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

共 79 条

[1] Measurements of Kinetics and Equilibria for the Condensed Phase Reactions of Hydroperoxides with Carbonyls to Form Peroxyhemiacetals [J].

Bakker-Arkema, Julia G. ;

Ziemann, Paul J. .

ACS EARTH AND SPACE CHEMISTRY, 2020, 4 (03) :467-475

[2]

Bianchi F., CHEM REV 2019

[3] Particle-Phase Chemistry of Secondary Organic Material: Modeled Compared to Measured O:C and H:C Elemental Ratios Provide Constraints [J].

Chen, Qi ;

Liu, Yingjun ;

Donahue, Neil M. ;

Shilling, John E. ;

Martin, Scot T. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2011, 45 (11) :4763-4770

[4] Functional Group Composition of Secondary Organic Aerosol Formed from Ozonolysis of α-Pinene Under High VOC and Autoxidation Conditions [J].

Claflin, Megan S. ;

Krechmer, Jordan E. ;

Hu, Weiwei ;

Jimenez, Jose L. ;

Ziemann, Paul J. .

ACS EARTH AND SPACE CHEMISTRY, 2018, 2 (11) :1196-1210

[5] Autoxidation of Organic Compounds in the Atmosphere [J].

Crounse, John D. ;

Nielsen, Lasse B. ;

Jorgensen, Solvejg ;

Kjaergaard, Henrik G. ;

Wennberg, Paul O. .

JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2013, 4 (20) :3513-3520

[6] Isothermal Evaporation of α-Pinene Ozonolysis SOA: Volatility, Phase State, and Oligomeric Composition [J].

D'Ambro, Emma L. ;

Schobesberger, Siegfried ;

Zaveri, Rahul A. ;

Shilling, John E. ;

Lee, Ben Hwan ;

Lopez-Hilfiker, Felipe D. ;

Mohr, Claudia ;

Thornton, Joel A. .

ACS EARTH AND SPACE CHEMISTRY, 2018, 2 (10) :1058-1067

[7] Sources of particulate-matter air pollution and its oxidative potential in Europe [J].

Daellenbach, Kaspar R. ;

Uzu, Gaelle ;

Jiang, Jianhui ;

Cassagnes, Laure-Estelle ;

Leni, Zaira ;

Vlachou, Athanasia ;

Stefenelli, Giulia ;

Canonaco, Francesco ;

Weber, Samuel ;

Segers, Arjo ;

Kuenen, Jeroen J. P. ;

Schaap, Martijn ;

Favez, Olivier ;

Albinet, Alexandre ;

Aksoyoglu, Sebnem ;

Dommen, Josef ;

Baltensperger, Urs ;

Geiser, Marianne ;

El Haddad, Imad ;

Jaffrezo, Jean-Luc ;

Prevot, Andre S. H. .

NATURE, 2020, 587 (7834) :414-+

[8] Thermodynamics of oligomer formation: implications for secondary organic aerosol formation and reactivity [J].

DePalma, Joseph W. ;

Horan, Andrew J. ;

Hall, Wiley A. ;

Johnston, Murray V. .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2013, 15 (18) :6935-6944

[9] Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition [J].

DeRieux, Wing-SyWong ;

Li, Ying ;

Lin, Peng ;

Laskin, Julia ;

Laskin, Alexander ;

Bertram, Allan K. ;

Nizkorodov, Sergey A. ;

Shiraiwa, Manabu .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2018, 18 (09) :6331-6351

[10]

Deyrieux C., EUR J LIPID SCI TECH

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