Kinetic model for the radical degradation of tri-halonitromethane disinfection byproducts in water

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60Co steady-state radiolysis with a kinetic computer model that includes water radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water, is provided.

► Radical-based mineralization of aqueous halonitromethane disinfection byproducts.
► Constructed kinetic computer model for tri-halogenated halonitromethane removal.
► Model predicted that superoxide reaction is unimportant for halonitromethanes.
► Measured superoxide reaction with chloropicrin was negligibly slow, <2×104 M−1 s−1.
► Determined that superoxide reaction with nitrate also insignificant at ∼104 M−1 s−1.