Acylperoxy Radicals as Key Intermediates in the Formation of Dimeric Compounds in α-Pinene Secondary Organic Aerosol

High molecular weight dimeric compounds constitute a significant fraction of secondary organic aerosol (SOA) and have profound impacts on the properties and lifecycle of particles in the atmosphere. Although different formation mechanisms involving reactive intermediates and/or closed-shell monomeric species have been proposed for the particle-phase dimers, their relative importance remains in debate. Here, we report unambiguous experimental evidence of the important role of acyl organic peroxy radicals (RO2) and a small but non-negligible contribution from stabilized Criegee intermediates (SCIs) in the formation of particle-phase dimers during ozonolysis of α-pinene, one of the most important precursors for biogenic SOA. Specifically, we find that acyl RO2-involved reactions explain 50-80% of total oxygenated dimer signals (C15-C20, O/C ≥ 0.4) and 20-30% of the total less oxygenated (O/C < 0.4) dimer signals. In particular, they contribute to 70% of C15-C19 dimer ester formation, likely mainly via the decarboxylation of diacyl peroxides arising from acyl RO2 cross-reactions. In comparison, SCIs play a minor role in the formation of C15-C19 dimer esters but react noticeably with the most abundant C9 and C10 carboxylic acids and/or carbonyl products to form C19 and C20 dimeric peroxides, which are prone to particle-phase transformation to form more stable dimers without the peroxide functionality. This work provides a clearer view of the formation pathways of particle-phase dimers from α-pinene oxidation and would help reduce the uncertainties in future atmospheric modeling of the budget, properties, and health and climate impacts of SOA.