1、| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BRITISH STANDARD BS EN ISO 14182:2000 BS 5
2、766-20:2000 The European Standard EN ISO 14182:1999 has the status of a British Standard ICS 65.120 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Animal feeding stuffs Determination of residues of organophosphorus pesticides Gas chromatographic methodThis British Standard, h
3、aving been prepared under the direction of the Consumer Products and Services Sector Committee, was published under the authority of the Standards Committee and comes into effect on 15 June 2000 BSI 06-2000 ISBN 0 580 34809 1 BS EN ISO 14182:2000 Amendments issued since publication Amd. No. Date Com
4、ments National foreword This British Standard is the official English language version of EN ISO 14182:1999. It is identical with ISO 14182:1999. The UK participation in its preparation was entrusted to Technical Committee AW/10, Animal feeding stuffs, which has the responsibility to: aid enquirers
5、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 promulgate them in the UK. A list of organizations represe
6、nted on this committee can be obtained on request to its secretary. Cross-references Attention is drawn to the fact that CEN and CENELEC Standards normally include an annex which lists normative references to international publications with their corresponding European publications. The British Stan
7、dards which implement these international or European publications 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. A British Standard does not purport to
8、include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, t
9、he EN ISO title page, the EN ISO foreword page, the ISO title page, pages ii to iv, pages 1 to 18, the annex ZA page and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued.EUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM ENISO14182 December199
10、9 ICS65.120 Englishversion AnimalfeedingstuffsDeterminationofresiduesof organophosphoruspesticidesGaschromatographicmethod (ISO14182:1999) AlimentsdesanimauxDterminationdesrsidusde pesticidesorganophosphorsMthodepar chromatographieenphasegazeuse(ISO14182:1999) FuttermittelBestimmungvonOrganophosphor
11、pestizid RckstndenGaschromatographischesVerfahren(ISO 14182:1999) ThisEuropeanStandardwasapprovedbyCENon15December1999. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodateli
12、stsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheCentralSecretariatortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguag
13、eandnotifiedtotheCentralSecretariathasthesamestatusast heofficial versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOM
14、MITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG CentralSecretariat:ruedeStassart,36B1050Brussels 1999CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.ENISO14182:1999ECorrected 20000322 Foreword ThetextoftheInternational
15、StandardfromTechnicalCommitteeISO/TC34“Agricultural foodproducts“oftheInternationalOrganizationforStandardization(ISO)hasbeentakenover asanEuropeanStandardbyTechnicalCommitteeCEN/TC327“Animalfeedingstuffs Methodsofsamplingandanalysis“,thesecretariatofwhichisheldbyNNI. ThisEuropeanStandardshallbegive
16、nthestatusofanationalstandard,eitherbypublication ofanidenticaltextorbyendorsement,atthelatestbyJune2000,andconflictingnational standardsshallbewithdrawnatthelatestbyJune2000. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizations ofthefollowingcountriesareboundtoimplementthi
17、sEuropeanStandard:Austria,Belgium, CzechRepublic,Denmark,Finland,France,Germany,Greece,Iceland,Ireland,Italy, Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandtheUnited Kingdom. Endorsementnotice ThetextoftheInternationalStandardISO14182:1999hasbeenapprovedbyCENasa EuropeanStandardw
18、ithoutanymodification. NOTE:NormativereferencestoInternationalStandardsarelistedinannexZA (normative). EN ISO 14182:1999Referencenumber ISO14182:1999(E) INTERNATIONAL STANDARD ISO 14182 Firstedition 1999-12-15 AnimalfeedingstuffsDeterminationof residuesoforganophosphorus pesticidesGaschromatographic
19、method Aliments des animaux Dtermination des rsidus de pesticides organo- phosphors Mthode par chromatographie en phase gazeuse EN ISO 14182:1999ii EN ISO 14182:1999 iii Contents Page Foreword.iv 1 Scope1 2 Normativereferences1 3 Principle1 4 Reagentsandmaterials1 5 Apparatus.3 6 Sampling.5 7 Prepar
