1、BRITISH STANDARD BS EN 13656:2002 Characterization of waste Microwave assisted digestion with hydrofluoric (HF), nitric (HNO 3 ), and hydrochloric (HCl) acid mixture for subsequent determination of elements The European Standard EN 13656:2002 has the status of a British Standard ICS 13.030.40 BS EN
2、13656:2002 This British Standard, having been prepared under the direction of the Building and Civil Engineering Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 22 October 2002 BSI 22 October 2002 ISBN 0 580 40625 3 National f
3、oreword This British Standard is the official English language version of EN 13656:2002. The UK participation in its preparation was entrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3, Characterization of waste, which has the responsibility to: A list of organizations
4、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 “International Standards Correspondenc
5、e Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itsel
6、f confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and pr
7、omulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 25 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
8、CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN13656 October2002 ICS13.030.40 Englishversion CharacterizationofwasteMicrowaveassisteddigestionwith hydrofluoric(HF),nitric(HNO 3 )andhydrochloric(HCl)acid mixtureforsubsequentdeterminationofelements CaractrisationdesdchetsDigestionassisteparm
9、icro ondesavecunmlangedacidesfluorhydrique(HF), nitrique(HNO 3)etchlorhydrique(HCI)pourla dterminationultrieuredlmentscontenusdansles dchets CharakterisierungvonAbfllenAufschlussmittels MikrowellengertmiteinemGemischaus Fluorwasserstoffsure(HF),Salpetersure(HNO 3)und Salzsure(HCI)frdieanschlieendeBe
10、stimmungder ElementeimAbfall ThisEuropeanStandardwasapprovedbyCENon19August2002. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcerni
11、ngs uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesa
12、mestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPEN
13、DENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2002CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN13656:2002EEN13656:2002(E) 2 Contents page Foreword . 3 1 Scope 5 2 Normativereferences . 5 3 Termsanddefi
14、nitions. 5 4 Safetyremarks 6 5 Sample 6 5.1 Samplepretreatment . 6 5.2 Massoftestportion 7 6 Equipment 7 6.1 Closedvesselsystem . 7 6.1.1 Microwaveunit 7 6.1.2 Digestionvessels . 7 6.2 Semiopenvesselsystem. 7 6.2.1 Microwaveunit 7 6.2.2 Digestionvessels . 8 6.3 Generalequipment . 8 7 Reagents 8 8 In
15、terferencesandsourcesoferror . 8 8.1 Generalinformations 8 8.2 Closedvesselsystem . 9 8.3 Semiopenvesselsystem. 9 9 Procedure. 9 9.1 Blanktest 9 9.2 Procedureforclosedvessels 9 9.2.1 Amountofsamplesandreagents . 10 9.2.2 Digestion. 10 9.2.3 ComplexationofHF 10 9.2.4 Preparationofthesolutionforanalys
16、is 10 9.3 Procedureforsemiopenvessels . 11 9.3.1 Amountofsamples. 11 9.3.2 DigestionandcomplexationofHF . 11 9.3.3 Preparationofthesolutionforanalysis 11 10 Testreport 12 AnnexA (normative)Calibrationofthepoweradjustment . 13 AnnexB (informative)Validation. . 14 Bibliography 25EN13656:2002(E) 3 Fore
17、word ThisdocumentEN13656:2002hasbeenpreparedbyTechnicalCommitteeCEN/TC292“Characterizationof waste“,thesecretariatofwhichisheldbyNEN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltext orbyendorsement,atthelatestbyApril2003,andconflictingnationalstandar
18、dsshallbewithdrawnatthelatest byApril2003. InthisEuropeanStandardtheannexAisnormativeandtheannexeBisinformative. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark, Finlan
