PAHs欧盟最新标准2014版

.ProductSafetyCommission(AfPS)GSSpecificationTestingandassessmentofpolycyclicaromatichydrocarbons(PAHs)inthecourseofawardingtheGSmark-Specificationpursuanttoarticle21(1)no.3oftheProductSafetyAct(ProdSG)–AfPSGS2014:01PAKStateofrevision:August4th,2014Disclaimer:Germanistheoriginaltextversion.Incaseofanydoubt,lackofclarityoranyothernonclearinterpretationthecontentoftheoriginalversionisvalid.Management:FederalInstituteforOccupationalSafetyandHealthFriedrich-Henkel-Weg1–2544149DortmundTelefon:0231/9071-0Telefax:0231/9071-2364'..TableofContentsPreliminaryobservations.....................................................................................................31Purpose/Intention..............................................................................................................32Basics.................................................................................................................................33Procedure...........................................................................................................................33.1Riskassessment.................................................................................................................33.2Categorisation.....................................................................................................................43.3Testingandassessment.....................................................................................................64Transitionalregulations/periods...........................................................................................64.1GSmarkcertificates,issuedfromJuly1st,2015onwards....................................................64.2GSmarkcertificates,issuedbeforeJuly1st,2015...............................................................64.3ReissuingofexistingGSmarkcertificates–exemptions.....................................................6Annex:Testinginstructions........................................................................................................81Aimandpurpose.....................................................................................................................82Method....................................................................................................................................82.1Briefdescription....................................................................................................................82.2Equipment............................................................................................................................82.3Chemicalsandsolutions.......................................................................................................83Preparationandexecution.......................................................................................................93.1Samplepreparation..............................................................................................................93.2Measuringprocedure..........................................................................................................103.3Specialcharacteristics........................................................................................................11Annex:Measuringconditionsforgaschromatography(forinformation)...................................12'..Testingandassessmentofpolycyclicaromatichydrocarbons(PAHs)inthecourseofawardingtheGSmarkPreliminaryobservationsOnAug.4th2014theProductSafetyCommission(AfPS)hasassignedtherequirementsofPAHtestinginthecourseofGSmarkcertificationasspecificationaccordingtoart.21ProductSafetyAct(ProdSG)para.1no.3.TheimplementationisachievedbymeansofthisPAHdocument.1.Purpose/IntentionProducts(pursuanttotheProductSafetyAct)mustcomplywithlegalrequirementstoavoidhealthrisks,e.g.art.30&31oftheLFBG(Foodstuffs,ConsumerGoodsandFeedstuffsCode–LFGB),theProhibitionofChemicalsOrdinance,andtheart.3oftheProdSG(ProductSafetyAct).Thisdocumentand,inparticular,thetestinginstructions(seeAnnex)specifytherequirementswithrespecttothelevelofPAHsinproducts.Inaddition,thedocumentharmonisesthetestingmethodologyforassessmentbyGSbodies.2.BasicsPAHcontaminationofmaterialsisprimarilyduetotheuseof:-PAHcontaminatedsofteningoilsinrubberandflexible(soft)plastics-PAH-contaminatedcarbonblackasablackpigmentinrubber,plasticsandpaints.PAHcontaminationhaspreviouslybeendetectednotonlyinrubberbutalsoinvarioustypesofplastic,e.g.ABSandPP,andvariouspaints/coatings,aswellasinavarietyofnaturalmaterials.3.ProcedureTheGSbodymusttakethefollowingstepsintoaccountbothintheprocessofawardinganewGSmarkandwithintheframeworkofmonitoringexistingGSmarkcertificates:1.Riskassessment2.Categorisation3.Testingandassessment3.1RiskassessmentTheGSbodymustcarryoutariskassessmentand,indoingso,definewhichrelevantcontact/gripandoperatingsurfacesoftheproductaretobeconsideredfortestingandwhicharenot,andmustmakearecordofthese(thismeansthattheGSbodymustfirstspecifythecontact/gripandoperatingareastowhichtherequirementsofthePAHdocumentmustbeapplied(specificationofPAHrelevance)).Theriskassessmentshouldbenotapplied,whereappropriate,iftherespective“Erfahrungsaustauschkreis”(“ExchangeofExperienceGroup”,EK)hasalreadydefinedaprocedurefortheproductorproductgroupwithregardtothecontact/grip'..andoperatingsurfacestobetested.AreferencetotheEK’sdefinitionistobeincludedinthedocumentationaccordingly.Materialsthatcannotbeaccessedorthatcanonlybeaccessedbyusingtoolsneednotbeassessed,withtheexceptionofsampleswithaconspicuousodour.Inprinciple,accountmustbetakenofallcontact/gripandoperatingsurfacesthatcancomeintodirectcontactwiththeskinorthatcanbeputintothemouthduringproperorforeseeableuse(butnotmisuse).13.2CategorisationDependingontheresultsoftheriskassessment,thecorrespondingproductpartsarethentobecategorised(seeTable1)andtobeanalysedontheiractualPAHcontentaccordingtotheanalysismethodbelow.Existingtestreportscanbetakenintoaccountiftheyarecompliantwiththe“Grundsatzbeschluss”(“principledecision”)ZEK-GB-2012-01oftheZEK(“CentralExchangeofExperienceGroup”)andtherequirementsofthisPAHdocument.Categorisationcanbedispensedwithiftherespective”Erfahrungsaustauschkreis”(“ExchangeofExperienceGroup”,EK)hasalreadydefinedacategorisationofthecontact/gripandoperatingsurfacesforaproductorproductgroup.DefinitionsforproductsorproductgroupsfromtheindividualEKsarepublishedontheZLSwebsite2andapplyfromthetimeofpublication.Table1presentsthemaximumlevelsofPAHinproductmaterials,whichmustnotbeexceeded.TheprovisionsofthisdocumentwithregardtothePAHcontentdonotapplyifotherlegislationlaysdowncorrespondingorfurtherrequirementsforthePAHcontent.Thisappliesonlytothematerialorcomponent/assemblyandnottotheproductasawhole.MaterialsandpartsoftheproductthatarenotcoveredbyotherlegislativeprovisionsmustbeassessedwithintheframeworkoftheprocedureforawardingtheGSmarkinaccordancewiththerequirementsofthePAHdocument.Itmustbeensuredthatthemethodoftestingcanactuallyachievethelimitofquantificationof0.2mg/kgforeachindividualPAHcomponent3.Atthesametime,methodandmatrixeffects,aswellasthemeasurementuncertainty,theefficiencyofextractionandlossesduringpurificationmustbeconsidered.BasedonthefindingsoftheUnitedStatesEnvironmentalProtectionAgency(EPA)(accordingtothelistintheZEKdocument04-11),thetotalof18PAHs(extendedsubstancelistoftheAtAV,thepredecessorcommitteeoftheAfPS)onlyconsidersPAHcomponentswhoselevelinthematerialisfoundtoexceed0.2mg/kg.1However,inordertoensureaconsistentandappropriateprocedureduringtheawardingofGSmark,itisnotgenerallynecessarytoanalyseallfreelyaccessiblesurfaces.Itisthisdocument’sintentiontolimittheconsiderationtorelevantcontact/gripandoperatingsurfaces.Itisnotexpedienttotestallproductpartsorsurfacesinorder“tobeonthesafeside”.2HomepageofZLS(CentralAuthorityoftheLaenderforSafety):3Example:Water-carryingpartsincoffeemachinesthatcomeintocontactwithfoodstuffs(e.g.water,etc.)aresubjecttotheFoodandFeedCodelegislationandarethereforeexcludedfromthePAHdocument’sfieldofapplication.However,gripsurfacesonthecoffeemachinemuststillbeassessedaccordingtotherequirementsofthePAHdocument.'