Source-Resolved Volatility and Oxidation State Decoupling in Wintertime Organic Aerosols in Seoul

Abstract. Organic aerosols (OA) are key components of wintertime urban haze, but the relationship between their oxidation state and volatility – critical for understanding aerosol evolution and improving model predictions – remains poorly constrained. While oxidation – volatility decoupling has been observed in laboratory studies, field-based evidence under real-world conditions is scarce, particularly during severe haze episodes. This study presents a field-based investigation of OA sources and their volatility characteristics in Seoul during a winter haze period, using a thermodenuder coupled with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Positive matrix factorization resolved six OA factors: hydrocarbon-like OA, cooking, biomass burning, nitrogen-containing OA (NOA), less-oxidized oxygenated OA (LO-OOA), and more-oxidized OOA (MO-OOA). Despite having the highest oxygen-to-carbon ratio (~1.15), MO-OOA exhibited unexpectedly high volatility, indicating a decoupling between oxidation state and volatility. We attribute this to fragmentation-driven aging and autoxidation under stagnant conditions with limited OH exposure. In contrast, LO-OOA showed lower volatility and more typical oxidative behavior. Additionally, NOA – a rarely resolved factor in wintertime field studies – was prominent during cold, humid, and stagnant conditions and exhibited chemical and volatility features similar to biomass burning OA, suggesting a shared combustion origin and meteorological sensitivity. These findings provide one of the few field-based demonstrations of oxidation–volatility decoupling in ambient OA and highlight how source-specific properties and meteorology influence OA evolution. The results underscore the need to refine OA representation in chemical transport models, especially under haze conditions.