A human intoxication incident attributed to pesticide abuse was investigated using cutting-edge analytical methodologies. An LC-ESI-MS/MS method, based on a hybrid solid-phase extraction protocol (hybrid-SPE), was applied for the detection and quantification of several pesticides and metabolites in human biological fluids. Concomitantly, an UHPLC-HRMS method was applied to investigate potential metabolites, assisted by a complementary GC-MS method to elucidate the presence of plausible pesticides co-formulants. The LC-ESI-MS/MS method exhibited acceptable mean recoveries at the lower limit of quantification (LLOQ) and three additional levels, varying from 85 to 106% for all analytes and matrices. In serum, urine, and gastric fluid samples, the suspect compounds, namely chlorpyrifos and myclobutanil, predominated. Gastric fluid samples contained the highest concentrations of chlorpyrifos (39,800 ng/mL) and myclobutanil (18,800 ng/mL), while the neonicotinoid imidacloprid was also quantified, below 30 ng/mL. Notwithstanding, the UHPLC-HRMS analysis unveiled several metabolites of chlorpyrifos and myclobutanil. In parallel, GC-MS analysis, corroborated the presence of several co-formulants in gastric fluid samples, exemplified by m - and o -xylene, and cyclohexanone. Overall, three analytical methods were implemented to elucidate the chemical causality of a human intoxication incident. The presence of suspected active substances, one additional, and several metabolites and co-formulants were documented.

中文翻译：

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调查人类农药中毒事件：强有力的分析方法的重要性

使用先进的分析方法对因农药滥用引起的人中毒事件进行了调查。基于混合固相萃取方案（杂交SPE）的LC-ESI-MS / MS方法用于检测和定量人类生物液中的几种农药和代谢物。同时，采用UHPLC-HRMS方法研究潜在的代谢物，辅之以互补的GC-MS方法来阐明可能存在的农药助剂。LC-ESI-MS / MS方法在较低的定量下限（LLOQ）和其他三个水平上均表现出可接受的平均回收率，所有分析物和基质的回收率从85％到106％不等。在血清，尿液和胃液样品中，可疑化合物（毒死rif和霉菌丁醇）占主导地位。胃液样品中毒死rif（39,800 ng / mL）和霉菌丁（18,800 ng / mL）的浓度最高，而新烟碱类吡虫啉的含量也低于30 ng / mL。尽管如此，UHPLC-HRMS分析显示了毒死rif和霉菌丁的几种代谢产物。同时，GC-MS分析证实了胃液样品中存在几种助剂，例如间二甲苯，邻二甲苯和环己酮。总体而言，实施了三种分析方法以阐明人中毒事件的化学因果关系。记录了可疑的活性物质，一种以及几种代谢物和共制剂的存在。低于30 ng / mL。尽管如此，UHPLC-HRMS分析显示了毒死rif和霉菌丁的几种代谢物。同时，GC-MS分析证实了胃液样品中存在几种助剂，例如间二甲苯，邻二甲苯和环己酮。总体而言，实施了三种分析方法以阐明人中毒事件的化学因果关系。记录了可疑的活性物质，一种以及几种代谢物和共制剂的存在。低于30 ng / mL。尽管如此，UHPLC-HRMS分析显示了毒死rif和霉菌丁的几种代谢物。同时，GC-MS分析证实了胃液样品中存在几种助剂，例如间二甲苯，邻二甲苯和环己酮。总体而言，实施了三种分析方法以阐明人中毒事件的化学因果关系。记录了可疑的活性物质，一种以及几种代谢物和共制剂的存在。实施了三种分析方法来阐明人中毒事件的化学因果关系。记录了可疑的活性物质，一种以及几种代谢物和共制剂的存在。实施了三种分析方法来阐明人中毒事件的化学因果关系。记录了可疑的活性物质，一种以及几种代谢物和共制剂的存在。