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The role of hydroxyl radicals (OH) as a daytime oxidant is well established on a global scale. In specific source regions, such as the marine boundary layer and polluted coastal cities, other daytime oxidants, such as chlorine atoms (Cl) and even bromine atoms (Br), may compete with OH for the oxidation of volatile organic compounds (VOCs) and/or enhance the overall oxidation capacity of the atmosphere. However, the number of studies investigating halogen-initiated secondary organic aerosol (SOA) formation is extremely limited, resulting in large uncertainties in these oxidative aging processes. Here, we characterized the chemical composition and yield of laboratory SOA generated in an oxidation flow reactor (OFR) from the OH and Cl oxidation of n -dodecane ( n -C 12 ) and toluene, and the OH, Cl, and Br oxidation of isoprene and α-pinene. In the OFR, precursors were oxidized using integrated OH, Cl, and Br exposures ranging from 3.1 × 10 10 to 2.3 × 10 12 , 6.1 × 10 9 to 1.3× 10 12 and 3.2 × 10 10 to 9.7 × 10 12 molecules cm −3 s −1 , respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied. In contrast, the extent of Br-initiated SOA oxidative aging was limited. SOA elemental ratios and mass yields obtained in the OFR studies were comparable to those obtained from OH and Cl oxidation of the same precursors in environmental chamber studies. Overall, our results suggest that alkane, aromatic, and terpenoid SOA precursors are characterized by distinct OH- and halogen-initiated SOA yields, and that while Cl may enhance the SOA formation potential in regions influenced by biogenic and anthropogenic emissions, Br may have the opposite effect. 

Abstract. Emission of organic aerosol (OA) from wood combustion is not well constrained;understanding the governing factors of OA emissions would aid in explainingthe reported variability. Pyrolysis of the wood during combustion is theprocess that produces and releases OA precursors. We performed controlledpyrolysis experiments at representative combustion conditions. The conditionschanged were the temperature, wood length, wood moisture content, and woodtype. The mass loss of the wood, the particle concentrations, and light-gasconcentrations were measured continuously. The experiments were repeatable asshown by a single experiment, performed nine times, in which the real-timeparticle concentration varied by a maximum of 20 %. Highertemperatures increased the mass loss rate and the released concentration ofgases and particles. Large wood size had a lower yield of particles than thesmall size because of higher mass transfer resistance. Reactions outside thewood became important between 500 and 600 ∘C. Elevatedmoisture content reduced product formation because heat received was sharedbetween pyrolysis reactions and moisture evaporation. The thermophysicalproperties, especially the thermal diffusivity, of wood controlled thedifference in the mass loss rate and emission among seven wood types. Thiswork demonstrates that OA emission from wood pyrolysis is a deterministicprocess that depends on transport phenomena.