Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO ≡ NO + NO) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEACRS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEACRS observations of NO and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO columns. Our results indicate that NEI NO emissions from mobile and industrial sources must be reduced by 30-60%, dependent on the assumption of the contribution by soil NO emissions. Upper tropospheric NO from lightning makes a large contribution to satellite observations of tropospheric NO that must be accounted for when using these data to estimate surface NO emissions. We find that only half of isoprene oxidation proceeds by the high-NO pathway to produce ozone; this fraction is only moderately sensitive to changes in NO emissions because isoprene and NO emissions are spatially segregated. GEOS-Chem with reduced NO emissions provides an unbiased simulation of ozone observations from the aircraft, and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NO oxidation products. However, the model is still biased high by 8±13 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

NOx lifetime relates nonlinearly to its own concentration; therefore, by observing how NOx lifetime changes with changes in its concentration, inferences can be made about the dominant chemistry occurring in an urban plume. We used satellite observations of NO2 from a new high-resolution product to show that NOx lifetime in approximately 30 North American cities has changed between 2005 and 2014 in a manner consistent with our understanding of NOx chemistry.

Abstract. The National Emission Inventory (NEI) of the US Environmental Protection Agency (EPA) reports a steady decrease in US NOx emissions over the 2005–2017 period at a rate of 0.1 Tg N a−1 (53 % decrease over the period), reflecting sustained efforts to improve air quality. Tropospheric NO2 columns observed by the satellite-based Ozone Monitoring Instrument (OMI) over the US show a steady decrease until 2009 but a flattening afterward, which has been attributed to a flattening of NOx emissions, contradicting the NEI. We show here that the steady 2005–2017 decrease in NOx emissions reported by the NEI is in fact largely consistent with observed network trends of surface NO2 and ozone concentrations. The OMI NO2 trend is instead similar to that observed for nitrate wet deposition fluxes, which is weaker than that for anthropogenic NOx emissions, due to a large and increasing relative contribution of non-anthropogenic background sources of NOx (mainly lightning and soils). This is confirmed by contrasting OMI NO2 trends in urban winter, where the background is low and OMI NO2 shows a 2005–2017 decrease consistent with the NEI, and rural summer, where the background is high and OMI NO2 shows no significant 2005–2017 trend. A GEOS-Chem model simulation driven by NEI emission trends for the 2005–2017 period reproduces these different trends, except for the post-2009 flattening of OMI NO2, which we attribute to a model underestimate of free tropospheric NO2. Better understanding is needed of the factors controlling free tropospheric NO2 in order to relate satellite observations of tropospheric NO2 columns to the underlying NOx emissions and their trends. Focusing on urban winter conditions in the satellite data minimizes the effect of this free tropospheric background.

Abstract. Retrievals of tropospheric NO2 columns from UV–visible observations of reflected sunlight require a priori vertical profiles to account for the variation in sensitivity of the observations to NO2 at different altitudes. These profiles vary in space and time but are usually approximated using models that do not resolve the full details of this variation. Currently, no operational retrieval simulates these a priori profiles at both high spatial and high temporal resolution. Here we examine the additional benefits of daily variations in a priori profiles for retrievals already simulating a priori NO2 profiles at sufficiently high spatial resolution to identify variations of NO2 within urban plumes. We show the effects of introducing daily variation into a priori profiles can be as large as 40 % and 3 × 1015 molec. cm−2 for an individual day and lead to corrections as large as −13 % for a monthly average in a case study of Atlanta, GA, USA. Additionally, we show that NOx emissions estimated from space-based remote sensing using daily, high-spatial-resolution a priori profiles are  ∼ 100 % greater than those of a retrieval using spatially coarse a priori profiles, and 26–40 % less than those of a retrieval using monthly averaged high-spatial-resolution profiles.

Lightning is one of the most important sources of upper tropospheric NOx; however, there is a large spread in estimates of the global emission rates (2–8 Tg N yr−1). We combine upper tropospheric in situ observations from the Deep Convective Clouds and Chemistry (DC3) experiment and global satellite‐retrieved NO2 tropospheric column densities to constrain mean lightning NOx (LNOx) emissions per flash. Insights from DC3 indicate that the NOx lifetime is ~3 h in the region of outflow of thunderstorms, mainly due to production of methyl peroxy nitrate and alkyl and multifunctional nitrates. The lifetime then increases farther downwind from the region of outflow. Reinterpreting previous analyses using the 3 h lifetime reduces the spread among various methods that have been used to calculate mean LNOx emissions per flash and indicates a global LNOx emission rate of ~9 Tg N yr−1, a flux larger than the high end of recent estimates.