含植物提取物类化妆品中55种禁用农药残留量的测定

国家标准含植物提取物类化妆品中55种禁用农药残留虽的测定征求意见稿编制说明一、工作简况1、任务来源本标准是根据国标委综合201841号文关于下达2018年第二批国家标准制订计划的通知)立项，由上海市质量监督检验技术研究院研究制定含植物提取物类化妆品中55种禁用农药残留量的测定国家标准。项目编号为20181013-T-469,计划应完成时间为2019年。2、主要工作过程起草阶段：通过向专业标准化技术委员会提出立项申请并通过国家标准委员会的立项审查后，上海市质量监督检验技术研究院等公司获得了含植物提取物类化妆品中55种禁用农药残留量的测定的标准研制项目。在此期间，从满足实际检测需要出发，开展了国内外相关资料的收集和确认工作，在资料的检索和信息的收集过程中，分析比较了大量的国内国外文献方法，在符合标准化工作规划和标准化计划要求的基础上，形成了检测标准方法草案，然后起草小组使用该标准草案对市场上的产品进行了收集和检测，起草小组根据样品检测数据和验证情况对标准文本乂进行了修改，在此基础上形成了征求意见稿及其编制说明。征求意见阶段：待进行。3、主要参加单位和工作组成员等本标准由全国质量监管重点产品检验方法标准化技术委员会(SAC/TC374)归口。本标准由上海市质量监督检验技术研究院等单位负责联合起草。二、标准编制原则和主要内容1、标准编制原则本标准通过大量的试验对含植物提取物类化妆品中55种禁用农药残留量的测定的检测方法摸索，反复论证，确定了方法的一系列重要参数：提取方法、仪器条件、方法检出限、回收率、精密度、线性范围等指标，开展了实际样品的检测，并对方法进行了验证。本标准遵循GB/T1.1-2000标准化工作导则第1部分：标准的结构和编写规则和GB/T20001.4-2001标准编写规则第4部分：化学分析方法的编写规则，并参考了国家食品药品监督管理总局发布的化妆品中禁用物质和限用物质检测方法验证技术规范。2、标准主要内容的论据2.1主要技术内容确定的依据起草单位接到标准制定任务后，成立了标准起草小组，在仪器设备、试验材料和资料检索等方面做了充分准备。首先进行国内外相关标准和文献资料的检索，根据查阅的资料，现有的测定化妆品中农药的方法主要为高效液相色谱-申联质谱法和气相色谱-质谱法。由于本标准涉及农药种类多，农药的性质各异，在查阅农药的相关检测标准和文献资料后，最终根据不同农药的性质确定高效液相色谱-申联质谱法和气相色谱-质谱法分别进行。并对前处理条件和不同仪器条件进行了深入的优化，以减少样品中的杂质对质谱的污染，降低背景十扰，提高检测灵敏度，并采用基质曲线外标法进行定量。2.2样品前处理条件的选择2.2.1样品提取溶剂的选择考虑到化妆品基体较为复杂，容易十扰样品的萃取过程，55种农药性质各异参考相关农药的国家检测标准和文献、本试验分别考察了乙腊，丙酮和乙酸乙酯三种常用农药提取溶剂，综合比较后发现乙腊对55种农药的提取效果较好。实验结果表明：3种溶剂都能有效提取化妆品中的农药，但乙腊提取出的杂质少，效果更好。乙腊作为一种通用的提取溶剂在农药残留检测方面已得到广泛应用，它不仅消除了有机氯溶剂的使用，对环境污染影响小，并且提取效率高杂质十扰少所以本试验最终选用乙腊为提取溶剂。2.2.2净化方法的选择标准文献中关于农药多残留的净化手段主要有不同填料种类的固相萃取柱（SPB净化和基质分散固相萃取（QuEChERS）以及凝胶渗透色谱（GPC）净化等方法。如何针对样本的特点及目标待测物的特性选用合理的净化技术是农药多残留分析的关键。对固相萃取柱（SPB净化和基质分散固相萃取（QuEChERS）以及凝胶渗透色谱（GPC）三种净化方法进行综合分析比较，由于化妆品中含较多的油脂而55种农药中的有机氯具有很强的脂溶性，通过硅酸镁柱或者硅胶柱等固相萃取柱，以及基质分散固相萃取净化手段都不能将其与脂肪类干扰物质分离，因此这两种净化方法也不适合。目前去除脂肪类干扰物最有效的方法是GPC去该方法利用化合物中各组分分子量大小不同，与柱填料之间的作用不同，导致洗脱时间不同来达到分离的目的通过对收集时间流速等条件的优化，故最终选用凝胶渗透色谱（GPC）法作为净化方法。2.3仪器条件的选择和优化2.3.1液相色谱-申联质谱检测方法仪器条件的建立仪器测定条件中的流动相类型、色谱柱类型、流动相梯度等参数参考了GB/T20769-2008并进行了相关的比较。质谱参数中的电喷雾电压、离子源温度，雾化气压力、气帘气压力，辅助气压力，去簇电压、碰撞气能量根据实验室现有设备进行了优化。本实验室建立的仪器条件是基丁AB6500上完成的。本方法仪器条件下的色谱图见图1。