1、PUBLISHED DOCUMENT PD CEN/TR 14589:2003 Characterization of waste State of the art document Chromium VI specification in solid matrices ICS 13.030.10 PD CEN/TR 14589:2003 This Published Document was published under the authority of the Standards Policy and Strategy Committee on 4 June 2003 BSI 4 Jun
2、e 2003 ISBN 0 580 41995 9 National foreword This Published Document is the official English language version of CEN/TR 14589:2003. The UK participation in its preparation was entrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3, Waste characterisation, which has the resp
3、onsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled
4、 “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for c
5、hange, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the CEN/TR title page, pages 2 to 39 and a back cover. The BSI copyright date displayed in
6、this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsTECHNICALREPORT RAPPORTTECHNIQUE TECHNISCHERBERICHT CEN/TR14589 May2003 ICS13.030.10 Englishversion CharacterizationofwasteStateoftheartdocument ChromiumVIspecificationinsolidmatrices
7、 CaractrisationdesdchetsEtatdelartSpcification pourladterminationduChromeVIdanslesmatrices solides CharakterisierungvonAbfllenBestimmungvonChromin AbfallStatusbericht ThisTechnicalReportwasapprovedbyCENon7April2003.IthasbeendrawnupbytheTechnicalCommitteeCEN/TC292. CENmembersarethenationalstandardsbo
8、diesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUn ited Kingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG Manag
9、ementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.CEN/TR14589:2003ECEN/TR14589:2003(E) 2 Contents Foreword. 3 Introduction 3 1 Scope . 3 2 Normativereferences . 4 3 Symbolsandabbreviations. 4 4 ChromiumVIspe
10、ciationinsolidmatrices . 6 5 Finalconclusions. . 19 Bibliography . 38CEN/TR14589:2003(E) 3 Foreword Thisdocument(CEN/TR14589)hasbeenpreparedbyTechnicalCommitteeCEN/TC292“Characterizationof waste“,thesecretariatofwhichisheldbyNEN. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorgan
11、izationsofthefollowing countriesareboundtoannouncethisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal, Slovakia,Spain,Sweden,SwitzerlandandtheUnitedKingdom. Introduction Speciationisoneof
12、thegrowingfeaturesofanalyticalchemistryofthelastyears.Itisnowrecognizedthatthe determinationoftotaltraceelementcontentsisnolongersufficient,becausethebiologicalandenvironmental impactofanelementisdictatedbythephysicochemicalforminwhichitispresentinthesample. Chromiumbelongstothecategoryofproblematic
13、elementsinanalyticalchemistry,becauseitbehavesasa valencechameleon.Thechemistryofchromiumcompoundsisrathercomplicated,inorganicchromiumcompounds mayoccurinoxidationstatesrangingfromIIto+VI1,2.However,innaturalsystems,Cr(III)andCr(VI)arethe moststableforms.BesidesCr(III)whichisanessentialtraceelement
14、formammals,includingman,Cr(VI) compoundsaregenotoxicandpotentiallycarcinogenicinhumans.Evidenceexistsforthecarcinogenityofcalcium, strontiumandzincchromate2,3.TheinoffensivenatureofCr(III)ionsresultsfromthefactthatinbiotic environment,itusuallyappearsinaquahydroxocomplexesoftheform() 3 6 2 ) ( - - n
15、 n n OH O H Cr andtheirsize excludesthemalmostentirelyfrompenetratingcellmembranes4. Fromchemicalpointofview,Cr(III)showssimilaritieswiththatofAl 2 O 3 :Cr 2 O 3 isamfoteric,albeitmorebasicthan acidic.Incontrast,Cr(VI)isstronglyacidic;allCr(VI)compounds,exceptforCrF 6 areoxocompounds: - 4 HCrO (hydr
16、ochromate), - 2 4 CrO (chromate)and - 2 7 2 O Cr (dichromate)specieswhicharepowerfuloxidants. Underenvironmentalconditions,dichromatesarenotformedatatotalchromiumconcentrationlessthan 0,01mol/l.CertainformsofCr(III)mayoxidizetoCr(VI)insoilsandthatCr(VI)maybereducedtoCr(III)inthe samesoil.Sinceundera
17、lkalinetoslightlyacidicconditions,Cr(VI)compoundsarenotstronglyabsorbedbymany soils,theycanbeverymobileinsurfaceenvironments.Ontheotherhand,undertheseconditions,Cr(III)readily precipitatesasCr(OH) 3 .Cr(VI)canbereducedtoCr(III)insoilsbyredoxreactionswithaqueousinorganicspecies, electrontransferatmin
18、eralsurfaces,reactionswithnonhumicorganicsubstancessuchascarbohydratesand proteinsorreductionbysoilhumicsubstances5.Thelatter,whichconstitutesthemajorityoftheorganicfraction inmostsoils,representsasignificantreservoirofelectrondonorsforCr(VI)reduction.Asaresult,theopposing solubilityandtoxicitychara
19、cteristicofCr(III)andCr(VI)andthepotentialforCr(III)oxidationinsoilrepresenta uniqueregulatorychallengefortheestablishmentofprotective,healthbasedcleanupstandardsforCr contaminatedsoils6.RemediationofCr(VI)containingsoilsthroughreductiontoCr(III)willlowerthehealthand ecologicalhazardofsuchsoils. Asa
