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HERO ID
7564596
Reference Type
Journal Article
Title
Updated Reaction Pathway for Dichloramine Decomposition: Formation of Reactive Nitrogen Species and N-Nitrosodimethylamine
Author(s)
Pham, HT; Wahman, DG; Fairey, JL
Year
2021
Is Peer Reviewed?
1
Journal
Environmental Science & Technology
ISSN:
0013-936X
EISSN:
1520-5851
Publisher
AMER CHEMICAL SOC
Location
WASHINGTON
Volume
55
Issue
3
Page Numbers
1740-1749
Language
English
PMID
33448793
DOI
10.1021/acs.est.0c06456
Web of Science Id
WOS:000618083600037
Abstract
The N-nitrosodimethylamine (NDMA) formation pathway in chloraminated drinking water remains unresolved. In pH 7-10 waters amended with 10 μM total dimethylamine and 800 μeq Cl2·L-1 dichloramine (NHCl2), NDMA, nitrous oxide (N2O), dissolved oxygen (DO), NHCl2, and monochloramine (NH2Cl) were kinetically quantified. NHCl2, N2O, and DO profiles indicated that reactive nitrogen species (RNS) formed during NHCl2 decomposition, including nitroxyl/nitroxyl anion (HNO/NO-) and peroxynitrous acid/peroxynitrite anion (ONOOH/ONOO-). Experiments with uric acid (a ONOOH/ONOO- scavenger) implicated ONOOH/ONOO- as a central node for NDMA formation, which were further supported by the concomitant N-nitrodimethylamine formation. A kinetic model accurately simulated NHCl2, NH2Cl, NDMA, and DO concentrations and included (1) the unified model of chloramine chemistry revised with HNO as a direct product of NHCl2 hydrolysis; (2) HNO/NO- then reacting with (i) HNO to form N2O, (ii) DO to form ONOOH/ONOO-, or (iii) NHCl2 or NH2Cl to form nitrogen gas; and (3) NDMA formation via ONOOH/ONOO- or their decomposition products reacting with (i) dimethylamine (DMA) and/or (ii) chlorinated unsymmetrical dimethylhydrazine (UDMH-Cl), the product of NHCl2 and DMA. Overall, updated NHCl2 decomposition pathways are proposed, yielding (1) RNS via and (2) NDMA via .
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