GCMS农药的一齐分析法.doc

1. 适用范围适用于制品，蔬菜中农药的检测。2. 编制依据依据日本厚生劳动省GCMS农药一齐分析法编制。3. 方法原理试样用乙腈提取后，经过净化、浓缩，用丙酮定容后用GCMS测定，外标法定量。4. 试剂4.1 乙腈，色谱级4.2 乙酸乙酯，色谱级4.3 丙酮，色谱级4.4氯化钠，分析纯4.5无水硫酸钠，分析纯4.6甲苯，色谱级4.7磷酸缓冲液 将磷酸二氢钾54.8g，磷酸氢二钾17.5g溶于1L蒸馏水中，PH约为6.05. 仪器设备5.1 Agilent 7890A,5975C5.2 食品加工器 5.3菜刀，案板5.4电子天平5.5均质机5.6布氏漏斗，分液漏斗，普通漏斗，滤纸5.7梨形瓶（250ml，100ml）5.8 锥形瓶（200ml，100ml）5.9 C18 固相萃取柱（1G 6ML）5.10氨基复合柱Carbon/NH2 （500MG 6ML）5.11真空泵6. 分析步骤6.1试料的制备（除不加样品外，试剂空白与样品同步处理）将送交实验室的不少于200克的样品于食品加工器搅细（对于大块状的样品可先用刀切成小块，再放于食品加工器中搅细）。粉碎后的样品装于一次性的塑料袋中备用。6.2提取准确称取10.0g（精确到0.1g）搅细的样品（原料称取20.0g）于均质杯中，加入70mL乙腈，以500010000 rpm 的速度均质5min,后过滤至200ml锥形瓶中；残渣中加入30mL乙腈，再过滤； 两次提取滤液合并到含有7gNaCl 的分液漏斗中；用20ml磷酸缓冲液，冲洗锥形瓶后倒入分液漏斗中；震荡5分钟，静置分层，取乙腈层（上层）；6.3浓缩将乙腈层在40C下减压浓缩至约20mL6.3净化 用乙腈10mL活化固相萃取柱（BE-C18）；将约20ml样品液过萃取柱后，用3mL 乙腈冲洗容器，并作为溶出液过柱子，溶出液约23ml用三角瓶接收；6.4干燥向三角瓶中加无水硫酸钠3-4勺干燥约15min；过滤，用40mL乙酸乙酯（1020ml23回）洗涤三角瓶，过滤，合并滤液；将滤液在40C下减压条件下浓缩，不要完全蒸干6.5净化用1：3的甲苯、乙腈混合液10mL活化固相萃取柱（EVNI-Carb/ LC NH2）；样品用3 ml 1：3的甲苯、乙腈混合液超声溶解，过萃取柱后，用（3+17）mL 1：3 的甲苯、乙腈混合液冲洗容器，并作为溶出液过柱子（分两次）收集溶出液；6.6浓缩将溶出液在减压条件下浓缩至近干，用2mL的丙酮溶解后供GCMS测定。7.分析条件7.1仪器条件a) 色谱柱：HP-5MS，30m250um0.25umb) 流速：1.0 mL/min。c) 程序升温：60保持2 min，以25/min 的速率升温至125，再以10/min的速率升至300保持10min。d) 传输线温度：280。e) 进样口温度：250。f) 进样方式：不分流进样。g) 进样量：2L。h) 电离能量：70 eV。i) 离子源温度：230。j) 扫描模式：SCAN扫描8 . 操作流程图：残渣中加入30ml乙腈过滤2mL丙酮溶解后供GCMS测定溶出液在减压条件下浓缩至近干（3+17）mL 1：3 的甲苯、乙腈冲洗容器，并作为溶出液过柱子（分两次）收集溶出液3 ml 1：3的甲苯、乙腈超声溶解，过萃取柱1：3的甲苯、乙腈混合液10mL活化滤液在40C下减压条件下浓缩至近干40mL乙酸乙酯（1020ml23回）洗涤三角瓶，过滤，合并滤液溶出液约23ml用三角瓶接收三角瓶中加无水硫酸钠3-4勺干燥约15min后过滤3mL 乙腈冲洗容器作为溶出液过柱固相萃取柱（BE-C18）净化20ml磷酸缓冲液，冲洗锥形瓶后倒入分液漏斗乙腈层40C下减压浓缩至约20mL震荡5分钟，静置分层，取乙腈层（上层）合并滤液到含有7gNaCl 的分液漏斗中过滤至200ml锥形瓶中称取样品10.0g约20ml样品液过萃取柱5000-10000转/min，5min乙腈70ml乙腈10mL活化固相萃取柱（EVNI-Carb/ LC NH2）净化9. GCMS农药一齐分析法检测明细序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）1Dichlorvos(DDVP)，Naled敌敌畏(二氯松)1851092200.012Mevinphos速灭磷1271641920.013Methacrifos乙丁烯酰磷 2081802400.014Ethoprophos丙线磷1581392000.015Salithion水杨硫磷2161832010.016Cadusafos硫线磷2131591580.017Phorate甲拌磷2602311210.018Dimethoate乐果87125930.019Terbufos丁硫磷2311031530.0110Cyanophos(CYAP)杀螟腈2431091250.0111Diazinon二嗪磷3041791520.0112Fonofos地虫磷2461371740.0113Phosphamidon磷胺1272641380.0114Isazophos米乐尔2571611720.0115Etrimfos氧嘧啶磷2921812770.0116Dichlofenthion(ECP)除