Understanding N-nitrosodimethylamine Formation in Water: Chloramine Chemistry, Kinetics, and A Proposed Reaction Pathway
Date of Graduation
Master of Science in Civil Engineering (MSCE)
Second Committee Member
Applied sciences, Chloramine, GC-MS, NDMA
The formation of N-nitrosodimethylamine (NDMA) in drinking water systems is a concern because of its potential carcinogenicity and occurrence at toxicologically relevant levels. The postulated mechanism for NDMA formation involves a substitution between dichloramine and amine-based precursors to form an unsymmetrical dimethylhydrazine (UDMH), which is then oxidized by ground-state molecular oxygen to form NDMA. However, this latter reaction is spin forbidden, thus likely occurs at a slow rate. It is hypothesized that the reaction between monochloramine and hydroxylamine (a nitrification product) may form an intermediate, which is involved in the NDMA formation pathway. This intermediate may also be generated from dichloramine decay, in the absence of hydroxylamine. In this study, a series of batch kinetic experiments were conducted to investigate the decomposition of chloramine species at pH 8.0 to 10.0 and the concomitant formation of NDMA. Chloramine species were quantified using UV/Vis spectroscopy (Direct UV) and colorimetric methods (Hach) and compared to simulations from the unified chloramine model. NDMA was quantified using GC-MS following liquid-liquid extraction. The model captured the decay of monochloramine and dichloramine adequately, with the exception of monochloramine at pH 10.0, possibly due to an interference from a previously reported unidentified chloramine decomposition compound (UC1). NDMA formation was pH dependent with the maximum yields at pH 9.0 and the fastest kinetics at pH 10.0. A second unidentified compound (UC2), with a mass spectrum identified as UDMH, was detected only at pH 9.0 and 10.0 in batch reactors with DMA and dichloramine. Importantly, NDMA formation appeared to be insensitive to the presence or absence of UC2, suggesting UC2 was not involved in NDMA formation. Hydroxylamine accelerates the decomposition of monochloramine. The reaction between DMA and hydroxylamine formed a third unidentified compound (UC3), preliminarily identified as acetoxime, which was not observed in the presence of monochloramine. Upon addition of hydroxylamine, NDMA yields decreased by more than half in batch reactors with DMA and monochloramine. On balance, the findings suggest the existence of a NDMA formation pathway that may not involve UDMH, and points to the need for studies with scavengers and donors of short-lived species from chloramine decay.
Pham, H. T. (2017). Understanding N-nitrosodimethylamine Formation in Water: Chloramine Chemistry, Kinetics, and A Proposed Reaction Pathway. Graduate Theses and Dissertations Retrieved from https://scholarworks.uark.edu/etd/1938
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