title: The effect of pre-oxidation on NDMA formation and the influence of pH.
abstract: N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated drinking water systems. Pre-oxidation of the NDMA precursors prior to chloramination can be a viable approach for water utilities to control the NDMA levels. This study examined the effects of (i) commonly used oxidants (i.e., chlorine, chlorine dioxide and ozone) in water treatment, (ii) oxidant concentration and contact time (CT), and (iii) pre-oxidation pH on the formation of NDMA from subsequent chloramination. Fifteen model precursors with NDMA molar yields ranging from approximately 0.1%-90% were examined. Pre-chlorination reduced NDMA formation from most precursors by 10%-50% except quaternary amine polymers (i.e., PolyDADMAC, PolyACRYL, PolyAMINE). Pre-oxidation with chlorine dioxide and ozone achieved the same or higher deactivation of NDMA precursors (e.g., ranitidine) while increasing NDMA formation for some other precursors (e.g., daminozid). The increases with chlorine dioxide exposure were attributed to the release of oxidation products with dimethylamine (DMA) moiety, which may form more NDMA upon chloramination than the unoxidizied parent compound. On the other hand, chlorine dioxide was effective, if a precursors NDMA yield were higher than DMA. The ozone-triggered increases could be related to direct NDMA formation from DMA which are released by ozonation of amines with DMA moiety, amides or hydrazines. However, hydroxyl radicals formed from the decomposition of ozone would be also involved in decomposition of formed NDMA, reducing the overall NDMA levels at longer contact times. pH conditions influenced significantly the effectiveness of deactivation of precursors depending on the type of precursor and oxidant used.
authors.affiliation: Department of Environmental Engineering and Earth Sciences, Clemson University, Anderson, SC 29625, USA.
authors.forename: Meric
authors.initials: M
authors.lastname: Selbes
authors.affiliation: Department of Environmental Engineering and Earth Sciences, Clemson University, Anderson, SC 29625, USA.
authors.forename: Daekyun
authors.initials: D
authors.lastname: Kim
authors.affiliation: Department of Environmental Engineering and Earth Sciences, Clemson University, Anderson, SC 29625, USA. Electronic address: tkaranf@clemson.edu.
authors.forename: Tanju
authors.initials: T
authors.lastname: Karanfil
mesh_terms: D000588:Amines / Q000737:chemistry; D004123:Dimethylamines / Q000737:chemistry; D004128:Dimethylnitrosamine / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D018508:Water Purification / Q000379:methods*
chemical_list: D000588:Amines; D004123:Dimethylamines; C034516:dimethylamine; D004128:Dimethylnitrosamine
keywords: Amines; Chloramination; NDMA; Pre-oxidation; Water treatment; pH