Interfacial Dimerization by Organic Radical Reactions during Heterogeneous Oxidative Aging of Oxygenated Organic Aerosols.

Abstract

Oxidative aging of atmospheric organic aerosols (OA) substantially modifies their chemical compositions, physical properties, and hence the various environmental impacts. Here, we report observations of a previously unrecognized process leading to dimer formation during heterogeneous •OH-initiated oxidative aging of oxygenated OA. Isomer-resolved ion mobility mass spectrometry measurements and reaction-diffusion kinetic simulations are in good agreement, elucidating new mechanisms of dimerization by organic radical (i.e., peroxy and alkoxy radicals) cross reactions using glutaric acid as a surrogate oxygenated OA. These radical reactions are predicted to occur more prominently near the gas-particle interface following oxidation, especially in diffusion-limited viscous OA particles. Chemical structure analysis shows that esters dominate the detected dimers, followed by organic peroxides and ethers, highlighting the importance of acyl peroxy and acyloxy radicals. Simulations suggest that the reported dimer formation through the new interfacial mechanism could be appreciable under both laboratory and ambient conditions. Therefore, the dimers that are formed and enriched at the gas-particle interface are expected to play a crucial role in the effective reactivity, volatility, viscosity, and hygroscopicity of aged OA particles.