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A large scale multi-laboratory suspect screening of pesticide metabolites in human biomonitoring: From tentative annotations to verified occurrences
Environment International ( IF 11.8 ) Pub Date : 2022-08-05 , DOI: 10.1016/j.envint.2022.107452
Carolin Huber 1 , Rosalie Nijssen 2 , Hans Mol 2 , Jean Philippe Antignac 3 , Martin Krauss 4 , Werner Brack 1 , Kevin Wagner 5 , Laurent Debrauwer 5 , Chiara Maria Vitale 6 , Elliott James Price 6 , Jana Klanova 6 , Borja Garlito Molina 7 , Nuria Leon 8 , Olga Pardo 9 , Sandra F Fernández 8 , Tamás Szigeti 10 , Szilvia Középesy 10 , Libor Šulc 6 , Pavel Čupr 6 , Inese Mārtiņsone 11 , Läsma Akülova 11 , Ilse Ottenbros 12 , Roel Vermeulen 13 , Jelle Vlaanderen 13 , Mirjam Luijten 14 , Arjen Lommen 2
Affiliation  

Within the Human Biomonitoring for Europe initiative (HBM4EU), a study to determine new biomarkers of exposure to pesticides and to assess exposure patterns was conducted. Human urine samples (N = 2,088) were collected from five European regions in two different seasons. The objective of the study was to identify pesticides and their metabolites in collected urine samples with a harmonized suspect screening approach based on liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) applied in five laboratories. A combined data processing workflow included comprehensive data reduction, correction of mass error and retention time (RT) drifts, isotopic pattern analysis, adduct and elemental composition annotation, finalized by a mining of the elemental compositions for possible annotations of pesticide metabolites. The obtained tentative annotations (n = 498) were used for acquiring representative data-dependent tandem mass spectra (MS2) and verified by spectral comparison to reference spectra generated from commercially available reference standards or produced through human liver S9 in vitro incubation experiments. 14 parent pesticides and 71 metabolites (including 16 glucuronide and 11 sulfate conjugates) were detected. Collectively these related to 46 unique pesticides.

For the remaining tentative annotations either (i) no data-dependent MS2 spectra could be acquired, (ii) the spectral purity was too low for sufficient matching, or (iii) RTs indicated a wrong annotation, leaving potential for more pesticides and/or their metabolites being confirmed in further studies. Thus, the reported results are reflecting only a part of the possible pesticide exposure.



中文翻译:

人类生物监测中农药代谢物的大规模多实验室可疑筛查:从初步注释到已验证的发生

在欧洲人类生物监测计划 (HBM4EU) 中,开展了一项研究,以确定农药暴露的新生物标志物并评估暴露模式。人类尿液样本(N = 2,088)是在两个不同季节从欧洲五个地区收集的。该研究的目的是通过五个实验室应用的基于液相色谱与高分辨率质谱 (LC-HRMS) 的统一可疑筛查方法来鉴定收集的尿液样本中的农药及其代谢物。组合数据处理工作流程包括全面的数据缩减、质量误差和保留时间 (RT) 漂移的校正、同位素模式分析、加合物和元素组成注释,最后通过挖掘元素组成以获取农药代谢物的可能注释来完成。获得的暂定注释 (n = 498) 用于获取代表性的数据相关串联质谱 (MS 2 ),并通过与从市售参考标准生成的参考光谱或通过人肝脏 S9体外孵化实验产生的参考光谱进行光谱比较来验证。检测到 14 种母体农药和 71 种代谢物(其中 16 种葡萄糖醛酸苷和 11 种硫酸盐结合物)。这些总共涉及 46 种独特的农药。

对于其余的暂定注释,要么 (i) 无法获取依赖于数据的 MS 2光谱,(ii) 光谱纯度太低,无法充分匹配,或 (iii) RT 指示错误的注释,可能会产生更多农药和/或其代谢物正在进一步研究中得到证实。因此,报告的结果仅反映了可能接触农药的一部分。

更新日期:2022-08-05
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