Secondary organic aerosol formation and primary organic aerosol oxidation from biomass-burning smoke in a flow reactor during FLAME-3

Abstract. We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OH_exp), typically peaking around three days of equivalent atmospheric photochemical age (OH_exp~3.9 × 10¹¹ molecules cm⁻³ s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeded the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility species, and possibly of unidentified VOCs as SOA precursors in biomass burning smoke. Chemical transformations continued even after mass concentration stabilized. Changes in the biomass-burning tracer f₆₀ ranged from substantially decreasing to remaining constant with increased aging. With increased OH_exp, oxidation was always detected (as indicated by f₄₄ and O/C). POA O/C ranged from 0.15 to 0.5, while aged OA O/C reached up to 0.87. The rate of oxidation and maximum O/C achieved differs for each biomass, and appears to increase with the initial O/C of the POA.