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A method for the determination of triazines (simazine, atrazine) and their metabolite 2-chloro-4,6-diamino-1,3,5-triazine by liquid chromatography-mass spectrometry with electrospray ionization (LC-MS/ESI) in human urine is described. The method outlines the sample preparation, which involves protein precipitation with acetonitrile and solid-phase extraction using C18 cartridges, and the qualitative and quantitative chromatographic analyses. The method may be used to assess occupational exposure to triazine herbicides following the urinary excretion of low levels of both the parent compounds and their metabolites.