Liquid phase transformation mechanism of β-caryophyllonic acid initiated by hydroxyl radicals and ozone in atmosphere

β-caryophyllonic acid (BCA), as an important precursor of aqueous secondary organic aerosols (aqSOA), has adverse effects on the atmospheric environment and human health. However, the key atmospheric chemical reaction process in which BCA participates in the formation of aqueous secondary organic aerosols is still unclear. In this study, the reaction mechanism and kinetics of BCA with ·OH and O3 were investigated by quantum chemical calculations. The initiation reactions between BCA and ·OH include addition and H-abstraction reaction pathways, subsequent intermediates will also react with O2, ultimately undergo a cracking reaction to generate small molecular substances. The reaction of BCA with O3 can generate primary ozone oxides and the Criegee Intermediates oIM3, subsequent main reaction products include keto-BCA, as well as other small molecule aqSOA precursors. The entire reaction process increases the O/C ratio of aqSOA in the aqueous phase and generates products of small molecules such as 4-formylpropionic acid, which plays an important role in the formation of aqSOA. At 298K, the transformation rate constants of BCA initiated by ·OH and O3 are 1.47 × 1010 M−1 s−1 and 3.16 × 105 M−1 s−1, respectively, the atmospheric lifetimes of BCA reacting with ·OH range from 0.86 h–5.40 h, while the lifetimes of BCA reacting with O3 range from 0.44 h–10.04 years. This suggests that BCA primarily reacts with ·OH. However, under higher O3 concentrations, its ozonolysis becomes significant, promoting the formation of aqSOA. According to the risk assessment, the toxicity of most transformation products (TPs) gradually decreased, but the residual developmental toxicity could not be ignored. In this paper, the atmospheric liquid phase oxidation mechanisms of sesquiterpene unsaturated derived acid were studied from the microscopic level, which has guiding significance for the formation and transformation of aqSOA in atmosphere. © 2024 Elsevier Ltd