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DOI	10.5194/acp-22-7259-2022
	Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation
	Ji, Yuemeng; Shi, Qiuju; Ma, Xiaohui; Gao, Lei; Wang, Jiaxin; Li, Yixin; Gao, Yanpeng; Li, Guiying; Zhang, Renyi; An, Taicheng
发表日期	2022
ISSN	1680-7316
EISSN	1680-7324
起始页码	7259
结束页码	7271
卷号	22 期号:11 页码:13
英文摘要	Small alpha-dicarbonyls represent the major precursors of secondary organic aerosol (SOA) and brown carbon (BrC) in the atmosphere, but the chemical mechanisms leading to their formation remain unclear. Here we elucidate the fundamental kinetics and mechanisms for aqueous-phase oligomerization of glyoxal (GL) using quantum chemical and kinetic rate calculations. Our results identify several essential isomeric processes for GL, including protonation to yield diol / tetrol and carbenium ions, nucleophilic addition of carbenium ions to diol / tetrol as well as to free methylamine / ammonia (MA / AM), and deprotonation to propagate oligomers and N-heterocycles. Both protonation and nucleophilic addition occur without activation barriers and are dominantly driven by electrostatic attraction. Deprotonation proceeds readily via water molecules in the absence of MA / AM but corresponds to the rate-limiting step for N-containing cationic intermediates to yield N-heterocycles. On the other hand, the latter occurs readily via a catalytic process by acidic anions (e.g., SO42-). A carbenium ion-mediated reaction rate of GL is 4.62 x 10(-3) s(-1) under atmospheric conditions, in good agreement with the experimental data. Our results provide essential mechanistic and kinetic data for accurate assessment of the role of small alpha-dicarbonyls in SOA and BrC formation.
学科领域	Environmental Sciences; Meteorology & Atmospheric Sciences
语种	英语
WOS研究方向	Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
WOS记录号	WOS:000806972400001
来源期刊	ATMOSPHERIC CHEMISTRY AND PHYSICS
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/273427
作者单位	Guangdong University of Technology; Guangdong University of Technology; Texas A&M University System; Texas A&M University College Station
推荐引用方式 GB/T 7714	Ji, Yuemeng,Shi, Qiuju,Ma, Xiaohui,et al. Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation[J],2022,22(11):13.
APA	Ji, Yuemeng.,Shi, Qiuju.,Ma, Xiaohui.,Gao, Lei.,Wang, Jiaxin.,...&An, Taicheng.(2022).Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(11),13.
MLA	Ji, Yuemeng,et al."Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.11(2022):13.