Chemical Evolution of Biomass Burning Aerosols across Wildfire Plumes in the Western U.S.: From Near-Source to Regional Scales.

The atmospheric processing of biomass burning organic aerosol (BBOA) and its implications for tropospheric aerosol physicochemical properties remain uncertain. To address this gap, we investigate the chemical transformation of BBOA from wildfire events in the western U.S., using data from aerosol mass spectrometers aboard the DOE G-1 aircraft and at the Mt. Bachelor Observatory (∼2800 m a.s.l.) during the summers of 2013 and 2019. This study captures dynamic changes in submicron particulate matter (PM) concentrations and chemical profiles within wildfire plumes that span a broad range of atmospheric ages, from fresh emissions (<30 min) to plumes transported for several days. As plumes age, the oxidation state of organic aerosols (OA) increases, accompanied by the formation of secondary aerosol components such as phenolic secondary OA (SOA) species, carboxylic acids, and potassium sulfate. Early plume evolution is marked by the evaporation of semivolatile components and the formation of alcohol and peroxide functional groups, while extended aging produces more oxidized species, including carboxylic acids and carbonyl compounds. Normalized excess mixing ratios (NEMRs) of OA to CO demonstrate a complex interplay between evaporation, SOA formation, and oxidative loss. Using positive matrix factorization (PMF), we identify distinct BBOA types representing various stages of atmospheric processing and assess the contributions of primary BBOA and secondary BBOA formed through atmospheric reactions. These findings shed light on the intricate mechanisms governing the evolution of BBOA characteristics within wildfire plumes, providing critical insights to improve atmospheric modeling of BBOA and better assess the environmental and climatic impacts of wildfire emissions.