液相色谱-申联质谱法测定的参考条件如下：a）a）色谱柱：ZORBAXEclipsePlusC18,1.8pm,2.1mmx100mm或相当者；b）流动相及梯度洗脱条件见表1;c）流速：A相：0.1%甲酸水，B相：乙腊，按表1进行梯度洗脱；表1流动相梯度洗脱条件时间（min）流速（mL/min）流动相A（0.1%甲酸水溶液）流动相B（乙睛）00.39552.00.39558.00.3406011.00.3010013.00.3010013.10.395515.00.3955d）柱温：35C；e）进样量：2（；f）离子源：ESI;g）扫描方式：正离子或负离子扫描；h）检测方式：多反应监测；i）电喷雾电压：5500V（+）和4500V（-）;j）雾化气压力：60psi;k）辅助加热气压力：60psi;l）气帘气压力：20psi;m）离子源温度：400C；n）监测离子对、碰撞气能量和去簇电压参见表2表2质谱参数:化合物中文名化合物英文名离子对m/z去簇电压（DP）/V碰撞气能量（CE）/V甲荼威Carbaryl202/145a4015202/1274040多菌灵Carbendazim192/160a4725192/1324741丁安敌（燕麦敌）Di-allate270/86.1a5023270/1095039特乐酚（地乐硝酚）Dinoterb239.1/207a-70-32239.1/176-70-48敌草隆Diuron233/72a5231233/1605233氟环哩Epoxiconazole330.1/121a5227330.1/101.25263苯吗琳fenpropimorph304/147.2a6539304/1176571精毗氟禾草灵fluazifop-p-butyl384/282a6325384/3286321丙焕氟草胺Flumioxazin355.2/299.2a7834355.2/326.77826碘苯睛Ioxynil369.8/126.8a-65-36369.8/242.8-65-26异菌服Iprodione332.2/247a4020332.2/2904017异恶哩草酮Isoxaflutole360/251.1a5822360/220.15851苯氧菊酯/亚胺菌Kresoxim-methyl314/206a3515314/2673518禾草敌Molinate188.1/126.1a4519188.1/98.145264久效磷Monocrotophos224/127a6621224/986617焕蟠特Propargite368.1/175.1a5321368.1/231.25317扑灭津Propazine230.1/188a6023230.1/1466030西玛津Simazine202.2/131.9a5520202.2/124.25522十三吗琳Tridemorph298.1/130.1a6535298.1/98.16540利谷隆linuron249/160a5223249/1825221,为定量离子对。fW-&e4甲荼威3314#4-2e4I.,51D1做-135特乐酚k10.7450ai-5io6eS-5e&453e&CeQ1多菌灵1一皿-w45-2.3e5-丁变敌n11137b105ID3et-2&E-npf-敌草隆ScSGeE-4eE-2aE氟环哩9Gil5tO1Ue6-日篮-gE苯吗琳、7,52*-6e5,5e5-5精毗氟禾草灵.454DcJj20e53e5715-r-5ib5ibCc5-EaS：卜圮&-W皿-1e5-丙焕氟草胺-1-510-9IB2b4J碘苯睛1富异菌服1s4J15.3e5；run-1105-tD苯氧菊酯4e5-3b5-1e5-FL-wfl_禾草敌4卜977-JV,_5立异恶喋草酮、据31c6MO510l.Ort.B.M-G.0#4久效磷4,0e4-3*E1C5嘉5-潟-n_ri一焕蟠特_J1179：E：-1e5-ft-ft扑灭津900ISS.i西玛津7,28510-ft)5108*4-4*4时十三吗琳854L.6e5-5e5-、3e5-2e5-1e5,利谷隆祯510eib图1液相色谱-串联质谱法测定的20种农药标准溶液的色谱图2.3.2气相色谱-质谱法检测方法仪器条件的建立仪器测定条件中的色谱柱类型、升温程序、碎片离子等参数参考了GB/T23200.8-2016,并根据实验室现有设备进行了优化。本方法仪器条件下的色谱图见图2。优化后的仪器条件如下：气相色谱测定参考条件如下：a）色谱柱规格：HP-5ms色谱柱,30m250m（粒径0.25m）,或相当者；b）色谱柱升温程序：70oC保持2min，以25oC/min升至150oC;以3oC/min升至200oC;以8oC/min升至280oC保持10minc）载气：家气，纯度翊9.999%，流速1.0mL/min；d）进样口温度：260C；e）进样量：1心f）进样方式：无分流进样，1.5min后打开分流阀和隔垫吹扫阀；质谱测定参考条件如下：g）电子轰击源：70eV；h）离子源温度：230C；i）GC-MS接口温度：280C；j）扫描方式：特征选择离子监测SIM（m/z）;h）采集参数如表3。