液相色谱-串联质谱法同时测定三七中508种农药残留

2019-07-27李雯婷毛秀红

分析测试学报 2019年7期

苗水，李雯婷，陈铭，周恒，兰岚，毛秀红，季申

(上海市食品药品检验所，上海 201203)

三七为五加科人参属植物三七Panaxnotoginseng(Burk)F.H.Chen的干燥根及根茎，主产于云南省文山州。其具有散瘀止血、消肿定痛之功效，是预防和治疗心脑血管疾病的首选药材，也是注射用血栓通、云南白药、片仔癀等药品的主要原料[1]。近年来三七的规模化人工种植日益普遍，在长达三年的生长过程中，三七易遭受各种病虫草害，因此种植过程中不可避免地使用农药。农药的过量或违规使用会导致三七药材中有农药残留，影响用药安全[2-3]。农药残留问题成为制约三七等药材走向国际市场的主要瓶颈之一。因此，亟需建立简便、高效的三七中农药残留的高通量检测方法，为农药的科学使用及政府监管提供技术支撑。

近年来，随着我国对中药材农药残留安全的重视，新的检测方法不断出现，如季申等[4-5]采用传统色谱方法分别测定了多种中药材的56种有机氯类农药与57种有机磷农药，分别采用电子捕获检测器与火焰光度检测器测定该两类农药，气相色谱双塔双柱法对阳性结果进行确证。但色谱方法需对农药进行色谱分离，单次进样可测定的农药数量仅几十种。近年来随着质谱技术发展，串联三重四极杆质谱在农药残留测定领域发挥着越来越重要的作用。较色谱方法而言，质谱法依据各农药的特征离子对定性定量，无需对各农药进行色谱分离，单次进样可测定的农药数量大大提高，且专属性好，针对中药材等复杂样本的抗基质干扰能力强。如季申等[6]建立了多种中药材中74种农药残留的液相色谱-串联质谱检测方法，黄莉莉等[7]建立了桑叶中100种农药残留的液相色谱-串联质谱测定方法，两种方法虽然测定农药种类较多，但前处理步骤较多，耗时费力，影响方法整体效能。

美国农业部Lehotay等[8]开发的QuEChERS前处理方法是对食品中农药残留测定技术的一次较大推进，该方法简便、快速、高效，依托该技术的食品中高通量多残留检测方法不断出现[9-14]。在中药材农残测定方面，季申等[15]采用气相色谱-串联三重四极杆质谱法实现了单次进样对黄芪中238种农药残留的检测，针对中药材特点对QuEChERS提取方法进行了改良。季申课题组还开发了中药中227种农药残留的气相色谱-串联三重四极杆质谱与液相色谱-串联三重四极杆质谱测定方法，采用缓冲盐QuEChERS方法提取，分散固相萃取净化，该方法已被中国药典2015年版四部通则[16]收载。然而中国药典所检测农药数量仍与食品安全国家标准有一定差距，如庞国芳等[17]针对桑枝、金银花、枸杞子和荷叶4种药材，开发了测定413种农药及相关化学品残留量的液相色谱-串联质谱法。为更好地满足中药材农药残留的监管需要，亟需进一步扩增检测农药数量。

本文在中国药典2015年版四部通则方法基础上，大幅扩增了农药数量，以改良的QuEChERS方法提取，分散固相萃取法(d-SPE)净化，采用液相色谱-串联三重四极杆质谱为检测手段，内标法定量，首次建立了单次进样可在20 min内测定三七中508种农药残留的高通量检测方法。

1 实验部分

1.1 仪器与试剂

Agilent 1290超高效液相色谱(美国Agilent公司)，AB SCIEX 6500三重四极杆质谱(美国AB SCIEX公司)；N-EVAPTM112型氮吹仪(美国Organomation公司)；IKA KS260C振荡器、IKA MS 2涡旋混合器(德国IKA公司)；UV2550紫外分光光度计(日本岛津公司)；旋转蒸发仪(瑞士BÜCHI 公司)。

