液相色譜-串聯(lián)質(zhì)譜法同時測定三七中508種農(nóng)藥殘留

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準有一定差距，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)藥標準品均購于德國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 標準溶液的配制

精密稱取各農(nóng)藥標準品及內(nèi)標適量，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的混合標準溶液；精密量取內(nèi)標儲備溶液適量，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混合標準溶液，以及50、100、200、400 μL的1 000 μg/L混合標準溶液，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)混合標準工作溶液。

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)及相對標準偏差(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、加標回收率低，且部分農(nóng)藥在標準溶液中不穩(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準溶液。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)標混合標準溶液的總離子流(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，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化合物在溶劑標準溶液與基質(zhì)標準溶液的響應(yīng)值不一致，表現(xiàn)為基質(zhì)標準溶液的儀器響應(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)匹配標準曲線的斜率/溶劑標準曲線的斜率)-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)標標準曲線法進行定量。

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)混合標準工作溶液，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，對應(yīng)峰面積與內(nèi)標峰面積的比值為縱坐標，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)的標準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 回收率與相對標準偏差將混合標準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加標水平下的平均回收率和相對標準偏差(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。