表335种农药及相关化学品标准物质保留时间，定量离子，定性离子序号中文名称英文名称保留时间min小星离于定性离子1定性离子21对二氯苯para-Dichlorobenzene4.66146(100)148(65)111(35)2二苯胺Diphenylamine12.028169(100)168(59)167(29)3为八八八也-BHC13.798219(100)183(120)221(47)4e六氯苯Hexachlorobenzene14.126284(100)286(81)282(51)53-AAA3-BHC14.997219(100)217(78)181(108)6丫八八八丫BHC15.284219(100)183(95)181(97)7快苯酰草胺Propyzamide15.776173(100)175(62)255(22)8&八八八&BHC16.439219(100)217(80)181(110)9白佳1清Chlorothalonil16.702266(100)264(77)268(49)10磷胺Phosphamidon18.179127(100)264(43)138(22)11乙烯菌核利（烯菌酮）Vinclozoline18.596285(100)212(130)198(122)12七氯Heptachlor18.815272(100)237(28)269(10)13甲草胺Alachlor19.015188(100)237(100)269(15)14艾氏剂Aldrin20.612263(100)265(65)293(40)15倍硫磷Fenthion21.137278(100)125(43)109(27)16三氯杀蟠醇Dicofol(kelthane)21.245139(100)141(31)250(23)17异艾氏剂Isodrin22.142193(100)263(46)195(83)18e环氧七氯Heptachloroepoxide22.767353(100)355(79)351(52)19克氯得（乙菌利）Chlozolinate23.247259(100)188(115)331(80)20氯丹Chlordane23.859373(100)375(96)377(51)21o,p-滴滴伊o,p-DDE24.189246(100)318(34)176(26)22a-硫丹后Endosulfan24.356241(100)265(66)339(46)23狄氏剂Dieldrin25.381277(100)79(460)279(96)24p,p-滴滴伊pp-DDE25.45318(100)316(80)246(139)25o,p-滴滴滴o,p-DDD25.747235(100)237(65)165(39)26腊却坐Myclobutanid25.789179(100)181(31)150(56)27氟硅哩Flusilazole25.914233(100)206(33)315(9)28异狄氏剂Endrin26.155263(100)317(30)345(48)293硫丹Endosulfan26.488241(100)265(66)339(46)30p,p-滴滴滴p,p-DDD26.896235(100)237(64)165(46)31o,p-滴滴涕o,p-DDT27.886235(100)237(63)165(37)32硫丹硫酸酉日Endosulfansulfate26.982272(100)387(45)389(30)33p,p-滴滴涕pp-DDT28.054235(100)237(65)165(41)34敌菌丹Captafol28.63179(100)151(8)80(31)35氯苯嚅嚏醇（异嚅菌醇）Fenarimol31.18139(100)219(62)330(28)魏皿渤m1EOZOZ使皿HOITOl0：inanmuDneoMUliLOj-4MI-f-1温L3.WL血3-“.-30m_葛00图2对二氯苯等35种农药标准溶液的色谱图2.4方法学参数2.4.120种农药的液相色谱-申联质谱法测定的20种农药方法学参数2.4.1.1线性范围：将不同浓度的20种农药标准工作溶液，按仪器条件进样分析，以目标色谱峰的峰面积为纵坐标，标准工作溶液浓度为横坐标进行线性回归，建立标准工作曲线,表4为20种农药的线性方程和相关系数结果表，表明在一定的范围内具有良好线性,线性相关系数0.999。表420种农药的的线性方程和相关系数化合物标准曲线方程线性范围（1g/mD相关系数R2甲荼威Y=33022X+293690.0050.10.9997多菌灵Y=494721X+1429830.00250.050.9965丁变敌（燕麦敌）Y=90198X+3666230.0250.50.9977特乐酚（地乐硝酚）Y=52503X+1278020.0050.10.9957敌草隆Y=24620X+1052920.0250.50.9999氟坏哩Y=362226X+1391280.0050.10.9993J苯吗琳Y=422773X+6827300.0050.10.9992精毗氟禾草灵Y=2585690X-301120.00050.010.9980丙焕氟草胺Y=24282X+515630.0510.9967碘苯睛Y=9089X+285030.0050.10.9961异菌服Y=54826X+2497460.0510.9962异恶喋草酮Y=278774X-23824700.0250.50.9918苯氧菊酯/亚胺园Y=33498X+4090330.0250.