PTV_GC_MS_MS同时测定烟草中202种农药残留_楼小华

1、PTV-GC-MS/MS 同时测定烟草中202种农药残留楼小华1,高川川1,朱文静1,张洪非2,唐纲岭2,边照阳2,巴金莎11.贵州省烟草质量监督检测站,贵阳市金阳新区云潭北路5500252.国家烟草质量监督检验中心,郑州高新技术产业开发区枫杨街2号450001摘要:研究了应用程序升温汽化进样-气相色谱-串联质谱(PTV-GC-MS/MS 技术检测烟草中202种农药品种221个组分的高效方法。以QuEChERS 技术快速提取烟草中残留农药并净化,PTV 进样后在TR-pesticide II 毛细管柱上分离,通过优化串联质谱参数,有效降低复杂基质干扰及农药组分重叠峰的相互串扰,以保留时间窗口和

2、特征SRM (选择性反应监测离子对定性、峰面积定量。结果表明:202种农药在0.012.50mg/L 范围内线性良好,相关系数为0.98000.9999,检测限0.00020.0100mg/kg ,加标回收率67.4%112.0%,RSD 0.30%20.30%。应用该方法对44个进口烟叶样品进行检测验证,效果良好。该方法对农药品种覆盖面广,前处理简便、快捷,节省溶剂;一次进样在46min 内可分析221个组分,准确、灵敏。关键词:程序升温汽化(PTV ;气相色谱-串联质谱;烟草;农药残留中图分类号:TS411.2文献标识码:B文章编号:1002-0861(201308-0045-13基金项目

3、:贵州省烟草专卖局资助项目“110种农药残留物在卷烟燃吸微环境中的归趋”(201031及“控制烟叶农残监测体系研究”(200908。作者简介:楼小华(1963,本科,高级工程师,主要从事气相色谱、质谱、三重四极杆串联质谱等分析烟草中农药残留研究。E-mail :louxh6311 电话:0851-*收稿日期:2012-11-02责任编辑:茹呈杰E-mail :rucj69 电话:0371-*Simultaneous Determination of 202Pesticide Residues in Tobacco by PTV -Gas Chromatography -Tandem Mass

4、SpectrometryLOU Xiaohua 1,GAO Chuanchuan 1,ZHU Wenjing 1,ZHANG Hongfei 2,TANG Gangling 2,BIAN Zhaoyang 2,and BA Jinsha 11.Guizhou Tobacco Quality Supervision &Test Station,Guiyang 550025,China2.China National Tobacco Quality Supervision &Test Center,Zhengzhou 450001,ChinaAbstract:An effectiv

5、e method for detecting 202pesticide residues (221componentsin tobacco was developedbyPTV-GC-MS/MS(Programmedtemperaturevaporizationsamplingtechnology-gaschromatography-tandem mass spectrometry.The pesticide residues in tobacco sample were extracted rapidly and purified with QuEChERS technique,then s

6、eparated on TR-pesticideII capillary chromatographic column after PTV sampling.The interference of complex matrix and peak overlapping of various pesticide components were reduced by means of optimizing tandem mass spectrometry parameters.Qualitative and quantitative analyses were conducted by reten

7、tion time window and SRM (selective reaction monitoringwith peak area respectively.The results showed that:1The 202pesticides kept good linear relationships in the range of 0.01-2.50mg/L with the correlative coefficients between 0.9800and 0.9999.The limits of detection (LODwere from 0.0002to 0.0100m

8、g/kg,and the recoveries of added standards ranged from 67.4%to 112.0%with the relative standard deviations (RSDof 0.30%-20.30%.2This method was verified with 44samples of imported tobacco leaves,and results were satisfied.3This method covered a wide range of pesticides,featured烟草科技/Tobacco Science &

