謝物的殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法

PAGE84PAGE85《植物性農(nóng)產(chǎn)品中含24種擬除蟲菊酯類共111種農(nóng)藥及其代謝物的殘留量的測(cè)定高效液相色譜-串聯(lián)質(zhì)譜法》的編制說(shuō)明（征求意見稿）1、工作概況1.1任務(wù)來(lái)源、起草單位、起草人本標(biāo)準(zhǔn)是依據(jù)深圳市分析測(cè)試協(xié)會(huì)下達(dá)的由深圳市質(zhì)量安全檢驗(yàn)檢測(cè)研究院（原深圳市農(nóng)產(chǎn)品質(zhì)量安全檢驗(yàn)檢測(cè)中心）承擔(dān)的名稱為《蔬菜和水果中24種擬除蟲菊酯類共111種農(nóng)藥或其代謝物殘留量的測(cè)定超高效液相色譜-串聯(lián)質(zhì)譜法》任務(wù)而研究制定的。項(xiàng)目負(fù)責(zé)單位：深圳市質(zhì)量安全檢驗(yàn)檢測(cè)研究院。項(xiàng)目參加單位：深圳市質(zhì)量安全檢驗(yàn)檢測(cè)研究院。該項(xiàng)目由宋世文負(fù)責(zé)，主要參加人員有：宋世文，宋曉儀，曾定玲。1.2簡(jiǎn)要起草過(guò)程本標(biāo)準(zhǔn)起草人在充分收集、認(rèn)真研究了國(guó)內(nèi)相關(guān)標(biāo)準(zhǔn)及文獻(xiàn)資料的基礎(chǔ)上，分析對(duì)比了國(guó)內(nèi)標(biāo)準(zhǔn)技術(shù)內(nèi)容方面的差異及原因，在遵循先進(jìn)性、科學(xué)性、實(shí)用性的原則下，建立了植物性農(nóng)產(chǎn)品中24種擬除蟲菊酯類共111種農(nóng)藥或代謝物殘留量的測(cè)定超高效液相色譜-串聯(lián)質(zhì)譜法。本方法適用于植物性農(nóng)產(chǎn)品中111種農(nóng)藥或代謝物殘留量的測(cè)定。經(jīng)實(shí)驗(yàn)室論證和分析，該方法的回收率、重復(fù)性和再現(xiàn)性等技術(shù)指標(biāo)均符合標(biāo)準(zhǔn)編制的要求。2.制訂本標(biāo)準(zhǔn)的意義和目標(biāo)2.1、填補(bǔ)國(guó)內(nèi)標(biāo)準(zhǔn)檢測(cè)項(xiàng)目空白：目前國(guó)內(nèi)使用的液相色譜串聯(lián)質(zhì)譜檢測(cè)農(nóng)藥殘留的主要有：GB23200.121-2021和GB/T20769-2008，本標(biāo)準(zhǔn)填補(bǔ)國(guó)內(nèi)檢測(cè)標(biāo)準(zhǔn)中農(nóng)藥殘留液相色譜串聯(lián)質(zhì)譜檢測(cè)18項(xiàng)空白，其中包括常見擬除蟲菊酯類農(nóng)藥殘留檢測(cè)的14項(xiàng)空白，其他常見農(nóng)藥4項(xiàng)空白。填補(bǔ)的18項(xiàng)空白是：1、氯氰菊酯，2、氯氟氰菊酯，3、氟氯氰菊酯，4、芐呋菊酯，5、生物丙稀菊酯，6、苯醚菊酯，7、苯醚氰菊酯，8、醚菊酯，9、氟硅菊酯，10、胺菊酯，11、丙稀菊酯，12、甲醚菊酯，13、炔咪菊酯，14、氟丙菊酯，15、甲基對(duì)硫磷，16、克螨特，17、百菌清，18、三氯殺螨醇。2.2、最大限度覆蓋農(nóng)業(yè)農(nóng)村部例行檢測(cè)的項(xiàng)目：農(nóng)業(yè)農(nóng)村部農(nóng)藥殘留例行檢測(cè)有68個(gè)項(xiàng)目，本標(biāo)準(zhǔn)覆蓋64個(gè)項(xiàng)目，較國(guó)內(nèi)現(xiàn)有標(biāo)準(zhǔn)還多6個(gè)，覆蓋率為91%。2.3、本標(biāo)準(zhǔn)方法檢測(cè)時(shí)間短：由于本方法所需檢測(cè)設(shè)備貴重，資源稀缺，本標(biāo)準(zhǔn)檢測(cè)優(yōu)化時(shí)間設(shè)計(jì)，以最大限度達(dá)到所有組分的優(yōu)化分離和定量定性檢測(cè)，同時(shí)滿足靈敏度工求，最后確定檢測(cè)時(shí)間為8分種。3、本標(biāo)準(zhǔn)中涉及農(nóng)藥類型3.1擬除蟲菊酯類殺蟲劑3.1.1理化性質(zhì)和結(jié)構(gòu)本類農(nóng)藥是模擬天然除蟲菊素合成的一類殺蟲劑，由菊酸、醇、酯鍵三部份組成，但更多數(shù)是以肟醚、醚、酮、烯烴等取代酯鍵的化合物。這類物質(zhì)，多難溶于水，可溶于多種有機(jī)溶劑，對(duì)光熱和酸穩(wěn)定，遇堿(pH>8)時(shí)易分解。目前使用較廣的擬除蟲菊酯類農(nóng)藥只有20多種。常見除蟲菊酯種類有氯氰菊酯、溴氰菊酯、氯氟氰菊酯、氟氯氰菊酯、氰戊菊酯和氯菊酯等等。圖-1：氯氰菊酯結(jié)構(gòu)圖2.1.2異構(gòu)體（以氯氰菊酯為例）氯氰菊酯(cypermethrin)在結(jié)構(gòu)上醇部分與CN基相連的碳原子(α碳)和環(huán)丙烷羧酸部位的1位和3位碳原子均為不對(duì)稱碳原子,因而該化合物有四對(duì)外消旋體(共8個(gè)異構(gòu)體)。其中手性的三碳環(huán)上兩個(gè)H在同側(cè)者稱為順式異構(gòu)體(簡(jiǎn)稱Cis,即5、6、7、8),在異側(cè)者稱為反式異構(gòu)體(簡(jiǎn)稱Trans,即1、2、3、4)。在順式異構(gòu)體中,由于α碳原子的手征性,又分為兩對(duì)外消旋體,其中5和8為一對(duì)外消旋體,6和7為一對(duì)外消旋體。反式異構(gòu)體也是如此,1和4為一對(duì)外消旋體,2和3為一對(duì)外消旋體。表-1：氯氰菊酯的８種異構(gòu)體順?lè)椿瘜W(xué)簡(jiǎn)稱代號(hào)殺蟲活性返式結(jié)構(gòu)Trans(S1R3S)(1)1高效體Trans(S1S3R)2低效或無(wú)效Trans(R1R3S)3低效或無(wú)效Trans(R1S3R)4高效體順式結(jié)構(gòu)Cis(S1R3R)5高效體Cis(S1R3S)6低效或無(wú)效Cis(R1R3R)7低效或無(wú)效Cis(R1R3S)8高效體表-2：８種氯氰菊酯的異構(gòu)體組成及比例名稱組組成順?lè)幢壤馓匦月惹杈挣ィ?+6+7+8）：（1+2+3+4）45:55外消旋體α-氯氰菊酯5:81：1外消旋體β-氯氰菊酯(5+8):(1+4)2：3外消旋體theta-氯氰菊酯1：41：1外消旋體zeta-氯氰菊酯(5+6):(1+2)45:55～55:45內(nèi)消旋體氯氰菊酯、溴氰菊酯、氯氟氰菊酯、氟氯氰菊酯、氯菊酯均有3個(gè)手性C原子，8個(gè)異構(gòu)體。2.1.3同位素與母離子菊酯類農(nóng)藥中經(jīng)常有氯。氯元素有35Cl和37Cl兩種穩(wěn)定同位素。核外電子構(gòu)型都為3S23P5，相對(duì)原子質(zhì)量分別為34.96和36.96，天然豐度分別為76%和24%。正常情況ESI源只有一個(gè)母離子，但由于氯元素同位素的天然豐度高，因而同時(shí)產(chǎn)生足量的兩個(gè)母離子可用于檢測(cè)。如：氯氰菊酯433.1和435.1；溴氰菊酯423和425；氟氯氰菊酯451和453；氯氟氰菊酯467.1和439.1。2.1.4用途本類農(nóng)藥是一類能防治多種害蟲的廣譜神經(jīng)毒素殺蟲劑，毒力比上一代殺蟲劑如有機(jī)氯、有機(jī)磷、氨基甲酸酯類提高多倍，具有強(qiáng)烈的觸殺作用，有些品種兼具胃毒或熏蒸作用，但都沒(méi)有內(nèi)吸作用。2.1.5毒理與不良反應(yīng)擬除蟲菊酯擾亂昆蟲神經(jīng)的正常生理，使之由興奮、痙攣到麻痹而死亡;擬除蟲菊酯缺點(diǎn)是對(duì)魚毒性高。2.2有機(jī)磷類殺蟲劑2.2.1理化性質(zhì)和結(jié)構(gòu)屬于有機(jī)磷酸酯或硫化磷酸酯類化合物，其基本化學(xué)結(jié)構(gòu)式如圖-3。