During the May-June 2016 International Cooperative Air Quality Field Study in Korea (KORUS-AQ), light synoptic meteorological forcing facilitated Seoul metropolitan pollution outflow to reach the remote Taehwa Research Forest (TRF) site and cause regulatory exceedances of ozone on 24 days. Two of these severe pollution events are thoroughly examined. The first, occurring on 17 May 2016, tracks transboundary pollution transport exiting eastern China and the Yellow Sea, traversing the Seoul Metropolitan Area (SMA), and then reaching TRF in the afternoon hours with severely polluted conditions. This case study indicates that although outflow from China and the Yellow Sea were elevated with respect to chemically unperturbed conditions, the regulatory exceedance at TRF was directly linked in time, space, and altitude to urban Seoul emissions. The second case studied, occurring on 09 June 2016, reveals that increased levels of biogenic emissions, in combination with amplified urban emissions, were associated with severe levels of pollutions and a regulatory exceedance at TRF. In summary, domestic emissions may be causing more pollution than by trans-boundary pathways, which have been historically believed to be the major source of air pollution in South Korea. The case studies are assessed with multiple aircraft, model (photochemical and meteorological) simulations, in-situ chemical sampling, and extensive ground-based profiling at TRF. These observations clearly identify TRF and the surrounding rural communities as receptor sites for severe pollution events associated with Seoul outflow, which will result in long-term negative effects to both human health and agriculture in the affected areas.

Abstract. Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul Metropolitan Area (SMA) during the Korean-United States-Air Quality (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested region downwind, respectively. The overall diurnal variations of ClNO2 in both sites appeared similar but the night time variation were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were sustained throughout the night at the TRF site. Significant levels of ClNO2 were sustained at both sites for 4–5 hours after sunrise. Airborne observations, box model calculations, and back trajectory analysis consistently show that this high levels of ClNO2 in the morning is likely due to the transport of air masses within the boundary layer. Box model results show that chlorine radical initiated chemistry can impact the regional photochemistry by elevating net ozone production rate up to ~ 25 % in the morning.

During the May-June 2016 International Cooperative Air Quality Field Study in Korea (KORUS-AQ), light synoptic meteorological forcing facilitated Seoul metropolitan pollution outflow to reach the remote Taehwa Research Forest (TRF) site and cause regulatory exceedances of ozone on 24 days. Two of these severe pollution events are thoroughly examined. The first, occurring on 17 May 2016, tracks transboundary pollution transport exiting eastern China and the Yellow Sea, traversing the Seoul Metropolitan Area (SMA), and then reaching TRF in the afternoon hours with severely polluted conditions. This case study indicates that although outflow from China and the Yellow Sea were elevated with respect to chemically unperturbed conditions, the regulatory exceedance at TRF was directly linked in time, space, and altitude to urban Seoul emissions. The second case studied, occurring on 09 June 2016, reveals that increased levels of biogenic emissions, in combination with amplified urban emissions, were associated with severe levels of pollutions and a regulatory exceedance at TRF. In summary, domestic emissions may be causing more pollution than by trans-boundary pathways, which have been historically believed to be the major source of air pollution in South Korea. The case studies are assessed with multiple aircraft, model (photochemical and meteorological) simulations, in-situ chemical sampling, and extensive ground-based profiling at TRF. These observations clearly identify TRF and the surrounding rural communities as receptor sites for severe pollution events associated with Seoul outflow, which will result in long-term negative effects to both human health and agriculture in the affected areas.

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea-United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the nighttime variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4-5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by 25% in the morning.

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations.