9、amp;Technology 2013年第8期(总第313期烟草化学/Tobacco Chemistry目前,烟草中的农药残留日益受到关注,国际上有28个国家及地区对卷烟和烟叶中残留最高限量做出规定的农药多达660余种。CORESTA农用化学品咨询委员会(ACAC2003年发布了农用化学品指导性残留限量的基本原则与实施意见,对99种农药残留提出了指导性限量(GRLs,2008年增加到了118种,今后将会继续增加。我国目前尚无系统的限量列表,主要参照ACAC限量作为进出口烟草贸易评价依据,残留农药的分析方法主要围绕此名单开发建立。为提高农药残留分析效率,传统的一种方法一种残留(特殊农药除外的检测

10、技术逐步被多种、多类农残的高通量残留分析技术所取代,仪器分析也从单纯的气相色谱(GC、液相色谱(LC,发展到气相(液相色谱-质谱联用(GC/ MS,LC/MS及液相色谱-串联质谱联用(LC-MS/MS,甚至全二维气相色谱-飞行时间质谱(GC×GC-TOF-MS1-4。美国和欧洲烟草中农药残留量的测定方法比较完备,方法分为单残留测定和同时多残留测定5-11;我国对烟草中多种农药残留分析方法作了大量研究12-13,并颁布了一系列农残检测方法标准14-17。以上研究动向总体表现在前处理逐渐简化、一次性分析农药残留品种逐步增加,大大提高了分析效率;但迄今尚无统一的方法发布。GC-MS/MS具

11、有高选择性、高灵敏度等优点18,对大多数热稳定性、挥发及半挥发性农药残留分析有着无可比拟的优势,然而此类技术应用在烟草中农药残留分析却少见报道。为此,建立了以QuEChERS技术一次性前处理、GC-MS/MS一针进样分析202种有机磷、有机氯、有机氮及杂环类、拟除虫菊酯类杀虫剂和杀菌剂,以及植物生长调节剂残留量的方法。1材料与方法1.1仪器和试剂Thermo Scientific Trace GC Ultra-TSQ Quantum XLS 气相色谱-三重四极杆串联质谱联用仪(美国ThermoFisher Scientific公司;Labnet VX200漩涡振荡器(美国Labnet公司;Ce

12、nturion K-241高速离心机(英国Centurion公司。44个进口烟叶(中部叶样品(贵州省烟叶进出口有限公司提供。乙腈、甲苯、正己烷、丙酮(色谱纯,德国Merck公司;超纯水(电阻率18.2M,自制;QuEChERS试剂盒(美国Agilent公司;24种有机氯杀虫剂、78种有机磷杀虫剂、11种氨基甲酸酯类杀虫剂、5种杂环类杀虫剂、14种拟除虫菊酯类杀虫剂、12种杀螨剂、39种杀菌剂、6种抑芽剂和13种除草剂标准品(纯度9599%,德国Augshurg公司,分别用正己烷或丙酮溶解并配制成单独的50mg/L的标准溶液,再以甲苯稀释配制成0.01 2.50mg/L的混合标准溶液;内标物“氯

13、唑磷”、“灭蚁灵”(纯度99%,德国Augshurg公司,分别配成0.2mg/L的甲苯溶液,储存于4冰箱备用。1.2样品处理1.2.1烟叶样品制备烟叶样品在40下烘干,粉碎,过20目筛,避光低温保存。1.2.2样品前处理(1提取:称取2g烟末样品于50mL具盖离心试管中,加10mL水充分浸润,静置10min。移取10mL乙腈和一定量的“氯唑磷”、“灭蚁灵”内标工作液到离心管中,漩涡振荡2min,加入QuEChERS试剂盒1(4g无水硫酸镁,1g氯化钠,1g柠檬酸钠和0.5g柠檬酸氢二钠和5mL甲苯,立即手持振荡,防止无水硫酸镁结块,以4000r/min的转速离心10min。(2净化:移取5mL