农药标准品均购于德国Dr.Ehrenstorfer GmbH公司；乙腈、甲醇均为色谱纯(美国Merck公司)；醋酸(分析纯，国药集团上海化学试剂公司)；甲酸、甲酸铵均为色谱纯(美国Sigma-Aldrich公司)。净化材料：N-丙基乙二胺(PSA)、石墨化碳黑(GCB)、十八烷基键合硅胶(C18)、硅胶(Silica)、提取管(50 mL，预装6 g无水硫酸镁、1.5 g无水醋酸钠)、净化管(15 mL，预装300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica、900 mg无水硫酸镁)均购于天津博纳艾杰尔科技有限公司。

1.2 标准溶液的配制

精密称取各农药标准品及内标适量，用乙腈或甲苯分别制成1 000 μg/mL的储备溶液；精密吸取农药储备溶液适量，用含0.05%醋酸的乙腈稀释成100 μg/L和1 000 μg/L的混合标准溶液；精密量取内标储备溶液适量，用乙腈稀释成6 μg/mL的溶液。

称取三七空白样品6份，每份3 g，按照“1.4 ”方法进行提取、净化和离心后，取上清液5 mL，置氮吹仪上于40 ℃水浴浓缩至约0.4 mL，分别加入50、100 μL的100 μg/L混合标准溶液，以及50、100、200、400 μL的1 000 μg/L混合标准溶液，用乙腈定容至1 mL，涡旋混匀，过0.22 μm微孔滤膜，取续滤液，得质量浓度分别为5、10、50、100、200、400 μg/L的系列基质混合标准工作溶液。

1.3 分析条件

1.3.1 色谱条件色谱柱：Agilent Poroshell 120 EC-C18(3.0 mm×150 mm，2.7 μm)；流动相：A为0.05%甲酸+5 mmol/L甲酸铵水溶液；B为0.05%甲酸+5 mmol/L甲酸铵甲醇。梯度洗脱程序：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；进样量：2.0 μL。

1.3.2 质谱条件离子源：电喷雾离子源(ESI)；扫描方式：正离子模式；检测方式：多反应监测(MRM)模式；电喷雾电压：5 500 V；雾化气压力：344.8 kPa；辅助气压力：344.8 kPa；气帘气压力：137.9 kPa；碰撞气压力：48.3 kPa；离子源温度：500 ℃；扫描时间：10 ms；碰撞室入口电压：10 V；碰撞室出口电压：12 V；监测离子对及其质谱参数见表1。

1.4 样品前处理

供试品粉碎后过50目筛，取约3 g(精确至0.01 g)置50 mL聚苯乙烯具塞离心管中，加入1%醋酸15 mL，涡旋使其充分浸润，放置30 min，精密加入15 mL乙腈与100 μL内标溶液，涡旋混匀，剧烈振荡(500次/min) 5 min，加入无水硫酸镁与无水醋酸钠(质量比4∶1)的混合粉末7.5 g，立即摇散，再次剧烈振荡(500次/min)3 min，于冰浴中冷却10 min，离心(4 000 r/min)5 min，待净化。精密移取上清液9 mL置于分散固相萃取净化管(预装300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica、900 mg无水硫酸镁)中，涡旋混匀，剧烈振荡(500次/min) 5 min，离心(4 000 r/min)5 min，精密移取上清液5 mL，置氮吹仪上于40 ℃水浴浓缩至约0.4 mL，加乙腈定容至1 mL，涡旋混匀，过0.22 μm微孔滤膜，取续滤液，即得。

表1 508种农药的保留时间(tR)、质谱参数、检出限、相关系数(r)、平均回收率(100 μg/kg)及相对标准偏差(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

