(海口)蔬菜中农药多残留检测基质标准溶液配置交流

1农业部热带农产品质量监督检验测试中心（海口）蔬菜中农药检测基质标准溶液配制交流21.气相色谱基质效应探讨2.液质联用基质效应探讨3.气质联用基质效应探讨主要内容31.气相色谱基质效应探讨基质效应：一般是指样品中除待测物以外的其它基质成分对待测物测定成分的影响，是一个很复杂的现象，并且在检测过程中是影响定量准确度的重要因素之一。现在美国及欧盟大部分都是用样品本底配置标准溶液用以校正。近年蔬菜抽查过程中我们也都采用基质标准进行定量分析。由于种类多，样品量大，有必要探讨哪些样品可否用一个基质代替。41.1数据分析近年蔬菜抽查主要做的种类有白菜、甘蓝、绿叶菜、瓜类、豆类、茄果及根菜，我们分析这几类蔬菜基质对有机磷农药的影响。下面以2009年4、7、10月份的三批数据为例进行归纳小结。我们所采用的分析方法是：比较每种有机磷农药在不同基质标准中的响应值即峰面积，由于峰面积值太大，直观上不好比较它们的差别，所以同批实验的同一农药均除以豆类基质标准的峰面积，以便于比较。规定同一农药的峰面积相差在10%（或等于）之内，基质对此农药的影响相似，可以相互取代；否则，不能取代。51.1数据分析图1：7种基质的色谱图Minutes1234567891011121314151617181920Millivolts406080100120140160180200220240260Millivolts406080100120140160180200220240260TRACEGC-Channel11baicai.datNameTRACEGC-Channel12ganlan.datNameTRACEGC-Channel13lvye.datNameTRACEGC-Channel14gua.datNameTRACEGC-Channel15dou.datNameTRACEGC-Channel16qieguo.datNameTRACEGC-Channel17gencai.datName61.1数据分析表1：4月份有机磷响应值之比白菜甘蓝绿叶瓜类豆类茄果根菜敌敌畏41.0581.0471.0491.01511.0421.034乙酰甲胺磷40.8380.9161.1881.00110.5330.899氧乐果40.8640.9891.0570.84010.4600.841久效磷41.1621.1291.1651.05010.7151.092甲基对硫磷41.0941.0161.0380.99611.0651.064毒死蜱41.0241.0011.0421.02511.0311.041对硫磷41.1001.0271.0351.00611.0211.085丙溴磷41.0540.9931.0070.96610.9761.046三唑磷40.6880.6181.1060.96710.9480.548伏杀硫磷40.9140.7321.1681.03810.8670.837敌百虫41.0240.9000.8350.85110.8251.010甲胺磷40.9990.9751.0780.89310.810.975甲拌磷41.1230.9111.1621.05211.3061.065磷胺40.9690.9011.0110.87710.6051.016马拉硫磷41.0901.0531.0961.07511.0581.084杀螟硫磷41.0911.0081.0570.97311.0651.039倍柳磷41.0851.0071.0661.00111.0781.068水胺硫磷40.7080.9251.2430.83810.4420.662亚胺硫磷40.7790.5841.1040.93010.3930.47171.1数据分析表2：7月份有机磷响应值之比白菜甘蓝绿叶瓜类豆类茄果根菜敌敌畏70.9901.0500.9981.05911.0520.999甲基对硫磷71.0271.0541.011.07911.0731.008氧乐果71.1021.3241.1411.43511.3641.001久效磷71.0511.2241.0251.33411.2730.958甲基对硫磷71.0271.0541.011.07911.0730.843毒死蜱71.0181.0400.9971.07111.0181.007对硫磷71.0231.0641.0061.10011.0701.005丙溴磷71.0051.0871.0131.08811.0841.002三唑磷71.1290.6280.8710.51010.3060.158伏杀硫磷70.9680.8970.9140.84510.7410.428敌百虫71.1161.1540.8711.18010.9991.13甲胺磷71.1721.1581.2311.10311.0720.984甲拌磷71.0441.0421.0181.05910.9860.915磷胺70.9951.1361.0381.15411.1551.058马拉硫磷71.0331.0541.0671.09111.0301.013杀螟硫磷71.1161.2021.0651.11811.0851.055倍柳磷71.0511.0841.0621.09011.0781.048水胺硫磷70.8930.7501.1200.85310.7370.348亚胺硫磷71.0391.1201.1260.84310.8020.44681.1数据分析表3：10月份有机磷响应值之比农药白菜甘蓝绿叶瓜类豆类茄果根菜敌敌畏100.9170.9201.0090.96311.0101.043乙酰甲胺磷100.7620.4710.4880.79510.5190.591氧乐果100.8681.1021.0820.51011.2811.413久效磷100.9720.9311.0030.47711.1291.113甲基对硫磷100.9500.9281.0280.94211.0261.016毒死蜱100.9850