Multiple evaluations of atmospheric behavior between Criegee intermediates and HCHO: Gas-phase and air-water interface reaction  

作　　者：Tianlei Zhang Mingjie Wen Chao Ding Yongqi Zhang Xiaohui Ma Zhuqing Wang Makroni Lily Junhai Liu Rui Wang 

机构地区：[1]Institute of Theoretical and Computational Chemistry,Shaanxi Key Laboratory of Catalysis,School of Chemical&Environment Science,Shaanxi University of Technology,Hanzhong 723001,China [2]School of Environmental Science and Engineering,Institute of Environmental Health and Pollution Control,Guangdong University of Technology,Guangzhou 510006,China [3]Shandong Key Laboratory of Biophysics,Institute of Biophysics,Dezhou University,Dezhou 253023,China [4]Environmental Research Institute,Shandong University,Qingdao 266237,China [5]Qinba Mountains of Bio-Resource Collaborative Innovation Center of Southern Shaanxi Province,Shaanxi University of Technology,Hanzhong 723001,China

出　　处：《Journal of Environmental Sciences》2023年第5期308-319,共12页环境科学学报（英文版）

基　　金：support from the National Natural Science Foundation of China(Nos:22073059,42107109);the GHfund B(No:20210702);the Key Cultivation Project of Shaanxi University of Technology(No:SLG2101);the Funds of Graduate Innovation of Shaanxi University of Technology(No:SLGYCX2120);the State Key Laboratory of Biological Resources and Ecological Environment of Qinba Areas“City-School Co-Construction”Special Research Project(No:SXC-2110).

摘　　要：Given the high abundance of water in the atmosphere,the reaction of Criegee intermediates(CIs)with(H_(2)O)_(2) is considered to be the predominant removal pathway for CIs.However,recent experimental findings reported that the reactions of CIs with organic acids and carbonyls are faster than expected.At the same time,the interface behavior between CIs and carbonyls has not been reported so far.Here,the gas-phase and air-water interface behavior between Criegee intermediates and HCHO were explored by adopting high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations.Quantum chemical calculations evidence that the gas-phase reactions of CIs+HCHO are submerged energy or low energy barriers processes.The rate ratios speculate that the HCHO could be not only a significant tropospheric scavenger of CIs,but also an inhibitor in the oxidizing ability of CIs on SO_(x) in dry and highly polluted areas with abundant HCHO concentration.The reactions of CH_(2)OO with HCHO at the droplet’s surface follow a loop structure mechanism to produce i)SOZ(■),ii)BHMP(HOCH_(2)OOCH_(2)OH),and iii)HMHP(HOCH_(2)OOH).Considering the harsh reaction conditions between CIs and HCHO at the interface(i.e.,the two molecules must be sufficiently close to each other),the hydration of CIs is still their main atmospheric loss pathway.These results could help us get a better interpretation of the underlying CIs-aldehydes chemical processes in the global polluted urban atmospheres.

关 键 词：Criegee intermediates HCHO Atmospheric behavior Air-water interface Chemical processes 

分 类 号：X131.1[环境科学与工程—环境科学]