Abstract：
An accurate and sensitive method for the determination of a total of 23 pesticides and their metabolites in human urine has been optimised. The methodology is based on a previously published method based on solid-phase extraction with methanol and acetone followed by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) in the selected reaction mode (SRM) with both positive and negative electrospray ionization (ESI+/-). The detection settings of the previous method, which allowed to determine the metabolites from 6 organophosphate and 2 pyrethroid pesticides, were optimised in order to include further pesticide groups, such as 11 neonicotinoids, 3 carbamates/thiocarbamates and 2 triazoles. The 5-windows method enduring 22 min was optimized with acceptable results in relation to accuracy (recoveries >75 %), precision (coefficients of variation <26 %) and linearity (R2> 0.9915). The limits of detection ranged between 0.012 ng/mL and 0.058 ng/mL. Samples from the German External Quality Assessment Scheme (G-EQUAS) encompassing 2 pyrethroids, 2 organophosphate and one neonicotinoid (6-chloronicotinic acid, a common metabolite of imidacloprid and acetamiprid) were analysed, and the latter, included in this newest optimization, provided good reference results. The method is optimal as a human biomonitoring tool for health risk assessment in large population surveys.
摘要：
已优化了一种准确，灵敏的方法，用于测定人尿中总共23种农药及其代谢产物。该方法基于先前发布的方法，该方法基于用甲醇和丙酮进行固相萃取，然后在选定的反应模式（SRM）中进行超高效液相色谱与串联质谱（UPLC-MS/MS），同时进行正电喷雾和负电喷雾电离（ESI/-）。上一种方法的检测设置，它可以确定6种有机磷和2种拟除虫菊酯农药的代谢物，进行了优化，以包括更多的农药组，例如11种新烟碱，3个氨基甲酸酯/硫代氨基甲酸酯和2个三唑。对持续22分钟的5窗口方法进行了优化，结果与准确性有关（回收率>75％），精度(变异系数<26%)和线性(R2>0.9915)。检测限范围为0.012ng/mL至0.058ng/mL。来自德国外部质量评估计划（G-EQUAS）的样品，包括2种拟除虫菊酯，2种有机磷酸酯和一种新烟碱（6-氯烟酸，分析了吡虫啉和啶虫脒的常见代谢物），而后者,包含在这个最新的优化中，提供了较好的参考结果。该方法是大型人口调查中健康风险评估的最佳人体生物监测工具。