(续表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(苯霜灵)12.9326.2294.2,208.114,211100.0050.993 8102(2.8)33Benazolin-ethyl(草除灵)10.2272.1198.0,170.022,311300.0050.999 397.3(7.8)34Bendiocarb(虫威)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(麦锈灵)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(新燕灵)12.7366.1104.9,320.022,111100.0050.998 688.7(13)42Benzyladenine(苄腺嘌呤)6.6226.190.5,148.150,251800.0050.995 661.2(8.6)43Bifenazate(联苯肼酯)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(灭虫菊酯)17.0339.3171.1,143.020,331600.0050.998 777.1(5.2)46Bitertanol(联苯三唑醇)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(硫线磷)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(多菌灵)9.0192.1160.1,132.121,401300.0050.999 290.1(2.4)64Carbetamide(双酰草胺)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-羟基呋喃丹)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(萎锈灵)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(灭螨猛)15.0235.0207.0,163.025,38800.010.999 229.9(3.6)72Chlorantraniliprole(氯虫酰胺)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(氯炔灵)10.5224.0172.0,154.011,221100.050.997 2105(9.8)75Chlorfenvinphos(毒虫畏)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(绿麦隆)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(草克乐)6.0205.9188.9,172.027,261000.010.999 486.6(3.6)84Chlortoluron(绿麦隆)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)

(续表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(异草酮)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(噻虫胺)5.5250.0169.1,132.017,20800.0050.999 787.6(6.0)94Coumaphos(蝇毒磷)12.9363.0307.0,227.022,352000.010.992 491.0(4.2)95Coumatetralyl(杀鼠醚)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(苄苯隆)11.2303.2184.7,119.025,33900.0050.996 889.2(10)99Cyanazine(氰草净)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(杀螟腈)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(环草敌)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(环锈隆)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(环丙津)8.7228.1186.0,108.124,321300.0050.998 591.5(4.1)111Cyproconazole(环唑醇)11.1,11.4292.1125.0,70.042,501300.0050.996 885.7(4.2),84.1(6.2)112Cyprodinil(嘧菌环胺)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(环丙磺酰胺)6.5375.1254.1,135.017,281200.0050.999 288.3(2.4)115Cyromazine(灭蝇胺)3.5167.185.0,125.124,241000.0050.997 040.0(12)116Daimuron(杀草隆)11.1269.2151.0,119.317,26800.0050.999 787.6(5.9)117Demeton(内吸磷)10.3259.088.9,60.920,50800.0050.994 788.2(14)118Demeton-S-methylsulphon(甲基内吸磷)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(敌草净)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(燕麦敌)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(除线磷)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(苄氯三唑醇)12.4328.1159.0,198.950,291000.0050.996 481.9(9.0)128Diclocymet(双氯氰菌胺)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(苯醚甲环唑)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(除虫脲)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(异戊乙净)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(乐果)5.9230.0199.0,125.013,291100.0050.999 390.6(3.5)

(续表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%140Dimethomorph(烯酰吗啉)10.4,10.9388.1301.1,165.129,42900.0050.993 686.4(14),102(12)141Dimethylvinphos(甲基毒虫畏)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(氨氟灵)13.1323.1305.1,247.020,241300.050.996 796.3(3.8)145Dinotefuran(呋虫胺)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(双苯酰草胺)9.2239.9167.1,133.629,351800.0050.999 783.6(4.6)148Dipropetryn(异丙净)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(乙拌磷亚砜)8.3291.0213.0,185.013,201000.0050.997 695.6(7.3)151Ditalimfos(灭菌磷)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(敌草隆)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(十二环吗啉)9.2282.2116.5,115.634,391800.0050.998 569.1(5.3)156Emamectin-benzoate(甲氨基阿维菌素)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(氟环唑)11.7330.1121.0,123.027,24900.0050.999 786.1(4.0)159Eprinomectin(依立诺克丁)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(乙环唑)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(硫草敌)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(乙虫腈)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(乙氧呋草黄)10.3287.1259.1,121.114,241300.0050.990 576.8(6.6)172Ethoprophos(灭线磷)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(伐灭磷)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(苯线磷)12.2304.1276.1,217.019,311600.0050.999 088.6(2.8)182Fenamiphos sulfone(苯线磷砜)7.3336.1308.1,266.021,281800.0050.999 385.9(4.4)183Fenamiphos sulfoxide(苯线磷亚砜)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(氧皮蝇磷)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(环酰菌胺)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(精唑禾草灵)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(拌种咯)9.7237.1202.0,139.927,471700.0050.999 391.8(2.7)195Fenpropidin(苯锈啶)9.5274.386.1,147.128,281800.0050.998 869.4(7.1)