19、d,France,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal, Spain,Sweden,SwitzerlandandtheUnitedKingdom.EN13656:2002(E) 4 Introduction Thepurposeofthemethodistobringtheelementstobedeterminedinmanytypesofwasteintosolutionto providearapiddigestionforanalysis.Elementsext
20、ractablebythisprocedurecaninmanyinstancesbedescribed astotal“.Onanotherhandtheycannotberegardedasavailableforleaching,astheextractionprocedureistoo vigoroustorepresentnaturalprocesses.EN13656:2002(E) 5 1Scope ThisEuropeanStandardspecifiesmethodsofmicrowaveassisteddigestionwithhydrofluoric(HF),nitric
21、(HNO 3 ) andhydrochloric(HCl)acidmixture.Solutionsproducedbythemethodsaresuitableforanalysise.g.byatomic absorptionspectrometry(FLAAS,HGAAS,CVAAS,GFAAS),inductivelycoupledplasmaemissionspectrometry (ICPOES)andinductivecoupledplasmamassspectrometry(ICPMS). Themethodisapplicabletothemicrowaveassisteda
22、ciddigestionofwasteforexampleforthefollowing elements:Al,Sb,As,B,Ba,Be,Ca,Cd,Cr,Co,Cu,Fe,Pb,Mg,Mn,Hg,Mo,Ni,P,K,Se,Ag,S,Na,Sr,Sn,Te, Ti,Tl,V,Zn. 2 Normativereferences ThisEuropeanStandardincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheapprop
23、riateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Standardonlywhenincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments)
24、. ENISO3696:1995, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987). 3 Termsanddefinitions ForthepurposesofthisEuropeanStandard,thefollowingtermsanddefinitionsapply. 3.1 digestion mineralizationoftheorganicmatterofasampleanddissolutionofitsmineralpart,moreorlesscompletely,when
25、 reactedwithareagentmixture 3.2 sample portionofmaterialselectedfromalargerquantityofmaterial ENV12506:2001 3.3 laboratorysample sampleorsubsample(s)senttoorreceivedbythelaboratory ENV12506:2001 3.4 testsample;analyticalsample sample,preparedfromthelaboratorysample,fromwhichtestportionsareremovedfor
26、testingoranalysis ENV12506:2001 3.5 testportion;analyticalportion quantityofmaterialofpropersizeformeasurementoftheconcentrationorotherpropertiesofinterest,removed fromthetestsample ENV12506:2001 NOTE1 Thetestportionmaybetakenfromthelaboratorysampledirectlyifnopreparationofsampleisrequired(e.g.with
27、liquids),butusuallyitistakenfromthepreparedtestsample.EN13656:2002(E) 6 NOTE2 Aunitorincrementofproperhomogeneity,sizeandfineness,needingnofurtherpreparation,maybeatestportion. 3.6 dryresidue drymatterexpressedasapercentagebymassafterdryingat105C5Ctotheconstancyofweight 3.7 digestionvessel specialfl
28、askwherethetestportionandtheacidmixturearefilledinandthedigestionisperformed 3.8 microwaveunit wholemicrowavedigestionsystem(ovenandassociatedequipment) 3.9 microwaveunitcavity innerpartofthemicrowaveunitinwhichthedigestionvesselislocatedandthemicrowavedigestionisperformed 3.10 focusedmicrowaveunit
29、microwaveunitinwhichaprecisecontroloftheelectricfieldismadebyusingawaveguide NOTE Microwavesarefocusedatthebottompartofthedigestionvessel. 4 Safetyremarks Allthisworkhastobeperformedbyskilledpersons. ThereagentsusedwithinthisEuropeanStandardarestronglycorrosiveandpartlyverytoxic.Safetyprecautions ar
30、eabsolutelynecessaryduetostrongcorrosivereagents,hightemperatureandhighpressure. Allprocedureshavetobeperformedinahoodorinclosedforceventilatedequipment.Bytheuseofstrong oxidisingreagentstheformationofexplosiveorganicintermediatesispossibleespeciallywhendealingwith sampleswithahighorganiccontent.Don
31、otopenpressurisedvesselsbeforetheyhavecooleddown.Avoid contactwiththechemicalsandthegaseousreactionproducts.Samplesandsolutionshavetobedisposedof accordingtoregulations. PeopleperformingthetestshallbeinformedonthespecificriskofHF. 5Sample 5.1 Samplepretreatment Thetestportionshouldbetransferredintot
32、hevesselasitiswithoutanypretreatmentifpossible.Thisis applicableonlyifthetestportionisrepresentativeforthelaboratorysampleandtheeffectivenessofthedigestion isproven. Iftheseconditionsarenotmetapretreatmentofthelaboratorysampleisnecessary.Thisprocedureshallnot changetheconcentrationoftheelementsofint
