Theoretical investigation of a potentially important formation pathway of organosulfate in atmospheric aqueous aerosols
Theoretical investigation of a potentially important formation pathway of organosulfate in atmospheric aqueous aerosols
复制标题
大气水气溶胶中有机硫酸盐潜在重要形成途径的理论研究
DOI：
10.1038/s41598-020-61968-2
复制
发表时间：
2020-04
影响因子：
4.6
通讯作者：
Jun Zhao
中科院分区：
文献类型：
--
作者：
Kunpeng Chen;Jun Zhao
有机硫酸盐在大气气溶胶的调节特性中起着重要作用。最近的研究表明，利用气溶胶质谱仪等先进仪器进行现场测量，有机硫酸盐很可能被解释为无机硫酸盐，有机硫酸盐的主要成分被认为是羟基甲烷磺酸盐（HMS）。本研究提出，除HMS外，其在大气气溶胶中未被发现的异构体羟甲基亚硫酸铵（HMSi）也可能是二氧化硫与甲醛水溶液反应的产物。量子化学模拟结果表明，HMS和HMSi的形成速度比其对应的共轭酸HMSA和HMSi的形成速度快几个数量级。此外，水的参与可以大大加快HMS/HMSA和HMSi的形成速度，而减缓HMHSi的形成速度，说明水在形成过程中的作用不可忽视。此外，利用计算参数实现的动力学模型表明，HMSi/HMHSi能显著改变大气水溶液气溶胶的pH值，而HMS/HMSA不能，HMHSi是HMS/HMSA和HMSi/HMHSi中含量最多的物质。因此，新发现的通过HMSi/HMHSi形成的途径应受到高度关注，其动力学参数应在未来的大气化学模型中得到应用。
Organic sulfate plays important roles in modulating properties of atmospheric aerosols. Recent studies showed that organic sulfate was likably interpreted as inorganic sulfate in field measurements using advanced instruments such as Aerosol Mass Spectrometer and the major contributor to organic sulfate was thought to be hydroxymethanesulfonate (HMS). This study proposed that besides HMS, its isomer hydroxymethyl sulfite (HMSi), which has not been identified in atmospheric aerosols, can emerge as the product of aqueous reactions between sulfur dioxide and formaldehyde. Results from quantum chemical modeling showed that formation of HMS and HMSi was several orders of magnitude faster than that of their corresponding conjugate acids, HMSA and HMHSi. In addition, water involvement can largely accelerate respectively the formation rate of HMS/HMSA and HMSi, but decelerate that of HMHSi, demonstrating the non-negligible role of water in the formation process. Furthermore, our kinetic model implemented with the calculated parameters indicates that HMSi/HMHSi but not HMS/HMSA can significantly alter the pH values of atmospheric aqueous aerosols and HMHSi is the most abundant species among HMS/HMSA and HMSi/HMHSi. Therefore, the newly-discovered pathway via HMSi/HMHSi formation should be of great concern and its kinetic parameters should be implemented in future models of atmospheric chemistry.
登录
查看更多内容
影响因子：
4.4
作者：
J. Mayer;W. Band
通讯作者：
J. Mayer;W. Band
中国泰山山顶云的化学成分和液滴尺寸分布
影响因子：
6.3
作者：
Li Jiarong;Wang Xinfeng;Chen Jianmin;Zhu Chao;Li Weijun;Li Chengbao;Liu Lu;Xu Caihong;Wen Liang;Xue Likun;Wang Wenxing;Ding Aijun;Herrmann Hartmut
通讯作者：
Herrmann Hartmut
影响因子：
5.5
作者：
Biczysko, Malgorzata;Panek, Pawel;Barone, Vincenzo
通讯作者：
Barone, Vincenzo
影响因子：
4.1
作者：
PLIMPTON, S
通讯作者：
PLIMPTON, S
影响因子：
5
作者：
Dixon, RW;Aasen, H
通讯作者：
Aasen, H