(续表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%196Fenpropimorph(丁苯吗啉)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(丰索磷)8.9309.0281.0,253.020,251600.0050.998 892.9(3.7)199Fensulfothion-oxon(氧丰索磷)6.2293.1265.0,237.020,211600.0050.998 791.9(4.5)200Fensulfothion-oxon-sulfone(氧丰索磷砜)8.9309.1281.0,253.015,231500.0050.999 993.1(4.5)201Fensulfothion-sulfone(丰索磷砜)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(氧倍硫磷亚砜)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(倍硫磷亚砜)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(麦草氟异丙酯)12.5364.1104.9,304.123,131000.0050.998 479.8(13)211Flamprop-methyl(麦草氟甲酯)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(氟啶虫酰胺)5.0230.1202.8,174.026,271100.0050.999 786.7(4.6)214Florasulam(双氟磺草胺)6.0360.0129.0,192.030,241400.0050.999 692.1(2.2)215Fluazifop-P-butyl(精吡氟禾草灵)14.5384.1328.1,282.124,291800.0050.999 288.6(4.4)216Fluazuron(吡虫隆)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(氟虫脲)15.6489.1158.1,141.125,69360.0050.999 481.8(3.9)221Flufenpyr-ethyl(氟哒嗪草酯)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(氟啶嘧磺隆钠)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(氟草烟-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(地虫硫磷)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(麦穗宁)6.1185.1157.1,156.131,391600.0050.997 075.2(5.4)248Furalaxyl(呋霜灵)10.1302.1242.1,95.120,351120.0050.999 687.3(2.7)249Furathiocarb(呋线威)14.6383.2252.1,195.017,251300.0050.999 391.2(5.5)250Furmecyclox(拌种胺)12.6252.1170.0,138.019,201000.0050.999 287.5(3.5)251Griseofulvin(灰黄霉素)8.1353.0165.0,214.925,251500.0050.999 689.0(4.2)

(续表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%252Halofenozide(氯虫酰肼)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(氟铃脲)13.7461.2157.9,141.122,631800.0050.996 982.4(13)258Hexazinone(环嗪酮)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(烯虫乙酯)19.4267.2108.9,123.023,201000.050.998 184.1(9.9)261Imazalil(烯菌灵)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(甲氧咪草烟)5.8306.1261.1,246.129,341600.050.992 881.2(10)264Imazapic(甲咪唑烟酸)5.9276.2231.1,216.032,321300.0050.999 272.0(3.3)265Imazaquin(灭草喹)6.8312.1267.1,199.130,391400.0050.999 156.0(4.8)266Imazethapyr(咪草烟)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(亚胺唑)14.8411.1124.9,341.833,211200.0050.998 365.7(3.4)269Imidacloprid(吡虫啉)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(茚虫威)13.7528.1293.0,249.019,231800.0050.998 895.6(6.4)272Ipconazole(种菌唑)13.7,13.9334.1125.0,70.060,601600.0050.998 579.2(4.5),80.4(6.7)273Iprobenfos(异稻瘟净)12.2289.1205.1,90.815,26600.0050.991 275.4(10)274Iprodione(异菌脲)12.3330.0244.9,247.020,201200.0050.990 4100(14)275Iprovalicarb(异丙菌胺)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(异硫磷)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(异丙威)8.8194.0152.0,137.011,131200.0050.998 689.2(2.5)282Isopropalin(异丙乐灵)16.3310.2226.0,206.126,24960.0050.998 881.1(3.3)283Isoprothiolane(稻瘟灵)11.1290.9188.9,231.030,15700.0050.996 4109(6.9)284Isoproturon(异丙隆)8.8207.172.0,165.124,201400.0050.999 787.6(3.8)285Isouron(异隆)7.4212.0169.9,114.124,311450.0050.994 268.9(4.8)286Isoxaben(异酰草胺)10.8333.2165.1,150.027,55700.0050.999 282.0(5.1)287Isoxadifen-ethyl(双苯唑酸)12.2296.2232.1,263.224,15700.0050.998 592.4(2.4)288Isoxaflutole(异氟草)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(伊维菌素)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(特胺灵)6.9280.2180.6,224.020,141600.0050.992 796.5(9.4)293Kresoxim-methyl(亚胺菌)12.3314.1267.1,116.010,201300.0050.996 798.6(13)294Lactofen(乳氟禾草灵)14.4479.1344.0,223.021,48600.0050.998 289.1(12)295Lenacil(环草定)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(马拉氧磷)7.2315.1269.0,127.011,171200.0050.999 790.0(5.5)300Malathion(马拉硫磷)11.1331.0285.0,127.010,171300.050.994 391.4(14)301Mandipropamid(双炔酰菌胺)10.7412.1328.1,356.120,141300.0050.998 790.6(9.2)302Mecarbam(灭蚜磷)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(灭锈胺)11.2270.1228.1,119.020,321500.0050.998 682.3(4.3)

