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形成之外:揭示有机硫酸盐非均相OH氧化的大气转化过程

Beyond the formation: unveiling the atmospheric transformation of organosulfates heterogeneous OH oxidation.

作者信息

Ng Sze In Madeleine, Chan Man Nin

机构信息

Earth System Science Programme, Faculty of Science, The Chinese University of Hong Kong, Hong Kong, China.

The Institute of Environment, Energy and Sustainability, The Chinese University of Hong Kong, Hong Kong, China.

出版信息

Chem Commun (Camb). 2023 Nov 23;59(94):13919-13938. doi: 10.1039/d3cc03700b.

Abstract

Organosulfates (OSs), characterized with a sulfate ester group (R-OSO), are abundant constituents in secondary organic aerosols. Recent laboratory-based investigations have revealed that OSs can undergo efficient chemical transformation through heterogeneous oxidation by hydroxyl radicals (˙OH, interchangeably termed as OH in this article), which freshly derives functionalized and fragmented OSs. The reaction not only contributes to the presence of structurally transformed OSs in the atmosphere of which sources were unidentified, but it also leads to the formation of inorganic sulfates (, SO) with profound implication on the form of aerosol sulfur. In this article, we review the current state of knowledge regarding the heterogeneous OH oxidation of OSs based on state-of-the-art designs of experiments, computational approaches, and chemical analytical techniques. Here, we discuss the formation potential of new OSs and SO, in light of the influence of diverse OS structures on the relative importance of different reaction pathways. We propose future research directions to advance our mechanistic understanding of these reactions, taking into account aerosol matrix effects, interactions with other atmospheric pollutants, and the incorporation of experimental findings into atmospheric chemical transport models.

摘要

有机硫酸盐(OSs)以硫酸酯基团(R-OSO)为特征,是二次有机气溶胶中的丰富成分。最近基于实验室的研究表明,OSs可通过羟基自由基(˙OH,本文中也可互换称为OH)的非均相氧化进行有效的化学转化,从而产生功能化和碎片化的OSs。该反应不仅导致大气中存在来源不明的结构转化OSs,还会导致无机硫酸盐(,SO)的形成,这对气溶胶硫的形态具有深远影响。在本文中,我们基于最新的实验设计、计算方法和化学分析技术,综述了关于OSs非均相OH氧化的当前知识状态。在此,我们根据不同OS结构对不同反应途径相对重要性的影响,讨论新OSs和SO的形成潜力。考虑到气溶胶基质效应、与其他大气污染物的相互作用以及将实验结果纳入大气化学传输模型,我们提出了未来的研究方向,以推进我们对这些反应的机理理解。

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