苗 水，李雯婷，陳 銘，周 恒，蘭 嵐，毛秀紅，季 申

(上海市食品藥品檢驗所，上海 201203)

三七為五加科人參屬植物三七Panaxnotoginseng(Burk)F.H.Chen的干燥根及根莖，主產(chǎn)于云南省文山州。其具有散瘀止血、消腫定痛之功效，是預(yù)防和治療心腦血管疾病的首選藥材，也是注射用血栓通、云南白藥、片仔癀等藥品的主要原料[1]。近年來三七的規(guī)?；斯しN植日益普遍，在長達三年的生長過程中，三七易遭受各種病蟲草害，因此種植過程中不可避免地使用農(nóng)藥。農(nóng)藥的過量或違規(guī)使用會導(dǎo)致三七藥材中有農(nóng)藥殘留，影響用藥安全[2-3]。農(nóng)藥殘留問題成為制約三七等藥材走向國際市場的主要瓶頸之一。因此，亟需建立簡便、高效的三七中農(nóng)藥殘留的高通量檢測方法，為農(nóng)藥的科學(xué)使用及政府監(jiān)管提供技術(shù)支撐。

近年來，隨著我國對中藥材農(nóng)藥殘留安全的重視，新的檢測方法不斷出現(xiàn)，如季申等[4-5]采用傳統(tǒng)色譜方法分別測定了多種中藥材的56種有機氯類農(nóng)藥與57種有機磷農(nóng)藥，分別采用電子捕獲檢測器與火焰光度檢測器測定該兩類農(nóng)藥，氣相色譜雙塔雙柱法對陽性結(jié)果進行確證。但色譜方法需對農(nóng)藥進行色譜分離，單次進樣可測定的農(nóng)藥數(shù)量僅幾十種。近年來隨著質(zhì)譜技術(shù)發(fā)展，串聯(lián)三重四極桿質(zhì)譜在農(nóng)藥殘留測定領(lǐng)域發(fā)揮著越來越重要的作用。較色譜方法而言，質(zhì)譜法依據(jù)各農(nóng)藥的特征離子對定性定量，無需對各農(nóng)藥進行色譜分離，單次進樣可測定的農(nóng)藥數(shù)量大大提高，且專屬性好，針對中藥材等復(fù)雜樣本的抗基質(zhì)干擾能力強。如季申等[6]建立了多種中藥材中74種農(nóng)藥殘留的液相色譜-串聯(lián)質(zhì)譜檢測方法，黃莉莉等[7]建立了桑葉中100種農(nóng)藥殘留的液相色譜-串聯(lián)質(zhì)譜測定方法，兩種方法雖然測定農(nóng)藥種類較多，但前處理步驟較多，耗時費力，影響方法整體效能。

美國農(nóng)業(yè)部Lehotay等[8]開發(fā)的QuEChERS前處理方法是對食品中農(nóng)藥殘留測定技術(shù)的一次較大推進，該方法簡便、快速、高效，依托該技術(shù)的食品中高通量多殘留檢測方法不斷出現(xiàn)[9-14]。在中藥材農(nóng)殘測定方面，季申等[15]采用氣相色譜-串聯(lián)三重四極桿質(zhì)譜法實現(xiàn)了單次進樣對黃芪中238種農(nóng)藥殘留的檢測，針對中藥材特點對QuEChERS提取方法進行了改良。季申課題組還開發(fā)了中藥中227種農(nóng)藥殘留的氣相色譜-串聯(lián)三重四極桿質(zhì)譜與液相色譜-串聯(lián)三重四極桿質(zhì)譜測定方法，采用緩沖鹽QuEChERS方法提取，分散固相萃取凈化，該方法已被中國藥典2015年版四部通則[16]收載。然而中國藥典所檢測農(nóng)藥數(shù)量仍與食品安全國家標(biāo)準(zhǔn)有一定差距，如龐國芳等[17]針對桑枝、金銀花、枸杞子和荷葉4種藥材，開發(fā)了測定413種農(nóng)藥及相關(guān)化學(xué)品殘留量的液相色譜-串聯(lián)質(zhì)譜法。為更好地滿足中藥材農(nóng)藥殘留的監(jiān)管需要，亟需進一步擴增檢測農(nóng)藥數(shù)量。

本文在中國藥典2015年版四部通則方法基礎(chǔ)上，大幅擴增了農(nóng)藥數(shù)量，以改良的QuEChERS方法提取，分散固相萃取法(d-SPE)凈化，采用液相色譜-串聯(lián)三重四極桿質(zhì)譜為檢測手段，內(nèi)標(biāo)法定量，首次建立了單次進樣可在20 min內(nèi)測定三七中508種農(nóng)藥殘留的高通量檢測方法。

1 實驗部分

1.1 儀器與試劑

Agilent 1290超高效液相色譜(美國Agilent公司)，AB SCIEX 6500三重四極桿質(zhì)譜(美國AB SCIEX公司)；N-EVAPTM112型氮吹儀(美國Organomation公司)；IKA KS260C振蕩器、IKA MS 2渦旋混合器(德國IKA公司)；UV2550紫外分光光度計(日本島津公司)；旋轉(zhuǎn)蒸發(fā)儀(瑞士BüCHI 公司)。

農(nóng)藥標(biāo)準(zhǔn)品均購于德國Dr.Ehrenstorfer GmbH公司；乙腈、甲醇均為色譜純(美國Merck公司)；醋酸(分析純，國藥集團上?；瘜W(xué)試劑公司)；甲酸、甲酸銨均為色譜純(美國Sigma-Aldrich公司)。凈化材料：N-丙基乙二胺(PSA)、石墨化碳黑(GCB)、十八烷基鍵合硅膠(C18)、硅膠(Silica)、提取管(50 mL，預(yù)裝6 g無水硫酸鎂、1.5 g無水醋酸鈉)、凈化管(15 mL，預(yù)裝300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica、900 mg無水硫酸鎂)均購于天津博納艾杰爾科技有限公司。

1.2 標(biāo)準(zhǔn)溶液的配制

精密稱取各農(nóng)藥標(biāo)準(zhǔn)品及內(nèi)標(biāo)適量，用乙腈或甲苯分別制成1 000 μg/mL的儲備溶液；精密吸取農(nóng)藥儲備溶液適量，用含0.05%醋酸的乙腈稀釋成100 μg/L和1 000 μg/L的混合標(biāo)準(zhǔn)溶液；精密量取內(nèi)標(biāo)儲備溶液適量，用乙腈稀釋成6 μg/mL的溶液。

稱取三七空白樣品6份，每份3 g，按照“1.4 ”方法進行提取、凈化和離心后，取上清液5 mL，置氮吹儀上于40 ℃水浴濃縮至約0.4 mL，分別加入50、100 μL的100 μg/L混合標(biāo)準(zhǔn)溶液，以及50、100、200、400 μL的1 000 μg/L混合標(biāo)準(zhǔn)溶液，用乙腈定容至1 mL，渦旋混勻，過0.22 μm微孔濾膜，取續(xù)濾液，得質(zhì)量濃度分別為5、10、50、100、200、400 μg/L的系列基質(zhì)混合標(biāo)準(zhǔn)工作溶液。

1.3 分析條件

1.3.1 色譜條件色譜柱：Agilent Poroshell 120 EC-C18(3.0 mm×150 mm，2.7 μm)；流動相：A為0.05%甲酸+5 mmol/L甲酸銨水溶液；B為0.05%甲酸+5 mmol/L甲酸銨甲醇。梯度洗脫程序：0～1.0 min，95%A；1.0～4.0 min，95%～40%A；4.0～8.0 min，40%～36%A；8.0～8.5 min，36%～32%A；8.5～9.0 min，32%～25%A；9.0～16.0 min，25%～5%A；16.0～20.0 min，5%A；20.0～20.1 min，5%～95%A。流速：0.40 mL/min；進樣量：2.0 μL。

1.3.2 質(zhì)譜條件離子源：電噴霧離子源(ESI)；掃描方式：正離子模式；檢測方式：多反應(yīng)監(jiān)測(MRM)模式；電噴霧電壓：5 500 V；霧化氣壓力：344.8 kPa；輔助氣壓力：344.8 kPa；氣簾氣壓力：137.9 kPa；碰撞氣壓力：48.3 kPa；離子源溫度：500 ℃；掃描時間：10 ms；碰撞室入口電壓：10 V；碰撞室出口電壓：12 V；監(jiān)測離子對及其質(zhì)譜參數(shù)見表1。

1.4 樣品前處理

供試品粉碎后過50目篩，取約3 g(精確至0.01 g)置50 mL聚苯乙烯具塞離心管中，加入1%醋酸15 mL，渦旋使其充分浸潤，放置30 min，精密加入15 mL乙腈與100 μL內(nèi)標(biāo)溶液，渦旋混勻，劇烈振蕩(500次/min) 5 min，加入無水硫酸鎂與無水醋酸鈉(質(zhì)量比4∶1)的混合粉末7.5 g，立即搖散，再次劇烈振蕩(500次/min)3 min，于冰浴中冷卻10 min，離心(4 000 r/min)5 min，待凈化。精密移取上清液9 mL置于分散固相萃取凈化管(預(yù)裝300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica、900 mg無水硫酸鎂)中，渦旋混勻，劇烈振蕩(500次/min) 5 min，離心(4 000 r/min)5 min，精密移取上清液5 mL，置氮吹儀上于40 ℃水浴濃縮至約0.4 mL，加乙腈定容至1 mL，渦旋混勻，過0.22 μm微孔濾膜，取續(xù)濾液，即得。

