Kinetics and mechanism of center dot OH-initiated atmospheric oxidation of organophosphorus plasticizers: A computational study on tri-p-cresyl phosphate
Kinetics and mechanism of center dot OH-initiated atmospheric oxidation of organophosphorus plasticizers: A computational study on tri-p-cresyl phosphate
复制标题
中心点 OH 引发有机磷增塑剂大气氧化的动力学和机理：磷酸三对甲苯酯的计算研究
DOI：
10.1016/j.chemosphere.2018.03.034
复制
发表时间：
2018
期刊：
影响因子：
8.8
通讯作者：
Du Zheng
中科院分区：
文献类型：
--
作者：
Li Chao;Zheng Shanshan;Chen Jingwen;Xie Hong-Bin;Zhang Ya-Nan;Zhao Yuanhui;Du Zheng
Understanding the atmospheric fate of organophosphorus plasticizers is important for their environmental risk assessment. However, limited information is available at present. In this study, density functional theory (DFT) calculations were performed to investigate the transformation mechanism and kinetics of tri-p-cresyl phosphate (TpCP) initiated by radical dotOH. Results show that the initial reactions are dominated by H-abstraction and radical dotOH addition to form TpCP-radical, TpCP–OH adducts and aryl phosphodiester. The H-abstraction pathways are more favorable than the radical dotOH addition pathways. The TpCP-radical and TpCP–OH adducts can further react with O2in the atmosphere to finally form benzaldehyde phosphate, hydroxylated TpCP and bicyclic radicals. Based on the transition state theory, the calculated rate constant (kOH) of TpCP with radical dotOH atT= 298 K is 1.9 × 10−12cm3molecule−1s−1with an atmospheric lifetime of 4.2 days, which demonstrates that gaseous TpCP is atmospherically persistent. This study provides a comprehensive investigation of the radical dotOH-initiated oxidation of TpCP, which is useful for understanding its mechanism of transformation and evaluating the risk in atmospheric environment.
