中華人民共和國出入境檢驗(yàn)檢疫行業(yè)標(biāo)準(zhǔn)進(jìn)出口糧谷和油籽中多種有機(jī)磷農(nóng)藥殘留量的檢測方法氣相色譜串聯(lián)質(zhì)譜法2006-01-26發(fā)布2006-08-16實(shí)施國家質(zhì)量監(jiān)督檢驗(yàn)檢疫總局I本標(biāo)準(zhǔn)的附錄A為規(guī)范性附錄，附錄B和附錄C為資料性附錄。本標(biāo)準(zhǔn)由國家認(rèn)證認(rèn)可監(jiān)督管理委員會(huì)提出并歸口。本標(biāo)準(zhǔn)系首次發(fā)布的出入境檢驗(yàn)檢疫行業(yè)標(biāo)1進(jìn)出口糧谷和油籽中多種有機(jī)磷農(nóng)藥殘留量的檢測方法氣相色譜串聯(lián)質(zhì)譜法1范圍本標(biāo)準(zhǔn)規(guī)定了進(jìn)出口糧谷和油籽中55種有機(jī)磷農(nóng)藥殘留量的氣相色譜-質(zhì)譜檢測方法。本標(biāo)準(zhǔn)適用于進(jìn)出口糙米、玉米、大豆、花生仁中55種有機(jī)磷農(nóng)藥殘留量的測定和確證。試樣用水-丙酮均質(zhì)提取或二氯甲烷快速溶劑提取，經(jīng)二氯甲烷液-液分配，以凝膠色譜柱凈化，再經(jīng)活性炭固相柱凈化，洗脫液濃縮并溶解定容后，供氣相色譜-質(zhì)譜檢測，外標(biāo)法定量。3試劑和材料除另有規(guī)定外，所用試劑均為分析純，水為二次蒸餾水。3.7.無水硫酸鈉：650℃灼燒4h,貯于密封容器中備用。3.1055種有機(jī)磷農(nóng)藥標(biāo)準(zhǔn)品：純度均≥95%。3.11標(biāo)準(zhǔn)儲(chǔ)備溶液：分別準(zhǔn)確稱取適量的每種農(nóng)藥標(biāo)準(zhǔn)品(見附錄A),用丙酮分別配制成濃度為3.12混合標(biāo)準(zhǔn)工作溶液：根據(jù)需要再用丙酮逐級稀釋成適用濃度的系列混合標(biāo)準(zhǔn)工作溶液。4儀器和設(shè)備4.1制樣工具4.2分析儀器4.2.1氣相色譜-質(zhì)譜儀(GC-MSD):配有質(zhì)量選擇檢測器。4.2.2凝膠色譜儀(GPC):配有單元泵和餾分收集器。4.2.3快速溶劑提取儀(ASE):配有樣品池和接受瓶。4.2.4均質(zhì)器：8000r/min～24000r/mi25.1試樣制備5.1.1糧谷類將樣品按四分法縮分至1kg,用磨碎機(jī)(4.1.1)全部磨碎并通過2.0mm圓孔篩?；靹?，均分成兩將樣品按四分法縮分至500g,用粉碎機(jī)(4.1.2)粉碎，使全部通過2.0mm圓孔篩?；靹?，均分成糧谷和油籽類試樣于0℃~4℃保存。在抽樣及制樣的操作過程中，必須防止樣品受到污染或發(fā)生6.1.1方法1(均質(zhì)提取)6.1.2方法2(ASE快速溶劑提取)b)壓力：1500Pa;將濃縮提取液轉(zhuǎn)移至250mL分液漏斗中，加入150mL氯化鈉水溶液和50mL二氯甲烷(ASE提前無需加二氯甲烷),振搖3min,靜置分層，收集二氯甲烷相。水相再用2×50mL二氯甲烷重復(fù)提取6.2.2凝膠色譜(GPC)凈化3b)流動(dòng)相：環(huán)己烷十乙酸乙酯(1+1);將5mL待凈化液按6.2.2.1規(guī)定的條件進(jìn)行凈化，合并餾分收集器中的收集液于50mL濃縮瓶用6mL正己烷預(yù)淋洗活性炭固相萃取柱(3.9),將樣液傾入柱中，用2mL正己烷洗滌，然后用20mL正己烷-乙酸乙酯(2+3)進(jìn)行洗脫。收集全部洗脫液于50mL濃縮瓶中，于40℃水浴中旋轉(zhuǎn)濃縮k)選擇監(jiān)測離子(m/z):參見表1和附錄B;通道時(shí)間/min選擇離子(amu)194,136,1852125,127,142,156,185,200,2463231,246,274,292,3044169,173,263,264,265,277,278,279,285,289,290,297,3145145,169,193,274,309,314,323,329,359,374,3776160,292,310,313,323,342,3847160,182,360,362.373,377如果樣液與標(biāo)準(zhǔn)工作溶液的選擇離子色譜圖中，在相同保留時(shí)間有色譜峰出現(xiàn)，則根據(jù)附錄B中每種有機(jī)磷農(nóng)藥選擇離子的種類及其豐度比進(jìn)行確證。