50.9995禾草敌Y=182970X-578300.0050.10.9980久效磷Y=81486X+273110.00250.050.9979焕蟠特Y=20938X+10300900.0510.9967扑灭津Y=438204X-986820.00250.050.9983西玛津Y=94631X-74130.0050.10.9966十三吗琳Y=115081X+861910.0050.10.9995利谷隆Y=48923X+2017620.0250.50.99852.4.1.2检出限和定量限向1.0g空白基质中定量添加20种农药标准溶液，按标准处理方法处理后，测定峰高信噪比为3:1和10:1时添加的20种农药的量确定本方法中各种农药的检出限和定量限如表5所示。表520种农药的检出限和定量限化合物检出限，mg/kg止量限，mg/kg甲荼威0.0050.01多菌灵0.00250.005丁变敌（燕麦敌）0.0250.05特乐酚（地乐硝酚）0.0050.01敌草隆0.0250.05氟坏H坐0.0050.01丁苯吗咻0.0050.01精毗氟禾草灵0.00050.001丙烷氟草胺0.050.1碘苯睛0.0050.01异菌服0.050.1异恶哩草酮0.0250.05苯氧菊酯/亚胺园0.0250.05禾草敌0.0050.01久效磷0.00250.005焕蟠特0.050.1扑灭津0.00250.005西玛津0.0050.01十三吗琳0.0050.01利谷隆0.0250.052.4.1.3方法的准确度和精密度试验选取三种有代表性的阴性空白样品基质（水基、乳液、膏霜类化妆品基质），分别添加低、中、高3个浓度水平进行加标回收实验，每一个添加水平重复测定6次，其回收率和精密度数据结果如表6表8所示。总体回收率在80%120%之间，相对标准偏差V10%。表6水基类化妆品基质三水平加标回收实验化合物测定水平（mg/kg）重复6次测定结果mg/kg平均回收率%变异系数甲荼威0.010.01000.00980.01020.00970.01000.010299.82.070.020.01840.01900.01880.01880.01860.018993.61.190.10.09200.09110.09360.09290.09210.089891.91.44多菌灵0.0050.00530.00520.00510.00510.00550.0052104.53.140.010.01010.01010.01000.01020.00960.010099.92.050.050.04450.04500.04510.04680.04770.047392.12.93丁变敌（燕麦敌）0.050.05320.05530.04950.05030.04950.0530103.64.610.10.10630.10420.10100.10300.09220.0961100.55.320.50.43390.42200.40580.38940.39360.401281.54.21特乐酚（地乐硝酚）0.010.01000.00950.00970.00940.00980.009897.02.370.020.01830.01870.01880.01780.01880.020193.73.990.10.10270.10150.10050.09800.09580.097599.32.65敌草隆0.050.05220.04990.05020.05050.05030.0501101.11.700.10.10230.10170.10330.10260.09920.1003101.61.490.50.47660.48100.47820.49390.47960.473996.11.46氟环n坐0.010.01090.01100.01090.01140.01110.0110110.71.580.020.02160.02130.02130.02110.02120.0214106.70.840.10.09890.10070.09750.09920.09750.096798.41.45丁苯吗啪c0.010.00970.00990.00960.01000.00980.010098.31.360.020.02090.02100.02090.02100.02060.0204103.91.200.10.09860.09770.10120.10200.09820.100199.61.75精毗氟禾草灵0.0010.00110.00110.00100.00100.00110.0010103.24.510.0020.00200.00200.00190.00190.00200.001896.55.210.010.00910.00840.00820.00960.00910.009389.55.96丙烷氟草胺0.10.11800.11460.11400.11590.11920.1134115.82.020.20.22680.22590.22500.22580.22420.2214112.40.8510.99781.00801.01401.00150.95850.997