Quantitative constraints on autoxidation and dimer formation from direct probing of monoterpene-derived peroxy radical chemistry

Abstract

Organic peroxy radicals (RO ₂) are key intermediates in the atmospheric degradation of organic matter and fuel combustion, but to date, few direct studies of specific RO ₂ in complex reaction systems exist, leading to large gaps in our understanding of their fate. We show, using direct, speciated measurements of a suite of RO ₂ and gas-phase dimers from O ₃-initiated oxidation of α-pinene, that ∼150 gaseous dimers (C _16–20H _24–34O _4–13) are primarily formed through RO ₂ cross-reactions, with a typical rate constant of 0.75–2 × 10 ⁻¹² cm ³ molecule ⁻¹ s ⁻¹ and a lower-limit dimer formation branching ratio of 4%. These findings imply a gaseous dimer yield that varies strongly with nitric oxide (NO) concentrations, of at least 0.2–2.5% by mole (0.5–6.6% by mass) for conditions typical of forested regions with low to moderate anthropogenic influence (i.e., ≤50-parts per trillion NO). Given their very low volatility, the gaseous C _16–20 dimers provide a potentially important organic medium for initial particle formation, and alone can explain 5–60% of α-pinene secondary organic aerosol mass yields measured at atmospherically relevant particle mass loadings. The responses of RO ₂, dimers, and highly oxygenated multifunctional compounds (HOM) to reacted α-pinene concentration and NO imply that an average ∼20% of primary α-pinene RO ₂ from OH reaction and 10% from ozonolysis autoxidize at 3–10 s ⁻¹ and ≥1 s ⁻¹, respectively, confirming both oxidation pathways produce HOM efficiently, even at higher NO concentrations typical of urban areas. Thus, gas-phase dimer formation and RO ₂ autoxidation are ubiquitous sources of low-volatility organic compounds capable of driving atmospheric particle formation and growth.