非衍生化超高效液相色谱-串联质谱法快速检测环境水中强极性农药及其代谢物

Nonderivatization method for determination of highly polar pesticides and their metabolites in environmental water by ultra-high performance liquid chromatography-tandem mass spectrometry

建立了一种简便、直接进样、非衍生化超高效液相色谱-串联质谱(UPLC-MS/MS)快速测定环境水样中乙烯利、草甘膦、草铵膦及其代谢物等6种强极性化合物残留的分析检测方法。环境水样经离心、过滤后,无需衍生,直接进样进行定量分析。样品经Waters Acquity UPLC HSS T3色谱柱(100 mm×2.1 mm,1.8μm)分离,以0.1%甲酸-5μmol/L亚甲基二膦酸水溶液、甲醇为流动相,在电喷雾离子源、正离子扫描和多反应监测模式(MRM)下进行分析,外标法定量。结果表明:6种化合物在各自线性范围内具有良好的线性关系,决定系数(R2)均大于0.99,在10~200μg/L添加水平下,6种化合物在环境水样中的平均回收率在75%~100%之间,日内相对标准偏差与日间相对标准偏差(n=6)分别为3.6%~7.0%和4.3%~7.5%。方法定量限在0.5~10.0μg/L之间。利用所建立的方法对3个地区10份地表水样进行检测。结果显示:乙烯利、草甘膦、草铵膦及其代谢物等6种化合物均未检出。该方法与衍生化方法相比,具有简便快速、重现性好、灵敏度高等优点,可以为环境水中乙烯利、草甘膦、草铵膦及其代谢物等强极性化合物检测提供参考。

A simple,direct injection and non-derivatized analytical method was developed for rapid determination of six highly polar compounds,including ethephon,glyphosate,glufosinate,aminomethylphosphonic acid,3-methylphosphinicopropionic acid,and glufosinate-N-acetyl in environmental water by ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The environmental water samples were centrifuged and filtered through 0.22μm filter membrane to remove solids and were directly injected for quantitative analysis without derivatization.The target compounds were separated by Waters Acquity UPLC HSS T3 column(100 mm×2.1 mm,1.8μm).Chromatographic separation was carried out by gradient elution with mobile phase A(water with 0.1%formic acid and 5μmol/L medronic acid)and mobile phase B(methanol).The target compounds were finally detected using electrospray ionization and multiple reaction monitoring mode(MRM).Quantitative analysis was performed using the external standard calibration curves.The results showed that all six compounds had good linear relationship within their respective linear ranges,and the coefficient of determination(R2)were higher than 0.99.The average recoveries of six compounds in water samples were from 75%to 100%at spiked levels ranging from 10μg/L to 200μg/L.The intraday and inter-day relative standard deviations(n=6)were 3.6%-7.0%and 4.3%-7.5%,respectively.The limits of quantification(LOQ)were 0.5-10μg/L.Ten surface water samples collected from three areas were detected using the established method,and the results showed that the six compounds were all not detected.Compared with other derivatization methods,this method has the advantages of simplicity,rapidity,good reproducibility,and high sensitivity,and it may provide reference for the detection of highly polar compounds such as ethephon,glyphosate,glufosinate,and their metabolites in environmental water.