title: Enhanced nitrogenous disinfection byproduct formation near the breakpoint: implications for nitrification control.
abstract: Increasing the chlorine to ammonia molar ratio and breakpoint chlorination are two control strategies practiced by drinking water treatment utilities experiencing nitrification during chloramination. The first strategy will increase dichloramine formation, which increases nitrosamine formation. Moreover, our results indicate that dichloramine is also an important factor for nitrile formation. Near the breakpoint, nitrosamine formation is over an order of magnitude higher than that observed during chloramination. We propose that there are two nitrosamine formation pathways active in the breakpoint chlorination region: (i) a relatively slow reaction of dichloramine with amine precursors in the presence of dissolved oxygen and (ii) a fast reaction involving reactive breakpoint chlorination intermediates. Lastly, in the presence of nitrite, if breakpoint chlorination is conducted to achieve a significant free chlorine residual, nitrosamines and nitramines will form through a reaction with nitrite and hypochlorite. However, nitrosamine formation will be much lower than when breakpoint chlorination is conducted with no significant free chlorine residual.
authors.affiliation: Department of Chemical Engineering, Yale University, Mason Lab 313b, 9 Hillhouse Avenue, New Haven, Connecticut 06520, USA.
authors.forename: I Marie
authors.initials: IM
authors.lastname: Schreiber
authors.forename: William A
authors.initials: WA
authors.lastname: Mitch
mesh_terms: D000814:Aniline Compounds / Q000138:chemical synthesis; D004128:Dimethylnitrosamine / Q000138:chemical synthesis; D004202:Disinfectants / Q000737:chemistry*; D007700:Kinetics; D009578:Nitrobenzenes / Q000138:chemical synthesis; D009584:Nitrogen / Q000737:chemistry*; D009602:Nitrosamines / Q000138:chemical synthesis
chemical_list: D000814:Aniline Compounds; D004202:Disinfectants; D009578:Nitrobenzenes; D009602:Nitrosamines; C015384:nitramine; D004128:Dimethylnitrosamine; D009584:Nitrogen