of22 504
Fig.2 Diagrampresentingthe
Drinkingwater
stepsofanalyticalprocedures
Wastewater
Sample collection
Surfacewater
Snow
Waterquality parameters
investigation
Sample
Acidificationincaseof
preparation totalAs/freezingincaseof
arsenicspecies
Filtration
ICP-MSparameters
optimization
Total As
Determinationaccording to
determination
ISO 17294–2 standard
by ICP-MS
Analyticalprocedure
validationand uncertainty
estimation
HPLC parameters
As species
optimization
determination
Analyticalprocedure
by HPLC/ICP-MS validationand uncertainty
estimation
Result
standard. The calibration curve for total arsenic was (n = 10) and certified value of the mentioned certified
constructedataconcentrationrangeof0.2–20.0μgL−1. reference material. Obtained value was equal to
In order to verify the linearity of calibration curves, 0.4176 ± 0.0071 μg L−1; however, certified value
approachbasedondrawingagraphofconstantresponse amountedto0.413±0.039μgL−1.Calculatedrecovery
for y/x values (wherey denotes the instrumentalsignal wasequalto101.1±1.7%,whichconfirmsthatsample
and x is the concentration of analytes in the standard matrix influence is negligible. Combined uncertainty of
solution) with acceptable deviation within ±5 % was totalarsenicwasestimatedtakingintoconsiderationthe
applied. The chosen operating range for each of the following sources of uncertainty: measurement repeat-
calibration curves was statistically verified by checking ability, calibration, and recovery. Expanded uncertainty
the homogeneity of variances using Snedecor’s F test. (U[%],k=2)estimatedfortotalarsenicusingBbottom-
Precision calculated by analysis of CRM of river water up^approachwasequalto7.1%.Itmaybeappliedtothe
SLRS-5 (National Research Council Canada, Ontario, concentrationrangeof0.2–20.0μgL−1.
Canada) amounted to 1.7 % (n = 10). The traceability
forthetotalarsenicmeasurementwasassessedbydeter- Arsenic species Arsenic species concentration was de-
mining the % bias between the measured concentration termined by commercially available HPLC/ICP-MS
504 Page8of22 EnvironMonitAssess(2016)188:504
Table2 CharacteristicsoftheanalyticalproceduresoftotalarsenicdeterminationandfivearsenicspeciesdeterminationinwaterbyICP-
MSandHPLC/ICP-MS,respectively
Analyticalprocedureparameters Measurementresult
TotalAs AsB As(III) DMA MMA As(V)
Retentiontime(min) – 1.7 2.1 2.4 4.2 6.3
Linearrange(μgL−1) 0.2–20.0 0.2–10.0 0.2–10.0 0.2–10.0 0.2–10.0 0.2–10.0
Correlationcoefficient 0.9999 0.9997 0.9998 0.9999 0.9998 0.9998
LOD(μgL−1)a 0.069 0.074 0.074 0.070 0.13 0.11
LOQ(μgL−1)b 0.21 0.22 0.22 0.21 0.39 0.33
Precision/retentiontime(%,CV) – 0.53 0.56 0.68 0.69 0.21
Precision/concentration(%,CV) 1.7 2.4 2.0 1.6 2.3 1.6
Recovery(%) 101 99 100 100 98 101
Uncertainty(%) 7.1 12.0 13.0 5.6 9.6 8.6
Parameterswerecalculatedasameanvaluefromtenreplicatedmeasurements
aLODwascalculatedasthreetimestheSDfromtheblanksamples(n=10)withtheadditionofthearsenicconcentration,whichwascloseto
theexpectedLODvalue
bLOQvalueswerecalculatedasthreetimestheappropriateLODvalues
techniqueaccordingtodevelopedandfullyvalidatedin of total arsenic was found in a sample collected in
ourlaboratorymethodologydescribedpreviously(ISO/ Wałbrzych—0.249±0.018μgL−1.
IEC 2005; Komorowicz and Baralkiewicz 2014). BIn- Surface water samples were collected from the
house^ traceabilitydefined as truenesswas assured by Kaczawa River and the Trująca Stream situated in the
analysisofspikedsamples.Uncertaintybudgetforeach Lower Silesia province. Samples from the Kaczawa
arsenicspecieswasestimatedaccordingtothebottom- River were taken at three different points (from
upapproach(GUM1993). WojcieszówGórny;aboveŚwierzawaCity;fromwater
intakeforLegnicacity).Obtainedresultsoftotalarsenic
concentration for mentioned samples ranged from
0.928 ± 0.066 to 2.84 ± 0.20 μg L−1. However, total
Resultsanddiscussion arsenicconcentrationinTrującaStreamwasfoundtobe
much higher than these determined in Kaczawa River.
