Leveraging aerosol data from multiple airborne and surface-based field campaigns encompassing diverse environmental conditions, we calculate statistics of the oxalate-sulfate mass ratio (median: 0.0217; 95% confidence interval: 0.0154 – 0.0296; R = 0.76; N = 2948). Ground-based measurements of the oxalate-sulfate ratio fall within our 95% confidence interval, suggesting the range is robust within the mixed layer for the submicrometer particle size range. We demonstrate that dust and biomass burning emissions can separately bias this ratio towards higher values by at least one order of magnitude. In the absence of these confounding factors, the 95% confidence interval of the ratio may be used to estimate the relative extent of aqueous processing by comparing inferred oxalate concentrations between air masses, with the assumption that sulfate primarily originates from aqueous processing.

Biomass burning is a primary emission source for a host of gas- and aerosol-phase compounds, which can damage environmental and human health. During the FIREX-AQ campaign in July and August of 2019, we measured reactive nitrogen species (NOx, NO2, HONO, HNO3 and p-NO3-), in wildfire plumes aboard NASA Langley’s Mobile Aerosol Characterization Laboratory (MACH-2). Nitrous acid (HONO) and nitric acid (HNO3) mixing ratios were measured at nominal 5-minute resolution using a dual mist chamber-ion chromatograph from five separate areas of fire in the western US and are the primary focus of this paper. Average HONO mixing ratios were significantly higher in young daytime smoke compared to young nighttime smoke, while no statistical differences were observed between young versus aged smoke during the day or night. In the largest fire sampled during the day, UV-A irradiation was highly correlated (R2 = 0.91) with HONO to nitrogen dioxide (NO2) ratios indicating that photo-enhanced heterogeneous NO2 to HONO conversion, likely facilitated by ground surfaces (e.g. soil, foliage, and dust), more than compensated for rapid photolytic loss of HONO.

Accurate fire emissions inventories are crucial to predict the impacts of wildland fires on air quality and atmospheric composition. Two traditional approaches are widely used to calculate fire emissions: a satellite-based top-down approach and a fuels-based bottom-up approach. However, these methods often considerably disagree on the amount of particulate mass emitted from fires. Previously available observational datasets tended to be sparse, and lacked the statistics needed to resolve these methodological discrepancies. Here, we leverage the extensive and comprehensive airborne in situ and remote sensing measurements of smoke plumes from the recent Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign to statistically assess the skill of the two traditional approaches. We use detailed campaign observations to calculate and compare emission rates at an exceptionally high resolution using three separate approaches: top-down, bottom-up, and a novel approach based entirely on integrated airborne in situ measurements. We then compute the daily average of these high-resolution estimates and compare with estimates from lower resolution, global top-down and bottom-up inventories. We uncover strong, linear relationships between all of the high-resolution emission rate estimates in aggregate, however no single approach is capable of capturing the emission characteristics of every fire. Global inventory emission rate estimates exhibited weaker correlations with the high-resolution approaches and displayed evidence of systematic bias. The disparity between the low resolution global inventories and the high resolution approaches is likely caused by high levels of uncertainty in essential variables used in bottom-up inventories and imperfect assumptions in top-down inventories.

Leveraging aerosol data from multiple airborne and surface-based field campaigns encompassing diverse environmental conditions, we calculate statistics of the oxalate-sulfate mass ratio (median: 0.0217; 95% confidence interval: 0.0154 – 0.0296; R = 0.76; N = 2948). Ground-based measurements of the oxalate-sulfate ratio fall within our 95% confidence interval, suggesting the range is robust within the mixed layer for the submicrometer particle size range. We demonstrate that dust and biomass burning emissions can separately bias this ratio towards higher values by at least one order of magnitude. In the absence of these confounding factors, the 95% confidence interval of the ratio may be used to estimate the relative extent of aqueous processing by comparing inferred oxalate concentrations between air masses, with the assumption that sulfate primarily originates from aqueous processing.

Nitrate aerosol plays an important role in affecting regional air quality as well as Earth’s climate. However, it is not well represented or even neglected in many global climate models. In this study, we couple the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) module with the four-mode version of the Modal Aerosol Module (MAM4) in DOE’s Energy Exascale Earth System Model version 2 (E3SMv2) to treat nitrate aerosol and its radiative effects. We find that nitrate aerosol simulated by E3SMv2-MAM4-MOSAIC is sensitive to the treatment of gaseous HNO3 transfer to/from interstitial particles related to accommodation coefficients of HNO3 (αHNO3) on dust and non-dust particles. We compare three different treatments of HNO3 transfer: 1) a treatment (MTC_SLOW) that uses a low αHNO3 in the mass transfer coefficient (MTC) calculation; 2) a dust-weighted MTC treatment (MTC_WGT) that uses a high αHNO3 on non-dust particles; and 3) a dust-weighted MTC treatment that also splits coarse mode aerosols into the coarse dust and sea salt sub-modes in MOSAIC (MTC_SPLC). MTC_WGT and MTC_SPLC increase the global annual mean (2005-2014) nitrate burden from 0.096 (MTC_SLOW) to 0.237 and 0.185 Tg N, respectively, mostly in the coarse mode. They also produce stronger nitrate direct radiative forcing (–0.048 and –0.051 W m–2, respectively) and indirect forcing (–0.33 and –0.35 W m–2, respectively) than MTC_SLOW (–0.021 and –0.24 W m–2). All three treatments overestimate nitrate surface concentrations compared with ground-based observations. MTC_WGT and MTC_SPLC improve the vertical profiles of nitrate concentrations against aircraft measurements below 400 hPa.

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global-scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole-to-pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7 to 48% of the top of the atmosphere clear sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance.