Aldehyde cool-flame chemistry explains a missing source of organic acids

Combustion emission is a significant source of organic acids, impacting atmospheric chemistry and climate. Their formation mechanisms, however, remain poorly understood, leading to underestimation in kinetic models. We investigate the cool-flame oxidation of key combustion intermediates-C₁-C₄ aldehydes and benzaldehyde. Using in-situ synchrotron vacuum ultraviolet photoionization mass spectrometry, we observe the direct conversion of aldehydes to organic acids, a process enhanced by HO₂ radicals. Quantum chemistry calculations reveal that the reaction of RC(O)O₂ with HO₂ on the singlet potential energy surface contributes to organic acids. Incorporating this pathway into a kinetic model significantly improves organic acid prediction. Despite the high-temperature nature of engine combustion, significant spatial and temporal inhomogeneities (e.g., near-wall regions and crevice volumes) lead to localized cool-flame conditions, facilitating organic acid formation and emission. Elucidating the acid formation under cool-flame conditions provides a critical mechanism for accurately modelling anthropogenic organic acid emissions and developing mitigation strategies.