20、consequenceofpreviousconsiderations,mostattentionispaidtoCr(VI)determinationinenvironmental matter.Unfortunately,justthistaskisdifficulttohandle.Intricaciesareprimarilybecauseofinstabilityofthe oxidationstatesofchromiumandthecomplexcharacterofenvironmentalsamples. 1Scope ThisEuropeandocumentdescribe
21、sthestateoftheartextractionanddeterminationmethodsforthetotalcontent ofhexavalentchromiuminrawwasteandothersolidmaterials.CEN/TR14589:2003(E) 4 2 Normativereferences Thisdocumentincorporatesbydatedorundatedreference,provisionsfromotherpublications.Thesenormative referencesarecitedattheappropriatepla
22、cesinthetextandthepublicationsarelistedhereafter.Fordated references,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisdocumentonlywhen incorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthepublicationreferredto applies(includingamendments).; AS2882: (Austr
23、alia): 1986 WatersDeterminationofchromium(VI)(diphenylcarbazidespectrophotometric method); ASTMD5257 1997 TestMethodforDissolvedHexavalentChromiuminWaterbyIonChromatography; ASTMD5281: 1998 StandardTestMethodforCollectionandAnalysisofHexavalentChromiumin AmbientAtmospheres; DSF38929: 1999 PackagingR
24、equirementformeasuringandverifyingfourheavymetalsandother dangeroussubstancespresentinpackagingandtheirreleaseintotheenvironment Part1:Requirementsformeasuringandverifyingfourmetalspresentinpackaging (lead,cadmium,chromiumVIandmercury); IRSA(Italy): 1986 AnalyticalMethodsforWastePhysicoChemicalParam
25、eters,MethodNo.16, HexavalentChromium (colorimetricreactionwithdiphenylcarbazide); ISO11083: 1994 WaterqualityPhotometricdeterminationofChromiumVIwith1.5diphenylcarbazide ; ISO38565: 1984 Determinationofhexavalentchromiumcontentofpigmentportionofliquidpaintor paintinpowderformspectrophotometricmetho
26、dwithdiphenylcarbazide ; DIN19734: 1999 SoilqualityDeterminationofChromium(VI)inphosphateextract; DIN3840524: 1987 Germanstandardmethodsfortheexaminationofwater,wastewaterandsludge; photometricdeterminationofChromium(VI)using1.5DPC ; DIN53780: 1999 PigmentsandextendersDeterminationofmattersolubleinw
27、aterhexavalent chromiumcontent 3 Symbolsandabbreviations Forthepurposesofthisdocument Error!Notextofspecifiedstyleindocument. ,thefollowingsymbolsand abbreviationsapply: III 52 / 50 R isthemassbiascorrectedmeasuredisotoperatioof 50 Crto 52 CrofCr(III)inthespikedsample; x 50 A istheatomicfractionof 5
28、0 Crinthesample; III x C istheconcentrationofCr(III)inthesample(mol/g,unknown); III s 50 A istheatomicfractionof 50 Crinthe 50 Cr(III)spike; III s C istheconcentrationofCr(III)inthe 50 Cr(III)spike(mol/g); VI s C istheconcentrationofCr(VI)inthe 53 Cr(VI)spike(mol/g); III s W istheweightofthe 50 Cr(I
29、II)spike(g);CEN/TR14589:2003(E) 5 VI x C istheconcentrationofCr(VI)inthesample(mol/g,unknown); B isthebiaspermassunit; c x ,c s istheconcentrationofanalysedsampleandspike,respectively(g/g); I isthetruenumberofcounts,thatmeansthenumberofcountsthatwouldhavebeendetectedif therehadbeennotdeadtime; I m i
30、sthenumberofcountsmeasuredonachannel; K isthemassdiscriminationfactor; M 1 ,M 2 istheatomicmassofisotope“1“and“2“,respectively; M x ,M s istheatomicmassofanalysedsampleandspike,respectively(g/mol); N i isthenumberofatoms; N x ,N s isthetotalnumberofatomsinunknownsampleandspike,respectively; R isther
31、ealisotoperatio; R isthemeasuredisotoperatio; R c ,R m isthecorrectedisotoperatioandthemeasureddeadtimecorrectedisotoperatiosofthesample, respectively; R t ,R m isthecertifiedisotoperatioandthemeasuredisotoperatiosofthestandardmaterial(deadtime corrected); W x ,W s istheweighofunknownsampleandspike,
32、respectively(g); isthepercentageofCr(III)oxidizedtoCr(VI)afterspiking(unknown); isthepercentageofCr(VI)reducedtoCr(III)afterspiking(unknown); isthedeadtime; Aliquat336 : methyltricaprylammonium; APDC: ammoniumpyrolidinedithiocarbamate; DDTC: diethyldithiocarbamate; DIN: directinjectionnebulization;
33、DPC: Diphenylcarbazide; DPP: differentialpulsepolarography; DPTA: Diethylenetriaminepentaacetic; HHPN: hydraulichighpressurenebulization;CEN/TR14589:2003(E) 6 HMDE: hangingmercurydropelectrode; HPLC: highpressureliquidchromatography; IC: ionchromatography; ICDPC : ionchromatographydiphenylcarbazide;
34、 ICICPMS : ionchromatographyinductivelycoupledplasmamassspectrometry; ICPMS: inductivelycoupledplasmamassspectrometry; ID: IsotopeDilutionmethod; LC: liquidchromatography; LiFDDC: lithiumbis(trifluoroethyl)dithiocarbamate; LL: Liquidliquidextraction; MIBK: methylisobuthylketone; NPP: normalpulsepola
35、rography; ORP: OxidationReductionPotential; SFE: Supercriticalfluidextraction; SIDMS: SpeciationIsotopeDilutionMassSpectrometry; TBDTC: dibuthyldithiocarbamate; TOC: TotalOrganicCarbon; TSN: thermospraynebulization; 4 ChromiumVIspeciationinsolidmatrices 4.1 ChromiumVIextractionfromsolidmatrices 4.1.
