1、DRAFT FOR DEVELOPMENT DD ENV 14138:2001 Lead and lead alloys Analysis by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma emissions spectrometry (ICP-ES), after separation by co-precipitation ICS 77.120.60 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LA
2、WDD ENV 14138:2001 This Draft for Development, having been prepared under the direction of the Engineering Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 21 December 2001 BSI 21 December 2001 ISBN 0 580 38084 X National forew
3、ord This Draft for Development is the English language version of ENV 14138:2001. This publication is not to be regarded as a British Standard. It is being issued in the Draft for Development series of publications and is of a provisional nature because, although the analytical procedures in the met
4、hod are generally recognized, the evaluation of the method via Round-Robin analyses, together with the resultant statistical validation, as required by CEN, has not yet been carried out. It should be applied on this provisional basis, so that information and experience of its practical application m
5、ay be obtained. Comments arising from the use if this Draft for Development are requested so that UK experience can be reported to the European organization responsible for its conversion into a European Standard. A review of this publication will be initiated 2 years after its publication by the Eu
6、ropean organization so that a decision can be taken on its status at the end of its three-year life. The commencement of the review period will be notified by an announcement in Update Standards. According to the replies received by the end of the review period, the responsible BSI Committee will de
7、cide whether to support the conversion into a European Standard, to extend the life of the prestandard or to withdraw it. Comments should be sent in writing to the Secretary of BSI Technical Committee NFE/22, Lead and lead alloys, at 389 Chiswick High Road, London W4 4AL, giving the document referen
8、ce and clause number and proposing, where possible, an appropriate revision of the text. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in thi
9、s document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. Summary of pages This document comprises a front cover, an inside front cover, the ENV title pa
10、ge, pages 2 to 14, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEANPRESTANDARD PRNORMEEUROPENNE EUROPISCHEVORNORM ENV14138 December2001 ICS77.120.60
11、 Englishversion LeadandleadalloysAnalysisbyflameatomicabsorption spectrometry(FAAS)orinductivelycoupledplasmaemission spectrometry(ICPES),afterseparationbycoprecipitation PlombetalliagesdeplombAnalyseparspectromtrie dabsorptionatomiquedanslaflamme(FAAS)oupar spectromtriedmissionplasmainductifcoupl(I
12、CP ES),aprssparationparcoprcipitation BleiundBleilegierungenAnalysedurchFlammen Atomabsorptionsspektrometrie(FAAS)oderEmission SpektrometriemitinduktivgekoppeltemPlasma(ICPES), nachAbtrennungdurchMitfllung ThisEuropeanPrestandard(ENV)wasapprovedbyCENon18November2001asaprospectivestandardforprovision
13、alapplication. TheperiodofvalidityofthisENVislimitedinitiallytothreeyears.AftertwoyearsthemembersofCENwillberequestedto submittheir comments,particularlyonthequestionwhethertheENVcanbeconvertedintoaEuropeanStandard. CENmembersarerequiredtoannouncetheexistenceofthisENVinthesamewayasforanENandtomaketh
14、eENVavailablepromp tly atnationallevelinanappropriateform.Itispermissibletokeepconflictingnationalstandardsinforce(inparalleltothe ENV)untilthefinal decisionaboutthepossibleconversionoftheENVintoanENisreached. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,Fra
15、nce,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2001CEN Allrightsofexploitationinanyfo
16、rmandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.ENV14138:2001EENV14138:2001(E) 2 Contents page Foreword4 1 Scope 5 2 Normativereferences 5 3 Principle5 3.1 Preparationofthetestsolution 5 3.2 Instrumentaltechniques . 6 3.2.1 Flameatomicabsorptionspectrometry(FAAS) . 6 3.2.2 Inductively
