Retrospective analysis of pesticide metabolites in urine using liquid chromatography coupled to high-resolution mass spectrometry

•A retrospective screening has been developed for pesticide metabolites in urine.•A customised database of 263 pesticide metabolites was built for suspect analysis.•26 pesticide metabolites were identified in urine samples.•8 metabolites were confirmed at concentration from 0.79 to 141.04 ng mL−1.•The urine samples were grouped according to their origin.

A comprehensive retrospective analysis of pesticide metabolites in urine was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS) that includes both post-run target (suspect screening) and non-target screening. An accurate-mass database comprising 263 pesticide metabolites was built and used for the post-run screening analysis. For non-target analysis, a “fragmentation-degradation” relationship strategy was selected. The proposed methodology was applied to 49 real urine samples from pregnant women. In the post-target analysis 26 pesticide metabolites were tentatively identified, 8 of which (2-diethylamino-6-methyl-pyrimidinol; 3-ketocarbofuran; 4,6-dimethoxy-2-pyrimidinamine; 4-hydroxy-2-isporopyl-6-methylpyrimidine; diethyl malate; diethyl maleate; N-(2-Ethyl-6-methylphenyl)-2-hydroxyacetamide and propachlor oxanilic acid ) were confirmed using analytical standards. Likewise, one unknown degradation product, methyl-N-phenylcarbamate was elucidated in the non-target screening. Finally, the real urine samples were grouped according to their origin applying a metabolomic approach.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide