Title

Mechanistic insight into the degradation of Nitrosamines via aqueous-phase UV Photolysis or a UV-based advanced oxidation process: quantum mechanical calculations

Authors

Daisuke Minakata, Michigan Technological UniversityFollow
Erica Coscarelli, Michigan Technological UniversityFollow

Document Type

Article

Publication Date

2018

Abstract

Nitrosamines are a group of carcinogenic chemicals that are present in aquatic environments that result from byproducts of industrial processes and disinfection products. As indirect and direct potable reuse increase, the presence of trace nitrosamines presents challenges to water infrastructures that incorporate effluent from wastewater treatment. Ultraviolet (UV) photolysis or UV-based advanced oxidation processes that produce highly reactive hydroxyl radicals are promising technologies to remove nitrosamines from water. However, complex reaction mechanisms involving radicals limit our understandings of the elementary reaction pathways embedded in the overall reactions identified experimentally. In this study, we perform quantum mechanical calculations to identify the hydroxyl radical-induced initial elementary reactions with N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine, and N-nitrosomethylbutylamine. We also investigate the UV-induced NDMA degradation mechanisms. Our calculations reveal that the alkyl side chains of nitrosamine affect the reaction mechanism of hydroxyl radicals with each nitrosamine investigated in this study. Nitrosamines with one- or two-carbon alkyl chains caused the delocalization of the electron density, leading to slower subsequent degradation. Additionally, three major initial elementary reactions and the subsequent radical-involved reaction pathways are identified in the UV-induced NDMA degradation process. This study provides mechanistic insight into the elementary reaction pathways, and a future study will combine these results with the kinetic information to predict the time-dependent concentration profiles of nitrosamines and their transformation products.

Publisher's Statement

© 2018 by the authors. Licensee MDPI, Basel, Switzerland.

Publisher's version of record: https://doi.org/10.3390/molecules23030539

Publication Title

Molecules

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

Recommended Citation

Minakata, D., & Coscarelli, E. (2018). Mechanistic insight into the degradation of Nitrosamines via aqueous-phase UV Photolysis or a UV-based advanced oxidation process: quantum mechanical calculations. Molecules, 23(3), 539. http://doi.org/10.3390/molecules23030539
Retrieved from: https://digitalcommons.mtu.edu/cee-fp/16

Version

Publisher's PDF