R和Rˊ為烷基、芳基、羥胺基或其他取代基團(tuán)，X為烷氧基、丙基或其它取代基，Y為氧或硫。圖-3：有機(jī)磷殺蟲劑的通式有機(jī)磷殺蟲劑大多呈油狀或結(jié)晶狀，工業(yè)品呈淡黃色至棕色，除敵百蟲和敵敵畏之外，大多是有蒜臭味。少數(shù)溶于水，如甲胺磷；多數(shù)不溶于水，易溶于有機(jī)溶劑如苯、丙酮、乙醚、三氯甲烷及油類，對(duì)光、熱、氧均較穩(wěn)定，但還是存在光化、氧化、熱解、異構(gòu)化現(xiàn)象。多數(shù)是酯或酰胺，遇堿易水解失去毒性。敵百蟲為白色結(jié)晶，能溶于水，遇堿可轉(zhuǎn)變?yōu)槎拘暂^大的敵敵畏。農(nóng)藥劑型主要有乳化劑、可濕性粉劑、顆粒劑和粉劑四大劑型。2.2.1:本項(xiàng)目屬有機(jī)磷類殺蟲劑：甲胺磷、對(duì)硫磷、甲基異柳磷等2.2.2異構(gòu)體許多有機(jī)磷農(nóng)藥的分子中含有手性原子,分子不對(duì)稱,因而有光學(xué)活性,有對(duì)映異構(gòu)體存在。工業(yè)合成的有機(jī)磷農(nóng)藥多數(shù)以消旋體的形式存在,只有少數(shù)被拆分成對(duì)映體，而生物活性卻有很大差別。有的手性原子是磷，如地蟲磷；有的是碳，如馬拉硫磷；有的兩個(gè)同時(shí)存在；有的因雙健有順?lè)到Y(jié)構(gòu)，如速滅磷。異構(gòu)體農(nóng)藥在色譜圖上有可能出現(xiàn)相連的兩個(gè)峰。2.2.3毒理學(xué)和代謝機(jī)理有機(jī)磷農(nóng)藥在體內(nèi)與膽堿酯酶形成磷酰化膽堿酯酶,膽堿酯酶活性受抑制,使酶不能起分解乙酰膽堿的作用,致組織中乙酰膽堿過(guò)量蓄積,使膽堿能神經(jīng)過(guò)度興奮,引起毒蕈堿樣、煙堿樣和中樞神經(jīng)系統(tǒng)癥狀。2.3氨基甲酸酯類殺蟲劑2.3.1理化性質(zhì)和結(jié)構(gòu)氨基甲酸酯類農(nóng)藥殺蟲劑為氨基甲酸的N-甲基取代酯類，有三類：（1）N-甲基氨基甲酸酯(如西維因)；（2）N，N-二甲基氨基甲酸酯(如涕滅威)；（3）氨基甲酸肟酯(如滅多威)。圖4—氨基甲酸酯類農(nóng)藥通式本類農(nóng)藥是在有機(jī)磷農(nóng)藥之后發(fā)展起來(lái)的合成農(nóng)藥，在水中溶解度較高。本類農(nóng)藥一般無(wú)特殊氣味，大多數(shù)品種毒性較有機(jī)磷酸酯類低，一般在酸性條件下較穩(wěn)定，遇堿易分解，暴露在空氣和陽(yáng)光下易分解，在土壤中的半衰期為數(shù)天至數(shù)周，個(gè)別較長(zhǎng)。2.3.2本項(xiàng)目屬氨基甲酸酯類殺蟲劑：克百威、仲丁威、涕滅威等。2.3.3毒理本類農(nóng)藥的毒性機(jī)理和有機(jī)磷類相似，都是哺乳動(dòng)物AchE的阻斷劑，主要是抑制膽堿酯酶活性，使酶活性中心絲氨酸的羥基被氨基甲酰化，因而失去酶對(duì)乙酰膽堿的水解能力，造成組織內(nèi)乙酰膽堿的蓄積而中毒。2.4本項(xiàng)目其他類農(nóng)藥2.4.1新煙堿類殺蟲劑吡蟲啉、啶蟲脒、呋蟲胺、噻蟲嗪。2.4.2苯甲酰脲類殺蟲劑除蟲脲、滅幼脲。2.4.3殺螨劑三氯殺螨醇、噠螨靈、乙螨唑、唑螨酯。2.4.4大環(huán)類酯類殺蟲劑阿維菌素、甲氨基阿維菌素苯甲酸鹽。2.4.5雜類殺蟲劑氟蟲腈、蟲螨腈、氯蟲苯甲酰胺、滅蠅胺。2.4.6三唑類殺菌劑丙環(huán)唑、三環(huán)唑、三唑醇、三唑酮。2.4.7甲氧基丙烯酸酯類殺菌劑吡唑醚菌酯、醚菌酯、嘧菌酯。2.4.8苯并咪唑類殺菌劑多菌靈、甲基硫菌靈。2.4.9雜類殺菌劑百菌清、氟啶脲、腐霉利、甲霜靈、烯酰嗎啉、異菌脲。2.4.10除草劑二甲戊靈、莠滅凈。2.4.11植物生長(zhǎng)調(diào)節(jié)劑多效唑、氯吡脲。2.4.12抗菌素稻豐散。三、國(guó)外、國(guó)內(nèi)有關(guān)標(biāo)準(zhǔn)情況的說(shuō)明目前暫未查詢國(guó)外有關(guān)液相色譜串聯(lián)質(zhì)譜農(nóng)藥殘留含量測(cè)定的相關(guān)標(biāo)準(zhǔn)。國(guó)內(nèi)農(nóng)產(chǎn)品中農(nóng)藥殘留檢測(cè)早期使用較為廣泛的有NY/T761-2008《蔬菜和水果中有機(jī)磷、有機(jī)氯、擬除蟲菊酯和氨基甲酸酯類農(nóng)藥多殘留的測(cè)定》，GB/T20769-2008《水果和蔬菜中450種農(nóng)藥及相關(guān)化學(xué)品殘留量的測(cè)定液相色譜-串聯(lián)質(zhì)譜法》?，F(xiàn)在，上述方法逐步被如下這些方法替代，這些方法是：GB23200.8-2016《水果和蔬菜中500種農(nóng)藥及相關(guān)化學(xué)品殘留量的測(cè)定氣相色譜-質(zhì)譜法》，GB23200.121-2021《植物源性食品中331種農(nóng)藥及其代謝物殘留量的測(cè)定液相色譜-質(zhì)譜聯(lián)用法》、GB23200.113-2018《植物源性食品中208種農(nóng)藥及其代謝物殘留量的測(cè)定氣相色譜-質(zhì)譜聯(lián)用法》、GB23200.112-2018《植物源性食品中9種氨基甲酸酯類農(nóng)藥及其代謝物殘留量的測(cè)定液相色譜-柱后衍生法》、GB23200.116-2019《植物源性食品中90種有機(jī)磷類農(nóng)藥及其代謝物殘留量的測(cè)定氣相色譜法》。但目前就液相色譜-串聯(lián)質(zhì)譜而言，現(xiàn)有的國(guó)標(biāo)方法存在一個(gè)明顯的缺點(diǎn)，那就是菊酯類農(nóng)藥，特別是最常用的氯氰菊酯、氯氟氰菊酯、氟氯氰菊酯等沒(méi)有列入，解決此問(wèn)題成為本項(xiàng)目主要目標(biāo)。四、標(biāo)準(zhǔn)的制（修）訂原則本標(biāo)準(zhǔn)是按照《深圳市分析測(cè)試協(xié)會(huì)團(tuán)體標(biāo)準(zhǔn)管理辦法》的要求進(jìn)行編制的，遵循先進(jìn)性、科學(xué)性、實(shí)用性的原則對(duì)新標(biāo)準(zhǔn)進(jìn)行編制。本標(biāo)準(zhǔn)注重科學(xué)性和可操作性的結(jié)合，利于推廣應(yīng)用。五、定量限、線性范圍和相關(guān)系數(shù)確定的依據(jù)5.1定量限、線性范圍和相關(guān)系數(shù)等的依據(jù)取空白基質(zhì)，添加111種農(nóng)藥0.005，0.01，0.02，0.05，0.1，0.2，0.5mg/kg（三氯殺螨醇為0.1，0.25，0.5，1，2.5mg/kg），當(dāng)被分析物的相關(guān)系數(shù)最大，并大于0.99，確定適合的5個(gè)點(diǎn)為線性范圍。本標(biāo)準(zhǔn)線性范圍見表5-2。當(dāng)被分析物≤0.1mg/kg的回收率在60～120%之間，＞0.1mg/kg回收率80-110%；同時(shí)信噪比S/N大于10；確定最低的濃度為定量限；參考驗(yàn)證單位結(jié)果，確保能夠驗(yàn)證；適合GB2763判定要求；最后盡量放寬定量限，使方法應(yīng)用的范圍最廣。本標(biāo)準(zhǔn)定量限為0.005-0.1mg/kg（見表5-1）。