Concurrent dominant pathways of multifunctional products formed from nocturnal isoprene oxidation

Determination of dominant chemical pathways toward the formation of nocturnal secondary organic aerosols (SOA) remains ambiguous by which nitrogen oxides (NO_x) always affect oxidation of volatile alkenes. Here, comprehensive chamber simulations on dark isoprene ozonolysis were conducted under different nitrogen dioxides (NO₂) mixing ratios to exam multiple functionalized isoprene oxidation products. Aside from that the oxidation processes were concurrently driven by nitrogen radical (NO₃) and small hydroxyl radicals (OH), ozone (O₃) cycloaddition at isoprene was launched initially regardless of NO₂ to rapidly form first-generation oxidation products, i.e., carbonyls and Criegee intermediates (CI) referred to carbonyl oxides. They could further undergo complicated self- and cross-reactions to produce alkylperoxy radicals (RO₂). Corresponding to yields of the C₅H₁₀O₃ tracer, weak OH pathway at night was credited to ozonolysis of isoprene but suppressed by unique NO₃ chemistry. Following the ozonolysis of isoprene, NO₃ played a crucial supplementary role in nighttime SOA formation. The ensuing production of gas-phase nitrooxy carbonyls (the first-generation nitrates) became dominant in the production of a sizeable pool of organic nitrates (RO₂NO₂). By contrast, isoprene dihydroxy dinitrates (C₅H₁₀N₂O₈) were outstanding with the elevated NO₂, related to typical second-generation nitrates. As such, the yielding number concentrations of dark SOA were promoted to approximately 1.8 × 10⁴ cm^-3 but presented a nonlinear relation with excess high-NO₂ condition. This study provides valuable insights into importance of multifunctional organic compounds from alkene oxidation to constitute nighttime SOA.