36、1 Samplepretreatment ToquantifytotalCr(VI)insolidmatrices,threecriteriamustbesatisfied: a) theextractionsolutionmustsolubilizeallformsofCr(VI); b) theconditionsoftheextractionmustnotinducereductionofnativeCr(VI)toCr(III); c) themethodmustnotcauseoxidationofnativeCr(III)containedinthesample.CEN/TR145
37、89:2003(E) 7 Thus,ithasbeenrecognizedthatCr(VI)mustbeleachedfromsamplesinanalkalinemediumratherthaninacidic mediuminordertoinhibitCr(VI)toCr(III)reductionbypossiblereductantspresentinsample2.Analkaline extractionprocedure,USEPASW846Method3060forthepreparationofsoilsamplesinviewofanalysisoftotal Cr(V
38、I)wasusedforanumberofyears.ButanUSEPAfundedresearchstudydidnotachievedconsistentresults amongsamplesusingthismethod7.TheresearchesconcludedthattheCroxidationstateismatrixspecificand maybeunstableandunpredictable(inenvironmentalsamples)onceitissolubilize ineitheranacidicorbasic aqueousextractionmediu
39、m8.Basedontheseconsiderations,inJune1997theUSEPApromulgatedSW846 Method3060AforinclusionintheThirdUpdatetotheTestMethodforEvaluatingSolidWaste,SW846,3 rd ed.5. Althoughthebasicchemistryhasremainedthesame,themodificationstoUSEPASW846Method3060have enhancedtheefficiencyoftheextractionprocess,principal
40、lybyreducingthesoilsampleweightanddecreasingthe ratioofsampleweighttoalkalinedigestvolume. 4.1.2 USEPASW846Method3060A9 4.1.2.1 SummaryofUSEPASW846Method3060A Thesolidsampleisdigestedusingamixedsolution(pH11,5)consistingofNa 2 CO 3 (0,28M)andNaOH(0,5M) andheatingat90C95Cfor60minutes,inordertodissolv
41、etheCr(VI)andstabilizeitagainstreductionto Cr(III) ForwastematerialsorsoilscontainingsolubleCr(III)greaterthanfourtimesthelaboratoryCr(VI)detectionlimit, Cr(VI)resultsobtainedusingthismethodmaybehighbiasedbecauseofmethodinducedoxidation.Thusthe methodrecommendstheadditionofMg(II)inaphosphatebufferto
42、thealkalineextractionsolutiontosuppressthis oxidation.WhenanalysingasampledigestfortotalCr(VI)itisappropriatetodeterminethereducing/oxidizing tendencyofeachsamplematrix.Thiscanbeaccomplishedbycharacterizationofeachsamplebymeansoffour majorredoxindicatingancillaryparameters: pH(USEPASW846Method160);
43、OxidationReductionPotential(ORP)(ASTMD149876); sulfides(USEPASW846,Method9030); TotalOrganicCarbon(TOC)(USEPASW846Method9060,ASTM1976). BasedontheresearchperformedonawidevarietyofsamplesusingUSEPASW846Method3060Aand departingfromtheconventionalinterpretativeapproachforQCdatafortotalmetals,dataassociatedwithlowor 0%Cr(VI)matrixspikerecoveriesmustbeevaluatedinaccordancewithestablishedredoxchemistryofCrinsoils orsediments.WithpHandORPhavingsuchsignificancewithregardstotheredoxstatusofasoilorsediment samplethemethodreferstoanEpHdiagramfor - 4 HCrO /Cr