在上述氣相色譜-質(zhì)譜條件下，55種有機(jī)磷農(nóng)45(規(guī)范性附錄)55種有機(jī)磷農(nóng)藥種類表序號農(nóng)藥名稱……--英文名稱化學(xué)分子式1甲胺磷MethamidophosC?H?NO?PS2敵敵畏Dicblorvas3乙酰甲胺磷AcephateCH?NO?PS4氧化樂果5甲基內(nèi)吸磷DemetonmethylC?H??O?PS?6丙線磷EthoprophosCHO?PS?7二溴磷NaledC?H?Br?Cl?O,P8百治磷DicrotophosC,H??NO?P9久效磷Monocrotophos甲基乙拌磷ThiometonC?H??O?PS樂果DimethoateC?H??NO?PS?特丁磷C?HzO?PS?地蟲硫磷FonofosC?H??OPS?二嗪磷DiazinonC?H??N?O?PS乙拌磷DisulfotonCH?O?PS?乙嘧硫磷除線磷DichlofenthionC?H?Cl?O?PS磷胺ⅡPhosphamidonⅡC?H?CINO?P甲基對硫磷Parathion-methylCH?NO?PS甲基立枯磷Tolclofos-methylC,H?Cl?O?PS皮蠅磷Fenchlorphos000299-84-3CH?Cl?O?PS砜吸磷Oxydemeton-methylC?H?O?PS?殺螟硫磷Fenitrothionv000122-14-5C?H??NO?PS甲基嘧啶磷PirimiphosmethylC?H??N?O?PS馬拉硫磷Malathion000121-75-5C?H??O?PS?倍硫磷FenthionCl?H??O?PS?毒死蜱ChlorpyrifosC?H??Cl?NO?PS水胺硫磷C?H?NO?PS毒壤磷TrichloronateCH?Cl?O?PS甲基溴硫磷BromophosC?HgBrCl?O?PS6表A.1(續(xù))序號農(nóng)藥名稱英文名稱化學(xué)分子式乙基安定磷023505-41-1C?H??N?O?PS毒蟲畏Chlorfenvinphos000470-90-6C??H?Cl?O?P稻豐散Phenthoate002597-03-7C?H?OPS?丁烯磷Crotoxyphos007700-17-6C??H??O?P殺撲磷Methidathion000950-37-8C?H?N?O,PS?乙基溴硫磷Bromophos-ethyl004824-78-6C?H?BrCl?O?PS殺蟲畏Tetrachlorvinphos000961-11-5CmH?CLO,P碘硫磷018181-70-9丙硫磷Prothiofos034643-46-4C?tH??Cl?O?PS?丙溴磷Profenofos041198-08-7C??H?BrCIO?PS脫葉磷000078-48-8C??H?OPS?豐索磷Fensulfothion000115-90-2C?H?O?PS?乙硫磷Ethion000563-12-2CHnOPS三唑磷Triazophos024017-47-8Ci?H??N?O?PS三硫磷Carbophenothion000786-19-6C??H?CIO?PS?敵瘟磷Edifenphos017109-49-8CHO,PS亞胺硫磷Phosmet000732-11-6C?H??NO?PS?苯硫磷002104-64-5C?H??NO.PS保棉磷Azinphosmethyl000086-50-0C?H??N?O?PS?伏殺硫磷Phosalone002310-17-0C?H??ClNO?PS?溴苯磷Leptophos021609-90-5C??H?BrCl?O?PS益棉磷Azinphos-ethyl002642-71-9C?H??N?O?PS?吡菌磷Pyrazophos013457-18-6C?H??N?O?PS吡唑硫磷Pyraclofos077458-01-6C??H??CIN?O?PS蠅毒磷Coumaphos000056-72-4C??H??ClO?PS7(資料性附錄)表B.1序號農(nóng)藥名稱保留時(shí)間/min特征碎片離子(amu)測定低限/(pg/g)定量定性豐度比1甲胺磷111、126、141100:10:07:500.052敵敵畏109.187.22237:100!12:070.053乙酰甲胺磷125、142、183100:11:12:060.024氧化樂果126、141、213100:12!11+060.105甲基內(nèi)吸磷143、169、230100:48:14:140.106丙線磷158.168、20023:100:14:400.0057二溴磷109、220、30117:100:07:100.108百治磷109、193、237100:10+12:090.059久效磷192、193,223100:16:10:060.02甲基乙拌磷157、158、185100:60:80:300.10樂果125、143,15721:100:20:100.01特丁磷186、203、288100:14:10:110.005地蟲硫磷109、137、17455:100:52:080.10二嗪磷179、276、28962:100:29:110.02乙拌磷153、186.24585:100:95:150.02乙嘧硫磷181、263,277100:65:11:330