17、coupledplasmaemissionspectrometry(ICPES). .6 4 Apparatus .6 4.1 General6 4.2 Volumetricglassware 6 4.3 Filtrationsystem . .6 4.4 Instruments.6 4.4.1 Flameatomicabsorptionspectrometer 6 4.4.2 Inductivelycoupledplasmaemissionspectrometer .7 5 Reagents.7 5.1 General7 5.2 Nitricacid(HNO 3 ) 7 5.2.1 Conc
18、entratednitricacid 7 5.2.2 Nitricacid1:1( V/V) 7 5.2.3 Nitricacid1:2( V/V) 7 5.3 Hydrochloricacid(HCl) . 7 5.3.1 Concentratedhydrochloricacid .7 5.3.2 Hydrochloricacid1:1( V/V) .7 5.4 Ammoniasolution 7 5.5 Purelead. 7 5.6 Manganesenitratesolution 8 5.7 Potassiumpermanganatesolution . .8 5.8 Standard
19、solutions 8 5.8.1 Standardsolutions(1g/l). 8 5.8.2 Standardsolutions(100mg/l). 8 5.8.3 Standardsolutions(10mg/l) .9 5.8.4 Multielementsolutions(either10mg/lor100mg/l) 9 6 Samplingandsamplepreparation . 9 7 Procedure .9 7.1 Preparationofthetestsolution 9 7.1.1 Dissolution9 7.1.2 Coprecipitationwithma
20、nganesedioxide. 9 7.1.3 Testsolution. 9 7.2 Preparationofthesynthetictestsolution .9 7.3 Preparationoftheblanktestsolution .10 7.4 Preparationofcalibrationsolutions 10 8 DeterminationofelementsbyFAAS. .10 8.1 General10 8.2 Calibrationandmeasurementofthetestsolution .11 8.3 Expressionofresults . .11
21、8.3.1 Analyterecoveryrate . .11 8.3.2 Analytecontentinthesample. .11 9 DeterminationofelementsbyICPES . 12 9.1 General12 9.2 Calibrationandmeasurementofthetestsolution .12ENV14138:2001(E) 3 9.3 Expressionofresults . .13 9.3.1 Analyterecoveryrate . .13 9.3.2 Analytecontentinthesample. .13 10 Testrepo
22、rt 13 Bibliography 14ENV14138:2001(E) 4 Foreword ThisEuropeanPrestandardhasbeenpreparedbyTechnicalCommitteeCEN/TC306,“Leadandleadalloys“,the secretariatofwhichisheldbyAFNOR. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoannouncethisEu
23、ropeanPrestandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden, SwitzerlandandtheUnitedKingdom. CAUTIONFORSAFETYANDTRAINING ThemethodsinthisPrestandardarerecommendedforthecertificationofreferencemateria
24、lsandasumpire methodsincasesofadispute.Theimportanceofeitherapplication,andtheparamountissueofsafety,requires thattheyshouldonlybecarriedoutbyfullytrainedanalystswhoareexperiencedinallrelevanttechniquesandthe precautionsnecessaryintheinherentlyhazardousenvironsofalaboratory,especiallythoserequiredwh
25、enusing particularlyhazardousapparatusandreagentsusedinsomeofthesemethods. Whereaparticularhazardexists,thisisgivenasa DANGERadjacenttothepointinthetextwheretheapparatus orreagentisreferenced.ENV14138:2001(E) 5 1Scope ThisEuropeanPrestandardspecifiesmethodsusingflameatomicabsorptionspectrometry(FAAS
26、)andinductively coupledplasmaemissionspectrometry(ICPES)forthedeterminationofelementsatlowcontentinleadforthe rangesgiveninTable1. HighercontentsthanthoselistedinTable1shouldbedeterminedaccordingtoENV13800. Table1Rangesofapplicationforthedeterminationofelements Rangesofapplications (% m/m) Element F
27、AAS ICPES As 0,0002 0,005 0,00005 0,005 Sb 0,0002 0,0025 0,0002 0,0025 Se 0,0002 0,005 0,0002 0,005 Sn 0,0005 0,005 0,0002 0,005 Te 0,00002 0,0025 0,00002 0,0025 Thesemethodsareintendedasthedefinitivemethodsincaseofdisputeforthedeterminationofelementsatlow contentinlead.Theyarealsorecommendedforthea
28、nalysisofCertifiedReferenceMaterials(CRM)and ReferenceMaterials(RM)whichareusedinanalysisaccordingtoENV12908. 2 Normativereferences ThisEuropeanPrestandardincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetextandthepubli
29、cationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Prestandardonlywhenincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments). EN12402, LeadandleadalloysM
30、ethodsofsamplingforanalysis. ENV12908, LeadandleadalloysAnalysisbyOpticalEmissionSpectrometry(OES)withsparkexcitation. ENV13800,LeadandleadalloysAnalysisbyflameatomicabsorptionspectrometry(FAAS)orinductively coupledplasmaemissionspectrometry(ICPES),withoutseparationoftheleadmatrix. ISO648, Laborator
31、yglasswareOnemarkpipettes. ENISO1042, LaboratoryglasswareOnemarkvolumetricflasks(ISO1042:1998). ENISO3696, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987). 3Principle 3.1 Preparationofthetestsolution Dissolutionofatestportioninnitricacid. Separationofanalytebycoprecipitation
