Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO_x ≡ NO + NO₂) 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 SEAC⁴RS 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_x from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC⁴RS observations of NO_x and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO₂ columns. Our results indicate that NEI NO_x emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NO_x emissions. Upper-tropospheric NO₂ from lightning makes a large contribution to satellite observations of tropospheric NO₂ that must be accounted for when using these data to estimate surface NO_x emissions. We find that only half of isoprene oxidation proceeds by the high-NO_x pathway to produce ozone; this fraction is only moderately sensitive to changes in NO_x emissions because isoprene and NO_x emissions are spatially segregated. GEOS-Chem with reduced NO_x 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_x oxidation products. However, the model is still biased high by 6 ± 14 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.

We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant–aerosol–halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional small sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are also included. Reactive gas-phase chlorine Cl^*, including Cl, ClO, Cl₂, BrCl, ICl, HOCl, ClNO₃, ClNO₂, and minor species, is produced by the HCl+OH reaction and by heterogeneous conversion of sea salt aerosol chloride to BrCl, ClNO₂, Cl₂, and ICl. The model successfully simulates the observed mixing ratios of HCl in marine air (highest at northern midlatitudes) and the associated HNO₃ decrease from acid displacement. It captures the high ClNO₂ mixing ratios observed in continental surface air at night and attributes the chlorine to HCl volatilized from sea salt aerosol and transported inland following uptake by fine aerosol. The model successfully simulates the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be largely explained by transport inland of the marine source. It does not reproduce the boundary layer Cl₂ mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night, which could be due to uncertainty in the rate of the ${\mathrm{ClNO}}_{\mathrm{2}}+{\mathrm{Cl}}^{-}$ reaction, but we have no explanation for the high observed Cl₂ in daytime. The global mean tropospheric concentration of Cl atoms in the model is 620 cm⁻³ and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the $\mathrm{HOBr}+{\mathrm{Cl}}^{-}$ reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO₂ chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC⁴RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NO_x ≡ NO + NO₂) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO₂) react significantly with both NO (high-NO_x pathway) and HO₂ (low-NO_x pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NO_x pathway and glyoxal (28 %) from both low- and high-NO_x pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC⁴RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NO_x emissions decrease (favoring the low-NO_x pathway for isoprene oxidation), but decrease more strongly as SO₂ emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NO_x (leading to a 7 % increase in isoprene SOA) and 48 % for SO₂ (35 % decrease in isoprene SOA). Reducing SO₂ emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM_2.5 from SO₂ emission controls.

We use an ensemble of surface (EPA CSN, IMPROVE, SEARCH, AERONET), aircraft (SEAC⁴RS), and satellite (MODIS, MISR) observations over the southeast US during the summer–fall of 2013 to better understand aerosol sources in the region and the relationship between surface particulate matter (PM) and aerosol optical depth (AOD). The GEOS-Chem global chemical transport model (CTM) with 25 × 25 km² resolution over North America is used as a common platform to interpret measurements of different aerosol variables made at different times and locations. Sulfate and organic aerosol (OA) are the main contributors to surface PM_2.5 (mass concentration of PM finer than 2.5 μm aerodynamic diameter) and AOD over the southeast US. OA is simulated successfully with a simple parameterization, assuming irreversible uptake of low-volatility products of hydrocarbon oxidation. Biogenic isoprene and monoterpenes account for 60 % of OA, anthropogenic sources for 30 %, and open fires for 10 %. 60 % of total aerosol mass is in the mixed layer below 1.5 km, 25 % in the cloud convective layer at 1.5–3 km, and 15 % in the free troposphere above 3 km. This vertical profile is well captured by GEOS-Chem, arguing against a high-altitude source of OA. The extent of sulfate neutralization (f = [NH₄⁺]/(2[SO₄²⁻] + [NO₃⁻]) is only 0.5–0.7 mol mol⁻¹ in the observations, despite an excess of ammonia present, which could reflect suppression of ammonia uptake by OA. This would explain the long-term decline of ammonium aerosol in the southeast US, paralleling that of sulfate. The vertical profile of aerosol extinction over the southeast US follows closely that of aerosol mass. GEOS-Chem reproduces observed total column aerosol mass over the southeast US within 6 %, column aerosol extinction within 16 %, and space-based AOD within 8–28 % (consistently biased low). The large AOD decline observed from summer to winter is driven by sharp declines in both sulfate and OA from August to October. These declines are due to shutdowns in both biogenic emissions and UV-driven photochemistry. Surface PM_2.5 shows far less summer-to-winter decrease than AOD and we attribute this in part to the offsetting effect of weaker boundary layer ventilation. The SEAC4RS aircraft data demonstrate that AODs measured from space are consistent with surface PM_2.5. This implies that satellites can be used reliably to infer surface PM_2.5 over monthly timescales if a good CTM representation of the aerosol vertical profile is available.

Formation of organic nitrates (RONO₂) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NO_x), but the chemistry of RONO₂ formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO₂) in the GEOS-Chem global chemical transport model with ∼ 25 × 25 km² resolution over North America. We evaluate the model using aircraft (SEAC⁴RS) and ground-based (SOAS) observations of NO_x, BVOCs, and RONO₂ from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO₂ species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO₂ in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO₂ were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO₃ accounts for 60 % of simulated gas-phase RONO₂ loss in the boundary layer. Other losses are 20 % by photolysis to recycle NO_x and 15 % by dry deposition. RONO₂ production accounts for 20 % of the net regional NO_x sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NO_x emissions. This segregation implies that RONO₂ production will remain a minor sink for NO_x in the Southeast US in the future even as NO_x emissions continue to decline.