表5-1：方法定量限中文順號(hào)農(nóng)藥名稱驗(yàn)證單位定量限mg/kg實(shí)驗(yàn)室定量限mg/kgS/N方法定量限mg/kg13-羥基克百威0.0050.0053040.0052阿維菌素0.010.005280.013胺菊酯0.0050.005450.014百菌清0.010.01490.015苯醚菊酯0.020.01140.026苯醚氰菊酯0.020.005100.027吡蟲啉0.0050.0053170.0058吡唑醚菌酯0.0050.0054210.0059芐呋菊酯0.010.005360.0110丙環(huán)唑0.0050.0052120.00511丙烯菊酯0.010.005470.0112丙溴磷0.0050.0051740.00513蟲酰肼0.0050.0053210.00514除蟲菊素A0.020.005210.0215除蟲菊素B0.020.02160.0216除蟲脲0.0050.005400.0117噠螨靈0.0050.0054970.00518稻豐散0.0050.0051530.00519敵百蟲0.0050.0058700.0120敵敵畏0.0050.005620.0121啶蟲脒0.0050.0057990.00522毒死蜱0.0050.005960.00523對(duì)硫磷0.010.005350.0124多菌靈0.0050.0059710.00525多效唑0.0050.0051440.00526惡霜靈0.0050.0051820.00527二甲戊靈0.0050.005690.0128二嗪農(nóng)0.0050.0055230.00529呋蟲胺0.0050.0051450.00530伏殺硫磷0.0050.0051810.00531氟胺氰菊醚0.0050.005870.00532氟丙菊酯0.010.005200.0133氟蟲腈0.0050.00512150.00534氟蟲腈砜0.0050.0057540.00535氟蟲腈啞砜0.0050.0056900.00536氟啶脲0.0050.005780.0137氟硅菊酯0.050.0113.50.0538氟甲腈0.0050.0053540.00539氟氯氰菊酯0.0050.00516.70.0140氟氰戊菊酯0.010.0110.20.0141腐霉利0.0050.01250.0142甲胺磷0.0050.0055600.00543甲拌磷0.0050.0052260.00544甲拌磷砜0.0050.0054320.00545甲拌磷亞砜0.0050.0058350.00546甲基對(duì)硫磷0.0050.01130.0147甲基硫菌靈0.010.0053710.0148甲基異硫磷0.0050.0053150.00549甲醚菊酯0.0050.01350.0150甲萘威0.010.0052490.0151甲氰菊酯0.0050.0052600.00552甲霜靈0.0050.0053410.00553甲維鹽0.0050.005770.0154久效磷0.0050.0053730.00555抗蚜威0.0050.0053950.00556克百威0.0050.0052460.00557克螨特0.010.005380.0158喹硫磷0.0050.005280.0159樂(lè)果0.0050.0054360.00560聯(lián)苯菊酯0.0050.00510830.00561磷胺0.0050.0053030.00562硫環(huán)磷0.050.05260.0563氯吡脲0.020.005500.0264氯蟲苯甲酰胺0.0050.0051220.00565氯氟氰菊酯0.0050.00520.60.0166氯菊酯0.0050.0052060.00567氯氰菊酯0.0050.005690.0168氯唑磷0.0050.0055620.00569馬拉硫磷0.0050.0051590.00570咪酰胺0.0050.0051910.00571醚菊酯0.0050.00521130.00572嘧菌酯0.0050.0056180.00573嘧霉胺0.0050.0052440.00574滅多威0.0050.0053150.00575滅線磷0.050.05110.0576滅蠅胺0.010.005340.0177滅幼脲0.0050.0051850.00578氰戊菊酯0.010.005340.0179炔咪菊酯0.010.01260.0180噻蟲嗪0.0050.0058740.00581三氯殺螨醇0.182三唑磷0.0050.0056000.00583三唑酮0.0050.005670.0184殺蟲脒0.0050.0051450.00585殺螟硫磷0.010.01150.0186殺撲磷0.0050.0051810.00587生物芐呋菊酯0.0050.005350.0188生物丙烯菊酯0.010.005400.0189霜霉威0.0050.0053940.00590霜脲氰0.0050.0051830.00591水胺硫磷0.010.005280.0192特丁磷0.0050.0051650.00593特丁磷砜0.0050.0051490.00594特丁磷亞砜0.0050.0053320.00595涕滅威0.0020.0051580.00596涕滅威砜0.0020.0051650.00597涕滅威亞砜0.0020.0051350.00598戊菌唑0.0050.0051600.00599烯酰嗎啉0.0050.0051710.005100辛硫磷0.0050.0051480.005101溴氰菊酯0.0050.005850.01102啞胺硫磷0.0050.0052850.005103氧化樂(lè)果0.0050.0055220.005104乙螨唑0.0050.0055080.005105乙酰甲胺磷0.0050.005770.01106異菌脲0.050.005170.05107茚蟲威0.0050.051040.005108蠅毒磷0.0050.0054080.005109莠滅凈0.0050.0055210.005110治螟磷0.0050.005290.01111仲丁威0.0050.0052910.005表5-2：線性范圍與相關(guān)系數(shù)中文順號(hào)農(nóng)藥名稱線性范圍mg/L相關(guān)系數(shù)13-羥基克百威0.005-0.10.9952阿維菌素0.005-0.20.9963胺菊酯0.005-0.20.9904百菌清0.01-0.20.9975苯醚菊酯0.01-0.20.9966苯醚氰菊酯0.005-0.20.9917吡蟲啉0.005-0.10.9948吡唑醚菌酯0.005-0.10.9969芐呋菊酯0.005-0.20.99410丙環(huán)唑0.005-0.10.99411丙烯菊酯0.005-0.20.99612丙溴磷0.005-0.10.99913蟲酰肼0.005-0.10.99714除蟲菊素A0.005-0.20.99115除蟲菊素B0.02-0.50.99916除蟲脲0.005-0.20.99117噠螨靈0.005-0.10.99418稻豐散0.005-0.10.99819敵百蟲0.005-0.20.99620敵敵畏0.005-0.20.99621啶蟲脒0.005-0.10.99922毒死蜱0.005-0.10.99723對(duì)硫磷0.005-0.10.99824多菌靈0.005-0.10.99425多效唑0.005-0.10.99126惡霜靈0.005-0.10.99227二甲戊靈0.005-0.20.99728二嗪農(nóng)0.005-0.10.99229呋蟲胺0.005-0.10.99230伏殺硫磷0.005-0.10.99631氟胺氰菊醚0.005-0.10.99232氟丙菊酯0.005-0.10.99033氟蟲腈0.005-0.10.99534氟蟲腈砜0.005-0.10.99135氟蟲腈啞砜0.005-0.10.99236氟啶脲0.005-0.20.99637氟硅菊酯0.01-0.20.99138氟甲腈0.005-0.10.99539氟氯氰菊酯0.005-0.20.99440氟氰戊菊酯0.01-0.20.99741腐霉利0.01-0.20.99542甲胺磷0.005-0.10.99543甲拌磷0.005-0.10.99644甲拌磷砜0.005-0.10.99645甲拌磷亞砜0.005-0.10.99846甲基對(duì)硫磷0.01-0.20.99947甲基硫菌靈0.005-0.20.99848甲基異硫磷0.005-0.10.99849甲醚菊酯0.01-0.20.99850甲萘威0.005-0.10.99151甲氰菊酯0.005-0.10.99552甲霜靈0.005-0.10.99953甲維鹽0.005-0.20.99254久效磷0.005-0.10.99955抗蚜威0.005-0.10.99756克百威0.005