(续表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(氰氟虫腙)14.4507.1286.8,178.040,331900.0050.996 578.6(4.9)311Metalaxyl(甲霜灵)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(叶菌唑)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(虫螨畏)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(灭虫威)10.9226.1169.1,121.114,261500.050.990 384.4(14)320Methomyl(灭多威)5.1163.1106.0,88.013,121000.0050.995 775.5(13)321Methoprotryne(盖草津)9.8272.1240.2,198.126,261000.0050.999 784.7(4.3)322Methoxyfenozide(甲氧虫酰肼)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(异丙甲草胺)12.0284.2252.0,176.222,361000.0050.999 792.6(4.6)325Metolcarb(速灭威)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(速灭磷)5.8,6.2225.1193.0,127.011,221200.050.998 679.1(12),91.8(13)331Molinate(草达灭)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(绿谷隆)7.9215.1148.1,126.025,25400.0050.992 698.3(13)335Monuron(灭草隆)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(敌草胺)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(烟嘧磺隆)6.8411.0181.9,213.135,251100.050.992 483.7(5.2)343Nitenpyram(烯啶虫胺)4.8271.1225.0,189.116,171000.0050.996 881.3(3.0)344Nitralin(甲磺乐灵)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(氧化乐果)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(稻思达)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(霜灵)6.6279.1219.1,132.116,431200.0050.999 490.4(10)357Oxamyl(杀线威)4.8237.1220.1,90.17,12900.050.996 594.2(13)358Oxasulfuron(环氧嘧磺隆)6.5407.0150.1,210.027,34800.0050.999 482.5(6.9)359Oxycarboxin(氧化萎锈灵)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(乙基对氧磷)8.5276.0248.0,220.014,221400.010.999 592.8(4.2)363Paraoxon-methyl(甲基对氧磷)6.6248.0231.0,202.024,271600.010.990 2101(7.9)

(续表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(对氧磷)8.2276.1219.8,248.120,12950.0050.998 495.4(4.2)365Pebulate(克草敌)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(蔬草灭)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(甜菜宁)9.5318.1168.1,136.019,34500.0050.990 675.6(9.5)372Phenthoate(稻丰散)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(伏杀硫磷)13.3368.0322.0,182.014,231600.050.999 197.1(14)377Phosfolan(硫环磷)6.2256.1139.9,167.934,221200.0050.999 093.4(3.8)378Phosmet(亚胺硫磷)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(哌丙灵)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(氨氟乐灵)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(猛杀威)11.1208.1109.0,151.023,13760.0050.999 882.2(13)396Prometon(扑灭通)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(敌稗)10.9218.1162.1,127.121,331200.0050.997 991.9(7.9)399Propaphos(丙虫磷)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(丙环唑)13.0342.1205.0,159.025,351700.010.999 186.4(3.2)404Propisochlor(异丙草胺)12.6284.1224.1,148.114,29600.0050.997 689.8(5.0)405Propoxur(残杀威)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(苄草丹)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(吡喃灵)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(除虫菊素)13.6373.3160.9,133.032,17700.0050.998 996.3(13)420Pyridaben(哒螨灵)16.8365.0147.0,309.031,19860.0050.999 391.3(7.6)421Pyridalyl(啶虫丙醚)18.7492.0183.0,204.023,261700.0050.998 849.1(3.5)