TotalarsenicconcentrationinwatermediaofPoland Inthiscase,sampleswerecollectedattwopoints.The
firstsamplewascollectedfromtheupperreachesofthe
Table3presentstheconcentrationofTAsandspeciated TrującaStream,justabovetheZłotyStokCity.Second
arsenicindrinkingwater,surfacewater,wastewater,and sample was taken close to the bridge located on the
snow in provinces of Wielkopolska, Kujawy-Pomera- Błotnica-Topola road, at the close of a uniform water
nia, and Lower Silesia. Results obtained for drinking body. Obtained results were as follows: 10.94 ± 0.78
water samples confirmed that total arsenic level was and 3778 ± 268 μg L−1. Such a high concentration of
significantly lower than 10 μg L−1 which is the maxi- totalarsenicinthesecondsamplefromTrującaStream
mum permissible concentration of arsenic in drinking must be caused by the local geochemical structure,
water,accordingtoguidelinesoftheWorldHealthOr- which includes deposits of arsenic. Złote Góry massif,
ganization(WHO2011),theUSEnvironmentalProtec- withinTrującaStreamislocated,ismostlycomposedof
tion Agency (USEPA 2009) and European Union mica slates of Proterozoic era relatively of the Lower
(Official Journal of the EU 1998). In the majority of Cambrian. Among them, there are slots of crystalline
the drinking water samples, collected from regions of dolomite limestone with arsenic ores. In this area, the
Wielkopolska,Kujawy-Pomerania, aswellasfromthe contact deposit with intrusive-hydrothermal character
areaofLowerSilesia,concentrationoftotalarsenicwas appears. Changes of dolomitic limestone in fine-
significantlybelow1μgL−1.Thehighestconcentration grained diopsidic rocks through supplying the silica
EnvironMonitAssess(2016)188:504 Page9of22 504
ConcentrationofTAs(c±U)−μ1)(k=2)(gL 0.236±0.017 1.010±0.072 0.435±0.031 0.525±0.037 <LOD 0.180±0.013 0.141±0.010 0.1210±0.0087 0.249±0.018 1.53±0.11 2.840±0.202 0.928±0.066 10.94±0.78 3778±268 0.351±0.025 0.363±0.026 0.1020±0.0072 0.324±0.023 0.150±0.011 0.780±0.074 1.82±0.13 83.1±5.9 <LOD forCRMSLRS-
3) 0 4 9 3 9 3 29 3 8 9 3 5 2 As
extendeduncertainty(n= RSSSAs(V) 40.241±0.0210.463±0.04 41.052±0.0902.10±0.18 70.451±0.0390.971±0.08 50.433±0.0370.690±0.05 5<LOD0.263±0.02 50.192±0.0160.452±0.03 30.152±0.0130.381±0.03 60.1024±0.00880.370±0.03 30.263±0.0230.501±0.04 30.959±0.0822.02±0.17 2.57±0.224.49±0.39 30.971±0.0841.92±0.17 10.19±0.8815.0±1.3 3775±32458.4±5.0 70.370±0.0320.908±0.07 50.2410±0.0210.456±0.03 40.942±0.0811.98±0.17 50.231±0.0200.503±0.04 30.162±0.0140.402±0.03 40.782±0.0671.81±0.16 1.18±0.102.23±0.19 1.81±0.1622.4±1.9 4<LOD0.256±0.02 V);certifiedvalueoftotal
entedwith SS 0.245±0.02 0.983±0.09 0.491±0.04 0.262±0.02 0.262±0.02 0.260±0.02 0.241±0.02 0.274±0.02 0.244±0.02 0.973±0.09 1.96±0.19 0.971±0.09 5.05±0.48 18.7±1.8 0.485±0.04 0.263±0.02 0.978±0.09 0.257±0.02 0.241±0.02 0.981±0.09 1.26±0.12 19.5±1.9 0.247±0.02 −1forAs(
s L
amplespre RSMMA <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD 0.281±0.027 <LOD <LOD μd0.11g
s n
gwater,surfacewater,wastewater,andsnow −μ1senicspecies(c±U)(gL)(k=2) RSSSRSSSAs(III)DMA <LOD0.260±0.034<0.254±0.014LOD<LOD0.98±0.13<LOD1.011±0.057 <LOD0.511±0.066<LOD0.512±0.029 0.121±0.0160.340±0.044<LOD0.262±0.015 <LOD0.240±0.031<LOD0.253±0.014 <LOD0.252±0.033<LOD0.250±0.014 <LOD0.261±0.034<LOD0.242±0.014 <LOD0.250±0.033<LOD0.262±0.015 <LOD0.250±0.033<LOD0.241±0.013 0.540±0.0701.58±0.21<LOD0.982±0.055 0.191±0.0252.09±0.27<LOD2.02±0.11 <LOD1.04±0.14<LOD1.006±0.056 0.342±0.0445.17±0.67<LOD5.03±0.28 <LOD18.4±2.4<LOD19.5±1.1 <LOD0.521±0.068<LOD0.503±0.028 0.153±0.0200.422±0.055<LOD0.258±0.014 <LOD1.010±0.13<LOD1.009±0.057 0.111±0.0140.333±0.043<LOD0.249±0.014 <LOD0.242±0.031<LOD0.251±0.014 <LOD0.98±0.13<LOD0.993±0.056 0.416±0.0541.48±0.19<LOD1.014±0.057 81±1142.0±5.5<LOD19.6±1.1 <LOD0.255±0.033<LOD0.252±0.014 −−μμ11gLforDMA,0.13gLforMMA,a