14、样品提取液上清液于10mL离心管中,加入QuEChERS试剂盒2(500mg无水硫酸镁+ 150mg N-丙基乙二胺键合固相吸附剂,PSA,涡旋振荡2min,以6000r/min的转速离心10min。吸取上清液,经0.22µm有机相滤膜过滤后进行GC-MS/MS分析。分析条件为:气相色谱(GC:进样模式:带PTV功能的不分流进样; Surge压力:150kPa(2min;进样口初始温度:70,进样后以4/s快速升至280;毛细管柱:TR-Pesticide II(50%苯基甲基聚硅氧烷,30m×0.25mm×0.25µm+5m×0.25

15、1;m Guard (预柱;载气:He;载气流速:1.2mL/min;程序升温:90(5min25/min180(15min5/min280(4.5min;后运行温度:320(5min。GC/MS传输线温度:270。串联质谱(MS/MS:离子源温度:250;发射电流:50A;离子化模式:EI;离子源:封闭式EI源;分析模式:timed-SRM (定时选择性反应监测;扫描宽度:0.002m/z;扫描周期0.4s;峰宽:Q10.7Da,Q30.7Da;碰撞气压力:1.5mTorr(Ar;色谱过滤峰宽:10s。液体自动进样器:进样体积:1L;进样模式:PTV进样;the advantages of

16、simple and rapid in pre-treatment,solvent saving and capable of analyzing221components accurately and sensitively within46minutes by a single sample injection.Keywords:Programmed temperature vaporization(PTV;Gas chromatography-tandem mass spectrometry(GC-MS/MS; Tobacco;Pesticide residue进样前后驻留模式:3和2s

17、 。2结果与讨论2.1样品前处理条件的选择2.1.1样品的提取鉴于烟草中的复杂基质,在乙腈、丙酮和乙酸乙酯3种常用提取溶剂中,乙腈对烟草样品中的蜡质、色素、糖类溶解最少或杂质可随水相分离,因此,作为提取溶剂的首选。在柠檬酸钠和柠檬酸氢二钠缓冲溶液条件下,在提取液中加入氯化钠可增加极性农药的回收率,减少共提取极性物糖类分解产物,减少提取物中水含量,降低基质增强效应。使用硫酸镁可显著增加上层乙腈的体积,通过减少水相的体积,更方便地促使极性农药进入有机相,提高回收率;并且硫酸镁吸水时放热,有利于提高提取效率;通过离心可以避免液-液分配时可能遇到的乳化现象。2.1.2样品的净化本法采用少量吸附试剂与提

18、取溶剂混合,然后采用离心机将固体吸附剂与净化的溶液分离。PSA 是弱离子交换的固相吸附剂,不保留农药,但能有效去除样品中极性干扰物质。用无水硫酸镁作吸水干燥剂,具有比无水硫酸钠吸水更快更彻底的优点,能有效避免水分直接进入GC ,避免影响色谱柱寿命。2.1.3内标物的选择“灭蚁灵”、“氯唑磷”是两种较为稳定的有机氯和有机磷杀虫剂,在烟草上不使用,本研究分别用来作为有机氯、拟除虫菊酯类农药和有机磷、有机氮及杂环类农药的内标物。以上提取、净化方法,其基本原理为近年来较常用作多农残分析的QuEChERS 法19-20,其试剂盒已商品化。2.2PTV 进样参数的优化程序升温汽化进样技术(PTV ,Pro

19、grammed Temperature Vaporization 由V ogt 等20首次公布,主要是通过增大进样体积、低温进样口吹扫多余溶剂、富集溶质、快速升温进入色谱柱,从而达到提高检测灵敏度的目的,适合于基质复杂样品中的农残分析18,21-23。由于烟草基质较为复杂,为保护色谱柱和离子源,本研究不采取大体积进样,而是利用PTV 进样口的程序升温技术,从较低温度开始,将极性较强、容易热分解的“敌百虫”、“甲胺磷”、“乙酰甲胺磷”、“氧化乐果”和“久效磷”等5种农药组分在低温下导入色谱柱,再以快速升温程序升至280,使全部农药组分进入色谱柱。以上述5种农药组分和24种有机磷农药组分作为代表物