-0.10.99557克螨特0.005-0.10.99858喹硫磷0.005-0.20.99859樂(lè)果0.005-0.10.99460聯(lián)苯菊酯0.005-0.10.99561磷胺0.005-0.10.99162硫環(huán)磷0.05-0.50.99463氯吡脲0.005-0.10.9964氯蟲苯甲酰胺0.005-0.10.99765氯氟氰菊酯0.005-0.20.99566氯菊酯0.005-0.10.99767氯氰菊酯0.005-0.10.99268氯唑磷0.005-0.10.99469馬拉硫磷0.005-0.10.99770咪酰胺0.005-0.10.999371醚菊酯0.005-0.10.99472嘧菌酯0.005-0.10.99373嘧霉胺0.005-0.10.99574滅多威0.005-0.10.99875滅線磷0.05-0.50.99976滅蠅胺0.005-0.10.99477滅幼脲0.005-0.10.99678氰戊菊酯0.005-0.20.99779炔咪菊酯0.01-0.20.99080噻蟲嗪0.005-0.10.99681三氯殺螨醇0.1-10.99182三唑磷0.005-0.10.99683三唑酮0.005-0.20.99284殺蟲脒0.005-0.10.99385殺螟硫磷0.01-0.20.99686殺撲磷0.005-0.20.99387生物芐呋菊酯0.005-0.10.99588生物丙烯菊酯0.005-0.20.99889霜霉威0.005-0.10.99990霜脲氰0.005-0.10.99291水胺硫磷0.005-0.10.99892特丁磷0.005-0.10.99793特丁磷砜0.005-0.10.99494特丁磷亞砜0.005-0.10.99795涕滅威0.005-0.10.99696涕滅威砜0.005-0.10.99997涕滅威亞砜0.005-0.10.99298戊菌唑0.005-0.10.99399烯酰嗎啉0.005-0.10.999100辛硫磷0.0050.10.994101溴氰菊酯0.005-0.20.996102啞胺硫磷0.005-0.10.999103氧化樂(lè)果0.005-0.10.991104乙螨唑0.005-0.10.991105乙酰甲胺磷0.005-0.10.994106異菌脲0.05-0.20.995107茚蟲威0.005-0.10.998108蠅毒磷0.005-0.10.994109莠滅凈0.005-0.10.999110治螟磷0.005-0.10.995111仲丁威0.005-0.10.994六、結(jié)果分析和結(jié)論6.1七種基質(zhì)檢測(cè)結(jié)果回收率和變異系數(shù)分析和結(jié)論以甘藍(lán)、菠菜、西紅柿、荔枝、橙、香菇、平菇為為基質(zhì)，進(jìn)行加標(biāo)回收試驗(yàn)，111種農(nóng)藥加標(biāo)濃度分別為低濃度:0.005-0.1mg/kg;中濃度：0.05-0.2mg/kg；高濃度0.1-1mg/kg。不同基質(zhì)檢測(cè)結(jié)果、回收率和變異系數(shù)見第七部份。七種基質(zhì)檢測(cè)結(jié)果分析結(jié)論見表6-1（數(shù)據(jù)來(lái)源見第七部份表7.1-1至7.7-6）。表6-1：七種基質(zhì)檢測(cè)結(jié)果回收率和變異系數(shù)分析和結(jié)論序號(hào)蔬菜名稱添加濃度范圍mg/kg回收率%范圍GB27404回收率要求回收率分析結(jié)論變異系數(shù)CV%范圍GB27404要求CV%范圍變異系數(shù)（CV%）分析結(jié)論1甘藍(lán)低濃度:0.005-0.160.8-115.2GB27404要求回收率范圍：被測(cè)組分含量＜0.1mg/kg:60-120%;被測(cè)組分含量≥0.1mg/kg,80-110%回收率符合GB27404在相應(yīng)添加濃度的要求。0.7-21.3GB27404要求：被測(cè)組分含量≤0.001mg/kg：CV%≤43。被測(cè)組分含量>0.001和≤0.01mg/kg：CV%≤30被測(cè)組分含量>0.01和≤0.1mg/kg：CV%≤21被測(cè)組分含量>0.1和≤1：CV%≤15被測(cè)組分含量>1CV%≤11不同基質(zhì)檢測(cè)值變異系數(shù)符合GB27404在相應(yīng)添加濃度的要求。中濃度:0.05-0.273.3-113.90.8-14.0高濃度:0.1-180.3-109.40.4-10.82菠菜低濃度:0.005-0.160.4-116.11.7-20.4中濃度:0.05-0.262.6-115.11.6-16.8高濃度:0.1-180.3-108.70.9-10.53西紅柿低濃度:0.005-0.161.5-109.83.7-19.0中濃度:0.05-0.260.7-113.83.1-20.7高濃度:0.1-180.1-109.62.3-13.24荔枝低濃度:0.005-0.161.2-119.83.8-20.1中濃度:0.05-0.266.7-119.91.3-14.8高濃度:0.1-180.2-109.92.2-10.95橙低濃度:0.005-0.160.0-119.42.1-20.3中濃度:0.05-0.262.3-119.90.9-20.1高濃度:0.1-180.2-109.92.2-10.96香菇低濃度:0.005-0.161.0-119.44.5-19.0中濃度:0.05-0.266.7-119.91.3-14.8高濃度:0.1-180.2-109.91.4-10.67平菇低濃度:0.005-0.160.0-118.61.5-18.4中濃度:0.05-0.266.5-119.91.9-17.9高濃度:0.1-180.1-109.81.8-9.76.2本方法59個(gè)組分與GB23200.113氣相色譜-串聯(lián)質(zhì)譜檢測(cè)分析和結(jié)論（數(shù)據(jù)來(lái)源見第七部份表7.8-1至7.8-2）表6-2：本方法59個(gè)組分與GB23200.113氣相色譜-串聯(lián)質(zhì)譜檢測(cè)分析和結(jié)論蔬菜名稱添加濃度范圍mg/kg檢測(cè)方法回收率%范圍相對(duì)相差%范圍GB27404要求回收率范圍GB27404要求精密度范圍回收率和相對(duì)相差分析結(jié)論大白菜低濃度:0.01GB23200.11365.0-111.00.2-28.4被測(cè)組分含量＜0.1mg/kg:60-120%;≤30回收率和精密度符合GB27404要求本項(xiàng)目74.1-114.8中濃度:0.05GB23200.11372.0%-118.00.3-21.0≤21本項(xiàng)目71.7-119.9七：七種基質(zhì)檢測(cè)結(jié)果、回收率和變異系數(shù)7.1、甘藍(lán)添加不同濃度檢測(cè)結(jié)果和回收率以甘藍(lán)為基質(zhì)，進(jìn)行加標(biāo)回收試驗(yàn)，111種農(nóng)藥加標(biāo)濃度分別低濃度為:0.005-0.1mg/kg;中濃度：0.05-0.2mg/kg；高濃度0.1-1mg/kg。