加拿大产品安全实验室手册方法

MethodMethodC03DeterminationofLeachableArsenic(As),Selenium(Se),Cadmium(Cd),Antimony(Sb)andBarium(Ba)inAppliedCoating SCOPE（范围Thismethoddescribesageneralprocedureforthedeterminationofleachablearsenic,selenium,cadmium,antimonyandbariumindecorativeorsurfacecoatingsmaterialsapplicabletoitem23oftheToysRegulation此方法适用于加拿大玩具法规（SOR/2011-17）23项，测试表面涂层及其类似物中的砷、硒、镉、StandardPracticeforUseoftheTermsPrecisionandBiasinASTMTestMethods.Volume14.02,ASTME177-90a(1996),pp.79-90. StandardPracticeforIntralaboratoryqualityControlProceduresandaDiscussiononReportingLow-LevelData.Volume11.01,ASTMD4210-89,pp.412-419,1998.JohnKeenanTaylor,QualityAssuranceofChemicalMeasurements.LewisPublishers,INC.328pages, NationalStandardofCanada-Methodsoftestfortoxictraceelementsinprotectivecoatings.CGSBStandardTestMethod1-GP-500.2,1-GP-500.3,1-GP-500.4,1-GP-500.5,1-GP-500.7.SpecificationsBoard.(December,1973).CGSBStandardTestMethod1-GP-500.2(December,1973). S.Krushkova,“UpdateofMethodC-03,DeterminationofLeachableArsenic(As),Selenium(Se),Cadmium(Cd),Antimony(Sb),andBarium(Ba)inAppliedCoatings”.ProductSafetyLaboratory,ProjectReportNo. A.Babcock,“DevelopmentofaStandardOperatingProcedurefortheAgilent7700xICP-MS”ProjectReportNo.2010-1249. LogbookLBC-55,“Agilent7500ceICP-MSwithCetacASX-500seriesAutoSampler”,andLogbookLBC-56,“AgilentICP-MS7700x”. S.Krushkova,“UpdateofMethodC-03,DeterminationofLeachableArsenic(As),Selenium(Se),Cadmium(Cd),Antimony(Sb),andBarium(Ba)inAppliedCoatings.”ProductSafetyLaboratory,ProjectReportNo.REAGENTSANDAPPARATUS(Note1)（试剂与设备 Inductivelycoupledplasmamassspectrometer(ICP-MS),Agilent7500ceorAgilent7700xequippedwithaninternalstandardsadditionTee/mixer. As,Se,Cd,Sb,Ba(+others)Multi-elementCalibrationStandard10.0ppm±0.5%,HighPurityorequivalent,traceabletoNIST,forcalibration. As,Se,Cd,Sb,Ba(+others)Multi-elementVerificationStandard,HighPurityorequivalenttraceabletNIST.Thecalibrationandverificationsstandardsshouldhavedifferentlotnumbersormanufacturer. Gallium,IndiumandBismuthstandards,1000ppm(nominal),SCPScienceorequivalent,traceabletoNIST,forinternalstandardsUltra-pure(18.2MΩ)超纯水（电阻率18.2Hydrochloricacid,concentrated(∼37%w/w),TraceMetalGrade,FisherNitricacid,concentrated(∼69%w/w),TraceMetalGrade,Fisher Tetrahydrofuran(THFHPLCGrade,CaledonLaboratoriesLtd.ScalpelorothersuitablescrapingElectricMortarandAirconvectionoven(60±3Sieves,250and500μmmesh,CertifiedservicebyW.S.TylerorSamplebottlesforsievedAnalyticalBalance,withaprecisionofWeighingGlassbeakers,50Digitalshakerormagnetic Filterpaper,WhatmanNo40.Whatman40#滤纸 Funnelstofit50mLflasksortubes.50ml漏斗Volumetricflasks,50mL,2Sampletubes,screwcap50mLcertifiedPipettesadjustable10-100μL,100-1000μL,0.500-2.50mL,1.00-移液器，10~100μL100~1000μL0.500~2.50mL,1.00~NISTSRM2710(MontanaSoil)orNISTSRM1633c(CoalFlyAsh),usedasacontrolorAqua-regiasolutionfortracemetalglasswareNote1:EquivalentmaterialsandapparatusmaybeScrapeofftheappliedcoatingfromthetestsamplewithascalpel,orothersuitablescrapingtool,beingcarefulnottoremoveanyoftheunderlyingsubstratematerial.Alternatively,thecoating(forexample:paintonmetalsurface)canberemovedwithtetrahydrofuran(THF)orasuitablesolvent.Collectintoanappropriateweightingvessel,evaporatethesolventfromtheremovedcoatinganddryinanairconvectionovenat60°C±3°Cforatleast1hour.Thismaytakeseveralhours.RecordthedryingtimeintheovenLogbook.Removethevesselfromtheovenandcoolinadesiccator.Transfertheremovedcoatingtoamortarandgrindthesamplewithapestle.Anelectricgrindermaybeusedwhenthesampleistoodifficulttogrindwithapestleandamortar.Sievethegroundcoatingwitha500μmsieve.Thesamplepassingthroughthe500μmsieveisthensievedthrougha250μmsieve.Theportionofthegroundcoatingthatpassesthe500μmanddoesnotpassthe250μmisusedfortheleachingtest.Placethesievedportioninaweighingvesselanddrytoconstantweight(tothenearest1mg)inanairconvectionovenat60°C±3°C.Thismaytakeaboutanhour.RecordthedryingtimeontheResultsofAnalysisdatasheet(FormC03F1.1SampleData.doc)andontheConstantWeightform(C03F3.0ConstantWeight.xls).Removethevesselfromtheovenandcoolinadesiccator.Transferasufficientamount(i.e.5g)ofthestandardreferencematerial(NIST2710orNIST1633c)toanappropriatevessel.Dryitasrequiredbythecertificateofanalysis,inanairconvectionovenat60°C±3°Cforatleast1hour.Removethevesselfromtheoven,coolandstoreinadesiccator.Preparethe5%(v/v)HClleachingsolutionbydiluting50mLofconcentrated(approx.37%w/w)hydrochloricacidto1000mLwithultra-purewater.DriedAccuratelytransferabout100mgofthedriedcoatingintoatared100mLbeakerandweightothenearest0.1mg.Add20mLofthe5%(v/v)HClleachingsolutionandimmediatelystartstirringfor10±1minutesat20°C±3°Cwiththeuseofdigitalshaker(speed140)oramagneticstirrer.Attheendofthe10±1minutes,immediatelyfilterthesolutionthroughaWhatmanNo.40filterpaperinafunnel,intoa50mLvolumetricflaskorcertified50mLsampletube.WashwithafewmLofultra-purewater;add1mLofconcentratednitricacid,andmakeuptovolumewithultra-purewater.Atleastthreereplicateanalysesshouldbeperformedoneachcoatingsample.准确称取约100mg干燥涂层至100ml烧杯中，精确至0.1mg。加入20ml5%（v/v）HCl萃取液在20±3℃条ControlAccuratelytransferabout100mgofthestandardreferencematerial(NIST2710orNIST1633c)intoatared100mLbeakerandweightothenearest0.1mg.Add20mLofthe5%(v/v)HClleachingsolutionandimmediatelystartstirringfor10±1minutesat20°C±3°Cwiththeuseofdigitalshaker(140speed)oramagneticstirrer.Attheendofthe10±1minutes,immediatelyfilterthesolutionthroughaWhatmanNo.40filterpaperinafunnel,intoa50mLvolumetricflaskorcertified50mLsampletube.WashwithafewmLofultra-purewater;add1mLofconcentratednitricacid,andmakeuptovolumewithultra-purewater.Preparethiscontrolinduplicate.MethodPrepareablanksolutionbyadding20mLofthe5%(v/v)HClleachingsolutiontoa100mLbeakerandimmediatelystartstirringfor10±1min.at20ºC±3ºCwiththeuseofdigitalshaker(speed140)oramagneticstirrer.Attheendofthe10±1min.immediatelyfilterthesolution,throughaWhatmanNo.40filterpaperinafunnel,intoa50mLvolumetricflaskorcertified50mLsampletube.WashwithafewmLofultra-purewater;add1mLofconcentratednitricacid,andmakeuptovolumewithultra-purewater.