20、选择PTV 条件(见图1:进样口初始温度50,最后温度280,吹扫时间2min 。由于溶剂为甲苯,初始温度过低,溶质在溶剂之前蒸发,峰高较低。进样口初始图1PTV 进样口不同初始温度对29种有机磷农药组分(全扫描峰高的影响Fig.1Influence of different initial temperatures of PTV injector on height of peak of 29organophosphorus pesticide components(full scan a.初始温度/initial temperature 50b.初始温度/initial temperatu

21、re 70c.初始温度/initial temperature 100图2“甲胺磷”(a 、“敌百虫”(b 、“乙酰甲胺磷”(c 、“氧化乐果”(d 和“久效磷”(e SRM 扫描色谱图(PTV 进样Fig.2SRM chromatogram of methamidophos(a,trichlorphon(b,acephate(c,omethoate(dand monocrotophos(e(with PTV injection温度70,最后温度280,吹扫时间2min 。溶质峰高较前一个条件提高410倍。进样口初始温度100,最后温度280,吹扫时间2min 。溶质峰高减低,且峰型拖尾。因此

22、,采用进样口初始温度70、升温速率4/s 、最后温度280和吹扫时间2min ,并在色谱柱前加预柱保护作为优选条件,“敌百虫”、“甲胺磷”、“乙酰甲胺磷”、“氧化乐果”和“久效磷”5个组分的峰型良好(图2。以上初始温度对其余沸点较高组分影响不大。2.3色谱柱的选择本研究曾使用非极性毛细管柱HP -101,中等极性柱HP -5MS ,DB -17和DB -1701,极性柱PEG -20M 和FFAP 等,长度分别为15和30m 。在质谱全扫描条件下,主要考察所有农药在上述色谱柱上的分离度。结果表明,上述色谱柱对一针进样的所有农药均存在分离度不佳、保留时间疏密不均等现象,特别是非极性柱和极性柱在某

23、一个保留时间存在35个组分的峰群重叠现象,不利于准确定性定量。最后选择由Thermo Scientific 公司提供的TR-Pesticide II 30m×0.25mm×0.25m+5m×0.25m 预柱(弱极性,具有良好的分离性能,其极限温度可达360,有利于高沸点农药组分如溴氰菊酯、烯酰吗啉的快速出峰,且在后运行阶段可将柱温升至300以上,以避免烟草中高沸点基质污染。虽仍存在一些重叠峰,但峰群较为匀称,分析周期缩短到了46min (图3。2.4SRM 质谱参数的优化先以全扫描方式确定每一种农药单标的保留时间,或以一定品种数量的混标以质谱农残专用谱库(Pest

24、icide Libraries 定性并确定保留时间,再通过更换不同的碰撞能量(CID 选择丰度相对较高、体现特征的母离子子离子对,同时得到离子对的丰度比。将每一种组分至少2个离子对及碰撞能量在Excel 表中进行编辑,或将查阅文献得到的优化参数通过EZmethod 功能直接导入到仪器方法中。为避免烟草基质的串扰而出现假阳性,采取“保留时间+定性定量离子对+丰度比”三重定性方式,使定性定量结果更加可靠。加上三重四极杆串联质谱具有高通量离子传输性能和碰撞室零串扰技术特点,有效解决了重叠农药组分和基质的干扰问题。202种农药的SRM 监测参数见表1。2.5烟草中常用农药的定性定量中国烟叶公司每年均发

25、布烟草上推荐使用的农药品种列表,限定能在烟草上使用的高效、低毒、低残留化学农药或生物农药品种。各产烟省均据此统一采购农药并下发给烟农;但不排除烟农市场上自行采购农药并在烟草上使用的可能。同时,世界各产烟国在烟草上所使用的农药品种不尽相同,ACAC 的GRLs 也很难兼顾到所有正在或将要使用的农药。各国与之配套1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26“3-羟基克百威”“乙酰甲胺磷”“啶虫脒”“甲草胺”“艾氏剂”“双甲脒”“益棉磷”“谷硫磷”“嘧菌酯”“苯霜灵”“氟草胺”“丙硫克百威”“排草丹”“联苯菊