表7.1-1：甘藍(lán)低濃度:0.005-0.1mg/kg檢測(cè)結(jié)果編號(hào)組分添加濃度mg/kgX1mg/kgX2mg/kgX3mg/kgX4mg/kgX5mg/kgX6mg/kg平均值mg/kgCV%13-羥基克百威0.0050.0052800.0053600.0051600.0052800.0049500.0053200.0052252.92阿維菌素0.010.0113400.0078400.0103600.0104600.0088400.0084400.00954714.33胺菊酯0.010.0108000.0103000.0106600.0105400.0101200.0106000.0105032.44百菌清0.010.0105800.0086200.0096400.0079600.0094600.0061000.00872718.05苯醚菊酯0.020.0220400.0212400.0209200.0212800.0208400.0195600.0209803.96苯醚氰菊酯0.020.0198000.0195600.0209600.0170400.0209200.0192000.0195807.37吡蟲啉0.0050.0052100.0049100.0050600.0052100.0047400.0050300.0050273.68吡唑醚菌酯0.0050.0053000.0043000.0042500.0048900.0052300.0052300.0048679.99芐呋菊酯0.010.0095400.0107000.0105000.0096400.0105800.0105400.0102505.010丙環(huán)唑0.0050.0053000.0050300.0052300.0051000.0051900.0052100.0051771.911丙烯菊酯0.010.0105800.0092800.0101800.0099400.0104000.0103600.0101234.612丙溴磷0.0050.0051600.0049300.0050700.0052200.0053900.0046700.0050734.913蟲酰肼0.0050.0053600.0051800.0052200.0052000.0050900.0052600.0052181.714除蟲菊素I0.020.0213200.0214400.0212400.0207200.0214000.0208800.0211671.415除蟲菊素II0.020.0218800.0191200.0212000.0198800.0208000.0214000.0207135.016除蟲脲0.010.0087600.0070000.0096400.0096200.0077000.0097800.00875013.317噠螨靈0.0050.0051400.0043700.0038000.0038500.0031800.0050100.00422518.018稻豐散0.0050.0052500.0053000.0052700.0052400.0053500.0051800.0052651.119敵百蟲0.010.0109200.0104400.0107400.0106400.0103800.0101400.0105432.620敵敵畏0.010.0107200.0106600.0106000.0102600.0104800.0105800.0105501.521啶蟲脒0.0050.0053300.0048200.0051600.0052200.0053800.0051100.0051703.922毒死蜱0.0050.0050700.0051000.0051400.0050900.0053500.0048400.0050983.223對(duì)硫磷0.010.0102600.0106000.0102000.0099800.0103200.0105200.0103132.224多菌靈0.0050.0033100.0050400.0041700.0031700.0039300.0049200.00409019.225多效唑0.0050.0052200.0048600.0050300.0043600.0045800.0053200.0048957.626惡霜靈0.0050.0039900.0053500.0045300.0048400.0046400.0052000.00475810.327二甲戊靈0.010.0090200.0094600.0081600.0095200.0105200.0101400.0094708.828二嗪農(nóng)0.0050.0052700.0051900.0053200.0051200.0050700.0052800.0052081.929呋蟲胺0.0050.0037400.0036800.0035300.0038100.0036200.0042100.0037656.330伏殺硫磷0.0050.0052400.0053500.0053300.0052000.0051300.0052800.0052551.631氟胺氰菊醚0.0050.0057600.0052600.0051800.0051400.0053200.0052000.0053104.332氟丙菊酯0.010.0109200.0106800.0102000.0106000.0102600.0099800.0104403.433氟蟲腈0.0050.0055000.0037400.0053800.0053900.0052100.0052800.00508313.134氟蟲腈砜0.0050.0037300.0039900.0044000.0039800.0046200.0042300.0041587.835氟蟲腈啞砜0.0050.0053700.0048100.0052600.0051600.0048800.0049600.0050734.436氟啶脲0.010.0103600.0108400.0100600.0094600.0072400.0078200.00929715.637氟硅菊酯0.050.0534000.0539000.0527000.0538000.0536000.0531000.0534170.838氟甲腈0.0050.0045700.0036300.0049800.0051900.0051100.0052800.00479313.039氟氯氰菊酯0.010.0106400.0105600.0099600.0101400.0101600.0102600.0102872.640氟氰戊菊酯0.010.0080800.0097600.0100400.0093200.0101800.0075000.00914712.141腐霉利0.010.0098200.0104000.0105600.0099000.0100000.0097200.0100673.342甲胺磷0.0050.0053100.0052200.0051200.0053900.0050900.0048400.0051623.843甲拌磷0.0050.0051000.0043400.0036900.0052600.0033400.0051400.00447818.344甲拌磷砜0.0050.0045600.0048400.0047600.0045300.0042600.0041500.0045176.045甲拌磷亞砜0.0050.0052900.0047800.0048700.0050600.0051800.0052800.0050774.246甲基對(duì)硫磷0.0050.0054600.0052100.0052500.0050400.0051600.0052800.0052332.747甲基硫菌靈0.010.0107600.0108000.0106000.0100600.0105200.0105800.0105532.548甲基異硫磷0.0050.0051200.0052900.0050500.0052100.0045000.0040700.0048739.949甲醚菊酯0.010.0103000.0101800.0103000.0097400.0104800.0097600.0101273.050甲萘威0.010.0107200.0106400.0106800.0105600.0106200.0105200.0106230.751甲氰菊酯0.0050.0042200.0050900.0045900.0048000.0038600.0046200.0045309.652甲霜靈0.0050.0040900.0053400.0041000.0050700.0044600.0042500.00455211.753甲維鹽0.010.0086200.0083000.0079200.0080800.0090400.0088000.0084605.154久效磷0.0050.0053300.0052700.0053900.0053900.0052200.0051600.0052931.855抗蚜威0.0050.0053800.0047900.0053600.0051300