线磷2792232810.0117Chlorpyrifos-methyl甲基毒死蜱2861252880.0118Tolclofos-methyl甲基立枯磷2652672500.0119Parathion-methyl甲基对硫磷2632332000.0120Pirimphos-methyl甲基嘧啶磷2902763050.0121Fenitrothion（MEP)杀螟硫磷2771252600.0122Dimethylvinphos甲基毒虫畏2952972040.0123Malathion马拉硫磷1731271580.0124Chlorpyrifos毒死蜱3142861970.0125Fenthion（MPP)倍硫磷2781691250.0126Parathion对硫磷2912182350.0127Fosthiazate噻唑膦1952832270.0128Chlorfenvinphos(E)毒虫威3232672690.0129Isofenphos异柳磷2131212550.0130Phenthoate(PAP)稻丰散2742461210.0131Quinalphos喹硫磷1461571560.0132Propaphos丙虫磷3042202620.0133Methidathion（DMTP)杀扑磷145853020.0134Tetrachlorvinphos(CVMP)杀虫畏3293313330.0135Butamifos草胺磷2862002320.0136Fenamiphos苯线磷3031542170.0137Prothiofos丙硫磷3092672390.0138Profenofos丙溴磷3391393370.0139Fenslufothion丰索磷2931563080.0140Ethion乙硫磷2311533840.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）41Triazophos三唑磷2572853130.0142Edifenphos克瘟散3101732010.0143Pyridaphenthion哒嗪硫酸3401991880.0144Piperophos派草磷3201401260.0145EPN苯硫磷1571691850.0146Anilofos莎稗磷2261251840.0147Phosalone伏杀磷1823671840.0148Pyraclofos吡唑硫磷3601391940.0149Molinate禾草敌126981870.0150Chlorpropham(Chlor IPC)氯苯胺灵2131271540.0151Benfluralin氟草胺2922642760.0152Dicloran氯硝胺2061761600.0153Atrazine莠去津2002152020.0154Dimethipin落长灵11876540.0155Tri-allate野麦畏2682701860.0156Bromobutide氯甲酰草胺1191202320.0157Simeconazole硅氟唑1212782110.0158Alachlor甲草胺1601882370.0159Dithiopyl氟硫草定3543062860.0160Fenchlorphos皮蝇磷2852871250.0161Quinoclamine灭藻醌2071722090.0162Cyanazine草净津2252122400.0163Bromofos溴柳氯苯胺3313291250.0164Fthalide四氯苯酞2432452720.0165Fipronil氟虫清3673693510.0166Endosulfan硫丹2413392390.0167Flutolanil氟酰胺1733231450.0168Chlorfenson杀螨酯3021111750.0169Isoprothiolane稻瘟灵2042902310.0170Tribufos脱叶磷1691702020.0171Myclobutanil腈菌唑1791811500.0172Kresoxim-methyl亚胺菌1161312060.0173Buprofezin噻嗪酮1051721750.0174Cyflufenamid环氟菌胺2944122230.0175Diclobutrazol苄氯三唑醇2702721590.0176Chlorfenapyr氟唑虫清4082472490.0177Azaconazole戊环唑2172191730.0178Bifenthrin联苯菊酯1811661650.0179Bromopropylate溴螨酯3411851830.0180Fenpropathrin甲氰菊酯1813492650.0181Bifenox治草醚 3413433100.