表1 508種農(nóng)藥的保留時間(tR)、質(zhì)譜參數(shù)、檢出限、相關(guān)系數(shù)(r)、平均回收率(100 μg/kg)及相對標(biāo)準(zhǔn)偏差(n=7)Table 1 Retention times(tR),MS parameters,limits of detection(LOD)，correlation coefficients(r)，average recoveries(spiked at 100 μg/kg) and RSDs(n=7) of 508 pesticides

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%30Azoxystrobin(腈嘧菌酯)10.3404.1372.1,344.118,321300.0050.998 095.9(2.6)31Beflubutamid(氟丁酰草胺)12.2356.1177.1,162.124,331300.0050.994 295.2(7.3)32Benalaxyl(苯霜靈)12.9326.2294.2,208.114,211100.0050.993 8102(2.8)33Benazolin-ethyl(草除靈)10.2272.1198.0,170.022,311300.0050.999 397.3(7.8)34Bendiocarb(蟲威)7.0224.2108.9,167.023,11550.0050.996 689.5(6.2)35Benfuracarb(丙硫克百威)14.3411.2190.1,195.016,31800.050.994 777.4(8.1)36Benodanil(麥銹靈)8.3323.9230.9,105.030,271600.0050.999 193.2(3.8)37Benoxacor(解草嗪)9.8260.0149.1,134.124,391500.0050.999 588.5(4.1)38Bensulide(地散磷)12.1398.1313.9,218.014,22840.0050.990 297.0(12)39Benthiavalicarb-isopropyl(苯噻菌胺)10.9382.4196.8,115.926,271530.0050.999 881.5(7.1)40Benziothiazolinone(噻霉酮)5.7152.0108.9,133.928,311600.0050.990 450.9(8.9)41Benzoylprop-ethyl(新燕靈)12.7366.1104.9,320.022,111100.0050.998 688.7(13)42Benzyladenine(芐腺嘌呤)6.6226.190.5,148.150,251800.0050.995 661.2(8.6)43Bifenazate(聯(lián)苯肼酯)11.5301.1170.1,198.129,151010.050.994 481.4(8.9)44Bioallethrin(生物丙烯菊酯)14.8303.2134.9,151.014,121000.0050.998 479.3(9.0)45Bioresmethrin(滅蟲菊酯)17.0339.3171.1,143.020,331600.0050.998 777.1(5.2)46Bitertanol(聯(lián)苯三唑醇)13.4338.2269.2,99.110,18900.010.997 284.0(7.6)47Boscalid(啶酰菌胺)11.0343.0307.1,140.026,251900.0050.998 083.5(7.5)48Bromacil(除草定)7.2261.1204.9,187.919,37740.0050.995 379.2(4.9)49Bromfenvinphos-methyl(甲基溴苯烯磷)11.5375.0126.8,170.019,51700.0050.991 895.6(9.7)50Bromobutide(溴丁酰草胺)11.6312.2194.1,119.018,281000.0050.990 383.3(14)51Bromuconazole(糠菌唑)11.3,12.3376.0173.0,159.038,371400.0050.996 4102(14),90.4(14)52Bupirimate(乙嘧酚磺酸酯)11.9317.1272.1,166.125,301400.0050.999 583.0(5.6)53Buprofezin(噻嗪酮)14.8306.2201.1,116.115,201200.0050.998 690.9(3.1)54Butachlor(丁草胺)15.1312.0238.1,162.217,33610.0050.999 289.2(3.3)55Butafenacil(氟丙嘧草酯)11.3492.1349.0,331.018,31900.0050.991 264.3(13)56Butamifos(抑草磷)13.0333.1179.9,152.015,241500.0050.992 281.1(13)57Butocarboxim(丁酮威)4.6245.1166.1,130.022,221000.0050.996 498.5(2.8)58Butoxycarboxim(丁酮砜威)4.6223.0105.9,165.913,11720.0050.993 588.2(13)59Buturon(炔草隆)8.8237.1126.9,98.837,581100.0050.994 392.9(8.5)60Butylate(丁草散)14.2218.2156.1,162.114,171000.0050.999 486.8(4.3)61Cadusafos(硫線磷)13.7271.0159.0,97.021,511010.0050.999 792.9(5.0)62Cafenstrole(唑草胺)11.2351.2100.1,72.017,42500.0050.996 689.0(15)63Carbendazim(多菌靈)9.0192.1160.1,132.121,401300.0050.999 290.1(2.4)64Carbetamide(雙酰草胺)6.7237.1192.1,118.110,16800.0050.997 784.5(6.9)65Carbofuran(克百威)7.3222.1165.1,123.016,271300.0050.994 775.5(4.4)66Carbofuran-3-hydroxy(3-羥基呋喃丹)5.8238.1181.1,163.114,231200.0050.998 494.4(5.3)67Carbosulfan(丁硫克百威)17.5381.2118.1,160.126,181500.0050.998 263.0(4.4)68Carboxin(萎銹靈)7.5236.1143.0,87.021,321100.0050.997 881.6(5.0)69Carfentrazone-ethyl(唑草酮)12.3412.1345.9,366.131,232200.0050.990 997.0(14)70Carpropamid(加普胺)12.6334.1139.1,195.932,16900.0050.999 687.5(3.9)71Chinomethionat(滅螨猛)15.0235.0207.0,163.025,38800.010.999 229.9(3.6)72Chlorantraniliprole(氯蟲酰胺)9.7483.9453.0,286.025,241000.0050.999 083.3(8.8)73Chlorbromuron(氯溴隆)10.8293.3203.9,182.125,211750.050.993 5117(7.9)74Chlorbufam(氯炔靈)10.5224.0172.0,154.011,221100.050.997 2105(9.8)75Chlorfenvinphos(毒蟲畏)12.9359.0155.0,127.016,221300.0050.998 391.8(4.8)76Chlorfluazuron(氟啶脲)16.1540.1382.9,158.033,241500.0050.998 279.9(8.8)77Chloridazon(氯草敏)5.9222.0104.0,146.030,361600.0050.998 984.9(6.1)78Chlorotoluron(綠麥隆)8.3213.172.0,139.951,33910.0050.998 986.1(3.7)79Chloroxuron(枯草隆)11.4291.172.1,72.161,611010.0050.999 284.3(4.7)80Chlorphoxim(氯辛硫磷)13.0333.1180.0,152.013,24620.0050.990 486.5(14)81Chlorpyrifos-methyl(甲基毒死蜱)13.6321.9125.0,289.927,201200.0050.998 385.0(5.0)82Chlorpyrifos-oxon(氧毒死蜱)12.0334.0277.9,306.030,161200.0050.999 086.3(6.6)83Chlorthiamid(草克樂)6.0205.9188.9,172.027,261000.010.999 486.6(3.6)84Chlortoluron(綠麥隆)8.3213.171.6,139.941,311000.0050.999 386.8(5.6)85Cinidon-ethyl(吲哚酮草酯)14.7394.1348.0,366.023,171600.0050.999 783.0(3.4)86Cinosulfuron(醚磺隆)6.4414.4182.6,215.026,211000.0050.997 193.7(3.8)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%87Clethodim(烯草酮)11.3,14.2360.1268.1,164.114,231200.0050.994 692.1(14),80.4(3.9)88Clodinafop-propargyl(炔草酯)12.2349.8265.7,90.925,371200.0050.997 796.2(2.6)89Clofentezine(四螨嗪)13.2303.0138.0,102.021,491000.0050.999 969.7(4.9)90Clomazone(異草酮)9.8240.2125.0,99.027,68800.0050.999 787.0(4.1)91Cloquintocet-mexyl(解毒喹)14.8336.1238.0,192.022,401000.0050.999 673.8(2.8)92Cloransulam-methyl(氯酯磺草胺)7.2430.0398.0,370.017,27800.0050.994 678.4(6.2)93Clothianidin(噻蟲胺)5.5250.0169.1,132.017,20800.0050.999 787.6(6.0)94Coumaphos(蠅毒磷)12.9363.0307.0,227.022,352000.010.992 491.0(4.2)95Coumatetralyl(殺鼠醚)11.3292.7175.0,131.332,281000.0050.998 687.8(4.2)96Crimidine(鼠立死)6.3172.0135.9,106.636,351200.0050.999 378.7(4.6)97Crufomate(育畜磷)12.1292.1236.0,108.025,351500.0050.999 491.7(4.3)98Cumyluron(芐苯隆)11.2303.2184.7,119.025,33900.0050.996 889.2(10)99Cyanazine(氰草凈)6.6241.1214.0,214.122,171500.0050.999 386.0(5.2)100Cyanofenphos(苯腈磷)12.5304.1276.0,157.018,311700.0050.998 490.5(5.4)101Cyanophos(殺螟腈)8.5244.1212.0,125.022,24750.0050.998 687.6(4.1)102Cyazofamid(氰霜唑)11.8325.0107.8,260.929,15760.0050.999 793.9(4.7)103Cycloate(環(huán)草敵)13.7216.182.9,154.021,161200.050.992 185.4(7.2)104Cycloxydim(噻草酮)14.1326.2280.1,180.118,281000.010.994 6100(13)105Cycluron(環(huán)銹隆)9.2198.888.9,71.921,371000.0050.999 484.3(4.2)106Cyhalofop- butyl(氰氟草酯)13.8375.2358.1,256.110,22800.010.996 079.5(14)107Cymiazole(螨蜱胺)5.8219.1203.0,170.939,481200.0050.995 389.0(14)108Cymoxanil(霜脲氰)6.0199.1110.9,128.022,13700.050.996 189.3(9.9)109Cyphenothrin(苯醚氰菊酯)16.3,16.6376.3151.2,123.015,28800.0050.997 986.4(7.6),89.9(14)110Cyprazine(環(huán)丙津)8.7228.1186.0,108.124,321300.0050.998 591.5(4.1)111Cyproconazole(環(huán)唑醇)11.1,11.4292.1125.0,70.042,501300.0050.996 885.7(4.2),84.1(6.2)112Cyprodinil(嘧菌環(huán)胺)12.5226.1108.1,93.135,441800.0050.999 657.8(3.3)113Cyprofuram(酯菌胺)7.6280.1252.2,183.814,231000.0050.995 787.9(4.1)114Cyprosulfamide(環(huán)丙磺酰胺)6.5375.1254.1,135.017,281200.0050.999 288.3(2.4)115Cyromazine(滅蠅胺)3.5167.185.0,125.124,241000.0050.997 