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使用气相色谱-三重四极杆质谱法测定两种拟除虫菊酯和新烟碱类接触生物标志物的队列友好型方案。

Cohort-friendly protocol for the determination of two urinary biomarkers of exposure to pyrethroids and neonicotinoids using gas chromatography-triple quadrupole mass spectrometry.

机构信息

Cyprus International Institute for Environmental and Public Health, Water and Health Laboratory, Cyprus University of Technology, Irenes 95, 3041, Limassol, Cyprus.

出版信息

Anal Bioanal Chem. 2019 Aug;411(20):5013-5021. doi: 10.1007/s00216-019-01925-9. Epub 2019 Jun 20.

DOI:10.1007/s00216-019-01925-9
PMID:31222408
Abstract

Neonicotinoids (NEOs) and synthetic pyrethroids (PYRs) are active ingredients of commercial pesticides and/or insecticides with extensive indoor and outdoor applications, worldwide. Improved exposure metrics are warranted for NEOs and PYRs, if we are to better understand their human health effects. A cohort-friendly protocol for determining non-specific biomarkers of exposure to NEOs and PYRs, e.g. 6-chloronicotinic acid (6-CN) and 3-phenoxybenzoic acid (3-PBA), respectively, in human urine voids was proposed. A series of optimization experiments were conducted to validate the bioanalytical protocol using gas chromatography coupled with triple quadrupole mass spectrometry (GC-QqQ-MS/MS) in MRM mode. The method reached low detection limits for both analytes (0.075 μg L for 6-CN and 0.050 μg L for 3-PBA) in a short preparation and analysis time. The method used small initial urine sample volume (2 mL), short extraction time (≈ 240 min for the batches of 32 samples) and instrumental analysis time (≈ 14 min) for both pesticide metabolites in a single run. This protocol could facilitate the assessment of population exposure metrics for these pesticides and their inclusion in health risk assessment. Graphical abstract.

摘要

新烟碱类(NEOs)和合成拟除虫菊酯(PYRs)是商业杀虫剂和/或农药的有效成分,在全球范围内有广泛的室内和室外应用。如果我们要更好地了解它们对人类健康的影响,就需要改进 NEOs 和 PYRs 的暴露度量。本研究提出了一种适合队列研究的方案,用于确定非特异性生物标志物,以分别检测尿液中 NEOs 和 PYRs 的暴露情况,如 6-氯烟碱酸(6-CN)和 3-苯氧基苯甲酸(3-PBA)。通过气相色谱-三重四极杆质谱联用(GC-QqQ-MS/MS)在 MRM 模式下进行了一系列优化实验,验证了生物分析方案。该方法对两种分析物(6-CN 的检测限为 0.075μg/L,3-PBA 的检测限为 0.050μg/L)具有较低的检测限,且在较短的准备和分析时间内完成。该方法使用小体积的初始尿液样本(2mL),较短的提取时间(32 个样本批次的提取时间约为 240 分钟)和仪器分析时间(单个运行中两种农药代谢物的分析时间约为 14 分钟)。该方案有助于评估人群对这些农药的暴露水平,并将其纳入健康风险评估。

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