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Determination of pyrethroid metabolites in human urine by capillary gas chromatography-mass spectrometry
Authors:K. -H. Kühn  G. Leng  K. A. Bucholski  L. Dunemann  H. Idel
Affiliation:(1) Institute of Hygiene, University of Düsseldorf, Moorenstr. 5, 40225 Düsseldorf, Germany;(2) Department of Analytical Chemistry, Medical Institute of Environmental Hygiene at the University of Düsseldorf, Auf'm Hennekamp 50, 40225 Düsseldorf, Germany
Abstract:Summary An analytical method for the simultaneous determination of the pyrethroid metabolites cis and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid, cis 3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid, 3-phenoxybenzoic acid and 4-fluoro-3-phenoxybenzoic acid in human urine samples is described. The urine is subjected to acid-induced hydrolysis followed by exhaustive solvent extraction, covering both conjugated and free acids, followed by a common derivatisation step yielding the corresponding methyl esters. Quantitation was by diastereomeric, capillary gas chromatography-mass spectrometry. It appears that 4-fluoro-3-phenoxybenzoic acid is a characteristic urinary marker for cyfluthrin exposure. The limits of determination are 0.5–1.0 mgrg L–1 urine depending on the metabolites concerned. The applicability of the method was tested on urine samples from pest control operators exposed occupationally to cypermethrin and cyfluthrin.
Keywords:Gas chromatography-mass spectrometry  Pyrethroid metabolites in urine  Urinary marker  4-fluoro-3-phenoxybenzoic acid  Cypermethrin and cyfluthrin
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