040.0(12)116Daimuron(殺草隆)11.1269.2151.0,119.317,26800.0050.999 787.6(5.9)117Demeton(內(nèi)吸磷)10.3259.088.9,60.920,50800.0050.994 788.2(14)118Demeton-S-methylsulphon(甲基內(nèi)吸磷)5.0263.0169.0,109.021,381000.050.992 797.9(13)119Demeton-S-methyl(砜吸磷)7.2231.289.0,60.812,41750.0050.999 288.9(3.3)120Demeton-S-methyl-sulfoxide(磺吸磷)4.8247.0168.9,104.918,17800.0050.999 081.2(3.5)121Desmetryn(敵草凈)8.1214.190.9,124.045,45820.0050.998 289.1(4.2)122Diafenthiuron(丁醚脲)16.0385.2328.9,278.228,411300.0050.994 479.6(3.4)123Diallate(燕麥敵)13.9270.0128.1,228.016,171000.0050.998 386.1(5.5)124Diazinon(二嗪磷)13.0305.1277.1,169.119,291300.0050.998 593.1(4.2)125Dichlofenthion(除線磷)11.4,15.3314.9258.9,286.923,17610.050.990 582.4(4.6),85.3(3.8)126Dichlormid(烯丙酰草胺)7.3208.1139.9,98.117,19800.0050.994 696.0(11)127Diclobutrazol(芐氯三唑醇)12.4328.1159.0,198.950,291000.0050.996 481.9(9.0)128Diclocymet(雙氯氰菌胺)11.7,12.1313.1172.6,137.320,471300.0050.991 6102(12),92.4(8.7)129Dicrotophos(百治磷)5.4238.1112.1,193.019,151060.0050.999 783.3(2.9)130Diethofencarb(乙霉威)10.2268.1226.1,180.114,25800.0050.998 077.2(12)131Difenoconazole(苯醚甲環(huán)唑)13.7406.1337.0,251.024,361500.0050.999 485.6(1.4)132Difenoxuron(枯秀隆)8.8287.1122.9,214.027,321000.0050.999 289.9(3.8)133Difenzoquat-methyl-sulfate(野燕枯)5.7250.2194.2,234.138,451800.0050.996 986.4(5.8)134Diflubenzuron(除蟲脲)12.3311.0158.0,141.021,451200.0050.997 382.4(4.4)135Dimefuron(唑隆)9.6338.7166.9,256.128,211000.0050.999 390.7(2.4)136Dimethachlor(二甲草胺)9.3256.1224.1,148.121,34900.0050.999 287.9(4.3)137Dimethametryn(異戊乙凈)12.1256.1186.1,138.128,371000.0050.999 882.9(3.3)138Dimethenamid(二甲吩草胺)10.9276.1244.1,168.120,331000.0050.999 889.6(5.1)139Dimethoate(樂果)5.9230.0199.0,125.013,291100.0050.999 390.6(3.5)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%140Dimethomorph(烯酰嗎啉)10.4,10.9388.1301.1,165.129,42900.0050.993 686.4(14),102(12)141Dimethylvinphos(甲基毒蟲畏)11.3331.0127.0,204.916,231100.0050.995 381.6(6.7)142Dimoxystrobin(醚菌胺)12.3327.2205.1,116.015,321100.0050.994 571.7(15)143Diniconazole(烯唑醇)13.7326.1159.0,70.042,531200.010.999 584.2(5.5)144Dinitramine(氨氟靈)13.1323.1305.1,247.020,241300.050.996 796.3(3.8)145Dinotefuran(呋蟲胺)4.5203.1129.1,157.116,11600.0050.999 384.9(3.4)146Dioxacarb(二氧威)5.8224.1167.1,123.29,20820.0050.996 874.1(13)147Diphenamid(雙苯酰草胺)9.2239.9167.1,133.629,351800.0050.999 783.6(4.6)148Dipropetryn(異丙凈)12.2256.2214.0,143.927,391150.0050.999 483.5(1.8)149Disulfoton sulfone(乙拌磷砜)8.6307.0261.0,153.014,171400.010.996 3102(4.5)150Disulfoton sulfoxide(乙拌磷亞砜)8.3291.0213.0,185.013,201000.0050.997 695.6(7.3)151Ditalimfos(滅菌磷)11.5299.9148.0,243.926,161370.0050.995 492.7(3.6)152Dithiopyr(氟硫草定)13.8402.1354.0,271.922,371700.0050.999 488.4(3.5)153Diuron(敵草隆)9.2233.0160.0,72.036,241500.0050.999 077.7(11)154DMST(N,N-二甲基氨基-N-甲苯)7.3215.1106.0,151.020,111000.0050.996 778.7(8.1)155Dodemorph(十二環(huán)嗎啉)9.2282.2116.5,115.634,391800.0050.998 569.1(5.3)156Emamectin-benzoate(甲氨基阿維菌素)14.9,15.4886.3157.8,302.151,381900.0050.998 868.6(4.6),70.5(15)157EPN(苯硫膦)13.9324.1296.0,157.018,301200.0050.999 092.8(2.5)158Epoxiconazole(氟環(huán)唑)11.7330.1121.0,123.027,24900.0050.999 786.1(4.0)159Eprinomectin(依立諾克丁)16.8914.5186.0,330.222,18700.0050.991 081.9(12)160EPTC(丙草丹)12.3190.1128.1,86.115,18800.0050.998 687.3(6.9)161Esprocarb(戊草丹)14.6266.170.9,90.519,281400.0050.997 293.9(3.9)162Etaconazole(乙環(huán)唑)11.7328.1158.9,204.934,231300.0050.999 686.4(3.4)163Ethametsulfuron-methyl(胺苯磺隆)7.5411.1196.1,168.123,39400.0050.998 573.5(4.1)164Ethidimuron(磺噻隆)5.5264.7207.9,114.119,251300.0050.999 785.4(5.0)165Ethiofencarb(乙硫苯威)8.2226.1106.9,164.121,11810.0050.996 497.3(12)166Ethiofencarb-sulfone(乙硫苯威砜)5.3258.0201.1,107.09,211200.050.996 6113(6.2)167Ethiolate(硫草敵)9.3162.071.9,99.922,15800.050.993 172.8(7.1)168Ethion(乙硫磷)15.1385.0199.0,142.914,361300.0050.993 294.5(12)169Ethiprole(乙蟲腈)10.6397.1350.9,255.027,471400.0050.999 887.3(4.2)170Ethirimol(乙嘧酚)7.2210.2182.1,140.128,301600.0050.992 373.4(15)171Ethofumesate(乙氧呋草黃)10.3287.1259.1,121.114,241300.0050.990 576.8(6.6)172Ethoprophos(滅線磷)11.9243.1215.0,130.917,291400.050.998 1102(13)173Ethoxyquin(乙氧喹啉)4.7218.2202.1,174.132,401400.050.990 944.0(9.3)174Etobenzanid(乙氧苯草胺)12.7340.2149.0,179.029,231500.0050.997 560.8(3.5)175Etofenprox(醚菊酯)18.0394.2359.2,177.115,211200.010.997 378.4(7.0)176Etoxazole(乙螨唑)15.6360.2141.0,304.140,261600.0050.999 379.1(2.7)177Etrimfos(乙嘧硫磷)6.2293.1265.0,125.024,421300.0050.998 592.5(3.9)178Famoxadone(唑菌酮)12.7392.2331.1,238.113,24700.0050.991 277.6(12)179Famphur(伐滅磷)8.0326.0217.0,280.927,191500.0050.999 592.6(4.4)180Fenamidone(咪唑菌酮)10.5312.1236.1,264.121,151300.0050.999 385.1(3.5)181Fenamiphos(苯線磷)12.2304.1276.1,217.019,311600.0050.999 088.6(2.8)182Fenamiphos sulfone(苯線磷砜)7.3336.1308.1,266.021,281800.0050.999 385.9(4.4)183Fenamiphos sulfoxide(苯線磷亞砜)7.1320.1292.1,233.021,341600.010.999 882.3(3.6)184Fenarimol(氯苯嘧啶醇)11.8331.0268.1,139.032,481800.0050.999 185.4(4.3)185Fenazaquin(喹螨醚)16.9307.2161.1,147.123,261000.0050.997 665.1(5.1)186Fenbuconazole(腈苯唑)12.1337.1125.0,70.038,241400.0050.998 192.8(4.6)187Fenchlorphos oxon(氧皮蠅磷)11.9304.9272.9,109.030,312000.010.990 088.6(13)188Fenfuram(甲呋酰胺)7.7202.1108.6,119.935,211100.0050.999 282.7(4.7)189Fenhexamid(環(huán)酰菌胺)11.5302.197.1,143.031,431800.010.999 491.6(4.4)190Fenobucarb(仲丁威)10.2208.294.6,152.123,101000.0050.995 174.9(5.8)191Fenothiocarb(苯硫威)12.2254.1160.0,71.713,50600.0050.999 088.0(6.3)192Fenoxaprop-ethyl(精唑禾草靈)14.4362.1288.0,121.123,341600.0050.994 982.4(8.0)193Fenoxycarb(苯氧威)12.1302.1116.1,256.116,191300.0050.999 887.8(7.2)194Fenpiclonil(拌種咯)9.7237.1202.0,139.927,471700.0050.999 391.8(2.7)195Fenpropidin(苯銹啶)9.5274.386.1,147.128,281800.0050.998 869.4(7.1)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%196Fenpropimorph(丁苯嗎啉)10.5304.3130.1,116.129,311800.0050.990 172.5(13)197Fenpyroximate(唑螨酯)16.2422.2366.1,215.124,351200.0050.998 785.8(2.5)198Fensulfothion(豐索磷)8.9309.0281.0,253.020,251600.0050.998 892.9(3.7)199Fensulfothion-oxon(氧豐索磷)6.2293.1265.0,237.020,211600.0050.998 791.9(4.5)200Fensulfothion-oxon-sulfone(氧豐索磷砜)8.9309.1281.0,253.015,231500.0050.999 993.1(4.5)201Fensulfothion-sulfone(豐索磷砜)9.3325.0297.0,269.016,231600.011.000 089.8(2.3)202Fenthion(倍硫磷)12.8279.0247.0,169.018,241700.010.999 990.9(8.3)203Fenthion-oxon(氧倍硫磷)10.0263.1231.0,216.022,321900.050.998 