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）82Clomeprop氯甲酰草胺2881481200.0183cyhalofop-butyl氰氟草酯2563572290.0184Acrinathrin氟酯菊酯1812892080.0185Pyrazophos吡菌磷2212323730.0186Fenarimol氯苯嘧啶醇 1392192510.0187Fluquinconazole氟喹唑3403422980.0188Cafenstrole唑草胺1001671880.0189Cyfluthrin氟氯氰菊酯1632062260.0190Halfenprox卤醚菊酯2652631830.0191Flucythrinate氟氰戊菊酯1991572250.0192Fenvalerate氰戊菊酯1672251810.0193Fluvalinate氟胺氰菊酯2502521810.0194Difenoconazole苯醚甲环唑3232653250.0195Deltamethrin溴氰菊酯1812532550.0196Azoxystrobin腈嘧菌酯3443883450.0197Dichlobenil敌草腈1711731000.0198Etridiazole土菌灵2111832130.0199Tecnazen四氯硝基苯2612032150.01100Demeton-S mrthyl砜吸磷1091421250.01101Ethalfluralin乙丁烯氟灵2763162920.01102Trifluralin氟乐灵3062642900.01103Dicrotophos百治磷127192670.01104Monocrotophos久效磷1271921640.01105Thiometon甲基乙拌磷2461581250.01106Quintozene五氯硝基苯2952372490.01107Propyzamide戊炔草胺1731751450.01108Tefluthrin七氟菊酯1771971410.01109Disulfoton乙拌磷881862740.01110Vinclozolin乙烯菌核利125931260.01111Thiobencarb(Benthiocarb)杀草丹2851872120.01112Chlorthal-dimethyl氯酞酸二甲酯1001252570.01113Triadimefon三唑酮3012993320.01114Isocarbophos水胺硫磷2081812100.01115Nitrothal-isopropyl酞菌酯136941130.01116Pendimethalin胺硝草2362122540.01117Penconazol戊菌唑2522812530.01118Pyrifenox比芬诺2481592500.01119Allethrin丙烯菊酯2621871710.01120mecarbam安硫磷131973290.01121Triadimenol三唑醇1681121280.01122Dimethamethrin异戊乙净2122132550.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）123Procymidone氟霉利2832852120.01124Oxadiazon恶草酮2581753020.01125Thifluzamide噻呋酰胺4494474290.01126Uniconazole P烯效唑2341312360.01127Oxyfluorfen乙氧氟草醚2523613020.01128Bupirimate白特粉2732081930.01129Isoxathion异恶唑硫磷3131051770.01130Pyriminobac methyl嘧草醚3022563300.01131Fluacrypyrim嘧螨酯1451893200.01132Sulprophos硫灭克磷3221401560.01133Trifloxystrobin肟菌酯1161312220.01134Carbophenothion三硫磷3422963440.01135Cyanofenphos苯腈磷1691411850.01136Quinoxyfen喹氧灵2372723070.01137Diflufenican吡氟草胺2663942460.01138Pyributicarb稗草畏1651081810.01139Phosmet亚胺硫磷1601611330.01140Tetradifon四氯杀螨砜3561592290.01141Cyhalothrin氯氟氰菊酯1811974490.01142Permethrin氯菊酯1831841650.01143Pyridaben哒螨灵1471483090.01144Cypermethrin氯氰菊酯1631652090.01145Pyrimidifen嘧螨醚1841861850.01146DCIP二氯异丙醚45771210.01147Allidochlor草多索138132560.01148Propachlor毒草胺120931760.01149Diphenylamine二苯胺1691681670.01150Desmedipham甜安宁1811351220.01151Simazine西玛津2011861730.01152Terbacil特曹定1611171630.01153Iprobenfos(IBP)丙基喜乐松204912460.01154Dimethenamid噻吩草胺2301542030.01155Acetochlor乙草胺2231621740.01156Metalaxyl甲霜灵2062492200.01157Promethrin扑草净1842412260.01158Terbutryn特丁净2261852410.01159Esprocarb禾草畏222162910.01160Metolachlor异丙甲草胺1622382400.01161Diethofencarb乙霉威2672251510.01162Tetraconazole四克利3363383370.01163Diphenamid双苯胺1671652390.