Organic vapors from Savannah and European Boreal fire emissions: Insights from photochemical and dark aging experiments in a smog chamber

Abstract. Biomass burning (BB) emits large amounts of pollutants in the particle and gas phases, with significant implications for air quality, human health and climate. Here, we investigate the emission of organic vapors from controlled burns of relatively understudied biomass fuels: woody plants and grasses from African savannah and European boreal forest surface using a high-resolution proton transfer reaction-mass spectrometer. To understand the effect of different oxidation regimes, organic vapors were aged in a 29 m³ Teflon chamber, where photochemical and dark aging were simulated. The average total primary emission factors (EFs) for organic vapors varied considerably with fuel type, ranging from 69 to 161 g kg^-1. Photochemical aging led to substantial depletion of furanics, phenolics and oxygenated aromatics, accompanied by enhancements of carbonyl B compounds and O-containing compounds C<6 across experiments. In contrast, dark aging under low-NO_x conditions produced minimal compositional changes. Hierarchical clustering of relative composition showed clear regime dependence, with regime-associated differences accounting for 73 % of the variance in group-level composition. Toluene and furan showed a strong negative correlation with secondary oxygenated volatile organic compounds (OVOCs), including anhydrides and small acids, consistent with their role as precursors. After 0.5 equivalent day of photochemical aging, organic vapors shifted to higher O/C (>0.70) and an increased fraction of C_xH_yO_z (z≥3). These results highlight the integral role of OH·-driven photo-oxidation in governing the atmospheric evolution and composition of BB organic vapors and underscore the need for secondary organic aerosols (SOA) models to include non-traditional precursors.