277.5(12)204Fenthion-oxon-sulfone(氧倍硫磷砜)5.8295.0217.1,104.126,341700.010.996 295.5(5.8)205Fenthion-oxon-sulfoxide(氧倍硫磷亞砜)5.7279.0264.0,247.026,361500.0050.998 289.2(3.7)206Fenthion-sulfone(倍硫磷砜)7.7311.0279.0,125.025,281700.010.999 486.9(4.9)207Fenthion-sulfoxide(倍硫磷亞砜)7.4295.0280.0,109.026,401700.010.999 484.6(4.1)208Fenuron(非草隆)5.7165.072.4,91.923,291180.0050.999 285.0(6.4)209Ferimzone(嘧菌腙)10.3255.1116.6,131.738,381500.0050.999 287.7(4.9)210Flamprop-isopropyl(麥草氟異丙酯)12.5364.1104.9,304.123,131000.0050.998 479.8(13)211Flamprop-methyl(麥草氟甲酯)11.1336.2303.9,303.912,12470.0050.990 392.0(12)212Flazasulfuron(嘧啶磺隆)9.4408.0182.1,301.124,20200.0050.999 480.2(4.6)213Flonicamid(氟啶蟲酰胺)5.0230.1202.8,174.026,271100.0050.999 786.7(4.6)214Florasulam(雙氟磺草胺)6.0360.0129.0,192.030,241400.0050.999 692.1(2.2)215Fluazifop-P-butyl(精吡氟禾草靈)14.5384.1328.1,282.124,291800.0050.999 288.6(4.4)216Fluazuron(吡蟲隆)15.2506.0348.9,158.026,261500.0050.999 080.8(3.1)217Flucarbazone(氟酮磺隆)5.8397.2129.8,114.918,641120.0050.993 880.2(7.3)218Fludioxonil(咯菌腈)10.7266.0228.9,185.325,31500.0050.990 083.4(13)219Flufenacet(氟噻草胺)11.5364.1194.1,152.116,281000.0050.995 193.4(13)220Flufenoxuron(氟蟲脲)15.6489.1158.1,141.125,69360.0050.999 481.8(3.9)221Flufenpyr-ethyl(氟噠嗪草酯)12.0409.1335.0,307.029,401600.0050.997 992.0(2.9)222Flumetsulam(唑嘧磺草胺)5.5326.1129.0,262.132,271300.0050.998 981.9(3.0)223Flumiclorac-pentyl(胺氟草酯)14.4441.2354.1,308.020,32800.0050.993 591.0(15)224Flumioxazin(丙炔氟草胺)9.5355.2327.1,299.125,351800.0050.999 197.4(8.0)225Fluometuron(氟草隆)8.0233.1188.1,160.128,371300.0050.994 878.9(8.5)226Fluopicolide(氟吡菌胺)10.9383.0173.0,145.032,701200.0050.997 491.9(6.5)227Fluopyram(氟吡菌酰胺)11.3396.6207.9,173.041,541500.0050.999 887.7(6.2)228Fluoroglycofen-ethyl(乙羧氟草醚)13.7448.1343.9,222.915,401200.010.994 883.7(14)229Fluoxastrobin(氟嘧菌酯)11.3459.1427.1,188.025,461000.0050.999 888.1(4.1)230Flupyrsulfuron-methyl-sodium(氟啶嘧磺隆鈉)10.4488.0178.0,333.128,271200.0050.992 083.0(15)231Fluquinconazole(氯喹唑)11.4376.1306.9,348.837,271450.0050.999 687.1(4.1)232Fluridone(氟啶草酮)9.7330.0308.8,290.156,431800.0050.999 889.0(3.7)233Flurochloridone(氟咯草酮)11.2312.0292.0,212.131,421600.0050.997 894.8(5.1)234Fluroxypyr-1-methylheptylester(氟草煙-1-甲庚酯)15.5367.0254.8,208.914,33500.0050.992 188.8(13)235Flurprimidol(抑嘧醇)10.9313.1270.1,269.134,471600.0050.999 982.7(5.6)236Flurtamone(呋草酮)10.3334.1247.1,178.137,581600.0050.998 783.1(3.0)237Flusilazole(氟硅唑)12.2316.1247.1,165.125,371000.0050.999 287.2(3.7)238Fluthiacet-methyl(嗪草酸甲酯)12.4404.0344.0,274.032,391600.0050.999 192.5(6.2)239Flutolanil(氟酰胺)11.1324.1262.1,242.126,351700.0050.999 192.7(5.4)240Flutriafol(粉唑醇)8.3302.1123.0,233.143,211100.0050.999 291.0(3.2)241Fluxapyroxad(氟唑菌酰胺)10.9382.1362.1,342.118,271650.0050.999 292.8(8.2)242Fonophos(地蟲硫磷)13.0247.0137.0,109.015,25800.0050.998 493.0(3.5)243Foramsulfuron(甲酰胺磺隆)7.4453.2182.0,272.129,19360.0050.999 375.1(4.6)244Forchlorfenuron(福芬素)9.1248.1129.0,155.024,251100.0050.999 050.2(3.1)245Formothion(安果)6.5258.1198.9,170.811,191200.10.991 591.4(14)246Fosthiazate(噻唑膦)8.1284.1228.0,104.014,321200.0050.999 583.1(5.6)247Fuberidazole(麥穗寧)6.1185.1157.1,156.131,391600.0050.997 075.2(5.4)248Furalaxyl(呋霜靈)10.1302.1242.1,95.120,351120.0050.999 687.3(2.7)249Furathiocarb(呋線威)14.6383.2252.1,195.017,251300.0050.999 391.2(5.5)250Furmecyclox(拌種胺)12.6252.1170.0,138.019,201000.0050.999 287.5(3.5)251Griseofulvin(灰黃霉素)8.1353.0165.0,214.925,251500.0050.999 689.0(4.2)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%252Halofenozide(氯蟲酰肼)10.6331.1275.1,104.97,23650.0050.991 290.9(14)253Halosulfuron-methyl(氯吡嘧磺隆)11.7435.0181.9,138.925,641000.0050.999 182.3(6.4)254Haloxyfop-methyl(氟吡甲禾磷)13.8376.1316.0,288.025,351800.0050.998 897.5(3.7)255Heptenophos(庚烯磷)8.9251.0126.9,125.117,191000.0050.998 480.8(4.0)256Hexaconazole(己唑醇)13.3314.1185.0,159.030,411300.010.998 185.5(4.2)257Hexaflumuron(氟鈴脲)13.7461.2157.9,141.122,631800.0050.996 982.4(13)258Hexazinone(環(huán)嗪酮)7.4253.0171.1,71.125,45460.0050.992 274.9(3.8)259Hexythiazox(噻螨酮)15.3353.1228.0,168.122,351600.0050.998 091.0(5.6)260Hydroprene(烯蟲乙酯)19.4267.2108.9,123.023,201000.050.998 184.1(9.9)261Imazalil(烯菌靈)8.2297.1255.0,159.025,301700.0050.999 680.2(5.7)262Imazamethabenz-methyl(咪草酸)7.1288.8257.1,215.026,321500.0050.998 377.6(3.6)263Imazamox(甲氧咪草煙)5.8306.1261.1,246.129,341600.050.992 881.2(10)264Imazapic(甲咪唑煙酸)5.9276.2231.1,216.032,321300.0050.999 272.0(3.3)265Imazaquin(滅草喹)6.8312.1267.1,199.130,391400.0050.999 156.0(4.8)266Imazethapyr(咪草煙)6.4290.1245.1,177.129,371300.0050.999 450.9(3.4)267Imazosulfuron(唑吡嘧磺隆)10.7413.0153.0,257.817,371110.0050.995 590.7(13)268Imibenconazole(亞胺唑)14.8411.1124.9,341.833,211200.0050.998 365.7(3.4)269Imidacloprid(吡蟲啉)5.6256.0209.1,175.123,281300.0050.996 880.1(5.8)270Inabenfide(抗倒胺)10.5339.1321.1,214.025,371310.050.994 790.2(6.5)271Indoxacarb(茚蟲威)13.7528.1293.0,249.019,231800.0050.998 895.6(6.4)272Ipconazole(種菌唑)13.7,13.9334.1125.0,70.060,601600.0050.998 579.2(4.5),80.4(6.7)273Iprobenfos(異稻瘟凈)12.2289.1205.1,90.815,26600.0050.991 275.4(10)274Iprodione(異菌脲)12.3330.0244.9,247.020,201200.0050.990 4100(14)275Iprovalicarb(異丙菌胺)11.3321.2119.1,203.120,121000.0050.990 294.1(7.9)276Isazofos(氯唑磷)11.4313.8162.2,97.024,451100.0050.999 790.0(4.1)277Isocarbamid(丁咪酰胺)6.1186.187.1,130.121,151000.0050.999 589.6(4.2)278Isocarbophos(水胺硫磷)8.8290.1230.8,121.015,37700.0050.993 391.8(8.7)279Isofenphos(異硫磷)13.3346.1287.1,245.08,19800.050.992 671.8(8.9)280Isomethiozin(丁嗪草酮)12.8269.1199.9,172.027,301800.0050.999 784.0(4.8)281Isoprocarb(異丙威)8.8194.0152.0,137.011,131200.0050.998 689.2(2.5)282Isopropalin(異丙樂靈)16.3310.2226.0,206.126,24960.0050.998 881.1(3.3)283Isoprothiolane(稻瘟靈)11.1290.9188.9,231.030,15700.0050.996 4109(6.9)284Isoproturon(異丙隆)8.8207.172.0,165.124,201400.0050.999 787.6(3.8)285Isouron(異隆)7.4212.0169.9,114.124,311450.0050.994 268.9(4.8)286Isoxaben(異酰草胺)10.8333.2165.1,150.027,55700.0050.999 282.0(5.1)287Isoxadifen-ethyl(雙苯唑酸)12.2296.2232.1,263.224,15700.0050.998 592.4(2.4)288Isoxaflutole(異氟草)8.6360.1251.0,220.025,541600.050.996 481.9(6.9)289Isoxathion(唑磷)13.1314.2105.0,296.220,13800.0050.999 189.6(3.6)290Ivermectin(伊維菌素)18.7892.5569.5,307.422,341000.010.996 384.7(9.4)291Kadethrin(噻嗯菊酯)13.8,15.2397.1170.9,379.217,10670.0050.994 187.9(14),99.2(15)292Karbutilate(特胺靈)6.9280.2180.6,224.020,141600.0050.992 