Elementary reaction-based kinetic model for the fate of N -nitrosodimethylamine under UV oxidation
Elementary reaction-based kinetic model for the fate of N -nitrosodimethylamine under UV oxidation
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基于基本反应的 N-亚硝基二甲胺在紫外氧化下的命运动力学模型
DOI：
10.1039/d1ew00262g
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Minakata, Daisuke
中科院分区：
文献类型：
--
作者：
Barrios, Benjamin;Kamath, Divya;Coscarelli, Erica;Minakata, Daisuke
紫外光解是一种去除污染水源中亚硝胺的有效方法。亚硝胺是一类具有高度致癌性的化合物，因此，它们对人类健康的威胁及其对环境的毒性令人严重关切。虽然母体亚硝胺的光化学参数及其初始反应途径已经被很好地理解，但亚硝胺降解产生的含氮物种和活性氮物种的命运尚未被阐明。在本研究中，我们建立了n-亚硝基二甲胺（NDMA）光解及其光化学转化产物的基本反应动力学模型。利用密度泛函理论和量子力学计算方法计算了水相激活能和反应自由能，研究了基本反应的动力学和热力学性质。我们生成了所有参与鉴定反应的物质的常微分方程，并求解得到了NDMA和降解产物在pH 3和pH 7下随时间变化的浓度曲线。并与文献中的实验结果进行了比较，验证了初步反应动力学模型的正确性。本文首次建立了NDMA与活性氮光化学反应的基本反应动力学模型。本研究结果对利用含氮化合物的亚硝化胁迫和高级氧化工艺（如UV/硝酸盐和UV/氯胺高级氧化工艺）的活跃研究领域具有重要影响。
UV photolysis is an effective process to remove nitrosamines from contaminated water resources. Nitrosamines represent a class of compounds with high potential for carcinogenicity and, therefore, there are serious concerns regarding their threat to human health and their environmental toxicity. Although the photochemical parameters of parent nitrosamines and their initial reaction pathways are well understood, the fate of nitrogen-containing species and reactive nitrogen species generated from nitrosamine degradation has not yet been elucidated. In this study, we develop an elementary reaction-based kinetic model for the photolysis of N-nitrosodimethylamine (NDMA) and the photochemical transformation products. We use density functional theory quantum mechanical calculations to calculate the aqueous-phase free energies of activation and reaction to investigate the kinetics and thermodynamics properties of the elementary reactions. We generate ordinary differential equations for all species involved in the identified reactions and solve them to obtain the time-dependent concentration profiles of NDMA and the degradation products at pH 3 and pH 7. The profiles are compared to experimental results in the literature to validate our elementary reaction-based kinetic model. This is the first study to develop an elementary reaction-based kinetic model for the photochemical reaction of NDMA and reactive nitrogen species. The findings of this study have a significant impact on the active research area of nitrosative stress and advanced oxidation processes that utilize nitrogen-containing compounds such as UV/nitrate and UV/chloramine advanced oxidation processes.