SN-T 2912-2011出口乳及乳制品中多種擬除蟲菊酯農(nóng)藥殘留量的檢測(cè)方法氣相色譜-質(zhì)譜法

中華人民共和國(guó)出入境檢驗(yàn)檢疫行業(yè)標(biāo)準(zhǔn)出口乳及乳制品中多種擬除蟲菊酯農(nóng)藥殘留量的檢測(cè)方法氣相色譜-質(zhì)譜法國(guó)家質(zhì)量監(jiān)督檢驗(yàn)檢疫總局I本標(biāo)準(zhǔn)按照GB/T1.1—2009給出的規(guī)則起草。請(qǐng)注意本文件的某些內(nèi)容可能涉及專利。本文件的發(fā)布機(jī)構(gòu)不承擔(dān)識(shí)別這些專利的責(zé)任。本標(biāo)準(zhǔn)由國(guó)家認(rèn)證認(rèn)可監(jiān)督管理委員會(huì)提出并歸口。本標(biāo)準(zhǔn)起草單位：中華人民共和國(guó)吉林出入境檢驗(yàn)檢疫局、中華人民共和國(guó)山西出入境檢驗(yàn)檢疫1出口乳及乳制品中多種擬除蟲菊酯農(nóng)藥殘留量的檢測(cè)方法3.4正已烷-乙酸乙酯(9+2,體積比):量取90mL正己梳和20mF.乙酸乙酯，混勻。3.62,6-二異丙基萘等17種農(nóng)藥標(biāo)準(zhǔn)品：純度大于等于98%。CAS編號(hào)見附錄A。3.72,6-二異丙基萘等17種農(nóng)藥標(biāo)準(zhǔn)儲(chǔ)備溶液：分別準(zhǔn)確稱取適量的2,6-二異丙基萘等17種農(nóng)藥標(biāo)準(zhǔn)品，用正己烷配制成濃度為100μg/mL的標(biāo)準(zhǔn)儲(chǔ)備溶液。該溶液在0℃~4℃冰箱中保存。3.82,6-二異丙基萘等17種農(nóng)藥標(biāo)準(zhǔn)工作溶液：根據(jù)需要用不含2.6-二異丙基萘等17種農(nóng)藥的空白4儀器與設(shè)備4.2分析天平：感量為0.01g。4.3分析天平：感量為0.1mg。3SN/T2912—2011>20～50>10～2047.2添加濃度范圍及回收率本方法添加濃度及回收率見表2。表2方法測(cè)定低限及回收率范圍農(nóng)藥名稱樣品種類測(cè)定低限mg/kg添加水平mg/kg平均回收率范圍%2,6-二異丙基萘牛奶285.3～109.4冰淇淋奶粉93.2～110.0奶酪_0,01七氟菊酯牛奶0/005冰淇淋奶粉奶酪牛奶冰淇淋5農(nóng)藥名稱樣品種類測(cè)定低限mg/kg添加水平mg/kg平均回收率范田%奶粉0.010.0167.5～96.10.0289.3～95.676.2～106.2奶酪0.0186.0～110.676.0～109.185.3～112.6烯蟲酯牛奶79.6～106.50.Q?80.6～103.289.3～100.9冰淇淋0.0166.0～91.20.0289.0～103.481.2～97.672.0～108.282.5～98.6奶粉85.3～99.3奶酪0.010.0185.5～105.484.2～112.383.1～102.3芐呋菊酯牛妍0.0180～116.777.5～104.280.0～105.0冰淇淋0.0189.0～109.30.0287.0～98.294.7～120.2奶粉0.010.0191.0～105.80.0281.7～96.878.3～98.1奶酪0.010.0178.5～89.50.0290.2～103.577.0～92.5聯(lián)苯菊酯牛奶0.0050.00573.5～106.20.0185.4～112.279.2～103.86表2(續(xù))農(nóng)藥名稱樣品種類測(cè)定低限mg/kg添加水平mg/kg平均回收率范圍%聯(lián)苯菊酯冰淇淋89.0～92.195.5～115.282.5～105.3奶粉85.4～105.383.2～105.290.2～112.1奶酪87.5～105.682.2～105.485.4～98.0甲氰菊酯牛奶86.5～98.585.7～114.885.4～100.8冰淇淋85.0～104.376.5～110.282.1～106.4奶粉85.0~116.288.7～100.988.5～104.2奶酪73.0～113.587.5～106.386.0～114.3牛奶90.5～110.481.2～101.891.0～106.7冰淇淋885～99.185.2～105.285.1～110.6奶粉75.0～94.185.0～106.286.1～105.2奶酪90.0～110.889.5～109.2789～106.07農(nóng)藥名稱樣品種類測(cè)定低限添加水平平均回收率范圍%氟丙菊酯牛奶冰淇淋奶粉奶酪氯菊酯(I,Ⅱ)牛奶冰淇淋奶粉奶酪85.0～106.7氟氯氰菊酯牛奶冰淇淋奶粉8農(nóng)藥名稱樣品種類測(cè)定低限添加水平mg/kg%奶酪氯氰菊酯牛奶冰淇淋奶粉奶酪0.02牛奶冰淇淋0101*奶粉奶酪醚菊酯牛奶冰淇淋9表2(續(xù))農(nóng)藥名稱樣品種類測(cè)定低限添加水平mg/kg%醚菊酯奶粉奶酪氰戊菊酯牛奶0.01冰洪低0.01勢(shì)酪牛奶冰洪淋奶粉奶酪溴氛菊酯牛奶農(nóng)藥名稱樣品種類測(cè)定低限添加水平平均回收率范圍%溴氰菊酯冰淇淋90.3～96.4奶粉奶酪79.5～102.2,6-二異丙基萘等17種擬除蟲菊酯類農(nóng)藥種類表表A.12,6-二異丙基萘等17種擬除蟲菊酯類農(nóng)藥種類表序號(hào)化學(xué)分子式2,6-二異丙基萘2,6-diisopropylnaphtalene24157-81-12七氟菊酯tefluthrin79538-32-2C,HCIF?O?3生物丙烯菊酯bioallethrinC??H??O?4烯蟲酯methoprene40596-69-8C??H??O?5芐呋菊酯resmethrinC??H??O?6聯(lián)苯菊酯bifenthrin82657-04-3C??H??CIF?O?7甲氰菊酯fenpropathrin64257-84-7C?H??NO?8氯氟氰菊酯cyhalothrin68085-85-8Cz?H??CIF?NO?9氟丙菊酯acrinathrinC?6HnF?NO?permethrin(I)52645-53-1C??H??Cl?O?