796.5(9.4)293Kresoxim-methyl(亞胺菌)12.3314.1267.1,116.010,201300.0050.996 798.6(13)294Lactofen(乳氟禾草靈)14.4479.1344.0,223.021,48600.0050.998 289.1(12)295Lenacil(環(huán)草定)8.7235.1153.1,136.023,45800.0050.998 294.0(4.5)296Leptophos(溴苯磷)17.1411.0171.0,379.028,241000.0050.998 752.7(3.5)297Linuron(利谷隆)10.5249.0182.0,160.022,251000.0050.999 481.0(4.3)298Lufenuron(氯芬新)14.8511.0158.3,141.025,71360.0050.998 093.1(4.1)299Malaoxon(馬拉氧磷)7.2315.1269.0,127.011,171200.0050.999 790.0(5.5)300Malathion(馬拉硫磷)11.1331.0285.0,127.010,171300.050.994 391.4(14)301Mandipropamid(雙炔酰菌胺)10.7412.1328.1,356.120,141300.0050.998 790.6(9.2)302Mecarbam(滅蚜磷)11.8330.1227.0,199.012,211300.0050.999 0104(7.4)303Mefenacet(苯噻酰草胺)11.2299.1147.6,120.019,44800.0050.998 983.6(5.5)304Mefenpyr-diethyl(吡唑解草酯)12.9373.1327.0,299.018,351200.0050.994 288.7(13)305Mepanipyrim(嘧菌胺)11.5224.177.0,106.150,341600.0050.999 564.3(4.6)306Mephospholan(地胺磷)6.8270.0196.0,139.619,421000.0050.994 473.9(4.6)307Mepronil(滅銹胺)11.2270.1228.1,119.020,321500.0050.998 682.3(4.3)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%308Mesosulfuron-methyl(甲基二磺隆)8.1504.1182.1,139.131,751710.0050.999 386.1(4.3)309Mesotrione(硝草酮)5.7340.1228.0,104.130,301000.0050.998 756.1(4.7)310Metaflumizone(氰氟蟲腙)14.4507.1286.8,178.040,331900.0050.996 578.6(4.9)311Metalaxyl(甲霜靈)9.0280.2248.1,220.114,191200.010.999 790.5(3.9)312Metamitron(苯噻草酮)5.8203.1175.1,145.023,231400.050.996 3106(7.3)313Metazachlor(吡唑草胺)8.5278.1210.1,134.115,33700.0050.996 994.7(12)314Metconazole(葉菌唑)13.1320.270.0,125.058,551200.0050.998 584.1(4.9)315Methabenzthiazuron(甲苯噻隆)8.6222.1165.0,150.022,44600.0050.999 374.7(2.8)316Methacrifos(蟲螨畏)9.8241.0209.0,125.012,261200.010.996 181.6(8.2)317Methamidophos(甲胺磷)3.8142.0125.0,94.019,211200.0050.999 477.2(2.4)318Methfuroxam(呋菌胺)9.6230.1136.9,110.930,211600.0050.999 888.2(2.8)319Methiocarb(滅蟲威)10.9226.1169.1,121.114,261500.050.990 384.4(14)320Methomyl(滅多威)5.1163.1106.0,88.013,121000.0050.995 775.5(13)321Methoprotryne(蓋草津)9.8272.1240.2,198.126,261000.0050.999 784.7(4.3)322Methoxyfenozide(甲氧蟲酰肼)11.1369.2313.2,149.110,24900.050.999 498.3(9.9)323Metobromuron(溴谷隆)8.4259.0169.9,148.124,191000.0050.999 889.9(2.5)324Metolachlor(異丙甲草胺)12.0284.2252.0,176.222,361000.0050.999 792.6(4.6)325Metolcarb(速滅威)6.9166.0109.1,94.017,43660.010.998 280.0(7.8)326Metosulam(磺草胺唑)7.0418.0175.0,140.038,701400.0050.999 786.3(2.3)327Metoxuron(甲氧隆)6.3229.1156.2,192.130,151000.0050.997 093.8(7.2)328Metrafenone(苯菌酮)13.3409.1209.1,227.020,29800.0050.997 073.9(4.4)329Metsulfuron-methyl(甲磺隆)6.7382.1167.1,141.030,301000.0050.997 170.9(6.0)330Mevinphos(速滅磷)5.8,6.2225.1193.0,127.011,221200.050.998 679.1(12),91.8(13)331Molinate(草達滅)11.5188.1126.1,55.119,341200.010.999 289.9(3.5)332Monalide(庚酰草胺)11.9240.185.0,92.825,481600.0050.998 594.5(4.0)333Monocrotophos(久效磷)5.3224.1193.0,127.011,221400.0050.998 581.8(5.1)334Monolinuron(綠谷隆)7.9215.1148.1,126.025,25400.0050.992 698.3(13)335Monuron(滅草隆)7.0199.172.0,126.021,34600.0050.999 789.6(3.5)336Moxidectin(莫昔克丁)17.9640.4528.3,498.211,161000.0050.993 880.3(15)337Myclobutanil(腈菌唑)11.3289.1125.0,70.050,241500.0050.998 885.9(3.9)338Naled(二溴磷)9.1378.8127.0,109.019,541200.0050.996 594.0(14)339Napropamide(敵草胺)11.9272.2199.1,171.126,261600.0050.998 984.0(6.1)340N-desethyl-pimiphos-methyl(N-去乙基甲基嘧啶磷)13.4278.0245.8,249.824,242570.050.998 095.6(11)341Neburon(草不隆)12.3275.1114.0,160.020,401800.0050.991 993.4(5.3)342Nicosulfuron(煙嘧磺隆)6.8411.0181.9,213.135,251100.050.992 483.7(5.2)343Nitenpyram(烯啶蟲胺)4.8271.1225.0,189.116,171000.0050.996 881.3(3.0)344Nitralin(甲磺樂靈)12.1346.1304.1,262.019,26770.0050.998 990.2(3.9)345Norflurazon(氟草敏)9.1304.0284.0,160.033,401800.0050.999 687.1(3.3)346Novaluron(氟酰脲)13.8493.1158.0,141.025,71860.0050.999 590.2(3.8)347Nuarimol(氟苯嘧啶醇)10.4315.1252.1,243.029,321900.0050.999 081.4(2.8)348Octhilinone(辛噻酮)11.6214.1101.6,83.821,531000.0050.999 686.7(4.2)349Ofurace(呋酰胺)7.0282.0254.1,160.017,371550.050.999 194.0(7.5)350Omethoate(氧化樂果)4.4214.0183.0,155.015,211100.010.999 181.7(3.5)351Orbencarb(坪草丹)13.1258.0124.7,100.031,181500.0050.998 882.2(5.5)352Orthosulfamuron(嘧苯胺磺隆)8.6425.2227.0,182.019,341500.0050.992 480.8(8.8)353Oxabetrinil(解草腈)10.1233.2146.9,189.113,111400.050.992 3106(15)354Oxadiargyl(稻思達)12.9341.0223.0,230.023,211800.0050.990 990.5(5.7)355Oxadiazon(草酮)15.1345.1303.0,220.019,281800.010.998 094.2(4.8)356Oxadixyl(霜靈)6.6279.1219.1,132.116,431200.0050.999 490.4(10)357Oxamyl(殺線威)4.8237.1220.1,90.17,12900.050.996 594.2(13)358Oxasulfuron(環(huán)氧嘧磺隆)6.5407.0150.1,210.027,34800.0050.999 482.5(6.9)359Oxycarboxin(氧化萎銹靈)6.2268.1175.0,147.021,321000.0050.999 690.3(3.0)360Oxyfluorfen(乙氧氟草醚)14.4362.0316.0,237.020,341400.0050.997 693.3(5.8)361Paclobutrazol(多效唑)11.1294.1165.0,125.031,521200.010.998 189.5(6.0)362Paraoxon-ethyl(乙基對氧磷)8.5276.0248.0,220.014,221400.010.999 592.8(4.2)363Paraoxon-methyl(甲基對氧磷)6.6248.0231.0,202.024,271600.010.990 2101(7.9)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%364Parathion-oxon(對氧磷)8.2276.1219.8,248.120,12950.0050.998 495.4(4.2)365Pebulate(克草敵)13.5204.0127.9,176.122,24460.0050.995 886.7(8.3)366Penconazole(戊菌唑)12.5284.1159.0,173.042,261100.0050.999 085.2(4.6)367Pencycuron(戊菌隆)13.3329.1218.1,125.022,351600.0050.990 198.5(12)368Penoxsulam(五氟磺草胺)7.3484.1444.1,195.134,381800.0050.998 479.6(8.1)369Pentanochlor(蔬草滅)12.2240.2141.9,106.925,391900.0050.993 3102(5.4)370Pethoxamid(烯草胺)11.6296.1131.1,250.128,17800.0050.995 686.8(7.9)371Phenmedipham(甜菜寧)9.5318.1168.1,136.019,34500.0050.990 675.6(9.5)372Phenthoate(稻豐散)12.4321.0275.0,247.08,141000.050.994 085.5(12)373Phorate(甲拌磷)13.4261.075.0,47.019,49800.0050.997 783.8(14)374Phorate-oxon-sulfone(氧甲拌磷砜)6.0277.0249.0,183.014,161400.050.995 883.5(10)375Phorate-sulfone(甲拌磷砜)8.7293.0247.0,171.09,161500.10.997 5103(11)376Phosalone(伏殺硫磷)13.3368.0322.0,182.014,231600.050.999 197.1(14)377Phosfolan(硫環(huán)磷)6.2256.1139.9,167.934,221200.0050.999 093.4(3.8)378Phosmet(亞胺硫磷)10.1318.0160.0,133.024,511500.050.998 398.5(12)379Phosphamidon(磷胺)6.5300.1227.0,174.119,191700.0050.999 486.8(2.8)380Phoxim(辛硫磷)13.1299.1153.1,129.011,161200.010.999 386.1(6.3)381Picolinafen(氟吡酰草胺)14.6377.1359.1,238.028,411600.050.995 0100(11)382Picoxystrobin(啶氧菌酯)12.0368.1205.1,145.113,301300.050.994 1100(12)383Pindone(鼠完)13.9231.2213.1,185.119,211260.010.995 966.0(3.9)384Pinoxaden(唑啉草酯)13.0401.2317.2,289.231,491500.0050.999 