The aqueous radiation chemistry of pesticides

Full text: The degradation of pesticides is an important issue affecting the users and the environment. Degradation rates influence the spatial and temporal application rates and the effects on crops sown in subsequent seasons. Free radical reactions have been widely suggested as important in the aqueous degradation chemistry of pesticides and we report direct measurements of free radical reactions of nine pesticides widely used in Australia. Steady-state gamma radiolysis and pulse radiolysis have been used to follow the chemistry of the reactions of OH, H, O2-,SO4-,CO2-,eaq- and other radical species with the nine pesticides. HPLC and mass spectrometry were used to determine the reaction products and the spectra and kinetics of the primary radical reactions and their products were followed by pulse radiolysis. Elucidation of the reaction mechanisms and the structures of the radical intermediates formed from the initial radical attacks has been aided by the use of molecular modelling programs to estimate the configuration and electron density of the intermediates. The results, particularly the rate constants for the Initial radical attack, do not suggest that photochemically generated free radicals play a large part in the degradation of these pesticides in the environment