33、erest. NOTEPretreatmentmayincludedryingorgrainsizereductionbelowaparticlesizeof250mforsolidwasteor homogenizingbyuseofahighspeedmixerorsonificationforliquidsamples. Themassoflaboratorysamplesshallbesufficientforthemultipledigestionproceduresanddeterminationofthe dryresidue.EN13656:2002(E) 7 5.2 Mass
34、oftestportion Themassoftestportionforasingledigestionhastobeselectedinaway,that: itisrepresentativeforthelaboratorysample; itcomplieswiththespecificationsofmanufacturerofthedigestionunit. NOTE Iftherepresentativetestportionexceedsthemanufacturersspecificationsthetestportionshouldbedevidedinto smalle
35、rquantitiesanddigestedseperately.Theindividualdigestsshouldbecombinedpriortoanalysis. Forrepresentativityreasonmassabove200mgistobepreferred.Unlessrecommendedbythemanufacturerthe amountoforganiccarbonshallnotexceed100mgbecauseofsafetyreasonsinthecaseofcloseddigestion vessel. 6Equipment 6.1 Closedves
36、selsystem 6.1.1Microwave unit Themicrowaveunitshallprovideprogrammablepowerwhichcanbeprogrammedtowithin10Wofthe requiredpower.Typicalunitsprovideanominal600Wto1200Wofpower.Ifnecessary(referringto manufacturesspecifications)calibrationofthemicrowaveunithastobeperformed(seeannexA). Themicrowaveunithas
37、tocomplytoEuropeanandnationalregulationsrelevanttomicrowaveradiation. Themicrowaveunitcavityhastobewellventilated.Ithastohaveanexhaustairtubewhichisconnectedtoa corrosionresistantlaboratoryairoutletsystemortheinstrumentisprovidedforuseinalaboratoryhood. Allelectronicsaresufficientlyprotectedagainstc
38、orrosionforsafeoperation.Allpartswhichcanhavecontactwith acidsortheirvapourshavetobecorrosionresistant. Themicrowaveunitshallbedesignedinawaythatguaranteeshomogeneousheatingofthesamples. Themicrowaveunitcavityhastobebuiltinawaythatevenincaseofleakageorexplosionofthevesselsthe safetyoftheoperatorscan
39、beguaranteed.Householdinstrumentsarenotsuitableforlaboratoryuse. NOTE Themicrowaveunitshouldincludeatemperatureand/orpressurecontrolsystem. 6.1.2 Digestionvessels Thevesselsusedinthemicrowaveunitshallbeequipedwithapressurerelievevalveoranothertechnical equipmentwhichavoidstheburstingofthevesselsatsu
40、ddenlyoccuringexcesspressure.Thematerialofthe vesselshastobeinerttotheacidsusedfordigestion.Thedigestionvesselshallwithstandthepressureofat least8bar.Iftheamountoforganiccarbonexceeds100mgithastobeensuredthatthedigestionvesselis capableofwithstandinghigherpressures. 6.2 Semiopenvesselsystem 6.2.1Mic
41、rowave unit Themicrowaveunitshallbeequipedwithpowercontrol.Typicalunitprovidesanominal200Wor300Wof releasedpower.Ifnecessary,calibrationofthemicrowaveunithastobeperformedbythemanufacturer. ThemicrowaveunitshallcomplywithEuropeanandnationalregulationsrelevanttomicrowaveradiation.EN13656:2002(E) 8 The
42、microwaveunitshallbedesignedforuseinalaboratoryhood. Fumeextractionequipment,usedtoextractacidvapoursfromthereactionvesselsduringthedigestion programme,shallhavesufficientflowratetopreventthereleaseofdangerousvapoursintothelaboratory. Allelectronicsshallbesufficientlyprotectedagainstcorrosionforsafe
43、operation.Allpartswhichcanbeincontact withacidsortheirvapoursshallbecorrosionresistant. 6.2.2 Digestionvessels Thevesselisworkingatatmosphericpressureandhastobeconnectedwitharefluxsystemtoavoidlossesof analytes.Thevesselshallcomplywiththemanufacturesspecificationsandshouldhaveaminimumvolumeof 50ml. Thematerialofthevesselshastobeinerttothereagentsusedfordigestion. NOTE Quartzorborosilicatedglassdigestionvesselsarenotuseablewhenhydrofluoricacidisused.Forexample polytetrafluorethylen(PTFE)digestionvesselscanbeused. 6.3 Generalequipment Thefollowing
