Determination and quantitation of sulfonylurea and urea herbicides in water samples using liquid chromatography with electrospray ionization mass spectrometric detection

Abstract

A multianalyte method has been developed for the confirmation and quantitation of five sulfonylureas, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, flazasulfuron and halosulfuron-methyl, and for three ureas, siduron, dymron (daimuron) and diuron (DCMU) in water. Samples were extracted from water by off-line solid-phase extraction (SPE) with a polystyrene polymer cartridge (PS2), an ODS C 18-bonded silica cartridge (C 18) and an N-vinylpyrrolidone polymer cartridge (Oasis). Analyte determination and quantitation were performed by liquid chromatography with mass spectrometry (LC–MS). Extraction efficiency experiments demonstrated the ability of this method to extract sulfonylureas and ureas from water samples. Confirmatory analysis was carried out by LC-electrospray mass spectrometry (LC–ESI–MS) instrumentation equipped with a single-quadrupole mass filter. MS data acquisition was performed by a single or two-ion selected ion monitoring (SIM) program. It is required for confirmation that LC–MS retention times of the analytes are within 1% of the retention times of the standards, and that the molecular ion or characteristic fragment ion is present for each analyte. Fragment ions from distinctive structures must be obtained to identify and characterize specific herbicide molecules. These were obtained by controlled decomposition of sulfonylurea and urea adduct ions after suitably adjusting the electrical field in the desolvation chamber. The eight herbicides were also measured in fortified pure water (water purified by a milli-Q system), tap water and river water. Average recoveries of the eight analytes from water samples were in the range of 70–120% with relative standard deviations (R.S.D.s) of <20%. The limit of quantitation (LOQ) for each of the eight herbicides was between 10 and 100 ng l −1.