气候变化领域集成服务门户(CCPortal): Theoretical investigation on the degradation of methyl vinyl ketone initiated by ·OH and ·Cl in the atmosphere and aqueous particles: Mechanism, kinetics, and environmental impact analysis

CCPortal

DOI	10.1016/j.atmosenv.2020.118107
	Theoretical investigation on the degradation of methyl vinyl ketone initiated by ·OH and ·Cl in the atmosphere and aqueous particles: Mechanism, kinetics, and environmental impact analysis
	Wang X.; Bao L.; Han D.; Wei Y.; He M.; Yuan S.
发表日期	2021
ISSN	1352-2310
卷号	246
英文摘要	The absence of studies on the tropospheric reaction mechanism of unsaturated ketones increases the difficulty for the accurate assessment of their environmental fate. Herein, the gaseous and aqueous chemistry of methyl vinyl ketone (MVK) with ·Cl and ·OH, as well as the ensuing radical (e.g., chloroperoxy and hydroxyperoxy radicals) reactions are investigated from a theoretical perspective. A new pathway for the formation of alkoxyl radicals from peroxyl radicals is presumed. The reaction activity of alkoxyl radicals takes the order of β–scission > with O2 > with H2O > Russell mechanism. The aqueous environment shows the negative solvent effect on these two systems. The “polarization” of the proportion of the addition and abstraction reactions is intensified by the solvent effect. Although the rate constants kMVK-Cl > kMVK-OH > kMVK-O3, ·OH-induced MVK reaction is still the dominant sink of MVK. If the effect of ·Cl is ignored, the atmospheric lifetimes of MVK will be overestimated by 12% and even more. The detailed reaction mechanisms and product information for the reaction of ·Cl with MVK are calculated for the first time. Low volatility oxygenated products (such as organic acids, α-dicarbonyls, and some C4 multifunctional molecules) produced in the title reactions may be an important bridge between unsaturated ketone and aqSOA. An increased eco-toxicity can occur from MVK to its degradation products in the ·Cl-MVK system, highlighting the necessity in the research of LMW unsaturated hydrocarbon on environmental risk assessment. © 2020 Elsevier Ltd
关键词	Aqueous SOA Chlorine chemistry Eco-toxicity Peroxyl radicals Rate constant Unsaturated ketone
语种	英语
scopus关键词	Degradation; Ketones; Rate constants; Risk assessment; Solvents; Unsaturated fatty acids; Abstraction reactions; Detailed reaction mechanisms; Environmental impact analysis; Environmental risk assessment; Multi-functional molecules; Theoretical investigations; Tropospheric reaction; Unsaturated hydrocarbons; Environmental impact; carboxylic acid; ketone; methylglyoxal; oxygen; peroxy radical; radical; water; aqueous solution; chemical reaction; degradation; environmental risk; hydrocarbon; ketone; reaction kinetics; risk assessment; solvent; theoretical study; toxicity; addition reaction; atmosphere; Daphnia; degradation; EC50; electrophilicity; environmental impact; fish; Fourier transform infrared spectroscopy; green alga; kinetics; LC50; nonhuman; polarization; priority journal; radical reaction; reaction analysis; reaction temperature; solvent effect
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/248701
作者单位	Key Lab of Colloid and Interface Chemistry, Shandong University, Jinan, 250100, China; School of Chemical Sciences, University of the Chinese Academy of Sciences, Beijing, 100049, China; School of Chemistry and Chemical Engineering, Heze University, Heze, 274015, China; Environment Research Institute, Shandong University, Qingdao, 266237, China
推荐引用方式 GB/T 7714	Wang X.,Bao L.,Han D.,et al. Theoretical investigation on the degradation of methyl vinyl ketone initiated by ·OH and ·Cl in the atmosphere and aqueous particles: Mechanism, kinetics, and environmental impact analysis[J],2021,246.
APA	Wang X.,Bao L.,Han D.,Wei Y.,He M.,&Yuan S..(2021).Theoretical investigation on the degradation of methyl vinyl ketone initiated by ·OH and ·Cl in the atmosphere and aqueous particles: Mechanism, kinetics, and environmental impact analysis.ATMOSPHERIC ENVIRONMENT,246.
MLA	Wang X.,et al."Theoretical investigation on the degradation of methyl vinyl ketone initiated by ·OH and ·Cl in the atmosphere and aqueous particles: Mechanism, kinetics, and environmental impact analysis".ATMOSPHERIC ENVIRONMENT 246(2021).