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）164Cyprodinil嘧菌环胺2242252100.01165Dimepiperate呱草丹2122132550.01166Butachlolr丁草胺1191451120.01167Paclobutrazol多效唑1761882370.01168Fenothiocarb苯硫威2361251670.01169Napropamide萘丙酰草胺271721280.01170Pretilachlor丙草胺1622022620.01171Methominostrobin苯氧菌胺1911962260.01172Flusilazole氟哇唑2333152340.01173Fenoxanil禾草灵1892931910.01174Cyproconazol环丙唑醇2221391250.01175Chlorobenzilate乙酯杀螨醇2512531390.01176Mepronil灭锈胺269119910.01177Carfentrazone-ethyl唑酮草酯3123403300.01178Benalaxyl苯霜灵1481762340.01179Propiconazole丙环唑1732592610.01180Tenylchlor噻吩草胺 1271412880.01181Tebuconazole戊唑醇2501252520.01182Bioresmethrin卡呋菊酯1231711430.01183Etoxazole乙螨唑3002043300.01184Fenoxycarb苯氧威1161862550.01185Tebfenpyrad吡螨胺3331713180.01186Butafenacil氟丙嘧草酯3313331800.01187Ethofenprox醚菊酯1631353760.01188Flumioxazin丙炔氟草胺3542872590.01189Indoxacarb噁二唑虫1502182640.01190Biphenyl敌鼠好1541531520.01191BHC（，-BHC）六六六2001082010.01192Swep灭草灵2191811830.01193Lindene（-BHC）林丹（-六六六）2191811830.01194Pyroquilon咯奎酮1731301440.01195Phenothiol酚硫杀2441551250.01196Oxabetrinil解草腈1031151290.01197Propanil敌稗1611632170.01198Metribuzin嗪草酮1981991440.01199Simetryn西草净 2131701550.01200Ametryn莠灭净2272122280.01201Bromacil除草定2052072310.01202Dichlofluanid抑菌灵2241231670.01203Diclocymet双氯氰菌胺2772211730.01204Methoprene烯虫酯1111531750.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）205Thiamethoxam噻虫嗪2121822470.01206Ethyclozate吲唑酯/吲熟酯1651672380.01207Triclamide水杨菌胺1481211200.01208Hxaconazole己唑醇2141752160.01209Fludioxonil咯菌腈2481541820.01210Nitrofen除草醚2832852020.01211Chlorpropylate丙酯杀螨醇2511392530.01212Oxadixyl恶霜灵1631321330.01213CNP邻苯基苯酚3172892360.01214Propargite（BPPS)炔螨特1351731070.01215Piperonyl butoxide胡椒基丁醚1761491770.01216Nitralin磺乐灵3162743000.01217Captafol敌菌丹791831070.01218Iprodione异菌脲3143161870.01219Tetramethrin胺菊酯1641231070.01220Bromuconazole糠菌唑1732142950.01221Bifenazate联苯肼酯3002581990.01222Furametpyr福拉比1572912980.01223Pentoxazone环戊恶草酮2851872870.01224Pyriproxyfen蚊蝇醚136226960.01225Mefenacet苯噻草胺1922981200.01226Fenoxaprop-ethyl恶唑禾草