Highly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO 3 radical

Zhao, Defeng; Pullinen, Iida; Fuchs, Hendrik; Schrade, Stephanie; Wu, Rongrong; Acir, Ismail-Hakki; Tillmann, Ralf; Rohrer, Franz; Wildt, Jürgen; Guo, Yindong; Kiendler-Scharr, Astrid; Wahner, Andreas; Kang, Sungah; Vereecken, Luc; Mentel, Thomas F.

page9682Highly oxygenated organic molecules (HOM) are found to play an important role in the formation and growth of secondary organic aerosol (SOA). SOA is an important type of aerosol with significant impact on air quality and climate. Compared with the oxidation of volatile organic compounds by ozone (Oinline-formula3) and hydroxyl radical (OH), HOM formation in the oxidation by nitrate radical (NOinline-formula3), an important oxidant at nighttime and dawn, has received less attention. In this study, HOM formation in the reaction of isoprene with NOinline-formula3 was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). A large number of HOM, including monomers (Cinline-formula5), dimers (Cinline-formula10), and trimers (Cinline-formula15), both closed-shell compounds and open-shell peroxy radicals (ROinline-formula2), were identified and were classified into various series according to their formula. Their formation pathways were proposed based on the peroxy radicals observed and known mechanisms in the literature, which were further constrained by the time profiles of HOM after sequential isoprene addition to differentiate first- and second-generation products. HOM monomers containing one to three N atoms (1–3N-monomers) were formed, starting with NOinline-formula3 addition to carbon double bond, forming peroxy radicals, followed by autoxidation. 1N-monomers were formed by both the direct reaction of NOinline-formula3 with isoprene and of NOinline-formula3 with first-generation products. 2N-monomers (e.g., Cinline-formula5Hinline-formula8Ninline-formula2Oinline-formulan(n=7–13), Cinline-formula5Hinline-formula10Ninline-formula2Oinline-formulan(n=8–14)) were likely the termination products of Cinline-formula5Hinline-formula9Ninline-formula2Oinline-formulanRadical⚫, which was formed by the addition of NOinline-formula3 to C5-hydroxynitrate (Cinline-formula5Hinline-formula9NOinline-formula4), a first-generation product containing one carbon double bond. 2N-monomers, which were second-generation products, dominated in monomers and accounted for inline-formula∼34 % of all HOM, indicating the important role of second-generation oxidation in HOM formation in the isoprene inline-formula+ NOinline-formula3 reaction under our experimental conditions. H shift of alkoxy radicals to form peroxy radicals and subsequent autoxidation (“alkoxy–peroxy” pathway) was found to be an important pathway of HOM formation. HOM dimers were mostly formed by the accretion reaction of various HOM monomer ROinline-formula2 and via the termination reactions of dimer ROinline-formula2 formed by further reaction of closed-shell dimers with NOinline-formula3 and possibly by the reaction of C5–ROinline-formula2 with isoprene. HOM trimers were likely formed by the accretion reaction of dimer ROinline-formula2 with monomer ROinline-formula2. The concentrations of different HOM showed distinct time profiles during the reaction, which was linked to their formation pathway. HOM concentrations either showed a typical time profile of first-generation products, second-generation products, or a combination of both, indicating multiple formation pathways and/or multiple isomers. Total HOM molar yield was estimated to be 1.2 %inline-formula M37inlinescrollmathml - normal 0.7 nobreak0.125em italic % + normal 1.3 0.125emnobreak italic % 27pt17ptsvg-formulamathimg8289cbb5af5ca258f7b499fc268e7228 acp-21-9681-2021-ie00001.svg27pt17ptacp-21-9681-2021-ie00001.png , which corresponded to a SOA yield of inline-formula∼3.6 % assuming the molecular weight of Cinline-formula5Hinline-formula9NOinline-formula6 as the lower limit. This yield suggests that HOM may contribute a significant fraction to SOA yield in the reaction of isoprene with NOinline-formula3.



Zhao, Defeng / Pullinen, Iida / Fuchs, Hendrik / et al: Highly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO3 radical. 2021. Copernicus Publications.


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