26、酯”“溴硫磷”“溴螨酯”“噻嗪酮”“仲丁灵”“硫线磷”“克菌丹”“甲萘威”“卡草胺”“克百威”“三硫磷”“灭螨猛”“-氯丹”3-HydroxycarbofuranAcephateAcetamiprideAlachlorAldrinAmitrazAzinphos-ethylAzinphos-methylAzoxystrobinBenalaxylBenfluralinBenfuracarbBentazonBifenthrinBromophos-ethylBromopropylateBuprofezinButralinCadusafosCaptanCarbarylCarbetamidCarbofur

27、anCarbophenothionChinomethionatChlordane-cis18013615218829329316016034426629216419818135934317226615914914411916434220637513794116160258147771323291482641491191653031855719097701159114915714826815151510251520520101010121520201015201220151010151514.9612.1035.7016.9519.8538.4338.9037.4546.0432.9311.83

28、39.0417.8236.2926.2536.0529.6221.9312.1724.5210.1517.2912.9933.1425.7927.030.0010.00020.0050.0020.00050.0010.0050.0050.0080.0050.0030.0010.0050.0010.00050.00080.0010.0050.0080.0080.0080.0050.00020.00050.0080.00050.99420.98810.99560.99610.99320.98890.99660.98120.98630.99560.98970.99220.99630.99610.98

29、750.99560.99440.99790.98680.98720.99430.98770.99470.99450.99520.998682.980.184.686.792.3102.287.995.279.986.395.092.592.497.6106.2104.3100.296.6104.478.980.2103.685.887.790.595.98.810.36.53.23.612.32.210.112.59.56.75.56.45.13.96.62.35.910.914.39.53.68.23.36.66.5序号名称英文通用名母离子/(m/z子离子/(m/z碰撞能/eV保留时间/mi

30、nLOD/(mg/L相关系数r2回收率/%变异系数CV/%图3221个农药组分选择性离子监测总离子流图(烟草基质中Fig.3SRM TIC of221pesticide components(tobacco matrix表1202种农药(221个组分的SRM质谱参数及检测限、回收率Tab.1SRM Mass parameters,LOD and recoveries of202pesticides(221components 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 5

31、5 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71“-氯丹”“杀螨酯”“毒虫畏”“氯甲磷”“乙酯杀螨醇”“丙酯杀螨醇”“百菌清”“毒死蜱”“甲基毒死蜱”“敌草索”“蝇毒磷”“苯腈膦”“氟氯氰菊酯-1”“氟氯氰菊酯-2”“氟氯氰菊酯-3”“氟氯氰菊酯-4”“氯氰菊酯-1”“氯氰菊酯-2”“氯氰菊酯-3”“氯氰菊酯-4”“环唑醇-1”“环唑醇-2”“二溴氯丙烷”“溴氰菊酯”“内吸磷”“异吸硫磷”“异吸硫磷砜”“二嗪农”“苄氯三唑醇”“除线磷”“敌敌畏”“禾草灵”“氯硝胺”“三氯杀螨醇”“百治磷”“狄氏剂”“恶醚唑-1”“恶醚唑-2”“甲氟磷”“乐果”

32、“烯酰吗啉-1”“烯酰吗啉-2”“烯唑醇”“敌螨普”“双苯酰草胺”Chlordane-transChlorfensonChlorfenvinphosChlormephosChlorobenzilateChloropropylateChlorothalonilChlorpyrifosChlorpyrifos-methylChlorthal-dimethylCoumaphosCyanofenphosCyfruthrin-1Cyfruthrin-2Cyfruthrin-3Cyfruthrin-4Cypermethrin-1Cypermethrin-2Cypermethrin-3Cypermethri

