Document Type
Article
Publication Date
3-1-2024
Department
Department of Civil, Environmental, and Geospatial Engineering
Abstract
N-Nitrosamines are potential human carcinogens frequently detected in natural and engineered aquatic systems. This study sheds light on the role of carbonyl compounds in the formation of N-nitrosamines by nitrosation of five secondary amines via different pathways. The results showed that compared to a control system, the presence of formaldehyde enhances the formation of N-nitrosamines by a factor of 5-152 at pH 7, depending on the structure of the secondary amines. Acetaldehyde showed a slight enhancement effect on N-nitrosamine formation, while acetone and benzaldehyde did not promote nitrosation reactions. For neutral and basic conditions, the iminium ion was the dominant intermediate for N-nitrosamine formation, while carbinolamine became the major contributor under acidic conditions. Negative free energy changes (< −19 kcal mol-1) and relatively low activation energies ( < 18 kcal mol-1) of the reactions of secondary amines with N2O3, iminium ions with nitrite and carbinolamines with N2O3 from quantum chemical computations further support the proposed reaction pathways. This highlights the roles of the iminium ion and carbinolamine in the formation of N-nitrosamines during nitrosation in the presence of carbonyl compounds, especially in the context of industrial wastewater.
Publication Title
Environmental science & technology
Recommended Citation
Pan, Y.,
Breider, F.,
Barrios, B.,
Minakata, D.,
Deng, H.,
&
von Gunten, U.
(2024).
Role of Carbonyl Compounds for N-Nitrosamine Formation during Nitrosation: Kinetics and Mechanisms.
Environmental science & technology,
58(10), 4792-4801.
http://doi.org/10.1021/acs.est.3c07461
Retrieved from: https://digitalcommons.mtu.edu/michigantech-p2/553
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.
Publisher's Statement
Copyright © 2024 The Authors. Published by American Chemical Society.
Publisher's record: https://doi.org/10.1021/acs.est.3c07461