Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.

Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution