Chloramination of organophosphorus pesticides found in drinking water sources

The degradation of commonly detected organophosphorus (OP) pesticides, in drinking water sources, was investigated under simulated chloramination conditions. Due to monochloramine autodecomposition, it is difficult to observe the direct reaction of monochloramine with each OP pesticide. Therefore, a model was developed to examine the reaction of monochloramine (NH(2)Cl) and dichloramine (NHCl(2)) with chlorpyrifos (CP), diazinon (DZ), and malathion (MA). Monochloramine was found not to be very reactive with each OF pesticides, k(NH2Cl,OP) = 11-21 M(-1) h(-1). While, dichloramine (NHCl(2)) was found to be 2 orders of magnitude more reactive with each of the OP pesticides than monochloramine, k(NHCl2,OP) = 2000-2900 M(-1) h(-1), which is still three orders of magnitude less than the hypochlorous acid reaction rate coefficient with each OP pesticide. For each pesticide, the reactivity of the three chlorinated oxidants was then found to correlate with half-wave potentials (E(1/2)) of each oxidant. With reaction rate coefficients for the three chlorinated oxidations as well as neutral and alkaline hydrolysis rate coefficients for the pesticides, the model was used to determine the dominant reaction pathways as a function of pH. At pH 6.5, OP pesticide transformation was mostly due to the reaction of hypochlorous acid and dichloramine. Above pH 8, alkaline hydrolysis or the direct reaction with monochloramine was the primary degradation pathway responsible for the transformation of OP pesticides. This demonstrates the ability of models to be used as tools to elucidate degradation pathways and parameterize critical reaction parameters when used with select yet comprehensive data sets. (c) 2009 Published by Elsevier Ltd.