Emissions from 15 agricultural fires in the southeastern U.S. were measured from the NASA DC‐8 research aircraft during the summer 2013 Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. This study reports a detailed set of emission factors (EFs) for 25 trace gases and 6 fine particle species. The chemical evolution of the primary emissions in seven plumes was examined in detail for ~1.2 h. A Lagrangian plume cross‐section model was used to simulate the evolution of ozone (O3), reactive nitrogen species, and organic aerosol (OA). Observed EFs are generally consistent with previous measurements of crop residue burning, but the fires studied here emitted high amounts of SO2 and fine particles, especially primary OA and chloride. Filter‐based measurements of aerosol light absorption implied that brown carbon (BrC) was ubiquitous in the plumes. In aged plumes, rapid production of O3, peroxyacetyl nitrate (PAN), and nitrate was observed with ΔO3/ΔCO, ΔPAN/ΔNOy, and Δnitrate/ΔNOy reaching ~0.1, ~0.3, and ~0.3. For five selected cases, the model reasonably simulated O3 formation but underestimated PAN formation. No significant evolution of OA mass or BrC absorption was observed. However, a consistent increase in oxygen‐to‐carbon (O/C) ratios of OA indicated that OA oxidation in the agricultural fire plumes was much faster than in urban and forest fire plumes. Finally, total annual SO2, NOx, and CO emissions from agricultural fires in Arkansas, Louisiana, Mississippi, and Missouri were estimated (within a factor of ~2) to be equivalent to ~2% SO2 from coal combustion and ~1% NOx and ~9% CO from mobile sources.

[1] The impact of aerosols on regional air quality and climate necessitates improved understanding of their emission and microphysical properties. The size distributions of black carbon (BC) and light scattering particles (LSP) were measured with a single particle soot photometer on board the NASA DC-8 aircraft during the ARCTAS mission 2008. Air sampling was made in the air plumes of both urban and forest fire emissions over California during the CARB (California Air Resources Board) phase of the mission. A total of eleven plumes were identified using SO 2 and CH 3 CN tracers for fossil fuel (FF) combustion and biomass burning (BB), respectively. The enhancements of BC and LSP in BB plumes were significantly higher compared to those in FF plumes. The average mass concentration of BC in BB plumes was more than twice that in FF plumes. Except for the BC/CO ratio, distinct emission ratios of BC/CO 2 , BC/CH 3 CN, CH 3 CN/CO, and CO/CO 2 were observed in the plumes from the two sources. Similarly, the microphysical properties of BC and LSP also showed distinct behaviors. The BC count median diameter (CMD) of 115 AE 5 nm in FF plumes was smaller compared to 141 AE 9 nm in the BB plumes. BC aerosols were thickly coated in BB plumes, the average shell/core ratios were 1.47 and 1.24 in BB and FF plumes, respectively. In the total mass of submicron aerosols, organic aerosols constituted about 67% in the FF plumes and 84% in BB plumes. The contribution of sulfate was also significant in the FF plumes.

Abstract. An understanding of gas-phase HNO3 transmission through an inlet is necessary to evaluate the quality of NOy measurements from an aircraft platform. A simple, inexpensive, low-volume Teflon inlet is described and its suitability as an aircraft inlet for gas-phase NOy is assessed. Aerosol transmission is not characterized, but inlet design and orientation probably discriminates against the majority of aerosol by mass. Laboratory data, in-flight HNO3 standard addition calibrations, and ambient NOy measurements from the 1997 North Atlantic Regional Experiment aircraft mission are used to characterize inlet transmission efficiencies and time constants. Laboratory tests show high transmission efficiencies for HNO3 which are relatively independent of ambient temperature and humidity. In-flight standard addition calibrations were carried out at ambient temperatures ranging from -20 ø to +8øC and relative humidities from 3% to 71%. These data suggest that nearly all the sampled air contacts an inlet surface, with 90% of added HNO3 being transmitted in -1.5 s. Ambient data are presented to demonstrate negligible hysteresis in 1-Hz NOy measurements, relative to variability observed in ozone data, from an air mass where HNO3 is expected to be a large fraction of the total NOy. Power spectra of ambient NOy (at temperatures from -35 ø to +35øC and relative humidities from 3% to 100%) and ozone measurements suggest an effective NOy instrument time constant of-2 s.

