Investigation of the Cyclohexene Oxidation Mechanism Through the Direct Measurement of Organic Peroxy Radicals

Monoterpenes, the second most abundant biogenic volatile organic compounds globally, are crucial in forming secondary organic aerosols, making their oxidation mechanisms vital for addressing climate change and air pollution. This study utilized cyclohexene as a surrogate to explore first-generation products from its ozonolysis through laboratory experiments and mechanistic modeling. We employed proton transfer reaction mass spectrometry with NH4+ ion sources (NH4+-CIMS) and a custom-built OH calibration source to quantify organic peroxy radicals (RO2) and closed-shell species. Under near-real atmospheric conditions in a Potential Aerosol Mass-Oxidation Flow Reactor, we identified 30 ozonolysis products, expanding previous data sets of low-oxygen compounds. Combined with simulations based on the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere and relevant literature, our results revealed that OH dominates over ozone in cyclohexene oxidation at typical atmospheric oxidant levels with H-abstraction contributing 30% of initial RO2 radicals. Highly oxidized molecules primarily arise from RO2 autoxidation initiated by ozone, and at least 15% of ozone oxidation products follow the overlooked nonvinyl hydroperoxides pathway. Gaps remain especially in understanding RO2 cross-reactions, and the structural complexity of monoterpenes further complicates research. As emissions decrease and afforestation increases, understanding these mechanisms becomes increasingly critical.