Identification of carbofuran and methiocarb and their transformation products in estuarine waters by on-line solid phase extraction liquid chromatography - Mass spectrometry

The degradation of the carbamate insecticides carbofuran and methiocarb in distilled and natural waters was determined. Degradation studies were carried out both under a xenon are irradiation and natural sunlight at pesticide concentrations of 50-100 mu g/L. 50-100 mt water sample were preconcentrated using automated online solid phase extraction (SPE) followed by liquid chromatography (LC), UV detection or post column fluorescence detection (EPA method 531.1 for carbamate insecticides). Structure identification was carried out by on-line SPE-LC-MS either with thermospray and/or high flow pneumatically assisted electrospray interfaces. Half-lives varying between 4-12.5 days for carbofuran and methiocarb were determined under natural sunlight exposure, being chemical hydrolysis the major degradation pathway. When using xenon are lamp irradiation both pesticides degraded very rapidly with half-lives varying from 0.3-1.7 hours. The various degradation products identified were: methiocarb sulfoxide, 4-methylthio-3,5-dimethylphenol,3-hydroxy-7-carbofuranphenol and 2-hydroxy-3-(2-methylprop-1-enyl)-phenyl-N-methylcarbamate.