484.7(4.8)385Piperalin(哌丙靈)7.7330.1230.5,139.736,371600.0050.999 065.5(5.4)386Piperophos(哌草磷)13.6354.1255.0,170.818,361200.0050.999 486.6(3.2)387Pirimicarb(抗蚜威)7.3239.1182.1,137.122,321500.010.997 377.1(12)388Pirimiphos-ethyl(乙基嘧啶磷)14.9334.1306.1,198.123,211800.0050.999 186.6(4.1)389Pirimiphos-methyl(甲基嘧啶磷)13.4306.1164.1,108.130,391600.0050.999 385.2(4.0)390Pretilachlor(丙草胺)14.2312.0252.1,132.123,63660.0050.997 681.8(5.1)391Primisulfuron-methyl(氟嘧磺隆)10.9491.0264.1,250.025,25550.0050.990 576.5(13)392Prochloraz(咪酰胺)13.2376.0308.0,70.017,45860.0050.998 6102(9.2)393Prodiamine(氨氟樂靈)14.8351.1267.0,291.124,211150.0050.998 688.1(9.5)394Profenofos(丙溴磷)10.3372.9344.9,302.918,261600.0050.998 993.8(3.0)395Promecarb(猛殺威)11.1208.1109.0,151.023,13760.0050.999 882.2(13)396Prometon(撲滅通)8.9226.1184.1,142.336,461200.0050.999 585.3(2.8)397Propachlor(毒草胺)8.7212.1170.0,94.118,361500.0050.996 895.0(3.0)398Propanil(敵稗)10.9218.1162.1,127.121,331200.0050.997 991.9(7.9)399Propaphos(丙蟲磷)12.4305.1220.8,202.921,321000.0050.999 687.1(5.3)400Propaquizafop(草酸)14.6444.1371.1,299.122,321300.0050.999 481.6(6.6)401Propargite(炔螨特)15.8368.2231.2,175.114,23800.0050.992 774.1(11)402Propetamphos(胺丙畏)11.4282.0138.0,156.025,19660.0050.992 181.4(11)403Propiconazole(丙環(huán)唑)13.0342.1205.0,159.025,351700.010.999 186.4(3.2)404Propisochlor(異丙草胺)12.6284.1224.1,148.114,29600.0050.997 689.8(5.0)405Propoxur(殘殺威)7.2210.1168.1,111.011,191300.050.992 5102(13)406Propoxycarbazone-sodium(丙苯磺隆)6.5421.1180.1,138.019,381200.0050.998 778.2(6.6)407Propyzamide(炔苯烯草胺)11.1256.0190.0,173.021,321600.0050.998 986.6(6.3)408Proquinazid(丙氧喹啉)16.5373.0331.0,288.920,331700.0050.999 459.2(3.5)409Prosulfocarb(芐草丹)14.1252.1128.1,91.118,301100.0050.999 584.3(4.4)410Prothioconazole(丙硫菌唑)13.0344.0326.0,189.016,28800.010.998 381.6(8.2)411Prothiophos(丙硫磷)17.1344.8241.0,132.927,69560.010.999 578.0(3.3)412Pymetrozine(吡蚜酮)4.5218.1105.0,78.027,581200.0050.998 746.1(3.8)413Pyracarbolid(吡喃靈)7.4218.196.9,106.936,351200.0050.999 187.5(12)414Pyraclofos(吡唑硫磷)13.0361.0257.0,333.030,221700.0050.999 282.6(3.2)415Pyraclostrobin(吡唑醚菊酯)13.1388.1296.1,194.119,171000.0050.994 483.0(9.5)416Pyraflufen-ethyl(吡草醚)12.5413.0339.0,289.028,401600.0050.997 590.6(6.8)417Pyrazophos(吡菌磷)13.2374.1222.1,194.129,442000.0050.998 180.5(3.4)418Pyrazosulfuron-ethyl(吡嘧磺隆)11.4415.1182.0,369.228,171300.0050.999 486.1(7.2)419Pyrethrin Ⅱ(除蟲菊素)13.6373.3160.9,133.032,17700.0050.998 996.3(13)420Pyridaben(噠螨靈)16.8365.0147.0,309.031,19860.0050.999 391.3(7.6)421Pyridalyl(啶蟲丙醚)18.7492.0183.0,204.023,261700.0050.998 849.1(3.5)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%422Pyridaphenthion(噠嗪硫磷)11.1341.1189.0,205.029,291700.0050.997 094.4(8.1)423Pyridate(噠草特)17.3379.1207.0,351.124,14800.0050.997 162.4(5.5)424Pyrifenox(啶斑肟)11.2,11.7295.0263.0,92.423,321300.050.996 284.4(13),79.0(9.4)425Pyriftalid(環(huán)酯草醚)9.8318.9139.1,179.236,411000.0050.999 385.2(3.7)426Pyrimethanil(嘧霉胺)10.4200.1107.1,183.133,331600.0050.997 966.5(4.8)427Pyriproxyfen(吡丙醚)15.3322.1227.1,185.121,321100.0050.999 286.6(4.6)428Pyrithiobac(嘧草硫醚)9.4327.1309.0,139.020,361500.050.995 570.3(4.1)429Pyroquilon(咯喹酮)6.9174.1132.0,117.031,431800.050.994 1102(5.2)430Pyroxsulam(啶磺草胺)6.7435.1195.1,166.137,471600.0050.991 572.4(4.2)431Quinalphos(喹硫磷)12.5299.1271.0,163.019,331300.0050.998 591.5(5.5)432Quinoclamine(滅藻醌)6.8208.2105.0,128.233,321300.050.998 7102(13)433Quinoxyfen(苯氧喹啉)15.3308.0197.0,214.044,471800.0050.999 566.8(3.4)434Rabenzazole(吡咪唑)8.7213.1172.0,145.132,38450.0050.999 072.6(1.8)435Resmethrin(芐呋菊酯)17.0339.2171.0,143.019,321750.0050.998 272.3(4.8)436RH5849(抑食肼)8.1297.0241.0,105.08,25800.0050.996 794.9(13)437Rotenone(魚藤酮)12.0395.1213.1,203.132,342000.0050.990 387.6(11)438Saflufenacil(苯嘧磺草胺)9.6501.2348.9,459.037,181700.0050.999 783.0(10)439Sebuthylazine(另丁津)10.3230.1174.0,146.016,311000.0050.997 978.3(5.2)440Sebuthylazine-desethyl(脫乙基另丁津)6.9202.1146.0,103.920,371000.050.994 880.4(3.6)441Secbumeton(密草通)8.8226.1169.8,113.925,311500.0050.999 785.6(4.3)442Sethoxydim(稀禾定)10.8,14.6328.2178.1,282.227,161400.0050.999 384.6(7.4),87.8(6.2)443Siduron(環(huán)草隆)10.5,10.7233.193.6,136.734,281400.0050.999 182.1(4.0)444Simazine(西瑪津)7.2202.1132.0,104.026,321500.050.997 2104(14)445Simeconazole(硅氟唑)10.6,11.6294.1134.9,209.026,191000.0050.994 8109(13),87.9(8.5)446Simeton(西瑪通)6.4198.2128.2,124.031,38850.0050.998 889.6(4.1)447Simetryn(西草凈)8.1214.0166.0,123.929,371300.0050.999 379.5(4.6)448Spiroxamine(螺環(huán)菌胺)10.5,10.7298.3144.1,100.118,311600.0050.997 893.1(14)449Spinosad A/D(螺甲螨酯)13.0732.5189.1,449.240,351300.050.995 465.5(6.7)450Sulcotrione(螺蟲乙酯)6.1329.0138.9,110.924,341500.0050.999 183.5(4.4)451Spirodiclofen(螺環(huán)菌胺)16.0411.1313.0,295.017,351400.0050.997 057.6(3.9)452Sulfallate(螺環(huán)菌胺)12.5224.0116.0,87.914,26700.0050.999 867.2(2.8)453Spiromesifen(磺草酮)15.4371.2273.1,255.117,321000.0050.997 658.4(9.8)454Sulfentrazone(菜草畏)7.3387.0307.0,273.029,401700.0050.999 082.5(4.8)455Spirotetramat(甲磺草胺)11.4374.2302.2,330.224,211000.0050.992 268.6(8.5)456Sulfometuron-methyl(甲嘧磺隆)6.9365.1149.8,199.028,291400.0050.998 383.7(9.4)457Sulfosulfuron(磺?；锹?10.2471.1211.1,261.016,241300.0050.997 689.4(6.2)458Sulfotep(治螟磷)12.6323.0295.0,170.914,201500.0050.998 192.6(8.5)459Sulfoxaflor(氟啶蟲胺腈)5.8277.9173.9,104.911,13900.050.995 487.0(15)460Sulprofos(丙硫磷)15.4323.0218.9,247.022,161800.0050.995 987.7(9.0)461Tau-fluvalinate(氟胺氰菊酯)17.0520.1208.1,181.123,35910.050.993 376.4(10)462TCMTB(苯噻硫氰)10.4239.1180.0,136.019,37710.0050.999 580.3(5.8)463Tebuconazole(戊唑醇)12.8308.1125.0,70.055,271900.050.999 684.5(15)464Tebufenozide(抑蟲肼)12.2353.2297.2,133.111,25900.050.991 184.5(14)465Tebufenpyrad(吡螨胺)14.5334.2171.0,147.132,352200.0050.998 587.1(4.8)466Tebupirimfos(丁基嘧啶磷)14.7319.1248.9,231.035,441000.0050.997 893.5(4.1)467Tebutam(牧草胺)11.8234.1192.0,90.520,491500.0050.997 288.1(5.1)468Tebuthiuron(丁噻隆)7.4229.0115.6,157.045,351800.050.997 888.7(10)469Tembotrione(環(huán)磺酮)8.9441.1341.1,304.912,251100.0050.990 871.4(10)470Temephos(雙硫磷)13.0,14.6467.0419.0,341.026,392200.0050.996 076.6(13),97.8(2.3)471Tepraloxydim(快捕凈)11.3342.2250.1,166.030,301000.010.998 783.1(3.9)472Terbumeton(特丁通)8.7226.1170.0,114.038,361000.0050.999 684.6(2.7)473Terbuthylazine-desethyl(去乙基特丁津)7.5202.1145.5,110.025,311000.0050.996 176.7(4.8)474Terbutryn(特丁凈)11.4242.1137.9,158.035,331000.0050.998 082.4(7.1)