.0049800.0053300.0051624.656克百威0.0050.0046600.0051300.0052900.0044000.0051500.0051300.0049607.057克螨特0.010.0097400.0091800.0102400.0096400.0096800.0091600.0096074.258喹硫磷0.010.0106600.0104000.0107000.0107000.0105600.0106600.0106131.159樂(lè)果0.0050.0042700.0052000.0051900.0049300.0050700.0051000.0049607.160聯(lián)苯菊酯0.0050.0052200.0049000.0050800.0051400.0045900.0045400.0049125.961磷胺0.0050.0047500.0043000.0049200.0050800.0033500.0041300.00442214.462硫環(huán)磷0.050.0528000.0460000.0512000.0508000.0472000.0441000.0486837.063氯吡脲0.020.0223200.0187600.0196800.0172000.0163200.0210400.01922011.864氯蟲苯甲酰胺0.0050.0049900.0049600.0052800.0052300.0053700.0048500.0051134.165氯氟氰菊酯0.010.0062800.0089400.0093000.0090600.0084200.0061000.00801718.066氯菊酯0.0050.0048200.0046800.0041500.0051000.0042200.0040500.0045039.467氯氰菊酯0.010.0088000.0076600.0107400.0088200.0069600.0082000.00853015.268氯唑磷0.0050.0044200.0053800.0041900.0038300.0044600.0044200.00445011.569馬拉硫磷0.0050.0047800.0048700.0041500.0052600.0038700.0034200.00439215.870咪酰胺0.0050.0048600.0030400.0049300.0052000.0046000.0051800.00463517.571醚菊酯0.0050.0047100.0048800.0051600.0051300.0049500.0051100.0049903.572嘧菌酯0.0050.0054100.0052100.0051100.0050600.0049800.0051100.0051472.973嘧霉胺0.0050.0044600.0053200.0053100.0043800.0050900.0045400.0048509.074滅多威0.0050.0052100.0049800.0051800.0053400.0053100.0051600.0051972.575滅線磷0.050.0534000.0517000.0510000.0481000.0454000.0516000.0502005.876滅蠅胺0.010.0100800.0106800.0105400.0101000.0104600.0106200.0104132.577滅幼脲0.0050.0053700.0053300.0053200.0052500.0053400.0050600.0052782.278氰戊菊酯0.010.0103000.0087600.0090800.0094400.0100400.0104000.0096707.079炔咪菊酯0.010.0083200.0093000.0101600.0094000.0106200.0103800.0096978.880噻蟲嗪0.0050.0052400.0049800.0050600.0043200.0051500.0047600.0049186.881三氯殺螨醇0.10.0998000.0878000.0806000.0852000.0758000.0862000.0859009.482三唑磷0.0050.0048800.0041000.0042900.0041100.0035700.0039700.00415310.483三唑酮0.010.0108600.0101600.0099800.0106000.0105200.0104600.0104303.084殺蟲脒0.0050.0052400.0051900.0049500.0051700.0050500.0052400.0051402.385殺螟硫磷0.010.0098600.0083200.0103400.0102600.0090600.0087200.0094279.086殺撲磷0.0050.0048400.0044100.0049000.0046700.0048700.0048600.0047584.087生物芐呋菊酯0.010.0101800.0090000.0085200.0098800.0096800.0098000.0095106.588生物丙烯菊酯0.010.0072200.0084600.0102200.0071600.0067600.0106400.00841019.989霜霉威0.0050.0042700.0032400.0031700.0046900.0051800.0052300.00429721.390霜脲氰0.0050.0052000.0048900.0042400.0040100.0035000.0052500.00451515.791水胺硫磷0.010.0107400.0105200.0102800.0100800.0106800.0103200.0104372.492特丁磷0.0050.0051000.0051400.0052500.0052800.0052200.0050200.0051681.993特丁磷砜0.0050.0045800.0044900.0045400.0044300.0037700.0041700.0043307.294特丁磷亞砜0.0050.0049100.0049100.0050400.0044800.0046700.0045200.0047554.995涕滅威0.0050.0048500.0046100.0049200.0050300.0044300.0045200.0047275.196涕滅威砜0.0050.0043500.0043800.0042900.0042300.0040000.0040700.0042203.697涕滅威亞砜0.0050.0053160.0048520.0048400.0045640.0047480.0048600.0048635.198戊菌唑0.0050.0046160.0044320.0042880.0044840.0039640.0042640.0043415.299烯酰嗎啉0.0050.0047120.0051120.0049600.0051480.0048920.0050640.0049813.3100辛硫磷0.0050.0038360.0044200.0044280.0041720.0040560.0038920.0041346.1101溴氰菊酯0.010.0089120.0087600.0100800.0099520.0093680.0084880.0092607.0102啞胺硫磷0.0050.0052440.0050720.0051320.0051120.0050960.0050920.0051251.2103氧化樂(lè)果0.0050.0052880.0049440.0051600.0051680.0051840.0050800.0051372.3104乙螨唑0.0050.0050520.0050760.0051640.0050960.0053040.0051560.0051411.8105乙酰甲胺磷0.010.0094320.0088880.0092560.0092320.0093200.0091680.0092162.0106