(续表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%422Pyridaphenthion(哒嗪硫磷)11.1341.1189.0,205.029,291700.0050.997 094.4(8.1)423Pyridate(哒草特)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(环酯草醚)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(灭藻醌)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(苄呋菊酯)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(鱼藤酮)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(脱乙基另丁津)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(环草隆)10.5,10.7233.193.6,136.734,281400.0050.999 182.1(4.0)444Simazine(西玛津)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(西玛通)6.4198.2128.2,124.031,38850.0050.998 889.6(4.1)447Simetryn(西草净)8.1214.0166.0,123.929,371300.0050.999 379.5(4.6)448Spiroxamine(螺环菌胺)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(螺虫乙酯)6.1329.0138.9,110.924,341500.0050.999 183.5(4.4)451Spirodiclofen(螺环菌胺)16.0411.1313.0,295.017,351400.0050.997 057.6(3.9)452Sulfallate(螺环菌胺)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(磺酰磺隆)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(氟啶虫胺腈)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(抑虫肼)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(环磺酮)8.9441.1341.1,304.912,251100.0050.990 871.4(10)470Temephos(双硫磷)13.0,14.6467.0419.0,341.026,392200.0050.996 076.6(13),97.8(2.3)471Tepraloxydim(快捕净)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(特丁净)11.4242.1137.9,158.035,331000.0050.998 082.4(7.1)

(续表1)

No.PesticidetR(min)Parent ion(m/z)Quantitative,qualitative ions(m/z)CE(V)DP(V)LOD(mg/kg)rAverage recovery(RSD)/%475Tetrachlorvinphos(杀虫畏)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(噻菌灵)5.8202.0175.0,131.135,451800.0050.999 153.5(4.0)479Thiacloprid(噻虫啉)6.1253.0186.0,126.020,301400.010.998 692.9(5.0)480Thiamethoxam(噻虫嗪)5.2292.0211.1,181.118,311100.0050.999 590.3(8.3)481Thiazopyr(噻唑烟酸)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(硫双威)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(唑虫酰胺)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(野麦畏)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(脱叶磷)16.6315.1169.0,225.121,161200.0050.999 183.1(2.9)496Trichlorfon(敌百虫)5.8256.9109.0,221.025,151300.010.994 8101(10)497Tricyclazole(三环唑)6.3190.0163.0,136.028,342000.0050.993 588.4(1.9)498Trietazine(草达津)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(杀铃脲)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(灭菌唑)10.1,11.6318.1125.0,191.244,28600.0050.999 292.5(14),93.8(6.5)505Valifenalate(缬菌胺)10.9,11.2399.1214.1,144.016,20730.0050.998 491.5(5.9),88.2(7.2)506Vamidothion(灭蚜硫磷)5.6288.0146.1,118.017,33800.0050.999 492.1(5.3)507Vernolate(灭草敌)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 结果与讨论

2.1 前处理方法的优化

早期QuEChERS法[8]采用乙腈提取，氯化钠盐析，该方法对大多数农药的回收率良好，但对部分碱性条件下不稳定农药(如百菌清和p，p'-滴滴涕等)的测定结果重现性差、加标回收率低，且部分农药在标准溶液中不稳定。针对上述问题，AOAC 2007.01方法[18]改用pH 5.0的醋酸盐缓冲体系，用含少量醋酸的乙腈配制标准溶液。本文在中国药典2015版四部通则<2341>方法[16]的基础上对样品前处理方法进行优化。

2.1.1 药材浸泡时间的选择三七的含水量低，且部分农药在碱性或中性条件下易降解，因此采用1%醋酸浸泡三七药材。以检出残留量较大的嘧菌酯、苯醚甲环唑、戊唑醇、氟环唑与嘧霉胺的三七阳性样品为研究对象，考察了不同浸泡时间(0、0.5、1、2 h)对提取效率的影响。结果表明，随着浸泡时间的增加，各农药的提取效率呈增加趋势，但浸泡0.5 h后提取效率相差不大，说明浸泡0.5 h即可将农药提取完全，因此选择浸泡时间为0.5 h，与中国药典2015版四部通则<2341>方法一致。

