Kinetics and mechanisms of pH-dependent degradation of halonitromethanes by UV photolysis

Abstract

Halonitromethanes (HNMs) are one of the most toxic groups of disinfection by-products. The pH-dependent degradation kinetics and pathways of four HNMs, namely bromonitromethane (BNM), dichloronitromethane (DCNM), dibromonitromethane (DBNM) and trichloronitromethane (TCNM), by ultraviolet (UV) photolysis at 254 nm were studied at pH 3-9. The UV photolysis in a dilute aqueous solution followed first-order kinetics. The photolysis rates of all four HNMs were low at pH 3-5, while that of TCNM was low at all pHs tested. Nevertheless, the photolysis rates of BNM, DCNM and DBNM increased with increasing pH, showing sharp increases as the pH neared their pK(a) values. The increases were correlated with their pH-dependent molar absorptivities, which were determined by the sizes of their deprotonated fractions. Homolysis was likely to be the major photolysis pathway for all four HNMs to produce halides, nitrite and nitrate at acidic pHs when the HNMs were not deprotonated. At high pHs, however, the conjugation systems of the deprotonated mono- and di-HNMs made heterolysis possibly the dominant pathway for the formation of carbon dioxide, nitrite and halides as major products for di-HNMs, and the formation of nitrite, halides and other unknown organics for mono-HNMs. The UV energy required for a 50% degradation of deprotonated HNMs in the real water sample was similar to that needed in UV disinfection processes, suggesting the effectiveness of UV photolysis in controlling HNMs that form conjugation systems at neutral to alkaline pHs.