title: Nitrosamine formation pathway revisited: the importance of chloramine speciation and dissolved oxygen.
abstract: Nitrosamine formation during chloramination previously has been linked to a reaction between monochloramine and organic nitrogen precursors via unsymmetrical dialkylhydrazine intermediates. Our results demonstrate the critical importance of dichloramine and dissolved oxygen. We propose a new nitrosamine formation pathway in which dichloramine reacts with secondary amine precursors to form chlorinated unsymmetrical dialkylhydrazine intermediates. Oxidation of these intermediates by dissolved oxygen to form nitrosamines competes with their oxidation by chloramines. Even when preformed monochloramine was applied, our model explained nearly all N-nitrosodimethylamine formation from the traces of dichloramine formed via monochloramine disproportionation. We suggest that, in contrast to unsymmetrical dialkylhydrazines, the weak, nonpolar nature of the N-Cl linkage in chlorinated unsymmetrical dialkylhydrazine intermediates enables incorporation of dissolved oxygen to form nitrosamines. With the improved understanding of the nitrosamine formation pathway, strategies are suggested that could significantly reduce nitrosamine formation during chloramination.
authors.affiliation: Department of Chemical Engineering, Yale University, 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: D002700:Chloramines / Q000737:chemistry*; D004123:Dimethylamines / Q000737:chemistry; D004128:Dimethylnitrosamine; D006863:Hydrogen-Ion Concentration; D009602:Nitrosamines / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D012722:Sewage; D018508:Water Purification
chemical_list: D002700:Chloramines; D004123:Dimethylamines; D009602:Nitrosamines; D012722:Sewage; C034516:dimethylamine; D004128:Dimethylnitrosamine; D010100:Oxygen