灵2883612610.01227Bitertanol联苯三唑醇1701681410.01228Fenbuconazole腈苯唑1981291250.01229Silafluofen硅醚菊酯2862582870.01230Famoxadone恶唑菌酮3302241960.01231EPTC丙草丹1891321600.01232Butylate丁草特1461561740.01233Chlormefos氯甲硫磷1542341210.01234Crimidine杀鼠嘧啶1561711580.01235OPP草枯醚1701691410.01236Xylylcarb灭杀威3222022660.01237Sulfotep治瞑磷1731891910.012382,6-Dichlorobenzamide2,6-二氯苯甲酰胺2701972710.01239Dioxathion敌恶磷1981991830.01240Pyrimethanil二甲嘧菌胺153184960.01241Prohydrojasmon茉莉酸诱导体3182612340.01242Tebupirimfos丁基嘧啶磷3222022660.01243MCPB ethyl禾田净115872110.01244Benfuresate呋草黄1632561350.01245Terbucarb特草克2052202060.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）246Cinmethylin环庚草醚1051231690.01247Fenpropimorph丁苯吗啉128129700.01248Carbetamide卡草胺2361651060.01249Chlorthiophos虫螨磷2222573600.01250Diniconazol烯唑醇2682702320.01251Pyraflufen-ethyl吡草醚4123492890.01252Lenacil环草定1531101360.01253Chloridazon杀草敏2212201050.01254Chlomethoxynil氯硝醚3132662830.01255Indanofan茚草酮3101743400.01256Phenothrin苯醚菊酯1831231840.01257Leptophos对溴磷3773751710.01258Azinphos ethyl乙基谷硫磷1601321040.01259Dialifos氯亚胺硫磷2083572100.01260Spirodiclofen螺螨酯3122593140.01261Oxpoconazole fumarate富马酸恶咪唑2941792080.01262Quizalofop-ethyl精喹禾灵2993722430.01263Dimethomorph烯酰吗啉3013873030.01264Tolfenpyrad唑虫酰胺3831711970.01265Fluthiacet-methyl氟噻乙草酯403405840.01266Chlorneb地茂散1932082060.01267Isoprocarb(MIPC)异丙威121136910.01268XMC克死威1221071210.01269Propoxur,PHC安丹1521101110.01270Chlorethoxyfos异柳磷2633012710.01271Di-allate燕麦敌2342361280.01272Carbofuran虫螨威1641491310.01273Furilazole解草呋2202622220.01274Chlorbufam(BIPC)氯草灵2231711440.01275Propazine扑灭津2142291720.01276Clomazone异恶草酮2041251270.01277Benoxacor解草酯2591201760.01278Spiroxamine葚孢菌素1001981260.01279Ethofumesate乙呋草黄2071612860.012802-(1-Naphthylacetamide)2 -（1-萘乙酰胺）1411851150.01281IsofenphosOxon氧异柳磷2292011210.01282Chlozolinate乙菌利2593311880.01283Thiabendazole噻菌灵2011742020.01284Bromophos-ethyl乙基溴硫磷3593033310.01285Chlorbenside氯杀螨1252681270.01286Disulfoton乙拌磷2131531850.01序号英文名中文名定量离子Q1Q2方法检出限（mg/kg）287Imazametha benzmethyl ester咪草酸甲酯1872142560.01288Flutriafol粉唑醇2191231640.01289Coumaphos蝇毒磷3622263340.01290Pyrazoxyfen苄草唑105230.02291TCMTB氰硫基甲硫基苯并噻唑1802381670.01292Flamprop-methyl麦草氟甲酯105772760.01293Tricyclazole三环唑1891621180.01294Carboxine萎锈灵235