異菌脲0.050.0517200.0503200.0461600.0474800.0456000.0519200.0488675.8107茚蟲威0.0050.0042840.0040720.0036680.0051480.0043560.0045760.00435111.4108蠅毒磷0.0050.0044680.0052120.0037840.0041480.0051000.0043000.00450212.3109莠滅凈0.0050.0047480.0045920.0039240.0041120.0050280.0042200.0044379.5110治螟磷0.010.0104480.0094720.0100640.0104640.0088880.0098480.0098646.2111仲丁威0.0050.0042760.0051680.0048600.0046240.0051680.0051400.0048737.5最大值21.3最小值0.7表7.1-2：甘藍(lán)低濃度:0.005-0.1mg/kg回收率編號(hào)組分添加濃度mg/kg回收率%1回收率%2回收率%3回收率%4回收率%5回收率%6平均值%CV%13-羥基克百威0.005105.6107.2103.2105.699.0106.4104.52.92阿維菌素0.01113.478.4103.6104.688.484.495.514.33胺菊酯0.01108.0103.0106.6105.4101.2106.0105.02.44百菌清0.01105.886.296.479.694.661.087.318.05苯醚菊酯0.02110.2106.2104.6106.4104.297.8104.93.96苯醚氰菊酯0.0299.097.8104.885.2104.696.097.97.37吡蟲啉0.005104.298.2101.2104.294.8100.6100.53.68吡唑醚菌酯0.005106.086.085.097.8104.6104.697.39.99芐呋菊酯0.0195.4107.0105.096.4105.8105.4102.55.010丙環(huán)唑0.005106.0100.6104.6102.0103.8104.2103.51.911丙烯菊酯0.01105.892.8101.899.4104.0103.6101.24.612丙溴磷0.005103.298.6101.4104.4107.893.4101.54.913蟲酰肼0.005107.2103.6104.4104.0101.8105.2104.41.714除蟲菊素A0.02106.6107.2106.2103.6107.0104.4105.81.415除蟲菊素B0.02109.495.6106.099.4104.0107.0103.65.016除蟲脲0.0187.670.096.496.277.097.887.513.317噠螨靈0.005102.887.476.077.063.6100.284.518.018稻豐散0.005105.0106.0105.4104.8107.0103.6105.31.119敵百蟲0.01109.2104.4107.4106.4103.8101.4105.42.620敵敵畏0.01107.2106.6106.0102.6104.8105.8105.51.521啶蟲脒0.005106.696.4103.2104.4107.6102.2103.43.922毒死蜱0.005101.4102.0102.8101.8107.096.8102.03.223對(duì)硫磷0.01102.6106.0102.099.8103.2105.2103.12.224多菌靈0.00566.2100.883.463.478.698.481.819.225多效唑0.005104.497.2100.687.291.6106.497.97.626惡霜靈0.00579.8107.090.696.892.8104.095.210.327二甲戊靈0.0190.294.681.695.2105.2101.494.78.828二嗪農(nóng)0.005105.4103.8106.4102.4101.4105.6104.21.929呋蟲胺0.00574.873.670.676.272.484.275.36.330伏殺硫磷0.005104.8107.0106.6104.0102.6105.6105.11.631氟胺氰菊醚0.005115.2105.2103.6102.8106.4104.0106.24.332氟丙菊酯0.01109.2106.8102.0106.0102.699.8104.43.433氟蟲腈0.005110.074.8107.6107.8104.2105.6101.713.134氟蟲腈砜0.00574.679.888.079.692.484.683.27.835氟蟲腈啞砜0.005107.496.2105.2103.297.699.2101.54.436氟啶脲0.01103.6108.4100.694.672.478.293.015.637氟硅菊酯0.05106.8107.8105.4107.6107.2106.2106.80.838氟甲腈0.00591.472.699.6103.8102.2105.695.913.039氟氯氰菊酯0.01106.4105.699.6101.4101.6102.6102.92.640氟氰戊菊酯0.0180.897.6100.493.2101.875.091.512.141腐霉利0.0198.2104.0105.699.0100.097.2100.73.342甲胺磷0.005106.2104.4102.4107.8101.896.8103.23.843甲拌磷0.005102.086.873.8105.266.8102.889.618.344甲拌磷砜0.00591.296.895.290.685.283.090.36.045甲拌磷亞砜0.005105.895.697.4101.2103.6105.6101.54.246甲基對(duì)硫磷0.005109.2104.2105.0100.8103.2105.6104.72.747甲基硫菌靈0.01107.6108.0106.0100.6105.2105.8105.52.548甲基異硫磷0.005102.4105.8101.0104.290.081.497.59.949甲醚菊酯0.01103.0101.8103.097.4104.897.6101.33.050甲萘威0.01107.2106.4106.8105.6106.2105.2106.20.751甲氰菊酯0.00584.4101.891.896.077.292.490.69.652甲霜靈0.00581.8106.882.0101.489.285.091.011.753甲維鹽0.0186.283.079.280.890.488.084.65.154久效磷0.005106.6105.4107.8107.8104.4103.2105.91.855抗蚜威0.005107.695.8107.2102.699.6106.6103.24.656克百威0.00593.2102.6105.888.0103.0102.699.27.057克螨特0.0197.491.8102.496.496.891.696.14.258喹硫磷0.01106.6104.0107.0107.0105.6106.6106.11.159樂(lè)果0.00585.4104.0103.898.6101.4102.099.27.160聯(lián)苯菊酯0.005104.498.0101.6102.891.890.898.25.961磷胺0.00595.086.098.4101.667.082.688.414.462硫環(huán)磷0.05105.692.0102.4101.694.488.297.47.063氯吡脲0.02111.693.898.486.081.6105.296.111.864氯蟲苯甲酰胺0.00599.899.2105.6104.6107.497.0102.34.165氯氟氰菊酯0.0162.889.493.090.684.261.080.218.066氯菊酯0.00596