Development of an analytical method based on solid-phase extraction and LC-MS/MS for the monitoring

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Pyrethroids,organophosphorus pesticides and fipronil have been listed as priority chemi-cals in human biomonitoring studies because of their wide use and potential health effects in humans.The determination of 13 pesticides,including pyrethroids (deltamethrin,cyper-methrin,permethrin,cyfluthrin,bifenthrin),organophosphorus (chlorpyrifos,chlorpyrifos-methyl,and malathion),fipronil,neonicotinoids (imidacloprid,acetamiprid and thiacloprid)and triazole (prothioconazole),together with 13 corresponding metabolites in human urine samples was achieved by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry.All targeted compounds,except malathion dicar-boxylic acid,were measured with a mean within-accuracy (n =5) of 71%-114% (RSD:1%-14%) and between-run (n =15) accuracy of 80%-118% (RSD:2%-14%).Limits of quantitation of the targeted analytes ranged from 0.1 to 16 pg/mL.The detection result of urine samples from 25 volunteers indicated that the detection frequencies of 3,5,6-trichloro-2-pyridinol(median:448 pg/mL),6-chloropyridine-3-carboxylic acid (median:193 pg/mL),2-methyl-3-phenylbenzoic acid (median:181 pg/mL),3-phenoxybenzoic acid (median:99 pg/mL),2-isopropyl-6-methyl-4-pyrimidinol (median:77 pg/mL),cyfluthrin (median:59 pg/mL),cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (cis-DCCA,median:53 pg/mL),trans-DCCA (median:25 pg/mL),prothioconazole (median:21 pg/mL),imidacloprid (median:7 pg/mL),and prothioconazole-desthio (median:1 pg/mL) were > 50%.The obtained results show that the validated method is suitable for the human biomonitoring of these current-use pesticides and their metabolites.
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