Table3Concentrationoftotalarsenicandarsenicspeciesindrinkin ConcentrationofarSamplesSpike−μ1)(gLRSSSAsB Drinkingwaterł1Szamotuy0.25<LOD0.242±0.029 ł2Inowrocaw1.0<LOD0.97±0.12 3Gniezno0.5<LOD0.480±0.058 4Jarocin0.25<LOD0.251±0.030ą5Wgrowiec0.25<LOD0.245±0.029 6Krotoszyn0.25<LOD0.262±0.031ł7Zotoryja0.25<LOD0.231±0.028 8Legnica0.25<LOD0.253±0.030ł9Wabrzych0.25<LOD0.241±0.029 Surfacewater 10Kaczawa1.0<LOD1.02±0.12River(WojciechówGórny)—11KaczawaRiverabove2.0<LOD1.97±0.24Świerzawa—12KaczawaRiverwaterintakeforLegnica1.0<LOD0.99±0.12ą—13TrujcaRiverbeforewastewaterinlet5.0<LOD4.96±0.60ą—14TrujcaRiverafterwastewaterinlet20.0<LOD21.3±2.6 Wastewaterł15Inowrocaw0.5<LOD0.513±0.062 16Krotoszyn0.25<LOD0.249±0.030ł17Szamotuy1.0<LOD1.02±0.12 18Jarocin0.25<LOD0.228±0.027ą19Wgrowiec0.25<LOD0.248±0.030 20Gniezno1.0<LOD0.98±0.12ł21Koziegowy1.0<LOD0.97±0.12 Snow 22Legnica20.0<LOD20.8±2.5ń23Pozna0.25<LOD0.242±0.029 −−μμ11LODvalues:0.074gLforAsB,0.074gLforAs(III),0.070−−—μ—μ1150.413±0.039gL,obtainedvalue0.4176±0.0071gL RSrealsample,SSspikedsample
504 Page10of22 EnvironMonitAssess(2016)188:504
occurred during neighboring syenite intrusion. After- sedimentationtankrefinedwastewaterisreceived.Ob-
ward,diopsidicarsenicandgoldrockswereintroduced tainedwastewaterhasreducedcontentofcontaminants
by hydrothermal silica. This process occurred funda- byapproximately90to96%,andinthisform,itgetsto
mentally in contact rocks (http://zlotystok.salwach. the channel which drains it to the Trująca Stream.
pl/przemysl/wydobycie_rud_arsenu). Deposits of Hence,thewastewaterintroducedtotheTrującaStream
arsenic were primarily exploited in the area of Złoty couldnothaveconsiderableimpactonincreaseofarse-
Stok. While exploitation of arsenic ores, another nicconcentrationinitswater,sohighconcentrationsof
deposit was found—gold. Gold, associated with the arsenic in this region are due to its geogenic
occurrence of arsenic ore, was most likely discovered characteristics.
intheseventhcentury,andtheoldestrecordofmining Total arsenic concentration in the wastewater sam-
operationsconductedherefromthethirteenthcentury.It ples collected in the Wielkopolska and Kujawy-
is thus the oldest gold mine in Poland, where the Pomerania was comparable with results obtained for
exploitation of ore arsenic and recovery of gold drinkingwatersamples.Thehighestconcentrationwas
continued until 1962 (http://www.kopalniazlota. determined in a sample collected from the wastewater
pl/pl/historia/historia-wydobycia-zlota). According to treatment plant in Koziegłowy in which concentration
opinion placed in the report about quality of rivers of ofthiselementwasequalto1.82±0.13μgL−1.
Lower Silesia province prepared by Regional Snowsamplesfromtwoprovincesweresubmittedto
Inspectorate of Environmental Protection in Wrocław, analysis. The first one was collected in the city of
the wastewater from mechanical-biological sewage Legnica situated in Lower Silesia province. Sampling
treatment plant in Złoty Stok City, as well as from point was situated near the copper smelter and the
mechanical-biologicalsewagetreatmentplantofMate- refinery. Sample was characterized by a dark layer of
rial and Paint Plant is released to the Trująca Stream atmospheric dust localized on its surface. Analysis re-
(RRIEP 2006, RIEPW 2001). However, in the plants vealed high concentration of arsenic equal to
mentioned above the wastewater comes under many 83.1 ± 5.9 μg L−1. Almost all of arsenic in mentioned
processes and after sedimentation of deposit in the sample(97%)wasintheformofAs(III),themosttoxic
Fig.3 TotalarsenicconcentrationindifferentsampletypesdeterminedbyICP-MSmethod