Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral

Abstract. Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O₃) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O₃ and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called "SVOCs") on the formation of OA (using the Volatility Basis Set – VBS) and O₃ (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O₃, OA, NO_x, ethylene (C₂H₄), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10^-11 cm³ s⁻¹; (2) a significant fraction (up to ~ 50 %) of the RO₂ + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O₃ were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO₂; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH₃COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O₃ and OA they form) varies between plumes.