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

Within minutes after emission, rapid, complex photochemistry within a biomass burning smoke plume 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 burn 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 semi-volatile to extremely low volatility organic compounds (here collectively called SVOCs ) on the formation of OA (using the Volatility Basis Set) and O3 (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O3, OA, PAN, NOx, and C2H4 to within measurement uncertainty using reasonable assumptions about the chemistry of the unidentified SVOCs. These assumptions were: (1) a resaction rate constant with OH of ~10-11cm3s-1, (2) a significant fraction (~50%) of the RO2+NO reaction resulting 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 SVOCs 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, which is consistent with our assumed fragmentation rate. 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