制备空白溶液：加入20ml5%（v/v）HCl萃取液在20±3℃条件下用数显震荡仪（140次/min）或磁力搅Preparea2.0%(v/v)nitricaciddilutingsolutionbydiluting20mLofconcentrated(approx.69%w/w)nitricacidto1000mLwithultra-purewater.Accuratelydilutetheworked-upleachatesolutionspreparedinsections4.5.1,4.6.1,4.7.1tentimesusing2.0%(v/v)nitricacid(see4.8).Prepareanacidsolutionconsistingof0.2%(v/v)hydrochloricacidand2.0%(v/v)nitricacidina2Lvolumetricflask.Use4mLofconc.HCland40mLofconc.HNO3andmakeupto2Lvolumewithultra-purewater.Thissolutionwillbeusedasablanksolution,topreparecalibrationstandardsolutions,toprepareverificationstandardsolution,andtodilutesamplesthatareoverthelineardynamicrangeofthe准备一个由0.（v）盐酸和2.0（v）硝酸组成的溶液：取4l浓盐酸和40浓硝酸，用超纯水定容至2L。该溶液用作空白溶液，也用来制备校正标准溶液，也用来制备标准溶液核查液，也用来稀释超过仪器校正线性范围之外的样品溶液。Prepareaseriesofatleastfiveworkingcalibrationstandardsinthelinearrangeofthedetectoroftheinstrumenttoobtainalinearcalibrationcurvewithacorrelationcoefficientofatleast0.99.Thesestandardsshouldbeinthefollowingrange:0ppbto200ppbdilutedfroma10ppmAs,Se,Cd,Sb,Ba(+others)multi-elementcalibrationstandardsolution(see3.2)(e.g.2,5,10,20,50,100,200).Makeupallcalibrationstandardsin0.2%(v/v)hydrochloricacidand2.0%(v/v)nitricacid(see5.1).Recordallinformation.(FormC03F2.1Std10ppm.doc)曲线。工作标准溶液应在如下范围内：由10ppmAs，Se，Cd，Sb，Ba等多元素混合标准溶液稀释Prepareabout100-250mLofa100ppbsolutionoftheinternalstandardsGa,In,Biin5%nitricacid.ThissolutionispumpedintotheinternalstandardadditionTee(onthebackoftheperistalticpump)whereitmixeswiththesamplebeforegoingtothespraychamberoftheICP-MS.制备100~250ml100ppb浓度的内标Ga，In，Bi溶液，介质为5%硝酸。该溶液随由ICP-MS内标管随PrepareanaccuracychecksolutionbydilutingtheInitialCheckVerificationStandard(see3.3)1000timeswiththesolutionpreparedin5.1.Thissolutionisusedtochecktheaccuracyofthecalibration(seeformC03F2.1Std10ppm.doc).Analysethecalibrationstandardsusingaminimumof9replicatereadingsintheICP-MSmethod.UsethesameICP-MSmethodL5$3Ga3.mfortheblanks,calibrationstandards,controls,andsamples.Obtainacalibrationcurveofioncountspersecondvs.concentrationandcheckitforsuitability(e.g.outliers&linearity/curvefitting)foreachelementbeforeproceedingwiththeanalysisofthesamples.用IPMS方法做校准曲线时分析工作标准溶液时最少9次重复读数。同样使用该IPMS方法分析空白，校准标准溶液，质控和样品。以离子的cp和浓度作校准曲线，并在处理分析数据前检查各元素的稳定性。Prepareanacidicsolutionof5%(v/v)ofconc.HNO3(e.g.50mLofconc.HNO3intoa1Lvolumetricflaskandmakeuptothe1Lmarkwithdistilledwater).ThissolutionwillbeusedasarinsesolutionduringtheanalysisontheICP-MS.AnalysethemethodblankbeforeandaftereachbatchofAnalysetheconcentrationofAs,Se,Cd,Sb,Ba(+others)verificationstandardsolutionbeforeandaftertheanalysis.Recordtheresultsinthelogbook.Analysethe50ppbcalibrationstandardsolutionbeforeandaftertheAnalysethecontrolsample(NIST2710orNIST1633c)andrecordtheresultsinthelogbookmethodcontrolAnalysethesamplesolutionsusingninereplicatereadingsintheICP-MSmethod.Ifnecessary,dilutethesamplewith0.2%HCland2.0%HNO3(aspreparedin§5.1)tokeeptheresultswithintherangeoftheCALCULATIONSANDREPORTING（计算和报告Calculatethepercentagebyweightofleachableelementsinthedrycoatingtestsampleaccordingtothefollowingequation:可溶出元素Leachableelementsw/wCi5010Df（m10,000,000）CiConcentrationofelementintheleachingsolutionppbfromtheinstrument；50Volumeofworked-upleachatefilteredrinsedacidified；10Dilutionofleachate；DfFurtherDilutionfactorifrequiredtostaywithincalibration；mmassgoftestsampleused；10,000,000=ppb/Wherethequantityofsamplefortestingissufficientandwherepracticable,theresultofanalysisshallbereportedastheaverageofaminimumofthreeindependentreplicatedeterminationshavingaprecisionwhichshouldnotdiffermorethanthespecificationsdefinedinsection.Whereapplicable,theaverage(x.x×10e)ofreplicatedeterminationsplusorminusStudent’st(forconfidencelevelof0.975)timesthestandarddeviation(s.s×10e)ofreplicatedeterminations(sforn>2)shallbecalculatedandtheresultofanalysisreportedinthefollowingformat:重复测试的平均值(x.x10e)加上或减去t（0.975的置信水平）倍的重复测试（n＞2）的标准偏差(s.s10e)和分析报告结果应按如下公式进行计算：t0.975(95levelofconfidence)isthevaluefortobtainedfromAppendixA,Figure4inMethodC00s=standarddeviationofthen=numberofvaluesinthedataAllresultslessthanthelimitofquantitation(LOQ)shallbereportedaspersectionToensuretheproperoperationoftheanalyticalinstrumentandthattheprecisionandaccuracyoftheanalyticalmeasurementsmeetthespecificationsofthemethod,thefollowingqualitycontrolproceduresshallbeconductedconcurrentlywiththeanalysisofthetestsample.ThenormalandcorrectoperationoftheICP-MSshallbeverifiedaccordingtothefollowingRuntheICP-MSTuneprogramandverifythatthevalues(ioncountspersecond)forthetuningsolutionelements(typicallyLi,Y,Tl)arewithinacceptablelimitsofthehistoricalvalues.Aslowdeclineinthenumbersistobeexpectedasthedetectorwearsoutoveraperiodofabouttwoyears.RecordthetuningelementvaluesintheICP-MSlogbookandincludeacopyofthetuneprogramprintoutinthesampleorreportfile.Ifthetuningvaluesaretoolow,re-tunetheinstrumenttogetacceptablevalues.MinimumacceptablevaluesforICP-MSAgilent7500aareLi6400,Y16000,Tl9600.TypicalsensitivityvaluesforICP-MSAgilent7700x(Nogasmode)areLi30000,Y100000,Tl6000.谐报告复印件。但如果调谐响应值太低，应重新调谐仪器达到可接受的值。ICP-MSAgilent7500a最小可接受的响应值分别为Li6400，Y16000，Tl9600。ICP-MS7700x(Nogas模式)一般灵敏度相应值分别为Li30000，Y100000，Tl6000.ThenormalandcorrectoperationofthetestmethodshallbeverifiedaccordingtothefollowingConductananalysisoftheleachateofNISTSRM2710orNISTSRM1633ctestedunderidenticalexperimentalconditions(exceptforgrindingandsieving)tothoseofthecoatingsample.RecordtheconcentrationofalloftheelementsintheICP-MSQClogbook.Verifythattheresultsarewithinacceptablelimitsonthecontrolchart,andifso,enteranoteinthesamplefolder(s)totheeffectthatthetestmethodwasfoundtobe"withincontrol".Ifthetestresultsofthecontrolsampleareoutsideofthecontrollimits,theentireanalyticalprocedureshallberepeated.在适当的条件下分析标准参考物质NISTSRM2710或NISTSRM1633c，记录所有元素的浓度。检查PRECISIONANDBIAS（精密度和偏离Repeatability:Thedeviationbetweenreplicatetestresults,asobtainedfromanalysisofNIST2710(MontanaSoil)bythesameanalystusingthesameinstrumentunderconstantoperatingconditions,inthenormalandcorrectoperationofthetestmethod,shouldnotdifferbymorethanthefollowingrepeatabilityl