(續(xù)表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%475Tetrachlorvinphos(殺蟲畏)12.2366.9126.7,240.918,271160.0050.997 988.7(3.4)476Tetraconazole(四氟醚唑)11.5372.0159.0,70.039,271300.050.993 594.9(14)477Tetramethrin(胺菊酯)14.3,14.7332.0314.0,286.012,131200.010.996 890.5(14),83.8(8.8)478Thiabendazole(噻菌靈)5.8202.0175.0,131.135,451800.0050.999 153.5(4.0)479Thiacloprid(噻蟲啉)6.1253.0186.0,126.020,301400.010.998 692.9(5.0)480Thiamethoxam(噻蟲嗪)5.2292.0211.1,181.118,311100.0050.999 590.3(8.3)481Thiazopyr(噻唑煙酸)12.3397.2377.1,335.036,401100.0050.997 294.4(7.2)482Thidiazuron(噻苯隆)7.2221.0102.0,128.022,231100.0050.999 041.6(3.6)483Thiencarbazone-methyl(噻酮磺隆)6.1391.0359.0,229.816,271300.0050.991 182.6(13)484Thiobencarb(禾草丹)13.3258.1125.0,89.021,68800.0050.998 577.4(3.1)485Thiodicarb(硫雙威)7.5355.1108.0,193.022,13800.0050.994 794.0(8.3)486Thiophanate-methyl(甲基托布津)7.0343.0151.0,268.029,151300.050.999 2106(6.3)487Tolclofos- methyl(甲基立枯磷)13.4301.0269.0,175.023,351300.010.998 388.1(3.7)488Tolfenpyrad(唑蟲酰胺)14.7384.2197.0,171.134,321200.0050.999 386.5(3.7)489Tolylfluanid(甲苯氟磺胺)12.6364.0238.0,137.021,38800.050.995 3103(9.6)490Topramezone(吡草磺)5.1364.0334.1,124.818,331100.0050.998 841.0(1.7)491Tralkoxydim(三甲苯草酮)15.3330.2284.2,138.118,27800.0050.997 592.9(12)492Tri-allate(野麥畏)15.4304.086.1,142.922,361400.0050.998 974.9(4.2)493Triazophos(三唑磷)11.5314.1178.0,162.129,251000.0050.998 792.3(3.9)494Triazoxide(咪唑嗪)8.6248.1123.7,177.042,471600.0050.999 121.5(5.0)495Tribufos(脫葉磷)16.6315.1169.0,225.121,161200.0050.999 183.1(2.9)496Trichlorfon(敵百蟲)5.8256.9109.0,221.025,151300.010.994 8101(10)497Tricyclazole(三環(huán)唑)6.3190.0163.0,136.028,342000.0050.993 588.4(1.9)498Trietazine(草達津)11.6230.0202.0,124.031,321200.0050.999 086.4(4.2)499Trifloxystrobin(肟菌酯)13.8409.1206.1,186.119,181100.0050.999 194.4(2.4)500Triflumizole(氟菌唑)13.8346.1278.1,73.114,221100.0050.990 498.6(12)501Triflumuron(殺鈴脲)13.0359.0156.0,139.023,461300.0050.998 192.2(4.0)502Triflusulfuron-methyl(氟胺磺隆)10.7493.2264.0,461.027,18970.0050.999 782.5(5.1)508Trinexapac-ethyl(抗倒酯)9.1253.2207.0,185.016,151000.0050.995 078.5(12)504Triticonazole(滅菌唑)10.1,11.6318.1125.0,191.244,28600.0050.999 292.5(14),93.8(6.5)505Valifenalate(纈菌胺)10.9,11.2399.1214.1,144.016,20730.0050.998 491.5(5.9),88.2(7.2)506Vamidothion(滅蚜硫磷)5.6288.0146.1,118.017,33800.0050.999 492.1(5.3)507Vernolate(滅草敵)13.4204.2128.1,85.915,191200.0050.999 885.0(8.8)508Zoxamide(苯酰草胺)12.9336.0204.0,159.024,561800.0050.995 190.3(7.7)IS-1Atrazine-D5(ethyl-D5)(氘代莠去津)8.8221.0178.8,101.135,35100---IS-2Fenthion-D6(o,o-dimethyl-D6)(氘代倍硫磷)12.6285.4249.9,168.918,24140---

