New mechanistic understanding for atmospheric oxidation of isoprene initiated by atomic chlorine

Abstract

Isoprene is the most abundant non-methane VOC and a significant SOA contributor. The atmospheric oxidation initiated by atomic chlorine is an important sink for isoprene, especially in certain regions with high Cl concentration, while its detailed oxidation mechanism remains unclear. In this work, we comprehensively investigated the reaction mechanism of isoprene with Cl using quantum chemistry calculation, and first elaborated the specific reaction mechanisms of chloroalkenyl peroxy radicals with HO₂/NO and the formation of 2-methylbut-3-enal, highlighting their important roles in the SOA formation. For the initial reactions, Cl additions to terminal carbons and H abstraction from CH₃ moiety of isoprene are the predominant reactions, which is consistent with previous research. Following the initial reactions, their subsequent reactions with O₂ and HO₂ (or NO) under different atmospheric conditions could lead to the formation of 17 highly oxidized molecules (HOMs), of which P10, P12, P16, P17, P19 and P33 generated by the subsequent reactions of the major first-generation products (MVK, CMBO, CMBA and MBO) have been detected in the reaction process of isoprene with Cl in the chamber experiment. In addition to auto-oxidation process, the reaction of chloroalkenyl peroxy radicals with HO₂/NO and their subsequent reactions are all easy to occur under atmospheric conditions, which could be crucial contributors to the formation of HOMs and SOA arising from the Cl initiated oxidation of isoprene. This study would be conducive to clarifying the atmospheric oxidation process of isoprene initiated by Cl and providing a new understanding of its SOA formation.

Keywords: Cl radical; HOMs; Isoprene; Oxidation mechanism; SOA formation.