Assessing formic and acetic acid emissions and chemistry in western U.S. wildfire smoke: implications for atmospheric modeling

Abstract

Formic acid (FA) and acetic acid (AA), two of the most abundant organic acids in the atmosphere, are typically underestimated by atmospheric models. Here we investigate their emissions, chemistry, and measurement uncertainties in biomass burning smoke sampled during the WE-CAN and FIREX-AQ aircraft campaigns. Our observed FA emission ratios (ERs) and emission factors (EFs) were generally higher than the 75^th percentile of literature values, with little dependence on fuel type or combustion efficiency. Rapid in-plume FA production was observed (2.7 ppb ppm_CO⁻¹ h⁻¹), representing up to ∼20% of the total emitted reactive organic carbon being converted to FA within half a day. AA ERs and EFs showed good agreement with the literature, with little or no secondary production observed within <8 hours of plume aging. Observed FA and AA trends in the near-field were not captured by a box model using the explicit Master Chemical Mechanism nor simplified GEOS-Chem chemistry, even after tripling the model's initial VOC concentrations. Consequently, the GEOS-Chem chemical transport model underestimates both acids in the western U.S. by a factor of >4. This is likely due to missing secondary chemistry in biomass burning smoke and/or coniferous forest biogenic emissions. This work highlights uncertainties in measurements (up to 100%) and even large unknowns in the chemical formation of organic acids in polluted environments, both of which need to be addressed to better understand their global budget.