We investigate regional sources contributing to CO during the Korea United States Air Quality (KORUS-AQ) campaign conducted over Korea (1 May to 10 June 2016) using 17 tagged CO simulations from the Community Atmosphere Model with chemistry (CAM-chem). The simulations use three spatial resolutions, three anthropogenic emission inventories, two meteorological fields, and nine emission scenarios. These simulations are evaluated against measurements from the DC-8 aircraft and Measurements Of Pollution In The Troposphere (MOPITT). Results show that simulations using bottom-up emissions are consistently lower (bias: −34 to −39%) and poorer performing (Taylor skill: 0.38–0.61) than simulations using alternative anthropogenic emissions (bias: −6 to −33%; Taylor skill: 0.48–0.86), particularly for enhanced Asian CO and volatile organic compound (VOC) emission scenarios, suggesting underestimation in modeled CO background and emissions in the region. The ranges of source contributions to modeled CO along DC-8 aircraft from Korea and southern (90°E to 123°E, 20°N to 29°N), middle (90°E to 123°E, 29°N to 38.5°N), and northern (90°E to 131.5°E, 38.5°N to 45°N) East Asia (EA) are 6–13%, ~5%, 16–28%, and 9–18%, respectively. CO emissions from middle and northern EA can reach Korea via transport within the boundary layer, whereas those from southern EA are transported to Korea mainly through the free troposphere. Emission contributions from middle EA dominate during continental outflow events (29–51%), while Korean emissions play an overall more important role for ground sites (up to 25–49%) and plumes within the boundary layer (up to 25–44%) in Korea. Finally, comparisons with four other source contribution approaches (FLEXPART 9.1 back trajectory calculations driven by Weather Research and Forecasting (WRF) WRF inert tracer, China signature VOCs, and CO to CO2 enhancement ratios) show general consistency with CAM-chem.

Organic aerosol (OA) is an important fraction of submicron aerosols. However, it is challenging to predict and attribute the specific organic compounds and sources that lead to observed OA loadings, largely due to contributions from secondary production. This is especially true for megacities surrounded by numerous regional sources that create an OA background. Here, we utilize in situ gas and aerosol observations collected on board the NASA DC-8 during the NASA-NIER KORUS-AQ (Korea-United States Air Quality) campaign to investigate the sources and hydrocarbon precursors that led to the secondary OA (SOA) production observed over Seoul. First, we investigate the contribution of transported OA to total loadings observed over Seoul by using observations over the Yellow Sea coupled to FLEXPART Lagrangian simulations. During KORUS-AQ, the average OA loading advected into Seoul was ∼ 1-3 μgsm -3 . Second, taking this background into account, the dilutioncorrected SOA concentration observed over Seoul was ∼ 140 μgsm -3 ppmv -1 at 0.5 equivalent photochemical days. This value is at the high end of what has been observed in other megacities around the world (20-70 μgsm -3 ppmv -1 at 0.5 equivalent days). For the average OA concentration observed over Seoul (13 μgsm -3 ), it is clear that production of SOA from locally emitted precursors is the major source in the region. The importance of local SOA production was supported by the following observations. (1) FLEXPART source contribution calculations indicate any hydrocarbons with a lifetime of less than 1 day, which are shown to dominate the observed SOA production, mainly originate from South Korea. (2) SOA correlated strongly with other secondary photochemical species, including short-lived species (formaldehyde, peroxy acetyl nitrate, sum of acyl peroxy nitrates, dihydroxytoluene, and nitrate aerosol). (3) Results from an airborne oxidation flow reactor (OFR), flown for the first time, show a factor of 4.5 increase in potential SOA concentrations over Seoul versus over the Yellow Sea, a region where background air masses that are advected into Seoul can be measured. (4) Box model simulations reproduce SOA observed over Seoul within 11% on average and suggest that shortlived hydrocarbons (i.e., xylenes, trimethylbenzenes, and semi-volatile and intermediate-volatility compounds) were the main SOA precursors over Seoul. Toluene alone contributes 9% of the modeled SOA over Seoul. Finally, along with these results, we use the metric ΔOA/ΔCO2 to examine the amount of OA produced per fuel consumed in a megacity, which shows less variability across the world than ΔOA=ΔCO.