Reactive Nitrogen Partitioning Enhances the Contribution of Canadian Wildfire Plumes to US Ozone Air Quality.

Quantifying the variable impacts of wildfire smoke on ozone air quality is challenging. Here we use airborne measurements from the 2018 Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) to parameterize emissions of reactive nitrogen (NOy) from wildfires into peroxyacetyl nitrate (PAN; 37%), NO3− (27%), and NO (36%) in a global chemistry‐climate model with 13 km spatial resolution over the contiguous US. The NOy partitioning, compared with emitting all NOy as NO, reduces model ozone bias in near‐fire smoke plumes sampled by the aircraft and enhances ozone downwind by 5–10 ppbv when Canadian smoke plumes travel to Washington, Utah, Colorado, and Texas. Using multi‐platform observations, we identify the smoke‐influenced days with daily maximum 8‐hr average (MDA8) ozone of 70–88 ppbv in Kennewick, Salt Lake City, Denver and Dallas. On these days, wildfire smoke enhanced MDA8 ozone by 5–25 ppbv, through ozone produced remotely during plume transport and locally via interactions of smoke plume with urban emissions. Plain Language Summary: Wildfires have torn across western North America over the last decade. Smoke from wildland fires in Canada can travel thousands of kilometers to US cities and reacts with urban pollution to create harmful ozone, a criteria pollutant regulated by the US Environmental Protection Agency. Accurately quantifying this impact is needed to inform US air quality policy, but is challenging due to complex physical and chemical processes. In this study, we analyze surface and airborne measurements, alongside a new variable‐resolution global chemistry‐climate model, to better understand these processes. We show that the near‐field conversion of nitrogen oxide (NOx) emissions from wildfires to peroxyacetyl nitrate (PAN) and other more oxidized forms reduces their localized impacts on ozone. PAN is the principal tropospheric reservoir for NOx radicals. When aged smoke plumes descend southward from Canada toward US cities, higher temperatures cause PAN to decompose and thus help production of ozone during smoke transport. On days when the observed ozone levels exceed the air quality limit (70 ppbv for 8‐hr average), wildfire smoke can contribute 5–25 ppbv. Key Points: Sequestration of wildfire NOx emissions in Canada as peroxyacetyl nitrate (PAN) enhances the downwind impacts on US O3 air qualityPyrogenic volatile organic compounds and PAN decomposition increase the contribution of aged Canadian smoke plumes to O3 in US citiesAccounting for these effects in a high‐resolution chemistry‐climate model improves simulation of smoke‐impacted high‐O3 events in US cities [ABSTRACT FROM AUTHOR]