Nighttime Chemical Transformation in Biomass Burning Plumes: A Box Model Analysis Initialized with Aircraft...

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO₃, N₂O₅, O₃, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO₃ production was approximately 1 ppbv hr^-1, while NO₃ and N₂O₅ were at or below 3 pptv, indicating rapid NO₃/N₂O₅ reactivity. Model analysis shows that >99% of NO₃/N₂O₅ loss is due to BBVOC + NO₃ reactions rather than aerosol uptake of N₂O₅. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO₃ (72, 53%, respectively) but O₃ oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO₂.