..Table1:MaximumPAHlevelstobecompliedwithforthematerialsinrelevantcontact/gripandoperatingsurfacesthataretobecategorisedbasedontheresultsoftheriskassessment.ParameterCategory1Category2Category3MaterialsindentedMaterialsnotMaterialsnotcoveredtobeputinthecoveredbycategorybycategory1or2mouth,1,withforeseeablewithforeseeableskinormaterialsofskincontactforcontactupto30toyswithlongerthan30seconds(shorttermintendedlong-seconds(long-termskincontact)termskincontactskincontact)or(longerthan30s)repeatedshort-termskincontact1)ToysintheOtherToysintheOtherscopeofproductsinscopeofproductsin2009/48/ECthescope2009/48/ECthescopeofProdSGofProdSGBENZO(a)PYRENE<0.2<0.2<0.5<0.5<1mg/kgBENZO(e)PYREN<0.2<0.2<0.5<0.5<1Emg/kgBENZO(a)ANTHRACENE<0.2<0.2<0.5<0.5<1mg/kgBENZO(b)FLUORANTHENE<0.2<0.2<0.5<0.5<1mg/kgBENZO(j)FLUORANTHENE<0.2<0.2<0.5<0.5<1mg/kgBENZO(k)FLUORANTHENE<0.2<0.2<0.5<0.5<1mg/kgCHRYSEN<0.2<0.2<0.5<0.5<1Emg/kgDIBENZO(a,h)ANTHRACEN<0.2<0.2<0.5<0.5<1Emg/kgBENZO(g,h,i)PERYLENE<0.2<0.2<0.5<0.5<1mg/kgINDENO(l,2,3-cd)PYRENE<0.2<0.2<0.5<0.5<1mg/kgACENAPHTHYLENE,ACENAPHTHENE,FLUORENE,PHENANTHRENE,<1<5<10<20<50PYRENE,sumsumsumsumsumANTHRACENE,FLUORANTHENEmg/kgNAPHTHALENEmg/kg<1<2<10Sum18PAH3mg/kg<1<5<10<20<50*Wording“short-termrepetitiveskincontact”fromsupplementtoREACHannexXVIIno.50(REGULATION(EU)No1272/2013)'..3.3TestingandassessmentThetestinginstructionsfoundintheannexdescribethestepsofsamplepreparation,extractionofthePAHs,purificationoftheextract,identificationandquantification;thesemustbeapplieduniformlybyalllaboratoriescarryingouttesting.TheGSbodyassessesthetestresultsanddecideswhethertheGSmarkcanbeawardedincompliancewiththeotherrequirements.4.Transitionalregulations/periodsFromJuly1st2015(issuedateoftheGSmarkcertificate),itiscompulsorytoapplythisdocumentwhenawardingtheGSmarktoproducts.ThedocumentZEK01.4-08willceasetobevalidfromJune30th2015.SincetestingforPAHlevelsinproductsconstitutesanoverarchingrequirementforalmostallofthemembersofallofthe”Erfahrungsaustauschkreise”(“ExchangeofExperienceGroups”),thefollowingprocedureisdefined:4.1GSmarkcertificates,issuedfromJuly1st2015onwards(incl.ongoingproceduresthatareconcludedafterJuly1st2015)CompulsoryapplicationofthisGSspecificationfromJuly1st2015onwards(exception:see4.3).4.2GSmarkcertificates,issuedbeforeJuly1st2015ExistingGSmarkcertificatesinitiallyremainvalid.Withintheframeworkofregularcheckstomonitorthemanufacturingprocess(atthelatestwithinoneyearor,incaseswheretheregularmonitoringperiodistwoyears,withintwoyears),therequirementsunderno.3oftheZEK(“CentralExchangeofExperienceGroup”)documentwithregardtotheriskassessmentmustbetakenintoaccount,regardlessofwhethertheproductwasfoundinthemanufacturingfacilityornot.If,intheprocess,itisfoundthatthecorrespondingrequirementsarenotmet,theGSmarkcertificatemustbewithdrawnimmediately.TheZEK”Grundsatzbeschluss”(“principledecision”)ZEK-GB-2006-01mustbecompliedwith.4.3ReissuingofexistingGSmarkcertificates–exemptionsForthereissuingofanexistingGSmarkcertificate,immediateconsiderationisnotrequiredinthefollowingcircumstances:Ifthecompanynameischanged,newGSmarkcertificatesareusuallyissued.However,sincetheproductdoesnotchangeintermsofconstructionorotherproperties,andthereissuingoftheGSmarkcertificateismoreorlessapureformality,itisnotnecessarytoconsidertherequirementsofthePAHdecisionuntilthetimeofthecheckwhichmustbeperformedforthepurposesofmonitoringthemanufacturingprocess.(Pleasenote:ThereissuingoftheGSmarkcertificatedoesnotalterthepreviouslydefinedperiodsforcarryingoutchecksontheproduct’smanufacturingprocess.)ThesameappliesbyanalogywhentheholderoftheGSmarkcertificatechangesaddressprovidednoneoftheproduct’spropertieschangeandtheproductdoesnotrequireanadditionalsafetycheck.'