氯菊酯(Ⅱ)permethrin(Ⅱ)氟氯氰菊酯(I)cyfluthrin(I)68359-37-5C?H??Cl?FNO?氟氯氰菊酯(Ⅱ)cyfluthrin(Ⅱ)氟氯氰菊酯(Ⅲ)cyfluthrin(Ⅲ)氟氯氰菊酯(IN)cyfluthrin(V)氯氛菊酯(I)cypermethin(I)52315-07-8C?H??Cl?NO?氯氛菊酯(Ⅱ)cypermethin(Ⅱ)氯氰菊酯(Ⅲ)cypermethin(Ⅲ)氯氰菊酯(IN)cypermethin(IV)氟氰戊菊酯(I)flucythrinate(I)70124-77-5C?H?F?NO,氟氰戊菊酯(Ⅱ)flucythrinate(Ⅱ)醚菊酯etofenprox80844-07-1C??H?O?fenvalerate(I)51630-58-1氰戊菊酯(Ⅱ)fenvalerate(Ⅱ)氟胺氰菊酯(I)fluvalinate(I)C??H?CIF?N?O?氟胺氰菊酯(Ⅱ)fluvalinate(Ⅱ)溴氰菊酯deltamethrin52918-63-5C??H??Br?NO?芐呋菊酯等17種擬除蟲菊酯類農(nóng)藥定量和定性選擇離子表B.1芐呋菊酯等17種擬除蟲菊酯類農(nóng)藥定量和定性選擇離子峰順序號(hào)保留時(shí)間min特征碎片離子定量定性豐度比第一段8.5min～12.0min2,6-二異丙基萘2七氟菊醋-10-55第二段12.0min～18.0min3生物丙烯菊酯4烯蟲酯第三段5芐呋菊酯61:100:47:36聯(lián)苯菊酯7甲氰菊酯97、181、34938:10019616第四段8氯氟氰菊酯4197、2034499氟丙菊酯第五段氯菊酯(I)氯菊酯(Ⅱ)第六段24.0min～26.2氟氯氰菊酯(I)氟氯氰菊酯(Ⅱ)氟氯氰菊酯(Ⅲ)氟氯氰菊酯(IV)氯氰菊酯(1)91、152、165氯氰菊酯(Ⅱ)91、152、165氯氰菊酯(Ⅲ)91、152、165氯氰菊酯(IV)91、152、165氟氰戊菊酯())氟氰戊菊酯(Ⅱ)醚菊酯表B.1(續(xù))峰順序號(hào)保留時(shí)間min特征碎片離子定量定性豐度比第七段26.2min～28.2min氰戊菊酯(I)27.28181、225、419100:56:73:22氰戊菊酯(Ⅱ)27.86181、225、419100:34+8:45氟胺氰菊酯(I)27.37181、252、502100:21:35:5氟胺氰菊酯(Ⅱ)181、252、502100:21:34:6第八段28.2min～34.0min溴氰菊酯-29.62100:38:19:68芐呋菊酯等17種擬除蟲菊酯類農(nóng)藥總離子流氣相色譜-質(zhì)譜圖2——七氟菊酯；3——生物丙烯菊酯；5——芐呋菊酯；7——甲氰菊酯：8——氯氟氰菊酯；9——氟丙菊酯；10—-氯菊酯(I);11——氯菊酯(Ⅱ);12——氟氯氰菊酯(I);13——氟氯氰菊酯(Ⅱ);14——氟氯氛菊酯(Ⅲ);t/min15——氟氯氰菊酯(IN);17——氯氰菊酯(Ⅱ);18——氯氰菊酯(Ⅲ);19——氯氰菊酯(IN);20——氟氰戊菊酯(I);21——氟氰戊菊酯(Ⅱ);22——醚菊酯；24——氰戊菊酯(Ⅱ);26——氟胺氰菊酯(Ⅱ);27——溴氰菊酯。ThisstandardisdraftedinaccordancewiththeGB/T1.1—2009.AttentionisrequiredtothecertaincontentThisfileisnotresponsibletoideThisstandardisproposedbyandisunderthechargeoftheCertificationandAccreditationAdminis-trationofthePeople'sRepublicofChina.ThisstandardwasdraftedbyJilinEntry-ExitInspectionandQuarantineBureauofthePeople'sRe-publicofChina,ShanxiEntry-ExitInspectionandQuarantineBureauofthePeople'sRepublicofChi-na,ChineseAcademyofInspectionandQuarantine.MaindraftersofthisstandardareXuePing,WangMingtai,DuLijun,ZhangFeng,ChenYong,SongJie,LiAijun.SN/T2912—2011Gaschromatography-massspecThisstandardspecifiesamultiplytesting-methodbygaschromatography-massspectrometry(GC-MS)fordetermining17pesticideresiduesincluding2,6-diisopropylnaphtalene,tefluthrin,bioalle.thrin,methoprene,resmethrin,bifenthrin,fenpropathrincyhalothrin,acrinathrin,permethrin,cynuthrin,cypermethrin,flucythrinate,ethofenprox,fenvalerate,fluvalinateI,anddeltamethrinetcindairyproductsforexport.Thisstandardisapplicabletomultiplydeterminingandconfirmingfor17pesticideresiduesincluding2,6-diisopropyInaphtalene,tefluthrin.bioallethrin,methoprene.resmethrin,bifenthrin,fenpropathrincyhalothrin,acrinathrin,permethrin,cynuthrin,cypermethritrflucythrinate,ethofenprox,fenvalerate,fluvalinateI,anddeltamethrinetc.inmilk,milkpoyder,condensedmilk,milkfat,cheese,icecreamandwheyforexport.Testsampleisextractedwithacetohitrile,saltWithsodiumchonde,take/theorganicphase,sequentiallycleaned-upwithCnSPEcolumn.andPorisilcolumn.Thegluateiecondensed.dissolvedanddilutedtoacer.tainvolumefordeterminationandcomtmationbyGCMswithpxtemalstandardmethod.Allthereagentsusedshouldbeanalyticallypureunlessotherwisespecified.“Water”isredistilledwa.ter.3.2n-Hexane:Gradeforresidualanalysis.3.3Ethylacetate:Gradeforresidueanalysis.3.4n-Hexane-ethylacetate(9+2,V/V):Volume90mLn-hexaneand20mLethylacetate,mixtohomogenous.3.6Standardsof17pesticidesincludingresmethrinetc.:Purity≥98%.CASNO.seeannexA.3.7Standardstocksolutionsof17pesticidesincludingresmethrinetc.:Accuratelyweighappropri-ateamountofstandards.Dissolveanddilutewithn-Hexanetomakestocksolutionswithafinalcon-3.8Standardworkingsolutionsof17pesticidesincludingresmethrihetc.:Makestandardworkingsolutionofrequiredconcentrationswithblanksamplewhichdonotcontains17targetedpesticides.Thesolutionismadeonlywhenused.3.9CigSPEcolumn:Cis,500mg,3mL3.10FlorisilSPEcolumn:Florisil,500mg,3mL.4Apparatusandequipment4.1GC-MS:Equippedwithelectrg-impactsource(El).4.2Analyticalbalance:Senseoff?.01g4.3Analyticalbalance:Senseof,0.1mg4.4Refiner:10000r/min.4.5Centrifuge:4000r/min.4.7Turbulentmixer.5Preparationandstorageoftestsample5.1PreparationoftestsampleTakeapproximately500gofrepresentativesample.Mixthoroughly.Putintocleancontainers.Sealandlabelthem.Testsamplesshouldbestoredatatemperaturerangedat0℃~4℃.Incourseofsamplingandsam-plepreparation,attentionshallbetakentoavoidcontaminationoranyfactorswhichmaycausethechangeofresidues'content.Weight2.0g(accurateto0.01g)ofmilk,icecream.Add0.5gNaCl,10mLacetonitrile,extractfor60swithrefiner,andcentrifugefor5minat4000r/min.Transfer5.0mLofacetonitrilephaseaccu-telyintoatube.thenevaporatedto1mLat40℃withpressurrclean-upprocedure.Weight2.0g(accurateto0.01g)ofcheese,milkpowder,whey,condensedmilk,milkfat.Add0.5gNaCl,5mLwater,10mLacetonitrile.Thenthesameasabove.6.2.1Cleaning-upwithCiaSPEcolumnPourthecondensedsamplesolutionintooneCgSPEcolumn(3.9)whichhasbeencon5mLacetonitrile.Elutewith4mLacetonitrile.Collecteluateintoone10mLtube;condensetonearlydrynessbyapressuredgasblowingconcentratorat40℃.Dissolvethern-hexanefornextstep.6.2.2Cleaning-upwithflorisilSPEcolumnTransfertheyieldedsamplesolution(6.2.1)intooneflorisilSPEcolumn(3.10),whichhasbeencon-ditionedwith5mLofn-hexane-ethylacetate(3.4).Elutewith5mLn-hexane-ethylacetate,collect40℃.Dissolvetheresiduewith0.5mLofn-hexane-ethylacetateforGC-MSdetermination.6.3.1GC-MSoperatingconditionChromatographiccolumn:TR-5MSsilicacapillarycolumn,30m×0.25mm(i.d.)×0.25μm,orequivalent.lonizationmode:El.Filamentcurrent:25μA.Carriergas:Helium,purity≥99.999%,flowrate1.0mL/min.Injectionmode:Splitlessinjection,setupaftertheautomaticdiversion0.75min.0Injectionvolume;1μL.1Acquiredmode:SIM.3Solventprotectiondelay:8.5min.6.3.2GC-MSdeterminationandBasingonproposedcontentoftargets,selectaworkingstandardsolutionwithsimilarconcentrationtothatofthesamplesolution.Bothresponseof17pesticidesincludingresmethrinetc.intheworkingstandardsolutionandthatinthesamplesolutionshouldbewithinthelinearrangeoftheinstrumentaldetection.Theworkingstandardsolutionisinjectedin-betweentheinjectionsofthesamplesolutionswithidenticalvolume.Theworkingstandardsolutionandthesamplesolutionaretestedaccordingtotheconditiondescribedinsection6.3.1.Arespectedpeakofsamplesolutionatthesameretentiontimeasthatoftheworkingstandardsolutionwillbeconformedifallselectedionsappearinthesub-tractedchromatogram,furthermoretherelativeionicabundancetolerancecanmeettheprescriptionlistedastable1.Onepositiveresultoftestsamplethoid-pesticides'standardsincludingresmethrinetc.areshownasthefigureC.1.abundance/%Allowedrelativedeviation/%20Blanktestwillbeconductedaccordingtotheproceduresabovewithoutsampleaddition.6.5CalculationandexpressionoftheresultCalculatetheresiduecontentofthe17pesticidesincludingresmethrinetc.inthetestsamplebyGC-MSdataprocessororaccordingtotheformula(1).……………………A?xm×1000whereX-theresiduecontentof17pesticidesinthetestsample,mg/kg;A—thepeakarea(orheight)ofJ7pesticidesinthesamplesolution;c—theconcentrationof17pesticidesinthestandardworkingsolution,ug/mL;V—thefinaldilutedvolume,mL;A,—thepeakarea(orheight)of7pesticideslnthestandardWorkingsolution;m—thecorrespondingmasscfthetestsamblerepresentingthefinalsamplesolution,g.Note:Theresultofcalculationshodldbedecuctedkithblankvalue.7LimitofdeterminationandrecoverySeetable2tofindthelimitofdeterminationofthemethod.CompoundSampledeterminationmg/kgmg/kg%2,6-DiisopropylnaphtaleneMilk82.3～108.184.2～110.385.3～109.491.0～103.384.6～112.3Milkpowder0.00581.5～104.293.2～110.00.00580.1～101.594.5～103.2TefluthrinMilk0.Q05.91.2～106.784.2～113.290.5～0585.5～104.290.5～113.4Milkpowder87.5～113.184.5～105.686.6～105.482.3～106.3BioallethrinMilk89.1～113.281.3~113.686.4～111.387.5～96.294.4～99.5Milkpowder67.5～96.189.3～95.6Table2(continued)Compoundmg/kg%MethopreneTable2(continued)%Compounddeterminationmg/kgFortifiedlevelmg/kgrecovery%68.5～90.082.0～105.792.5～110.875.5～106.182.5～105.585.0～105.3Cheese90.8～110.191.0～103.382.5～106.4Permethrin(I,Ⅱ)Milk78.5～91.292.5～10584.0～97.373.0～93.771.5～95.089.5～102.3Milkpowder80.5～110.8851～112.595.7～109.089.5～111.585.0～106.786.1～95.4CynuthrinMilk84.0～95.385.4～95.778.4～92.284.8～115.286.3～112.886.1～105.3Milkpowder78.6～95.088.6～114.385.2～106.3Cheese87.5～112.385.0～98.583.0～92.3Table2(continued)Compounddeterminationmg/kgFortifiedlevelmg/kgrecovery%CypermethrinMilk76.5～94.776.2～102.182.5～110.388.5～104.789.5～108.185.0～118.2Milkpowder85.5～103.585.2～110.485.2～106.390.5～102.382.7～110.275.0～88.6Milk90.7～112.487.0～98.180.1～94.0835～110.588.5～105.383.7～110.8Milkpowder75.5～89.482.5～98.376.2～108.390.5～110.6852～102.395.3～105.2EthofenproxMilk63.5～90.293.1～98.085.4～106.378.5～102.071.6～100.586.0～106.2Milkpowder80.5～93.296.0～118.195.3～112.8Table2(continued)%Table2(continued)CompoundSampleLimitofdeterminationmg/kgFortifiedlevelmg/kgRangeofrecovery%DeltamethrinMilkpowder0.010.0188.5～106.40.0290.5～106.40.282.6～96.2Cheese0.010.0179.5～102.40.0290.5～120.50.286.3～102.1(Normative)No.CASNo.Formula12,6-DiisopropyInaphtalene24157-81-1C?H??2TefluthrinC?H??CIF?O?3BioallethrinC??H??O?4Methoprene40596-69-8C?H?O5ResmethrinC??H??O?6Bifenthrin82657-04-3C?H??CIF?O?7Fenpropathrin64257-84-7C??HgNO?8Cyhalothrin68085-85-8C?H??CIF?NO?9AcrinathrinC??H??F?NO?C??H??Cl?O?Permethrin(Ⅱ)Cyfluthrin(I)68359-37-5C?H??Cl?FNO?Cyfluthrin(Ⅱ)Cyfluthrin(Ⅲ)Cyfluthrin(N)Cypermethin(I)C?H??Cl?NO?Cypermethin(Ⅲ)Cypermethin(NyFlucythrinate(I)Flucythrinate(ⅡEtofenprox80844-07-1C??HaO?Fenvalerate(I)Fenvalerate(Ⅱ)Fluvalinate(I)69409-94-5C??H?CIF?N?O?Fluvalinate(Ⅱ)DeltamethrinC?H??Br?NO?No.12,6-Diisopropylnaphtalene.2Stage2:12.0min~18.0min3Bioallethrin4MethopreneStage3:18.0min～21.2min56Bifenthrin7FenpropathrinStage4:21.2min~22.5min89Stage5:22.5min~24.0minPermethrin(IDPermethrin(Ⅱ)Stage6:24.0min～26.2minFlucythrinate(I)Flucythrinate(Ⅱ)TableB.1(continued)PeakNo.CompoundRentionminlonFragmentsQuatitationQualificationAbundanceRatioS