Isomer-Resolved Reactivity of Organic Peroxides in Monoterpene-Derived Secondary Organic Aerosol

被引：20

作者：

Yao, Min ^{[1
]}

Li, Ziyue ^{[1
]}

Li, Chenxi ^{[1
]}

Xiao, Huayun ^{[1
]}

Wang, Shunyao ^{[2
]}

Chan, Arthur W. H. ^{[2
]}

Zhao, Yue ^{[1
]}

机构：

[1] Shanghai Jiao Tong Univ, Sch Environm Sci & Engn, Shanghai 200240, Peoples R China

[2] Univ Toronto, Dept Chem Engn & Appl Chem, Toronto, ON M5S 3E5, Canada

来源：

ENVIRONMENTAL SCIENCE & TECHNOLOGY | 2022年 / 56卷 / 08期

基金：

中国国家自然科学基金;

关键词：

secondary organic aerosol;   monoterpene oxidation; particle-phase reactivity; organic peroxides; oligomers; kinetic modeling; ALPHA-ACYLOXYHYDROPEROXY ALDEHYDES; HIGHLY OXYGENATED MOLECULES; MASS-SPECTROMETRY; PARTICLE FORMATION; PINENE OZONOLYSIS; RELATIVE-HUMIDITY; GLASS-TRANSITION; PHASE REACTIONS; ACIDS; VOLATILITY;

D O I：

10.1021/acs.est.2c01297

中图分类号：

X [环境科学、安全科学];

学科分类号：

08 ; 0830 ;

摘要：

Organic peroxides play a vital role in the formation, evolution, and healthimpacts of atmospheric aerosols, yet their molecular composition and fate in the particle phaseremain poorly understood. Here, we identified, using iodometry-assisted liquid chromatog-raphy mass spectrometry, a large suite of isomer-resolved peroxide monomers(C8-10H12-18O5-8) and dimers (C15-20H22-34O5-14) in secondary organic aerosol formedfrom ozonolysis of the most abundant monoterpene (alpha-pinene). Combining aerosolisothermal evaporation experiments and multilayer kinetic modeling, bulk peroxides werefound to undergo rapid particle-phase chemical transformation with an average lifetime ofseveral hours under humid conditions, while the individual peroxides decompose on timescalesof half an hour to a few days. Meanwhile, the majority of isomeric peroxides exhibit distinct particle-phase behaviors, highlighting theimportance of the characterization of isomer-resolved peroxide reactivity. Furthermore, the reactivity of most peroxides increaseswith aerosol water content faster in a low relative humidity (RH) range than in a high RH range. Such non-uniform water effectsimply a more important role of water as a plasticizer than as a reactant in influencing the peroxide reactivity. The high particle-phasereactivity of organic peroxides and its striking dependence on RH should be considered in atmospheric modeling of their fate andimpacts on aerosol chemistry and health effects.

引用

页码：4882 / 4893

页数：12

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