*CE:collision energy;DP:declustering potential

2 結(jié)果與討論

2.1 前處理方法的優(yōu)化

早期QuEChERS法[8]采用乙腈提取，氯化鈉鹽析，該方法對大多數(shù)農(nóng)藥的回收率良好，但對部分堿性條件下不穩(wěn)定農(nóng)藥(如百菌清和p，p'-滴滴涕等)的測定結(jié)果重現(xiàn)性差、加標(biāo)回收率低，且部分農(nóng)藥在標(biāo)準(zhǔn)溶液中不穩(wěn)定。針對上述問題，AOAC 2007.01方法[18]改用pH 5.0的醋酸鹽緩沖體系，用含少量醋酸的乙腈配制標(biāo)準(zhǔn)溶液。本文在中國藥典2015版四部通則<2341>方法[16]的基礎(chǔ)上對樣品前處理方法進行優(yōu)化。

2.1.1 藥材浸泡時間的選擇三七的含水量低，且部分農(nóng)藥在堿性或中性條件下易降解，因此采用1%醋酸浸泡三七藥材。以檢出殘留量較大的嘧菌酯、苯醚甲環(huán)唑、戊唑醇、氟環(huán)唑與嘧霉胺的三七陽性樣品為研究對象，考察了不同浸泡時間(0、0.5、1、2 h)對提取效率的影響。結(jié)果表明，隨著浸泡時間的增加，各農(nóng)藥的提取效率呈增加趨勢，但浸泡0.5 h后提取效率相差不大，說明浸泡0.5 h即可將農(nóng)藥提取完全，因此選擇浸泡時間為0.5 h，與中國藥典2015版四部通則<2341>方法一致。

圖1 凈化材料用量對三七皂苷類成分凈化效果的影響Fig.1 Effect of purification material amount on notoginsenosides removal efficiency

圖2 508種農(nóng)藥及內(nèi)標(biāo)混合標(biāo)準(zhǔn)溶液的總離子流(TIC)色譜圖Fig.2 Total ion chromatograms of 508 pesticides and internal standards solution

2.1.2 凈化材料的選擇在中國藥典2015版四部通則方法的凈化材料(即300 mg PSA、300 mg C18、90 mg GCB、300 mg Silica)基礎(chǔ)上，進一步優(yōu)化了凈化材料配比。以三七提取液中所含的主要皂苷類成分為指標(biāo)，采用中國藥典2015版的高效液相色譜法測定凈化前、后提取液中三七皂苷R1、人參皂苷Rg1、人參皂苷Rb1、人參皂苷Re總量，評價凈化效果。圖1結(jié)果顯示，GCB用量對皂苷總量幾乎無影響，C18對皂苷的去除效果不明顯，但兩者對三七中其他干擾成分有一定凈化作用，故選擇上述藥典方法的用量。Silica與PSA對總皂苷的去除效果最為明顯，但當(dāng)PSA用量增至300 mg以上時，皂苷總量下降不明顯；隨著Silica用量的增加，皂苷總量下降明顯，而Silica用量超過600 mg時，凈化材料所占體積增加，無法從凈化管中移取5 mL凈化液進行濃縮，故PSA和Silica用量分別選擇為300、600 mg。

綜上，最終確定凈化材料的配比為300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica。此時，凈化步驟總皂苷的去除率達94.3%，凈化效果較好。優(yōu)化條件下508種農(nóng)藥的總離子流色譜圖見圖2。

2.2 基質(zhì)效應(yīng)的評價

基質(zhì)效應(yīng)是痕量分析的常見現(xiàn)象。樣品基質(zhì)中的共提取干擾物影響待測化合物的儀器響應(yīng)值，使得相同濃度的目標(biāo)化合物在溶劑標(biāo)準(zhǔn)溶液與基質(zhì)標(biāo)準(zhǔn)溶液的響應(yīng)值不一致，表現(xiàn)為基質(zhì)標(biāo)準(zhǔn)溶液的儀器響應(yīng)發(fā)生增強或抑制。本文采用下式對目標(biāo)化合物的基質(zhì)效應(yīng)進行評價：基質(zhì)效應(yīng)=[(基質(zhì)匹配標(biāo)準(zhǔn)曲線的斜率/溶劑標(biāo)準(zhǔn)曲線的斜率)-1]×100%[19]。結(jié)果發(fā)現(xiàn)，僅有136種農(nóng)藥的基質(zhì)效應(yīng)不明顯(<20%)，372種農(nóng)藥均產(chǎn)生中等或較強的基質(zhì)抑制效應(yīng)(≥20%)。為克服基質(zhì)效應(yīng)的影響，采用基質(zhì)匹配內(nèi)標(biāo)標(biāo)準(zhǔn)曲線法進行定量。

2.3 方法學(xué)驗證

2.3.1 線性關(guān)系與檢出限按照“1.2”方法配制基質(zhì)混合標(biāo)準(zhǔn)工作溶液，采用本方法進行前處理和測定。以各組分的質(zhì)量濃度為橫坐標(biāo)，對應(yīng)峰面積與內(nèi)標(biāo)峰面積的比值為縱坐標(biāo)，進行回歸分析。結(jié)果表明，508種農(nóng)藥均在0.005～0.4 mg/L范圍內(nèi)呈良好線性關(guān)系，相關(guān)系數(shù)(r)均大于0.99。由于待測農(nóng)藥數(shù)量多，難以逐一稀釋至每個農(nóng)藥的最低檢出濃度，因此以實際檢測到各農(nóng)藥2個MRM反應(yīng)的標(biāo)準(zhǔn)曲線最低濃度作為檢出限，得到方法檢出限(LOD)為0.005～0.1 mg/kg(見表1)。

2.3.2 回收率與相對標(biāo)準(zhǔn)偏差將混合標(biāo)準(zhǔn)儲備溶液添加到三七空白樣品中，按“1.4”方法分別制得加標(biāo)水平為10、50、100、200 μg/kg的樣品溶液，每個水平重復(fù)7次。其中，100 μg/kg加標(biāo)水平下的平均回收率和相對標(biāo)準(zhǔn)偏差(RSD)見表1，除8種農(nóng)藥外，其余500種農(nóng)藥的回收率為50.2%～117%。

對各加標(biāo)水平下508種農(nóng)藥的回收率百分比進行分析。結(jié)果顯示，10 μg/kg加標(biāo)水平下有412種農(nóng)藥的回收率為70%～120%，占農(nóng)藥總數(shù)的81%；50 μg/kg加標(biāo)水平下有485種農(nóng)藥的回收率為70%～120%，占總數(shù)的95%；100 μg/kg加標(biāo)水平下有468種農(nóng)藥的回收率為70%～120%，占總數(shù)的92%；200 μg/kg加標(biāo)水平下有477種農(nóng)藥的回收率為70%～120%，占總數(shù)的94%。各加標(biāo)水平下的RSD均不大于15%。

2.4 實際樣品分析

3 結(jié) 論

本文采用改良的QuEChERS方法對樣品進行提取與凈化，建立了快速檢測三七中508種農(nóng)藥殘留的液相色譜-串聯(lián)質(zhì)譜方法。本方法樣品前處理簡便、快速，靈敏度與準(zhǔn)確度滿足農(nóng)藥殘留檢測要求，可用于三七中農(nóng)藥多殘留的快速測定，為三七中農(nóng)藥的合理規(guī)范使用提供了技術(shù)參考。