.10除線磷223、225、251100:77:29:390.02磷胺Ⅱ127、193、22773:100111:120.05甲基對硫磷20.08200、233、246100:10:07:080.10甲基立枯磷20.26125、175、250100:16:05:110.05皮蠅磷20.63247、275、287100:38:56:680.10砜吸磷20.84109、125,142100:56:32:100.02殺螟硫磷21.20214、247、260100:10:06:540.10甲基嘧啶磷21.33262、276、305100:25:82:730.05馬拉硫磷21.73158,173、25607:40:100:100.05·倍硫磷22.03169,245、263100:18:08:060.05毒死蜱22.14197、258、29163:68:34:1000.01水胺硫磷22.44203、214、23083:33123:1000.10毒壤磷22.63196,269、271100:17:88:610.058表B.1(續(xù))序號農(nóng)藥名稱保留時(shí)間/min特征碎片離子(amu)測定低限/(pg/g)定量定性豐度比甲基溴硫磷22.82213,250、316100:06:05:020.10乙基安定磷23.20290、304、318100:25:71:990.02毒蟲畏23.98267、269、29565:100:65:230.02稻豐散24.12246、247、320100:26:14:080.05丁烯磷24.47127、166、19444:100:23:080.05殺撲磷24.65125、146、302100:15:08:060,02乙基溴硫磷24.84242.303、331100:37:83:380.10殺蟲畏25.22204,240、331100:06:10:960.10碘硫磷25.89250、259、362100:09:05:050.01丙硫磷26.09239、267、269100:29:92:380.10丙溴磷26.24208、297、33939:100:38:920.05脫葉磷26.45169、226、25813:100:28:300.10豐索磷28.25236.264,308100:16:15:160.02乙硫磷28.88199、231、3380.10三唑磷29.54161、257、28515:100:40:290.02三硫磷29.83157、199、29645:100:26:080.05敵瘟磷29.9974:100:36:160.10亞胺硫磷32.85133,161,317100:07:11:080.05苯硫磷33.17157、169、18516:100:60:330.10保棉磷34.95132,157、161100:75+08:110.05伏殺硫磷35.07182、183,36932:100:11:130.10溴苯磷35.16171、375,379100:100:73:290.10益棉磷36:96132、186、20786:100:06;050.05吡菌磷37.24221、232,26523:100:37:100.05吡唑硫磷37.50194、210、290100:58:10:080.10蠅毒磷39.17226、306、334100:53:11:150.109(資料性附錄)55種有機(jī)磷農(nóng)藥標(biāo)準(zhǔn)物氣相色譜-質(zhì)譜選擇離子色譜圖(GC-MSD)3——乙酰甲胺磷；5——甲基內(nèi)吸磷：7-—二溴磷；10-—甲基乙拌磷；12—-特丁磁；15-—乙拌磷；16--乙嘧硫磷；18-—磷胺Ⅱ;26-倍硫磷：27毒死蜱；29--毒壤磷；30——甲基溴硫磷：32-—毒蟲畏；33—-稻豐散；36——乙基溴硫磷；43---乙硫磷；46---敵瘟磷；52-—益棉磷；annex.ThisstandardwasdraftedbytheJilinEntry-ExitInspectionandQuarantineBureauofthePeople'sRepublicofChina.ThismaindrafterofthisstandardisMuJun,WangMingtai,ZouMingqiang,WuJian,ZhaoQingsong,MaShumin,LuChunmei.Note:ThisEnglishversion,atranslationfromtheChinesetext,issolelyforguldanceDeterminationoforganophosphrouspesticidesresiduesGaschromatographymassspectrometrymethodThisstandardspecifiesthedeterminationandconfirmationof55organophosphrouspesticidesresi-duesbygaschromatography-massspectrometryincerealsandoilseedsforimportandexport.CleanedupbypassingthroughonGPCandact3.1Acetone:pesticidegrade.3.3Cyclohexane:pesticidegrade.3.5n-Hexane:pesticidegrade.3.8Sodiumchlorideaq3.10Organophosphrouspesticidesstandard:Purity≥95%.