20、ationoftestsample5 8 Procedure.6 9 Expressionofresults7 10 Confirmationofidentity8 11 Precision.8 12 Testreport8 AnnexA(informative)Examplesofgaschromatographicoperatingconditionsfororganophosphorus pesticides.9 AnnexB(informative)Resultsofinterlaboratorytests.10 Bibliography18 EN ISO 14182:1999iv F
21、oreword ISO(theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISO memberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnical committees.Eachmemberbodyinterestedinasubjectforwhichatechnicalcommitteehasbeenestablishedhas t
22、herighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmental,in liaisonwithISO,alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnical Commission(IEC)onallmattersofelectrotechnicalstandardization. InternationalStandardsaredraftedinaccordan
23、cewiththerulesgivenintheISO/IECDirectives,Part3. DraftInternationalStandardsadoptedbythetechnicalcommitteesarecirculatedtothememberbodiesforvoting. PublicationasanInternationalStandardrequiresapprovalbyatleast75%ofthememberbodiescastingavote. Attentionisdrawntothepossibilitythatsomeoftheelementsofth
24、isInternationalStandardmaybethesubjectof patentrights.ISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights. InternationalStandardISO14182waspreparedbyTechnicalCommitteeISO/TC34, Agricultural food products, SubcommitteeSC10, Animal feeding stuffs. AnnexesAandBofthisInternationalStandard
25、areforinformationonly. EN ISO 14182:1999 1 AnimalfeedingstuffsDeterminationofresiduesof organophosphoruspesticidesGaschromatographicmethod 1 Scope ThisInternationalStandardspecifiesagaschromatographicmethodforthedeterminationoftheresiduesof organophosphoruspesticidesinanimalfeedingstuffs. Themethodi
26、sapplicabletoanimalfeedingstuffscontainingresiduesofoneormoreofthefollowingorgano- phosphoruspesticides:azinphos-ethyl,azinphos-methyl,bromophos,carbophenothion,chlorpyrifos,chlorpyrifos- methyl, diazinon, dimethoate, ethion, fonofos, malathion, methidathion, parathion, parathion-methyl, pirimiphos-
27、ethylandpirimiphos-methyl. Thelowerlimitofdeterminationfortheseorganophosphoruspesticidesis0,01 g/g. NOTE Themethodisprobablyequallyapplicabletootherorganophosphoruspesticidessuchasmethaccrifosand fenitrothion,butithasnotbeenvalidatedforthesepesticides. 2 Normativereferences Thefollowingnormativedoc
28、umentscontainprovisionswhich,throughreferenceinthistext,constituteprovisionsof thisInternationalStandard.Fordatedreferences,subsequentamendmentsto,orrevisionsof,anyofthese publicationsdonotapply.However,partiestoagreementsbasedonthisInternationalStandardareencouragedto investigatethepossibilityofapp
29、lyingthemostrecenteditionsofthenormativedocumentsindicatedbelow.For undatedreferences,thelatesteditionofthenormativedocumentsreferredtoapplies.MembersofISOandIEC maintainregistersofcurrentlyvalidInternationalStandards. ISO3696, Water for analytical laboratory use Specification and test methods. ISO6
30、498, Animal feeding stuffs Preparation of test samples. 3Principle Atestportionisextractedwithacetone.Thefilteredextractisdilutedwithwaterandasaturatedsodiumchloride solution.Thepesticidesarepartitionedindichloromethane.Theconcentratedextractispurifiedona chromatographiccolumnof10%water-deactivateds
31、ilicagel.Gaschromatographicdeterminationiscarriedout withaphosphorus-selectivedetectororamass-selectivedetector. 4 Reagentsandmaterials Useonlyreagentsofrecognizedanalyticalgradeandwithapuritysuitableforpesticideresidueanalysis. Checkthepurityofthereagentsbyperformingablanktestunderthesameconditions
32、asusedinthemethod.The chromatogramshouldnotshowanyinterferingimpurity. WARNINGSomeoftheorganicsolventsaresuspectedcarcinogens.Usewithcare. EN ISO 14182:19992 4.1Water,complyingwithatleastgrade3inaccordancewithISO3696. 4.2Hexane 4.3Acetone 4.4Dichloromethane 4.5Ethylacetate 4.6Silicagel,withamassfrac
33、tionofwaterof10%. Activatesilicagel60,particlesize63mto200m,at130Covernightandcoolinadesiccator.Aftercoolingto roomtemperature,pourthesilicagelintoanair-tightglasscontainerandaddsufficientdistilledwatertobringthe finalmassfractionofwaterto10%.Shakethecontainermechanicallyorbyhandvigorouslyfor30sanda
34、llowto standfor30minwithoccasionalshaking.After30minthesilicagelisreadyforuse.Itmaynotbestoredformore than6h. 4.7Elutingsolvent,dichloromethaneinhexane(50%volumefraction). Mixequalvolumesofdichloromethane(4.4)andhexane(4.2). 4.8Inertgas,e.g.nitrogen. 4.9Sodiumsulfate,anhydrous. 4.10Sodiumchloridesat
