Abstract

The objective of this study consists of being able to develop a precise, reliable, easy, cheap and quick method to identify and quantify the presence of pesticide metabolites and their parents in human urine. In order to reach our purpose we selected the pesticides and their metabolites with intended uses on permanent crops such as orchards and vineyard. The activity planning started with the identification of the target list carried out by UHPLC-MS/MS and GC-MS/MS, succeeded by several tests oriented to determine the best sample treatment having recourse to instrumental analysis in the range 5–100 ng/mL. Several purifications were also investigated combining different adsorbents (PSA, EMR-lipid and final polish pouch). The use of formic acid during the extraction step has no impact on the recoveries, whereas the PSA adsorbent in the cleanup step negatively affects the results for all investigated metabolites. Any substantial differences were not observed in urine matrix for parent compounds achieving recoveries higher than 80% and RSD less than 20%. The final polish in combination or not with Enhanced Matrix Removal EMR-lipid did not show statistically significant difference in term of trueness and precision for both metabolites and parents, as evaluated by one-way ANOVA. The 3-OH THPI was the most critical compound with not acceptable results for linearity, trueness and precision.

摘要

本研究的目标包括能够开发一种精确、可靠、简单、廉价和快速的方法来识别和量化人类尿液中农药代谢物及其母体的存在。为了达到我们的目的，我们选择了预期用于果园和葡萄园等永久性作物的杀虫剂及其代谢物。活动计划首先通过 UHPLC-MS/MS 和 GC-MS/MS 进行目标列表的识别，然后通过几项测试来确定最佳样品处理方法，并求助于仪器分析，范围为 5–100 ng/毫升。还研究了结合不同吸附剂（PSA、EMR-脂质和最终抛光袋）的几种纯化。在萃取步骤中使用甲酸对回收率没有影响，而净化步骤中的 PSA 吸附剂会对所有研究的代谢物的结果产生负面影响。对于实现高于 80% 的回收率和低于 20% 的 RSD 的母体化合物，在尿液基质中未观察到任何显着差异。通过单向方差分析评估，最终抛光结合或不结合增强型基质去除 EMR 脂质在代谢物和母体的真实性和精确度方面没有显示出统计学上的显着差异。3-OH THPI 是最关键的化合物，其线性度、正确度和精密度的结果不可接受。通过单向方差分析评估，最终抛光结合或不结合增强型基质去除 EMR 脂质在代谢物和母体的真实性和精确度方面没有显示出统计学上的显着差异。3-OH THPI 是最关键的化合物，其线性度、正确度和精密度的结果不可接受。通过单向方差分析评估，最终抛光结合或不结合增强型基质去除 EMR 脂质在代谢物和母体的真实性和精确度方面没有显示出统计学上的显着差异。3-OH THPI 是最关键的化合物，其线性度、正确度和精密度的结果不可接受。