699.61.96碘苯腊0.010.00860.00840.00890.00900.00800.008685.84.110.020.01720.01830.01660.01690.01710.017286.13.460.10.10110.09950.10050.10020.09960.095899.41.91异菌服0.10.11710.11540.11800.11640.11050.1133115.12.420.20.23180.23060.22020.22460.22380.2256113.11.9211.00141.00810.99041.00331.02421.0026100.51.10异恶n坐草酮0.050.04590.04460.04450.04410.04540.044189.61.640.10.10840.11160.11460.11190.10950.1075110.62.360.50.50270.52060.49380.50040.49490.4937100.22.06苯氧菊酯/亚胺菌0.050.04790.04670.04900.04850.04830.048396.21.620.10.10860.10160.10600.10810.09770.1055104.64.000.50.44280.47830.46710.48540.48500.458793.93.57禾草敌0.010.01110.01070.01080.01100.01110.0108109.31.510.020.02110.02140.02070.02080.02090.0210104.91.250.10.09910.09570.09700.09700.09780.096197.11.25久效磷0.0050.00570.00570.00540.00560.00530.0057111.53.540.010.01130.01110.01150.01150.01120.0112113.11.520.050.05190.04990.05080.05110.05150.0526102.61.79快蟠特0.10.12180.12000.11690.09760.10680.1207114.08.510.20.20580.24090.21070.20680.22100.2201108.86.041.01.02610.91570.94640.80931.00590.910993.68.31扑灭津0.0050.00550.00540.00550.00540.00550.0054108.91.390.010.01050.01060.01060.01080.01060.0108106.51.340.050.04710.04930.04850.04800.04610.046295.02.70西玛津0.010.01120.01090.01110.01100.01110.0108110.01.340.20.02130.02170.02200.02140.02120.0206106.82.230.10.09890.09720.09830.09780.10070.099698.71.28十三吗啪C0.010.01020.01010.01010.01010.01000.0101100.90.520.020.02070.02030.02040.02030.02050.0203102.10.770.10.09810.09740.09810.09770.09680.096697.50.65利谷隆0.050.05350.05180.05320.05380.05340.0523106.01.480.10.10440.10530.10380.10320.10190.1051103.91.200.50.48280.48950.50500.48890.49040.478297.81.86表7乳液类化妆品基质三水平加标回收实验化合物测定水平mg/kg重复6次测定结果mg/kg平均回收率%变异系数甲荼威0.010.00970.00980.00960.00940.00990.009596.51.710.020.01820.01880.01820.01790.01810.017990.91.800.10.08870.08850.08730.08800.08740.089388.20.89多菌灵0.0050.00490.00480.00480.00490.00500.004997.61.550.010.01000.00980.01000.01050.01000.0108101.93.540.050.04680.04760.04520.04710.04510.046192.62.20丁变敌（燕麦敌）0.050.03440.04370.04200.04090.04290.041481.78.160.10.08760.08490.08620.07510.08470.096585.87.970.50.49680.48320.46910.40080.42040.440690.48.29特乐酚（地乐硝酚）0.010.00880.00950