Homogeneous and heterogeneous atmospheric ozonolysis of chlorobenzene:Mechanism, kinetics and ecotoxicity assessment

Nuan Wen; Mingxue Li; Yanru Huo; Yuxin Zhou; Jinchan Jiang; Yuhui Ma; Qingyuan Gu; Ju Xie; Maoxia He

doi:10.1016/j.chemosphere.2023.140303

Homogeneous and heterogeneous atmospheric ozonolysis of chlorobenzene:Mechanism, kinetics and ecotoxicity assessment

Chemosphere. 2023 Dec:343:140303. doi: 10.1016/j.chemosphere.2023.140303. Epub 2023 Sep 26.

Authors

Nuan Wen¹, Mingxue Li¹, Yanru Huo¹, Yuxin Zhou¹, Jinchan Jiang¹, Yuhui Ma¹, Qingyuan Gu¹, Ju Xie², Maoxia He³

Affiliations

¹ Environment Research Institute, Shandong University, Qingdao, 266237, PR China.
² School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, PR China.
³ Environment Research Institute, Shandong University, Qingdao, 266237, PR China. Electronic address: hemaox@sdu.edu.cn.

PMID: 37769920
DOI: 10.1016/j.chemosphere.2023.140303

Abstract

The reactions between chlorobenzene(CB) and ozone have been studied comprehensively in this paper. Chlorobenzene is a commonly found chlorinated aromatic volatile organic compound(VOC), and its emission into the atmosphere can cause harm to the ecosystem and human health. The frequent occurrence of mineral particles from sandstorms exerts a significant influence on the atmospheric chemistry of the troposphere. Mineral particles are abundant in SiO₂ and Al₂O₃ content. Therefore, we investigated the homogeneous and heterogeneous reaction processes of CB and ozone in the atmosphere by using density functional theory (DFT) method at the M06-2X/6-311++g(3df,2p)//M06-2X/6-31+g(d,p) level. The atmospheric fate, reaction rate and toxicity evaluation of CB ozonation were studied in the gas-phase section. Toxicity evaluation results showed that ozonation of CB could effectively reduce its toxicity. For the heterogeneous process, we simulated three types of SiO₂ clusters and nine types of (Al₂O₃)n clusters, and studied the configurations of CB adsorbed on the cluster surfaces. We found that adsorption of CB on the SiO₂ clusters was achieved through hydrogen bonding, while adsorption of CB on the Al₂O₃ clusters was achieved through both hydrogen bonding and metal bonding. The energy for CB adsorption on the (Al₂O₃)n cluster surface was higher than that for the Si_xO_y(OH)_z cluster surface, and both types of clusters exhibited efficient adsorption of CB. As the Si_xO_y(OH)_z clusters grew larger, the rates for the reactions between O₃ and CB increased. CB travelled long distances along the Al₂O₃ clusters, leading to an extended influence range.

Keywords: Chlorobenzene; Heterogeneous; Homogeneous; Ozonation.