“3.11Standardstocksolution:AccuratelyweighanadequateamountofOrganophosphrouspesticidesstandard(seeannexA)anddissolveinasmallvolumeofacetone.Dilutewithacetonetoformastandardstocksolutionof100pg/mL~1000pg/mLinconcentration.4.1Samplingtools4.1.1Grinder.4.1.5Samplecontainer:Wi4.2.3Acceleratedsolvente4.2.5Rotaryvacuumevaporator.4.2.6Columnofanhydroussodiumsulfate:7.5cm~1.5cm(i.d.),packedwith5cmheightofan-hydroussodiumsulfate.4.2.7Conicalflask:250mL,withstopp4.2.10Membranefilter:0.45μm.testsamples,sealandlabel.cleansamplecontainers,sealandlabel.Thetestsamplesofcerealsandoilseedsshouldbestoredbelow0C～4℃.Inthecourseofsampling6.1.1Method1(Homogenizeextra6.1.2.1ASEoperatinWeighca20g(accurateto0.1g)ofthetestsampleintoasamplepoolwithstopper,proceedassection6.1.2.1.filter.b)Mobilephase:Cyclohexane-ethylacetate(1+1);6.2.3SPECleanupn-hexaneforGC-MSdeterminationandconfirmation.Time/min12125,127,142,156,1853231,246,274,292,3044169,173,263,264,265,277,278,279,285,289,290,297,3145145,169,193,274,309,314,323,329,359,374,3776160,292,310,313,3237ardworkingsolutionwithsimilarpeakheighttothatofthesamplesoluforGC-MSchromatogram(TIC)ofthestandard,seefigureA.1inannexA.As-thepeakarea(height)ofperTableA.1No.PesticidesPesticidesCAS.No1甲胺磷Methamidophos010265-92-6C?H?NO?PS2敵敵畏Dichlorvos000062-73-7C?H?Cl?O?P3乙酰甲胺磷Acephate030560-19-1C?H?NO?PS4氧化樂果Omethoate001113-02-6C?H?NO?PS5甲基內(nèi)吸磷Demetonmethyl000919-86-8C?H??O?PS?6丙線磷Ethoprophos013194-48-4C?H?O?PS?7二溴磷Naled000300-76-5C?H,Br?Cl?O?P8百治磷Dicrotophos000141-66-2—9久效磷Monocrotophos006923-22.4C?H??NO?P甲基乙拌磷Thiometon000640-15-3C?H?gO?PS?樂果Dimethoate000060-51-5C?H??NO?PS?特丁磷Terbufos013071-79-9C?H??O?PS?地蟲硫磷Fonofos000944-22-9C?H??OPS?二嗪磷Diazinon000333-41-5C?H??N?O?PS乙拌磷Disulfoton000298-04-4C?H??O?PS?