图1 净化材料用量对三七皂苷类成分净化效果的影响Fig.1 Effect of purification material amount on notoginsenosides removal efficiency

图2 508种农药及内标混合标准溶液的总离子流(TIC)色谱图Fig.2 Total ion chromatograms of 508 pesticides and internal standards solution

2.1.2 净化材料的选择在中国药典2015版四部通则方法的净化材料(即300 mg PSA、300 mg C18、90 mg GCB、300 mg Silica)基础上，进一步优化了净化材料配比。以三七提取液中所含的主要皂苷类成分为指标，采用中国药典2015版的高效液相色谱法测定净化前、后提取液中三七皂苷R1、人参皂苷Rg1、人参皂苷Rb1、人参皂苷Re总量，评价净化效果。图1结果显示，GCB用量对皂苷总量几乎无影响，C18对皂苷的去除效果不明显，但两者对三七中其他干扰成分有一定净化作用，故选择上述药典方法的用量。Silica与PSA对总皂苷的去除效果最为明显，但当PSA用量增至300 mg以上时，皂苷总量下降不明显；随着Silica用量的增加，皂苷总量下降明显，而Silica用量超过600 mg时，净化材料所占体积增加，无法从净化管中移取5 mL净化液进行浓缩，故PSA和Silica用量分别选择为300、600 mg。

综上，最终确定净化材料的配比为300 mg PSA、300 mg C18、90 mg GCB、600 mg Silica。此时，净化步骤总皂苷的去除率达94.3%，净化效果较好。优化条件下508种农药的总离子流色谱图见图2。

2.2 基质效应的评价

基质效应是痕量分析的常见现象。样品基质中的共提取干扰物影响待测化合物的仪器响应值，使得相同浓度的目标化合物在溶剂标准溶液与基质标准溶液的响应值不一致，表现为基质标准溶液的仪器响应发生增强或抑制。本文采用下式对目标化合物的基质效应进行评价：基质效应=[(基质匹配标准曲线的斜率/溶剂标准曲线的斜率)-1]×100%[19]。结果发现，仅有136种农药的基质效应不明显(<20%)，372种农药均产生中等或较强的基质抑制效应(≥20%)。为克服基质效应的影响，采用基质匹配内标标准曲线法进行定量。

2.3 方法学验证

2.3.1 线性关系与检出限按照“1.2”方法配制基质混合标准工作溶液，采用本方法进行前处理和测定。以各组分的质量浓度为横坐标，对应峰面积与内标峰面积的比值为纵坐标，进行回归分析。结果表明，508种农药均在0.005～0.4 mg/L范围内呈良好线性关系，相关系数(r)均大于0.99。由于待测农药数量多，难以逐一稀释至每个农药的最低检出浓度，因此以实际检测到各农药2个MRM反应的标准曲线最低浓度作为检出限，得到方法检出限(LOD)为0.005～0.1 mg/kg(见表1)。

2.3.2 回收率与相对标准偏差将混合标准储备溶液添加到三七空白样品中，按“1.4”方法分别制得加标水平为10、50、100、200 μg/kg的样品溶液，每个水平重复7次。其中，100 μg/kg加标水平下的平均回收率和相对标准偏差(RSD)见表1，除8种农药外，其余500种农药的回收率为50.2%～117%。

对各加标水平下508种农药的回收率百分比进行分析。结果显示，10 μg/kg加标水平下有412种农药的回收率为70%～120%，占农药总数的81%；50 μg/kg加标水平下有485种农药的回收率为70%～120%，占总数的95%；100 μg/kg加标水平下有468种农药的回收率为70%～120%，占总数的92%；200 μg/kg加标水平下有477种农药的回收率为70%～120%，占总数的94%。各加标水平下的RSD均不大于15%。