气候变化领域集成服务门户(CCPortal): Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere

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DOI	10.1073/PNAS.2017442117
	Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere
	Vasquez K.T.; Crounse J.D.; Schulze B.C.; Bates K.H.; Teng A.P.; Xu L.; Allen H.M.; Wennberg P.O.
发表日期	2021
ISSN	00278424
起始页码	33011
结束页码	33016
卷号	117 期号:52
英文摘要	The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry’s law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions. © 2020 National Academy of Sciences. All rights reserved.
英文关键词	Atmospheric chemistry; Hydrolysis; Isoprene; NOx; Organic nitrates
语种	英语
scopus关键词	deuterium oxide; free radical; isoprene; isoprene derived hydroxy nitrate; nitrate; nitric acid; nitrogen oxide; unclassified drug; water; ambient air; Article; atmosphere; atmospheric chemistry; chemistry; controlled study; forest; gas; hydrolysis; isomer; liquid; nuclear magnetic resonance; priority journal; simulation; volume
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/179638
作者单位	Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, United States; Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, United States; Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, CA 91125, United States; Center for the Environment, Harvard University, Camb, MA 02138, United States; Daly City, CA 94014, United States
推荐引用方式 GB/T 7714	Vasquez K.T.,Crounse J.D.,Schulze B.C.,et al. Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere[J],2021,117(52).
APA	Vasquez K.T..,Crounse J.D..,Schulze B.C..,Bates K.H..,Teng A.P..,...&Wennberg P.O..(2021).Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere.Proceedings of the National Academy of Sciences of the United States of America,117(52).
MLA	Vasquez K.T.,et al."Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere".Proceedings of the National Academy of Sciences of the United States of America 117.52(2021).