33、n-4Cyproconazol-1Cyproconazol-2DBCPDeltamethrinDemeton-SDemeton-s-methylDemeton-S-methyl sulfoneDiazinonDiclobutrazolDichlofenthionDichlorovosDiclofop methylDicloranDicofolDicrotophosDieldrinDifenoconazol-1Difenoconazol-2DimefoxDimethoateDimethomorph-1Dimethomorph-2DiniconazolDinocapDiphenamid373175

34、325154139253266314286301226169226226226226163163163163222222157251109142169304270223185253206251193277325325154125301301268253239266111269121111141133258271223163141206206206206127127127127125125751728179109179159205931621761391272412672671114727327323223616718101051515201525251510151515151010101020

35、2058151015151510121510151010202010151010151025.9228.0523.486.4431.1531.1414.3419.9616.4820.3340.3322.9641.4441.6641.7741.8841.9042.3042.4042.9020.9821.986.5945.7012.7811.2617.8614.0820.2616.117.9924.1412.8821.259.7828.8644.8044.965.4012.8346.3347.2231.2814.0022.070.00050.0010.0010.0010.0020.0020.008

36、0.0020.0020.0080.0020.0040.0010.0010.0010.0020.0010.0080.0080.0150.00080.0040.0050.00050.0050.00050.0050.0010.00050.0080.0010.00080.010.0050.0050.010.99960.98470.98520.99550.99000.99310.98440.99650.99410.98920.99630.99930.99680.99350.98810.98520.99620.98840.99290.98000.99990.98630.99650.99660.98210.

37、99670.98850.99270.99960.98550.99750.98990.98440.99280.98740.9898101.197.3110.283.384.687.775.3102.393.679.885.293.2100.4103.578.269.596.776.586.267.498.982.2112.0101.279.688.575.079.296.9103.296.5102.5107.585.778.668.71.70.69.53.16.610.69.95.512.512.53.910.00.73.69.915.92.96.39.818.71.65.03.83.214.4

38、5.714.411.65.06.63.11.65.110.313.219.6序号名称英文通用名母离子/(m/z子离子/(m/z碰撞能/eV保留时间/minLOD/(mg/L相关系数r2回收率/%变异系数CV/% (续表172 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116“乙拌磷”“乙拌磷砜”“灭菌磷”“吗菌灵-1”“吗菌灵-2”“克瘟散”“-硫丹

39、”“-硫丹”“硫丹硫酸酯”“异狄氏剂”“苯硫磷”“乙硫磷”“灭线磷”“醚菊酯”“乙螨唑”“乙嘧硫磷”“氨磺磷”“苯线磷”“苯线磷砜”“苯线磷亚砜”“皮蝇硫磷”“杀螟硫磷”“甲氰菊酯”“除螨酯”“倍硫磷”“倍硫磷亚砜”“氰戊菊酯-1”“氰戊菊酯-2”“氟氰戊菊酯-1”“氟氰戊菊酯-2”“氟节胺”“粉唑醇”“氟胺氰菊酯-1”“氟胺氰菊酯-2”“灭菌丹”“安果”“地虫硫磷”“-六六六”“-六六六”“-六六六”“-六六六(林丹”“七氯”“顺-环氧七氯”“反-环氧七氯”“庚虫磷”DisulfotonDisulfoton sulfonDitalimfosDodemorph-1Dodemorph-2Edif

40、enphosEndosulfan-alphaEndosulfan-betaEndosulfan sulfateEndrinEPNEthionEthoprophosEtofenproxEtoxazolEtrimfosFamphurFenamiphosFenamiphos-sulfonFenamiphos-sulfoxidFenchlorphosFenitrothionFenpropathrinFensonFenthionFenthion sulfoxideFenvalerate-1Fenvalerate-2Flucythrinate-1Flucythrinate-2FlumetralinFlut

41、riafolFluvalinate-1Fluvalinate-2FolpetFormothionFonofosHCH-alphaHCH-betaHCH-deltaHCH-gamma(LindanHeptachlorHeptachlorepoxid-cisHeptachlorepoxid-transHeptenophos14221329915415417327227227228116938420016330029221830329230428527726526827829441941919919914314325225226017224621721721721733728928912410912

