Aqueous OH Radical Reaction Rate Constants for Organophosphorus Flame Retardants and Plasticizers: Experimental and Modeling Studies
Aqueous OH Radical Reaction Rate Constants for Organophosphorus Flame Retardants and Plasticizers: Experimental and Modeling Studies
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有机磷阻燃剂和增塑剂的水基 OH 自由基反应速率常数：实验和建模研究
DOI：
10.1021/acs.est.7b05429
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发表时间：
2018
影响因子：
11.4
通讯作者：
Qin Weichao
中科院分区：
文献类型：
--
作者：
Li Chao;Wei Gaoliang;Chen Jingwen;Zhao Yuanhui;Zhang Ya-Nan;Su Limin;Qin Weichao
有机磷酸酯 (OPE) 的水·OH 反应速率常数 (kOH) 对于评估其环境归趋和高级氧化过程 (AOP) 中的去除潜力至关重要。本文采用实验和计算机方法来获得各种 OPE 的 kOH 值。确定的 18 个 OPE 的 kOH 从 4.0 × 108M–1s–1 到 1.6 × 1010M–1s–1 不等。基于实验的kOH值，开发了一个定量结构-活性关系模型，该模型涉及重原子数量、含量指数和C原子最大负电荷的分子结构信息，用于预测其他OPE的kOH。此外，选择了适当的密度泛函理论（DFT）和溶剂化模型，与过渡态理论一起用于预测三种代表性OPE的kOH。计算的 DFT 与实验 kOH 值 (kcal/kexp) 之间的偏差在 2 以内。OPE 在天然水中的半衰期估计为 0.5-22791.3 天，在 AOP 中为 0.044-19.7 s，表明 OPE 在天然水中具有潜在的持久性，并且可以被 AOP 快速消除。确定的 kOH 值和硅方法为评估 OPE 在水生环境中的命运提供了科学基础。
Aqueous ·OH reaction rate constants (kOH) for organophosphate esters (OPEs) are essential for assessing their environmental fate and removal potential in advanced oxidation processes (AOPs). Herein experimental andin silicoapproaches were adopted to obtainkOHvalues for a variety of OPEs. The determinedkOHfor 18 OPEs varies from 4.0 × 108M–1s–1to 1.6 × 1010M–1s–1. Based on the experimentalkOHvalues, a quantitative structure–activity relationship model that involves molecular structural information on the number of heavy atoms, content index, and the most negative charge of C atoms was developed for predictingkOHof other OPEs. Furthermore, appropriate density functional theory (DFT) and solvation models were selected, which together with transition state theory were employed to predictkOHof three representative OPEs. The deviation between the DFT calculated and the experimentalkOHvalues (kcal/kexp) is within 2. Half-lives of the OPEs were estimated to be 0.5–22791.3 days in natural waters and 0.044–19.7 s in AOPs, indicating the OPEs are potentially persistent in natural waters and can be quickly eliminated by AOPs. The determinedkOHvalues and thein silicomethods offer a scientific base for assessing OPEs fate in aquatic environments.