乙嘧硫磷Etrimfos038260-54-7C?H?N?O?PS除線磷Dichlofenthion000097-17-6C?HCl?O?PS磷胺ⅡPhosphamidonⅡ013171-21-6C?H??CINO?P甲基對硫磷Parathion-methyl000298-00-0CH?NO?PS甲基立枯磷Tolclofos-methyl057018-04-9CH??Cl?O?PS皮蠅磷Fenchlorphos000299-84-3CH?ClO?PS砜吸磷Oxydemeton-methyly017040-19-6殺螟硫磷Fenitrothion000122-14-5C?H??NOPS甲基嘧啶磷Pirimiphosmethyl029232-93-7C??H?N?O?PS馬拉硫磷Malathion000121-75-5C?H??O?PS?倍硫磷Fenthion000055-38-9C?H?O?PS?毒死蜱Chlorpyrifos002921-88-2CH??Cl?NO?PS水胺硫磷Isocarbophos024353-61-5C,,H??NO,PS毒壤磷Trichloronate000327-98-0C?H??Cl?O?PSNo.PesticidesPesticides甲基溴硫磷BromophosC?H?BrCl?O?PS乙基安定磷C?H?N?O?PS毒蟲畏ChlorfenyinphosC??H??ClO?P稻豐散PhenthoateC?H??O?PS?丁烯磷Crotoxyphos殺撲磷MethidathionC?H??N?O?PS乙基溴硫磷Bromophos-ethytC?H??BrCl?O?PS殺蟲畏TetrachlorvinphosC??HCL?O?P碘硫磷丙硫磷ProthiofosC??H??Cl?O?PS?丙溴磷Profenofos脫葉磷TributylphosphororeithioateC??H?OPS?豐索磷FensulfothionC??H?O?PS?乙硫磷C?H??O?P?S?三唑磷TriazophosC?H??N?O?PS三硫磷CarbophenothionC??H??CIO?PS?敵瘟磷Edifenphos亞胺硫磷C??H??NO?PS?苯硫磷保棉磷AzinphosmethylC?H??N?O?PS?伏殺硫磷PhosaloneC??H??CINO?PS?溴苯磷C?H?BrCl?O?PS益棉磷Azinphos-ethylC??H??N?O?PS?吡菌磷PyrazophosC??H?N?O?PS吡唑硫磷PyraclofosC??H??CIN?O?PS蠅毒磷C?HCIO?PSNo.PesticidesTime/minCharacteristicfragmention(amu)Limit/(eg/g)determinationconfirmationabundanceratio1Methamidophos2Dichloryos37:100:12:073Acephate4Omethoate5Demetonmethyl6Ethoprophos23:100:14:407Naled8Dicrotophos9MonocrotophosThiometonDimethoate21:100:20:10TerbufosFonofos55:100:52:08Diazinon62:100:29:11Disulfoton85:100:95:15EtrimfosDichlofenthion223、225、251PhosphamidonⅡ73:100:11:12Parathion-methyl200,233、246Tolclofos-methylFenchlorphos247、275、287Oxydemeton-methylFenitrothion214,247、260Pirimiphosmethyl262、276,305Malathion07:40:100:10FenthionChlorpyrifos63:68:34:100Isocarbophos203、214、23083:33:23:100TrichloronateNo.PesticidesTime/minCharacteristicfragmention(amu)Limit/(pg/g)determinationconfirmationabundanceratioBromophos22.82213、250,316100:06:05:070.10Pirimiphosethyl23.20290、304,318100:25:71:990.02Chlorfenvinphos23.98267.269、29565:100:65:230.02Phenthoate246、247,320°100:26'14:080.05Crotoxyphos24.47127、166、19444:100:23:080.05Methidathion24.65125、146,302100:15+08:060.02Bromophos-ethyl24.84242、303,3310.10Tetrachlorvinphos25.22204、240、331100:06:10:960.10todofenphos25.89250,259,362100:09:05:050.01Prothiofos26.092