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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. Major Findings: Research using the AM4VR model demonstrates that wildfire nitrogen emissions are rapidly sequestered as peroxyacyl nitrates ($PAN$), which remain stable during long-range transport before decomposing to release NO and fuel ozone O3 production in distant urban areas. These findings reveal that such chemical evolution can increase surface O3 levels by 5 to 25 ppbv in cities thousands of kilometers downwind, particularly when pyrogenic organic compounds interact with existing urban pollution.
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Reactive Nitrogen Partitioning Enhances the Contribution of Canadian Wildfire Plumes to US Ozone Air Quality
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