Abstract

N-Nitrosodimethylamine (NDMA) is an emerging disinfection byproduct, and we show that use of chlorine dioxide (ClO2) has the potential to increase NDMA formation in waters containing precursors with hydrazine moieties. NDMA formation was measured after oxidation of 13 amines by monochloramine and ClO2 and pretreatment with ClO2 followed by postmonochloramination. Daminozide, a plant growth regulator, was found to yield 5.01 ± 0.96% NDMA upon reaction with ClO2, although no NDMA was recorded during chloramination. The reaction rate was estimated to be ∼0.0085 s-1, and on the basis of our identification by mass spectrometry of the intermediates, the reaction likely proceeds via the hydrolytic release of unsymmetrical dimethylhydrazine (UDMH), with the hydrazine structure a key intermediate in NDMA formation. The presence of UDMH was confirmed by gas chromatography-mass spectrometry analysis. For 10 of the 13 compounds, ClO2 preoxidation reduced NDMA yields compared with monochloramination alone, which is explained by our measured release of dimethylamine. This work shows potential preoxidation strategies to control NDMA formation may not impact all organic precursors uniformly, so differences might be source specific depending upon the occurrence of different precursors in source waters. For example, daminozide is a plant regulator, so drinking water that is heavily influenced by upstream agricultural runoff could be at risk.

Original languageEnglish (US)
Pages (from-to)11429-11437
Number of pages9
JournalEnvironmental Science and Technology
Volume49
Issue number19
DOIs
StatePublished - Sep 1 2015

Fingerprint

Dimethylnitrosamine
Amines
chlorine
mass spectrometry
oxidation
agricultural runoff
Oxidation
hydrazine
growth regulator
disinfection
reaction rate
gas chromatography
drinking water
water
Mass spectrometry
Agricultural runoff
Plant Growth Regulators
amine
chlorine dioxide
Water

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Role of Chlorine Dioxide in N-Nitrosodimethylamine Formation from Oxidation of Model Amines. / Gan, Wenhui; Bond, Tom; Yang, Xin; Westerhoff, Paul.

In: Environmental Science and Technology, Vol. 49, No. 19, 01.09.2015, p. 11429-11437.

Research output: Contribution to journalArticle

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