.9491.0331.02011.0221.040对硫磷100.9460.9751.0410.94311.0411.038丙溴磷100.9730.9421.0480.94811.0231.017三唑磷101.6351.8512.1671.52811.9981.814伏杀硫磷101.0561.7741.8741.16011.6521.842敌百虫101.0110.9970.8920.81711.0171.015甲胺磷101.0981.0641.2100.87911.0701.184甲拌磷101.1791.1321.1821.49911.0771.213磷胺100.9390.9671.0540.87010.9551.181马拉硫磷101.06411.0901.09110.9911.090杀螟硫磷101.1000.9571.1311.08110.9671.186倍柳磷101.0880.9991.0901.08810.9961.077水胺硫磷103.0735.7615.7676.58114.9135.992亚胺硫磷101.9922.322.0051.12811.9622.0891.2结果与讨论1.通过对表1.2.3数据简单的分析发现：敌敌畏、甲基对硫磷、毒死蜱、对硫磷、丙溴磷、马拉硫磷和倍硫磷这7种有机磷在这三批实验中峰面积相差均小于（或等于）10%，见表4。因此我们认为这几类农药可能受到基质的影响较小，可以考虑用一种基质来配置其基质标准溶液。对于其它12种有机磷农药情况并非这么简单，下面我们逐一进行分析。10表4：7种有机磷峰面积相差比较。注：4、7、10分别代表4月、7月、10月份的数据农药白菜甘蓝绿叶瓜类豆类茄果根菜极差敌敌畏41.0581.0471.0491.01511.0421.0340.058敌敌畏70.9901.0500.9981.05911.0520.9990.069敌敌畏100.9170.9201.0090.96311.0101.0430.093甲基对硫磷41.0941.0161.0380.99611.0651.0640.098甲基对硫磷71.0271.0541.0101.07911.0731.0080.079甲基对硫磷100.9500.9281.0280.94211.0261.0160.100毒死蜱41.0241.0011.0421.02511.0311.0410.042毒死蜱71.0181.0400.9971.07111.0181.0070.074毒死蜱100.9850.9491.0331.02011.0221.0400.091对硫磷41.1001.0271.0351.00611.0211.0850.100对硫磷71.0231.0641.0061.10011.0701.0050.100对硫磷100.9460.9751.0410.94311.0411.0380.098丙溴磷41.0540.9931.0070.96610.9761.0460.088丙溴磷71.0051.0871.0131.08811.0841.0020.088丙溴磷100.9730.9421.0480.94811.0231.0170.075马拉硫磷41.0901.0531.0961.07511.0581.0840.096马拉硫磷71.0331.0541.0671.09111.031.0130.091马拉硫磷101.0641.0001.0901.09110.9911.0900.100倍柳磷41.0851.0071.0661.00111.0781.0680.085倍柳磷71.0511.0841.0621.0911.0781.0480.090倍柳磷101.0880.9991.0901.08810.9961.0770.094111.2结果与讨论Minutes4567891011mAU25050075010001250mAU25050075010001250didiweijiajiduiliulindusipiduiliulinbingxiulinmalathionTRACEGC-Channel16std-0714-D1J-2-dou.datNameTRACEGC-Channel11std-0715-D1J-1-baicai.datName图2：7种有机磷的白菜和豆类基质标准比较Minutes8.28.38.48.58.68.78.88.99.0mAU2505007501000mAU2505007501000malaliulinbeiliulinTRACEGC-Channel16std-0714-D2J-2-dou.datNameTRACEGC-Channel11std-0715-D2J-1-baicai.datab121.2结果与讨论通过4月份的实验，发现乙酰甲胺磷分别在白菜甘蓝根菜、瓜类豆类中的响应比较接近；同时7月份实验也表明乙酰甲胺磷在这几类菜中没有明显的差别；而10月份数据表明乙酰甲胺磷在白菜甘蓝根菜、瓜类豆类响应值差别很大。所以我们认为：乙酰甲胺磷不能简单的用某种基质标准来代替。1.乙酰甲胺磷：00.20.40.60.811.21.4乙酰甲胺磷4甲基对硫磷7乙酰甲胺磷10白菜甘蓝绿叶瓜类豆类茄果根菜131.2结果与讨论图3：乙酰甲胺磷的白菜和豆类基质标准比较Minutes5.45.55.65.75.85.96.06.16.26.36.4mAU50010001500mAU50010001500yixianjiaanlinTRACEGC-Channel15std-D1J-dou.datNameTRACEGC-Channel11std-D1J-baicai.dat1.乙酰甲胺磷：141.2结果与讨论通过4月份的实验，发现氧乐果分别在白菜瓜类、甘蓝豆类中的响应比较接近；但是7、10月份实验表明氧乐果在白菜和瓜类及甘蓝和豆类中的响应又有很大的变化。所以我们认为：氧乐果不能简单的用某种基质标准来代替。2.氧乐果：00.20.40.60.811.21.41.