35、uratedsolution 4.11Pesticidereferencestandards,asfollows: azinphos-ethylS-(3,4-dihydro-4-oxobenzod1,2,3triazin-3-ylmethyl) O,O-diethyl phosphorodithioate; azinphos-methylS-(3,4-dihydro-4-oxobenzod1,2,3triazin-3-ylmethyl) O,O-dimethyl phosphorodithioate; bromophosO-4-bromo-2,5-dichlorophenyl O,O-dime
36、thyl phosphorothioate; carbophenothionS-4-chlorophenylthiomethyl O,O-diethyl phosphorothioate; chlorpyrifosO,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate; chlorpyrifos-methylO,O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate; diazinonO,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl
37、phosphorothioate; dimethoateO,O-dimethyl S-methylcarbamoylmethyl phosphorodithioate; ethionO,O,O,O-tetraethyl S,S-methylene di(phosphorodithioate); fonofosO-ethyl S-phenyl ethylphosphonodithioate; malathiondiethyl(dimethoxythiophosphorylthio)succinate; methidathionS-2,3-dihydro-5-methoxy-2-oxo-1,3,4
38、-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate; parathionO,O-diethyl O-4-nitrophenyl phosphorothioate; parathion-methylO,O-dimethyl O-4-nitrophenyl phosphorothioate; pirimiphos-ethylO-2-diethylamino-6-methylpyrimidin-4-yl O,O-diethyl phosphorothioate; pirimiphos-methylO-2-diethylamino-6-meth
39、ylpyrimidin-4-yl O,O-dimethyl phosphorothioate; NOTE Thecommonnamesandthechemicalnames(betweensquarebrackets)accordingtoIUPACnomenclature,arein accordancewithISO17501. EN ISO 14182:1999 3 4.12Internalstandard:tributylphosphate. 4.13Pesticidestandardsolutions 4.13.1Stocksolutions,ofconcentration1000g
40、/ml. Prepareastocksolutionofeachpesticidereferencestandard(4.11)andoftheinternalstandard(4.12)asfollows. Weigh,tothenearest0,1mg,amassofapesticidereferencestandard(4.11)ortheinternalstandard(4.12)which willresultinasolutionwithacontentofreferencestandardorinternalstandardof1000g/ml.Whileweighing, ob
41、servethecleannessofthestandardmaterial.Transfertheweighedmassintoavolumetricflasks,dissolvein ethylacetate(4.5)anddilutetovolumewithethylacetate. Thesesolutionsarestablefor6monthswhenstoredat4Cinthedark. 4.13.2Intermediatesolutions,ofconcentration10g/ml. Pipette1mlofeachstocksolution(4.13.1)intoindi
42、vidual100mlvolumetricflasks.Dilutetovolumewithethyl acetate(4.5).Thesolutionsarestablefor1monthwhenstoredat4Cinthedark. NOTE Thestabilityofproperlystoredpesticidestandardsisverywidelyknown.Investigationshaveshownthatallneat pesticidestandardstestedarestablefor15yearswhenstoredat 18Candthatstocksolut
43、ionsofpesticidestandardsin tolueneof1mg/kgarestableforatleast3yearswhenstoredat 18C. Arecommendedpracticeforlongerstorageisasfollows.Transferportionsofthepreparedstandardsolutionsto ambervialswithPTFE-linedscrewcaps.Weighthevialsandstoreat 20C.Whenneeded,removeavialfromthe freezer,bringtoroomtempera
44、tureandweigh.Ifaccumulatedlossinmass(duetoevaporation)is10%ormoreof theprefrozennetmass,discardthevial.Weighandrefreezestockstandardsandintermediatesolutionsthatarein useformorethan1month(usuallyin25mlvials).Otherwise,thepreparedstandardsolutions(usuallyin2ml vials)maybestoredat4Candshallbediscarded
45、after1month. 4.13.3Workingsolutions,ofconcentration0,5g/ml. Pipette5mlofeachintermediatesolution(4.13.2)into100mlvolumetricflasksanddilutetovolumewithethyl acetate(4.5).Thesolutionsarestablefor1monthwhenstoredat4Cinthedark(see4.13.2). 4.14Blanksamplesolutions,ofthesametypeasthesamplesbeinganalysed,b
46、utfreeofpositives,resulting frompreviousdeterminations. 5 Apparatus Beforeuse,washallglasswarethoroughlywithdetergentfreeofinterferingsubstances,rinsewithwater,thenwith acetoneanddry. Avoidtheuseofplasticscontainersanddonotlubricatethestopcockswithgrease,otherwiseimpuritiescouldbe introducedintothes
47、olvents. Usuallaboratoryequipmentandinparticularthefollowing. 5.1Separatingfunnels,ofcapacities500mland1000ml,withpolytetrafluoroethylene(PTFE)stopcocksand stoppers. 5.2Filteringflasks,ofcapacity500ml. 5.3Bchnerfunnel,madeofporcelain,withinternaldiameter90mm. 5.4Graduatedtubes,ofcapacity10ml,withpol
48、ytetrafluoroethylene(PTFE)stoppers. EN ISO 14182:19994 5.5Glasschromatographictube,about300mminlength,8mmto10mminternaldiameter,withcoarsefritted plateofporositygradeP100(poresizeindex40 mto100 m2)orglasswoolplug. 5.6Rotaryvacuumevaporator,providedwithround-bottomflasksofcapacities100mland500ml,andawater bathsetat40C. 5.7Mechanicalshakerorhigh-speedblender 5.8Gaschromato