We determine enhancement ratios for NO_x, PAN, and other NO_y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO_x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NO_x emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the reactivity of specific anthropogenic volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved model representation of ASOA driven by the observations, we attribute 340 000 PM2.5-related premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM2.5 (the Global Exposure Mortality Model) results in up to 900 000 deaths. A limitation of this study is the extrapolation from cities with detailed studies and regions where detailed emission inventories are available to other regions where uncertainties in emissions are larger. In addition to further development of institutional air quality management infrastructure, comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area.

An extensive set of primary and secondary pollutants was measured at a ground site in a remote location in the Yellow River Delta, China during the Ozone Photochemistry and Export from China Experiment (OPECE) from March to April 2018. The measurements include volatile organic compounds (VOCs), peroxyacyl nitrates (PANs), ozone (O3), particulate species, nitrogen oxides (NOx), and SO2. Observed VOC mixing ratios were comparable to those measured in heavily polluted cities in the U.S. and China. The VOC source signatures suggest a strong influence from Oil and Natural Gas (O&NG) emissions with potentially large contributions from Liquified Petroleum Gas (LPG) sources as well. Consistently elevated concentrations of O3, PAN, and its rarely measured homologs peroxybenzoylic nitric anhydride (PBzN) and peroxyacrylic nitric anhydride (APAN) at the OPECE site indicate complex photochemistry in a heterogeneous VOC environment. Diagnostic 0‐D box model simulations are used to investigate the budgets of ROx (OH + HO2 + RO2), and the rate and efficiency of O3 production. Model sensitivity calculations indicate that O3 production at OPECE site is VOC limited in spring. This suggests that reduction in VOCs should be a priority for reducing O3, where production and fugitive emissions from O&NG provide an attractive target. While initial reductions in NOx might increase O3 production, reduction of NOx along with VOCs will be a necessary step to achieve long‐term ozone reduction.

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the anthropogenic reactivity of specific volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved modeling representation of ASOA driven by the observations, we attribute 340,000 PM2.5 premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM2.5 (the Global Exposure Mortality Model) results up to 900,000 deaths. A limitation of this study is the extrapolation from regions with detailed data to others where data is not available. Comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area.

Detailed comparisons of airborne CH₂O measurements acquired by tunable diode laser absorption spectroscopy with steady state box model calculations were carried out using data from the 2006 INTEX-B campaign in order to improve our understanding of hydrocarbon oxidation processing. Select previous comparisons in other campaigns have highlighted some locations in the boundary layer where steady state box models have tended to underpredict CH₂O, suggesting that standard steady state modeling assumptions might be unsuitable under these conditions, and pointing to a possible role for unmeasured hydrocarbons and/or additional primary emission sources of CH₂O. Employing an improved instrument, more detailed measurement-model comparisons with better temporal overlap, up to date measurement and model precision estimates, up to date rate constants, and additional modeling tools based on both Lagrangian and Master Chemical Mechanism (MCM) runs, we have explained much of the disagreement between observed and predicted CH₂O as resulting from non-steady-state atmospheric conditions in the vicinity of large pollution sources, and have quantified the disagreement as a function of plume lifetime (processing time). We show that in the near-field (within ~4 to 6 h of the source), steady-state models can either over-or-underestimate observations, depending on the predominant non-steady-state influence. In addition, we show that even far field processes (10–40 h) can be influenced by non-steady-state conditions which can be responsible for CH₂O model underestimations by as much as a factor of 2. At the longer processing times in the 10 to 40 h range during Mexico City outflow events, MCM model calculations, using assumptions about emissions of high-order NMHCs, further indicate the potential importance of CH₂O produced from unmeasured and multi-generation hydrocarbon oxidation processing, particularly methylglyoxal and 3-hyroxypropanal