32、withmanganesedioxide. Dissolutionoftheprecipitate,madeuptoadefinedvolume. Determinationoftheanalyteconcentrationusingoneofthetwotechniquesdescribedin3.2.ENV14138:2001(E) 6 3.2 Instrumentaltechniques 3.2.1 Flameatomicabsorptionspectrometry(FAAS) Theanalyteconcentrationinthetestsolutionisobtainedby: n
33、ebulizationofthetestsolutionintotheflameofanatomicabsorptionspectrometer; measurementoftheabsorptionoftheresonancelineenergyofthespectrumfromtheelementattherelevant wavelength(absorbance); comparisonwiththatofcalibrationsolutionsofthesameelement. 3.2.2 Inductivelycoupledplasmaemissionspectrometry(IC
34、PES) Theanalyteconcentrationinthetestsolutionisobtainedby: nebulizationofthetestsolutionintotheplasmaofaninductivelycoupledplasmaopticalemission spectrometer; measurementoftheintensityoftheemissionsignalfromthespectrumoftheelementtobedeterminedatthe relevantwavelength; comparisonwiththatofcalibratio
35、nsolutionsofthesameelement. 4Apparatus 4.1General Useordinaryapparatusasavailableinachemicallaboratory. Allglasswaretobeusedshallbecleanedwithdilutedhydrochloricacid(5.3.2)andthoroughlyrinsedwithwater. 4.2 Volumetricglassware 4.2.1 Onemarkvolumetricflasksofcapacities25ml,100ml,500mland1000mlinaccord
36、ancewithENISO 1042classA. 4.2.2 Onemarkpipettesofcapacities5ml,10ml,15ml,20ml,25mland50mlinaccordancewithISO648 classA. 4.3Filtration system VacuumfiltrationsystemwithafiltermembraneofPTFE,orothermaterialinerttonitricacid,ofabout5m porosity(filteringdiameter20mmto50mm). 4.4Instruments 4.4.1 Flameato
37、micabsorptionspectrometer Flameatomicabsorptionspectrometer(FAAS)equippedwithlaminarflowburnerssuitableforacetyleneair, hydrogenairoracetylenenitrousoxideflames,andwithradiationsourcessuchashollowcathodelamps(HCL)or electrodelessdischargelamps(EDL)asappropriatetotheelementtobedetermined. Theinstrume
38、ntshallbeusedinaccordancewiththemanufacturersinstructionsandtheperformancechecked(see alsoISO/DIS132042andISO/DIS132043). DANGER Toavoidanyrisktopersonnelduetoemissionofacidandleadfumes,theoffgasshallbe exhaustedexternally.ENV14138:2001(E) 7 4.4.2 Inductivelycoupledplasmaemissionspectrometer Inducti
39、velycoupledplasmaemissionspectrometer(ICPES),eitherasimultaneousinstrumentwiththerelevant wavelengthsinstalledorasequentialinstrumentwhereamonochromatorsystemallowstheselectionof wavelengths(seealsoISO/DIS122351). Theinstrumentshallbeusedinaccordancewiththemanufacturersinstructionsandtheperformances
40、checked (seealsoISO/DIS122352). DANGER Toavoidanyrisktopersonnelduetoemissionofacidandleadfumes,theoffgasshallbe exhaustedexternally. 5Reagents 5.1General Forallstagesofanalysis,unlessotherwisestated,useonlyreagentsofrecognisedanalyticalgrade,preferably withanactualanalysis,suitablefortraceanalysisa
41、ndonlywaterofatleastgrade2,asspecifiedinENISO3696. Prepareallsolutionsusingthesamecontainerofeachreagent. 5.2 Nitricacid(HNO 3 ) 5.2.1 Concentratednitricacid Nitricacidofhighpurity,which 20 =1,41g/ml. 5.2.2 Nitricacid1:1( V/V) Addtoonevolumeofwater,inasuitablecontainer,thesamevolumeofconcentratednit
42、ricacid(5.2.1)andmix thoroughly. 5.2.3 Nitricacid1:2( V/V) Add200mlconcentratednitricacid(5.2.1)to400mlwaterina1000mlbeakerandmixthoroughly. 5.3 Hydrochloricacid(HCl) 5.3.1 Concentratedhydrochloricacid Hydrochloricacidofhighpurity,which 20 =1,18g/ml. 5.3.2 Hydrochloricacid1:1( V/V) Add400mlofconcent
43、ratedhydrochloricacid(5.3.1)to400mlwaterina1000mlflask.Thisacidisusedtoclean allglasswarewhichshouldbesoakedforatleast1hpriortouse,thenrinsedthoroughlywithwater. 5.4 Ammoniasolution Ammoniasolutionofhighpuritywhich 20 =0,88g/ml. 5.5 Purelead Forthedeterminationoftherecoveryrateoftheanalyte(see7.2),v
44、erypurelead(99,9999% m/m)shouldbeused. However,leadoflowerpuritymaybeusedprovidedthattheanalyteisnotpresentinanamountthatcouldbe significanttothedeterminationrequired.ENV14138:2001(E) 8 5.6 Manganesenitratesolution Dissolve(7,000,01)gofhydratedmanganesenitrate(Mn(NO 3 ) 2 4H 2 O)inwater,transfertoa100mlvolumetric flask,makeuptothemarkwithwaterandmixthoroughly. 5.7 Potassiumpermanganatesolution Weigh(3,200,01)gofpotassiumpermanganate(KMnO 4 )intoa600mlbeaker,add400mlwaterandswi