.00930.00870.00890.009390.83.500.020.01770.01760.01740.01760.01680.016786.52.470.10.08910.09110.09250.09320.08610.094391.03.34敌草隆0.050.04690.05010.04880.04850.04820.048396.92.120.10.09670.09890.10030.09770.10140.094998.32.410.50.46730.46640.46000.46420.45690.468792.80.99氟坏H坐0.010.01090.01080.01100.01090.01070.0108108.60.760.020.02050.02100.02110.02040.02020.0198102.52.370.10.09190.09210.09310.09490.09590.097794.32.45J本吗琳0.010.00990.00990.01020.00970.00990.009999.11.910.020.02150.02070.02090.02120.02140.0208105.51.610.10.09720.09750.09480.09810.09990.098897.71.74精毗氟禾草灵0.0010.00100.00090.00100.00090.00090.001095.64.950.0020.00160.00200.00190.00200.00180.001792.09.420.010.00790.00810.00890.00900.00880.008184.75.57丙焕氟草胺0.10.11100.11310.11270.11430.10720.1086111.22.490.20.21400.21890.22450.22750.20940.1975107.65.0810.88730.86950.90800.92480.94180.969491.73.97碘苯睛0.010.00890.00940.00900.00970.01000.008592.56.020.020.01950.02110.02070.01950.02040.0208101.73.440.10.09510.09340.09390.09150.09420.093693.61.28异菌服0.10.11640.11340.11720.11430.11240.1126114.41.760.20.23340.22480.22070.22680.19820.2072109.26.0610.88000.93410.94190.96160.92910.971293.63.41异恶哩草酮0.050.04220.04180.04170.04210.03980.041082.92.130.10.10490.10430.10540.10410.09950.0968102.53.410.50.44230.44660.44350.46350.46170.478991.23.17苯氧菊酯/亚胺菌0.050.05010.04780.04530.05040.04840.045295.74.680.10.10430.10370.11150.10780.11770.1165110.25.450.50.49630.48320.48050.44680.48050.461495.03.72禾草敌0.010.01070.01040.01050.01050.01020.0105104.61.790.020.02080.02060.02070.02050.02020.0201102.41.290.10.09320.09410.09580.09370.09360.092893.91.12久效磷0.0050.00550.00560.00540.00530.00530.0052107.82.490.010.01150.01070.01130.01120.01150.0115112.62.700.050.05650.05610.05170.05190.05410.0556108.73.89焕蟠特0.10.09720.12210.11200.09940.11130.1093108.58.430.20.21370.21220.20470.19920.22290.2365107.46.2210.97840.86230.87580.83080.88210.914089.15.71扑灭津0.0050.00540.00540.00530.00520.00520.0053105.81.380.010.01010.01060.01030.01030.00990.0093100.84.380.050.04230.04410.04370.04470.04410.045388.12.33西玛津0.010.01040.01060.01100.01030.01000.0109105.33.600.20.02110.02130.02160.01990.02000.0191102.44.660.10.08900.08780