..Theaboveprocedurecanalsobeappliedinrelationtoduplicatecertificates(alsoreferredtoasOEMcertificates).Insuchcases,areviewpursuanttotherequirementsofthePAHdocumentmuststrictlybecarriedoutbythetimeofthenextproduct-manufacturingcheckaccordingtotheperiodsalreadydefinedinthe“maincertificate”or,atthelatest,byDecember28th2015.Monitoringintervalsbeyondthisdatearenotpermissibleinsuchcases.WithregardtotheOEMcertificatesandthereforealsothe“maincertificates”,thePAHdocument–asspecified–mustbeappliedbyDecember28th2015atthelatest.'..Annex:TestinginstructionsHarmonisedmethodforthedeterminationofpolycyclicaromatichydrocarbons(PAHs)inpolymers1AimandpurposeDeterminationofpolycyclicaromatichydrocarbons(PAHs)inpolymersamples.2Method2.1Briefdescription2.1.1StandardmethodArepresentativepartialsampleistakenofthematerialandcutupintopieceswithamaximumsizeof2–3mmusingscissors,wirecutters,etc.Then,500mgofthesampleisweighedintoacontainerandextractedwith20mloftoluene(towhichaninternalstandardhasbeenadded)for1hat60°Cinanultrasonicbath.Analiquotistakenfromtheextractonceithascooleddowntoroomtemperature.Inthecaseofpolymers(e.g.plasticsorrubberproducts)forwhichmatrixproblemsariseduringtheanalysis,anadditionalpurificationstepiscarriedoutusingcolumnchromatography.Quantificationisperformedonagaschromatographwithamass-selectivedetector(GC/MSD)usingtheSIMmethod.2.1.2MethodforinsufficientquantitiesIfthetotalmassofmaterialtobeanalysedislessthan500mg,oneshouldproceedasfollows:Identicalmaterialsfromtheproductcanbecombinedandconsideredasonesample.However,additionalproductspecimensmustnotbeused.Iflessthan50mgofmaterialisavailableforindividualsamples,thesearenottested.Iftheavailablemassofchopped-upmaterialisbetween50mgand500mg,thesamplemustbetestedaccordingto2.1.1andthequantityoftolueneconvertedoradaptedinproportion.Theactualmassofthesampleistoberecordedinthetestreportaccordingly.2.2Equipment•Ultrasonicbathwithaminimumpowerof200Wandabathareaof706cm2,correspondingto0.28W/cm2,withoutabasketandwithaninternalorexternalthermostat•Gaschromatographwithamass-selectivedetector2.3Chemicalsandsolutions2.3.1Chemicals•Toluene'..•InternalstandardsoStandard1:Naphthalene-d8oStandard2:Pyrene-d10oranthracene-d10orphenanthrene-d10oStandard3:Benzo[a]pyrene-d12orperylene-d12ortriphenylbenzeneAtleastthreeinternalstandardsmustbeused;theseareaddedtotheextractionsolvent(toluene).•Externalstandard:18PAHsubstancesaccordingtoTable1orthoselistedunderno.3.2,asamixorindividually•Petroleumether•Silicagel•Sodiumsulfate2.3.2CalibrationsolutionsTheconcentrationsofthecalibrationsolutionsmustbechosensothatathree-pointcalibrationcoversaworkingrangeof0.1to10mg/kginthesamples.Thiscorrespondstoaconcentrationrangeof2.5to250ng/mlinthecalibrationsolutions.3Preparationandexecution3.1SamplepreparationArepresentativepartialsampleistakenofthematerial.Thefragmentsproducedbychoppingupthesamplestobeanalysed(usingscissors,wirecutters,pliers,etc.)shouldhaveamaximumsizeof2–3mm.3.1.1Extraction500mgofthesampleisplacedinaglass”Bördelglas”(“vial”).Tothis20mloftoluene,previouslyamendedwithinternalstandards,areadded.Thesampleisthenextractedfor1hintheultrasonicbathatatemperatureof60°Cthroughout.Forthispurpose,thevialsareplacedorsuspendedintheultrasonicbathwithoutusingabasket.Thevialsarethenremoved,theextractislefttocooltoroomtemperatureandshakenbriefly,andanaliquotistakenfromtheextractandmeasuredeitherdirectlyorfollowingdilutionwithtoluene.3.1.2ColumnchromatographyextractionstepForsomepolymers(e.g.plasticorrubberproducts),especiallythosethatdissolvewellintolueneunderthedescribedextractionconditions,itisnecessarytocleantheextractusingadsorptionchromatographyonsilicagel.Forthispurpose,aclean-upcolumnwith“Hahnschliff”(“stopcock”)(approx.220mmx15mm)isfilledwithglasswool,4gofsilicageland1cmofsodiumsulfate.Thesilicagelisdeactivatedbeforehandbyadding10%water(thecorrespondingvolumeofwaterisaddedtothesilicagelinaglassflask,andthemixtureishomogenisedontherotary'..evaporatorfor1hatstandardpressureandroomtemperature.Thesilicagelcanthenbestoredinthesealedglassflaskatroomtemperature).Thepackedcolumnisconditionedwith10mlofpetroleumether.Thealiquotoftolueneextractisthenevaporatedtoavolumeofapprox.1mlontherotaryevaporatorandpouredintothecolumn.Thepointedflaskisrinsedoutwithapprox.20mlofeluent,whichisthenalsotransferredtotheclean-upcolumn.Elutionisperformedwith50mlofpetroleumether.Thecollectedpetroleumethereluateisamendedwith1mloftolueneandevaporatedtoavolumeofapprox.1mlunderanitrogenstream(e.g.ontheTurboVap).Thisisthenmadeuptoadefinedvolumewithtoluene,andtheextractisanalysedbyGC-MS.3.2MeasuringprocedureThemethodofdeterminationtobeappliedisgaschromatographywithamass-selectivedetectorintheSIMmode.Thefollowing18PAHsaretobedetermined:•Naphthalene•Acenaphthylene•Acenaphthene•Fluorene•Phenanthrene•Anthracene•Fluoranthene•Pyrene•Chrysene•Benzo[a]anthracene•Benzo[b]fluoranthene•Benzo[k]fluoranthene•Benzo[j]fluoranthene•Benzo[a]pyrene•Benzo[e]pyrene•Indeno[1,2,3-cd]pyrene•Dibenzo[a,h]anthracene•Benzo[g,h,i]perylene3.2.1MeasuringconditionsforgaschromatographyTheequipmentparameters(temperatures,columns,masstraces)maybechosenbytheindividuallaboratoryoraredeterminedbytheanalytes.3.2.2AnalysisInternalstandards:atleastthreeinternalstandardsmustbeused.Forthesethreestandards,theinternalstandardsandthecorrectionrangesaredefinedasfollowed:'..ParameterInternalstandardswithrecommendedreference•NaphthaleneNaphthalene-d8•AcenaphthylenePyrene-d10oranthracene-d10orphenanthrene-d10•AcenaphthenePyrene-d10oranthracene-d10orphenanthrene-d10•FluorenePyrene-d10oranthracene-d10orphenanthrene-d10•PhenanthrenePyrene-d10oranthracene-d10orphenanthrene-d10•AnthracenePyrene-d10oranthracene-d10orphenanthrene-d10•FluoranthenePyrene-d10oranthracene-d10orphenanthrene-d10•PyrenePyrene-d10oranthracene-d10orphenanthrene-d10•Benzo[a]anthracenePyrene-d10oranthracene-d10orphenanthrene-d10•ChrysenePyrene-d10oranthracene-d10orphenanthrene-d10•Benzo[b]fluorantheneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Benzo[k]fluorantheneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Benzo[j]fluorantheneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Benzo[a]pyreneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Benzo[e]pyreneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Indeno[1,2,3-cd]pyreneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Dibenzo[a,h]anthraceneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Benzo[g,h,i]peryleneBenzo[a]pyrene-d12orperylene-d12ortriphenylbenzene•Externalcalibration:foreachindividualPAH,atleastathree-pointcalibrationmustbecarriedoutwithreferencetotheinternalstandardisationsetoutabove.Aworkingrangeof0.1to10mg/kgisrecommendedhere.•Concentrationsabovethecalibrationrangecanbedeterminedbydilutingtheextract.3.2.3LimitofquantificationThelimitofquantificationformaterialsamplesis0.2mg/kgperparameter.3.3SpecialcharacteristicsBecauseitisrelativelyvolatilecomparedtotheother17PAHs,naphthaleneconstitutesaparameterthatishardtoassessinproductsthatcomeintocontactwiththeskin.Experiencefromthetestinginstitutesindicatesthatitispossibletoidentifyinstancesofbothnaphthalenedepletioninmaterialsandsecondarycontamination.Theresultobtainedfornaphthalenethereforeonlyeverreflectsthetestspecimen’scurrentsituationatthetimeofmeasurement.'..Annex:Measuringconditionsforgaschromatography(forinformation)Injectedvolume:1µlpulsedsplitlessColumn:HT825m,ID0.22mm,filmthickness:0.25µmInjectortemperature:280°CTransfer-linetemperature:260°CInitialtemperature:50°CInitialtime:2minHeatingrate:11°C/minFinaltemperature:320°CFinaltime:8min3,418D-naphthalene8,186D-phenanthrene23,182D-benzo[a]pyrene3,459Naphthalene5,586Acenaphthylene5,845Acenaphthene6,634Fluorene8,235Phenanthrene8,337Anthracene11,217Fluoranthene11,914Pyrene16,830Benzo(a)anthracene16,982Chrysene21,860Benzo(b+j)fluoranthene21,964Benzo(k)fluoranthene23,055Benzo(e)pyrene23,302Benzo(a)pyrene27,974Indeno(ghi)perylene28,121Dibenzo(ah)anthracene28,549Benzo(ghi)perylene'.