Effects of Nitrate Radical Levels and Pre-Existing Particles on Secondary Brown Carbon Formation from Nighttime Oxidation of Furan

Furans are predominant heterocyclic volatile organic compounds in the atmosphere from both primary and secondary sources, such as direct emissions from wildfires and atmospheric oxidation of dienes. The formation of secondary organic aerosols (SOAs) from the oxidation of furans has been reported. Previous research has shown that furan SOA generated from nighttime oxidation contributes to brown carbon (BrC) formation; however, how nighttime oxidant levels [represented by nitrate radical (NO3) levels] and pre-existing particles influence the SOA chemical composition and BrC optical properties is not well constrained. In this study, we conducted chamber experiments to systematically investigate the role of these two environmental factors in furan-derived secondary BrC formation during the nighttime. Our results suggest that the bulk compositions of SOA measured as ion fragment families by an aerosol mass spectrometer are unaffected by changes in NO3 levels but can be influenced by the presence of pre-existing ammonium sulfate particles. Based on the mass absorption coefficient profiles of SOA produced under different experimental conditions, BrC light absorption was enhanced by higher NO3 levels and reduced by the presence of pre-existing ammonium sulfate seed particles, suggesting that NO3- initiated oxidation of furan can promote the formation of light-absorbing products, while pre-existing particles may facilitate the partitioning of nonabsorbing organics in the aerosol phase. Furthermore, molecular-level compositional analysis reveals a similar pattern of chromophores under various studied environmental conditions, in which highly oxygenated monomers (e.g., C4H4O6 and C4H3NO7), dimers, and oligomers can all contribute to BrC chromophores. Taken together, the NO3 levels and pre-existing particles can influence secondary BrC formation by altering SOA compositions, which is critical for assessing BrC optical properties in a complex environment.

Automated summary

Furans are important volatile organic compounds in the atmosphere, and their oxidation can lead to the formation of secondary organic aerosols (SOAs) that contribute to brown carbon (BrC) formation. The levels of nighttime oxidants and pre-existing particles can influence the chemical composition and optical properties of SOAs and BrC. This study found that higher levels of nighttime oxidants enhance BrC light absorption, while the presence of pre-existing particles reduces it.