.493.683.0102.084.481.090.19.467氯氰菊酯0.0188.076.6107.488.269.682.085.315.268氯唑磷0.00588.4107.683.876.689.288.489.011.569馬拉硫磷0.00595.697.483.0105.277.468.487.815.870咪酰胺0.00597.260.898.6104.092.0103.692.717.571醚菊酯0.00594.297.6103.2102.699.0102.299.83.572嘧菌酯0.005108.2104.2102.2101.299.6102.2102.92.973嘧霉胺0.00589.2106.4106.287.6101.890.897.09.074滅多威0.005104.299.6103.6106.8106.2103.2103.92.575滅線磷0.05106.8103.4102.096.290.8103.2100.45.876滅蠅胺0.01100.8106.8105.4101.0104.6106.2104.12.577滅幼脲0.005107.4106.6106.4105.0106.8101.2105.62.278氰戊菊酯0.01103.087.690.894.4100.4104.096.77.079炔咪菊酯0.0183.293.0101.694.0106.2103.897.08.880噻蟲嗪0.005104.899.6101.286.4103.095.298.46.881三氯殺螨醇0.199.887.880.685.275.886.285.99.482三唑磷0.00597.682.085.882.271.479.483.110.483三唑酮0.01108.6101.699.8106.0105.2104.6104.33.084殺蟲脒0.005104.8103.899.0103.4101.0104.8102.82.385殺螟硫磷0.0198.683.2103.4102.690.687.294.39.086殺撲磷0.00596.888.298.093.497.497.295.24.087生物芐呋菊酯0.01101.890.085.298.896.898.095.16.588生物丙烯菊酯0.0172.284.6102.271.667.6106.484.119.989霜霉威0.00585.464.863.493.8103.6104.685.921.390霜脲氰0.005104.097.884.880.270.0105.090.315.791水胺硫磷0.01107.4105.2102.8100.8106.8103.2104.42.492特丁磷0.005102.0102.8105.0105.6104.4100.4103.41.993特丁磷砜0.00591.689.890.888.675.483.486.67.294特丁磷亞砜0.00598.298.2100.889.693.490.495.14.995涕滅威0.00597.092.298.4100.688.690.494.55.196涕滅威砜0.00587.087.685.884.680.081.484.43.697涕滅威亞砜0.005106.397.096.891.395.097.297.35.198戊菌唑0.00592.388.685.889.779.385.386.85.299烯酰嗎啉0.00594.2102.299.2103.097.8101.399.63.3100辛硫磷0.00576.788.488.683.481.177.882.76.1101溴氰菊酯0.0189.187.6100.899.593.784.992.67.0102啞胺硫磷0.005104.9101.4102.6102.2101.9101.8102.51.2103氧化樂(lè)果0.005105.898.9103.2103.4103.7101.6102.72.3104乙螨唑0.005101.0101.5103.3101.9106.1103.1102.81.8105乙酰甲胺磷0.0194.388.992.692.393.291.792.22.0106異菌脲0.05103.4100.692.395.091.2103.897.75.8107茚蟲威0.00585.781.473.4103.087.191.587.011.4108蠅毒磷0.00589.4104.275.783.0102.086.090.012.3109莠滅凈0.00595.091.878.582.2100.684.488.79.5110治螟磷0.01104.594.7100.6104.688.998.598.66.2111仲丁威0.00585.5103.497.292.5103.4102.897.57.5最大值115.221.3最小值60.80.7表7.1-3：甘藍(lán)中濃度:0.05-0.2mg/kg檢測(cè)結(jié)果編號(hào)組分添加濃度mg/kgX1X2X3X4X5X6平均值CV%mg/kgmg/kgmg/kgmg/kgmg/kgmg/kgmg/kg13-羥基克百威0.050.053140.049030.051960.051560.050330.050630.0511082.82阿維菌素0.050.046380.054840.046120.050130.052810.046360.0494407.63胺菊酯0.050.05110.051560.051060.049840.049570.050930.0506771.64百菌清0.050.052940.044970.052870.052160.043210.051990.0496908.85苯醚菊酯0.050.053190.052740.050870.052550.052790.052460.0524331.56苯醚氰菊酯0.050.052870.051680.052790.052940.050150.053440.0523122.37吡蟲啉0.050.05150.052740.051380.050330.049220.049160.0507222.88吡唑醚菌酯0.050.05320.052830.052890.052210.050950.049270.0518922.99芐呋菊酯0.050.056430.050370.052630.051420.053220.052830.0528173.910丙環(huán)唑0.050.052430.049050.053260.053320.050330.05160.0516653.311丙烯菊酯0.050.051030.051650.052320.051250.053080.053740.0521782.112丙溴磷0.050.052240.053980.052040.047480.049540.047960.0505405.213蟲酰肼0.050.054340.052240.050850.048370.051560.05190.0515433.814除蟲菊素I0.050.052750.051390.052710.051990.052790.051890.0522531.115除蟲菊素II0.050.047610.052390.047110.048650.041540.043240.0467578.316除蟲脲0.050.047480.045560.046640.043910.04780.04850.0466483.617噠螨靈0.050.05280.051420.053070.04830.049910.046850.0503925.018稻豐散0.050.050820.051580.050580.049350.039210.051940.0489139.919敵百蟲0.050.047910.04950.047980.049060.040010.047810.0470457.520敵敵畏0.050.053470.053750.051440.052320.05290.053360.0528731.621啶蟲脒0.050.053940.053510.051340.053040.051150.053420.0527332.322毒死蜱0.050.049860.053150.049810.050570.050780.0498