Ground-based Investigation of HO x and Ozone Chemistry in Biomass Burning Plumes in Rural Idaho

Abstract. Ozone (O3), a potent greenhouse gas that is detrimental to human health, is typically found in elevated concentrations within biomass burning (BB) smoke plumes. The radical species OH, HO2, and RO2 (known collectively as ROx) have central roles in the formation of secondary pollutants including O3 but are poorly characterized for BB plumes. We present measurements of total peroxy radical concentrations ([XO2] ≡ [HO2] + [RO2]) and additional trace-gas and particulate matter measurements from McCall, Idaho during August 2018. There were five distinct periods in which BB smoke impacted this site. During BB events, O3 concentrations were enhanced as evidenced by ozone enhancement ratios (ΔO3/ ΔCO) that ranged up to 0.25 ppbv ppbv−1. [XO2] was similarly elevated during some BB events. Overall, quantified instantaneous ozone production rates (P(O3)) were only slightly impacted by the presence of smoke as NOx enhancements were minimal. Measured XO2 concentrations were compared to zero-dimensional box modeling results to evaluate the effectiveness of the Master Chemical Mechanism (MCM) and GEOS-Chem mechanisms during periods of BB influence and overall agreed within 31 %. One period of BB influence had distinct measured enhancements of 15 pptv XO2 that were not reflected in the model output, likely due to the presence of an unmeasured HOx source, quite likely nitrous acid (HONO). To our knowledge, this is the first BB study featuring peroxy radical measurements.