.08870.09370.09050.095090.83.24十三吗琳0.010.00990.00990.00980.00970.01000.009898.50.930.020.01990.02040.02010.02020.02010.0194100.11.760.10.09400.09290.09260.09340.09470.094293.60.86利谷隆0.050.05140.05060.05000.05170.05000.0508101.51.400.10.09810.10300.10150.09750.10320.1036101.12.690.50.48560.46050.46440.46270.47610.464493.82.09表8膏霜类化妆品基质三水平加标回收实验化合物测定水平mg/kg重复6次测定结果mg/kg平均回收率%变异系数甲荼威0.010.00990.01050.01070.01050.01040.0109105.03.180.020.02050.01940.01970.02080.01990.0203100.52.630.10.09630.09790.09920.09760.10030.097798.21.42多菌灵0.0050.00430.00470.00480.00460.00460.004491.53.720.010.00900.00940.00870.00860.00910.008488.64.080.050.04710.04670.04720.04620.04380.047792.93.01丁变敌（燕麦敌）0.050.05450.05190.05260.05240.05400.0534106.31.900.10.11360.11060.11330.11830.11170.1096112.82.750.50.51170.49460.50160.50020.49520.5050100.31.28特乐酚（地乐硝酚）0.010.00880.00850.00930.00910.00970.009491.34.920.020.02100.01910.01990.01920.02070.019099.14.360.10.09170.09030.09220.09170.09340.096492.62.28敌草隆0.050.04810.04790.04680.04930.04910.050197.12.460.10.10350.10660.10600.10180.10290.1078104.82.270.50.47480.47440.49950.49600.49840.482997.52.41氟坏H坐0.010.00920.00960.00980.00920.00950.009394.32.640.020.01730.01850.01870.01880.01830.018892.03.180.10.09080.08230.08410.08430.08450.084685.13.43J本吗琳0.010.01020.01110.01110.01140.01190.0127113.97.490.020.02000.02070.02050.02210.02240.0236107.76.420.10.12210.11610.10830.11230.11270.1157114.54.08精毗氟禾草灵0.0010.00100.00090.00090.00090.00100.000994.23.930.0020.00180.00190.00190.00180.00200.001993.83.200.010.00820.00870.00880.00850.00860.008785.92.42丙焕氟草胺0.10.09910.10100.10010.10310.10340.1012101.31.650.20.20010.20960.21390.20480.19910.2068102.92.7410.89670.88000.89500.85720.87190.905688.42.04碘苯睛0.010.00870.00810.00930.00940.00910.009590.25.890.020.01870.01860.01900.01840.02010.018594.43.280.10.08510.09000.09130.08880.09090.089789.32.53异菌服0.10.10080.09650.10150.09530.09840.098498.52.410.20.21230.21560.21500.20740.19290.2032103.94.1610.91180.95130.84900.83310.87940.936089.35.32异恶哩草酮0.050.04360.04470.04350.04470.04090.041386.23.840.10.09170.08420.08820.09170.08650.090488.83.410.50.46550.46130.43600.43670.42520.420888.24.20苯氧菊酯