42、52439797109237237235245772311581352701531091951961962701098977109279225225107107107107200200130931371811811811813022532538910101010101515151581610810221022151310132020201881010222220202020155888881215151014.5426.9329.8218.3018.6033.0326.9030.8233.0330.1335.9431.7611.4442.7326.0114.8122.7028.1635.593

43、5.3817.5418.5836.6117.4120.2331.4944.0044.5042.1443.0127.4218.9043.8643.9625.0814.1013.9812.4913.2614.7613.6517.3023.5923.9010.650.0080.010.0080.0080.010.00050.00050.00050.00050.0050.0080.0080.0020.010.0080.010.0080.010.010.0050.0010.0020.0080.0020.010.00080.00080.0020.0010.0010.0040.0050.0050.00020

44、.00020.00020.00020.00050.00050.00050.0020.98530.98700.98750.99500.98660.99960.99650.99490.99900.98670.98580.99500.99910.98530.99740.99820.98990.98440.98660.99560.99920.99400.98630.99520.98540.99930.99800.99130.99650.98880.98110.99660.99410.99980.99290.99770.99400.99970.99360.99430.984779.875.670.080

45、.372.695.6100.692.594.084.882.480.095.589.199.076.577.869.272.388.6100.2106.582.388.970.296.392.695.585.690.887.283.369.999.296.6104.893.596.393.495.490.714.017.213.36.011.72.24.65.43.35.56.610.53.35.42.217.36.013.315.67.93.48.99.01.018.66.65.13.34.48.710.70.611.05.53.05.56.82.34.55.97.3序号名称英文通用名母离子

46、/(m/z子离子/(m/z碰撞能/eV保留时间/minLOD/(mg/L相关系数r2回收率/%变异系数CV/% (续表1117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161“六氯苯”“环嗪酮”“抑霉唑”“异稻瘟净”“异菌脲”“氯唑磷”(内标“水胺硫磷”“异柳磷”“甲基异柳磷”“异丙乐灵”“稻瘟

47、灵”“异-唑磷”“稻瘟净”“高效氯氟氰菊酯”“马拉氧磷”“马拉硫磷”“嘧菌胺”“地胺磷”“甲霜灵”“吡唑草胺”“虫螨畏”“甲胺磷”“杀扑磷”“灭虫威”“灭虫威砜”“灭多威”“烯虫酯”“甲氧氯”“异丙甲草胺”“速灭磷(E”“速灭磷(Z”“灭蚁灵”(内标“久效磷”“二溴磷”“除草醚”“酞菌酯”“o,p'-DDD”“o,p'-DDE”“o,p'-DDT”“氧化乐果”“杀线威”“p,p'-DDD”“p,p'-DDE”“p,p'-DDT”“多效唑”HexachlorobenzeneHexazinonImazalilIprobenfosIprodioneIs

48、azophos(ISIsocarbophosIsofenphosIsofenphos-methylIsopropalinIsoprothiolaneIsoxathionKitazinLambda-cyhalothrinMalaoxonMalathionMepanipyrimMephosfolanMetalaxylMetazachlorMethacrifosMethamidophosMethidathionMethiocarbMethiocarb sulftoneMethomylMethopreneMethoxychlorMetolachlorMevinphos(EMevinphos(ZMire

49、x(ISMonocrotophosNaledNitrofenNitrothal-isopropylo,p'-DDDo,p'-DDEo,p'-DDTOmethoateOxamylp,p'-DDDp,p'-DDEp,p'-DDTPaclobutrazole28417121520431425728921324128029031316920812717322319623413324014114515320010523522716219219227219214528323623731823715616223524623523624971145912451191361851992382041771411819999208140174117180805810912188147169133127127237127109253148165246165791451651761651252010201515151010810151515101010151510205101561081020