The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection.@en

Previous studies have examined the effects of peptide bond and unsaturated bond on the formation of disinfection by-products (DBPs). However, limited information has been available for the impact of reduced sulfur group on the formation of DBPs. This study investigated the formation of carbonaceous and nitrogenous DBPs (C-DBPs and N-DBPs) with a similar structure of ‘’CX3R” (X = H, Cl, Br or I, R = functional group), including trihalomethanes, haloacetaldehydes, haloketones, haloacetonitriles, haloacetamides and halonitromethanes, during chlor(am)ination of three reduced sulfur compounds (RSCs), such as N-acetylcysteine, glutathione and glutathiol. Results showed that all DBPs except dichloroacetonitrile (DCAN) continuously increased with increasing Cl2 or NH2Cl doses in this study. The chlor(am)ination of three RSCs with lower disinfectant doses (the molar ratio of disinfectant to precursor ≤5) generated low DBPs compare to non-RSCs. More chloroform was observed in alkaline condition, while weak acidic condition was in favor of DCAN and dichloroacetamide formation. The results of frontier electron density calculation reported that the much higher reactivity for Cl2 and NH2Cl toward reduced sulfur group in RSCs protects other groups, which account for the formation of CX3R-type DBPs. This phenomenon has important environmental implications. When RSCs are present in the water, Cl2 or NH2Cl will reacts preferably with them rather than non-RSCs to form RSO3H as the major products. Hence, the trade-offs of between the products generated upon S-chlorination, which account for the formation RSO3H, and alkyl halogenation and N-chlorination, which account for the formation of CX3R-type DBPs, influence the formation of CX3R-type DBPs.@en