The role of a suburban forest in controlling vertical trace gas and OH reactivity distributions - a case study for the Seoul metropolitan area.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

Freezing-Induced Simultaneous Reduction of Chromate and Production of Molecular Iodine: Mechanism, Kinetics, and Practical Implications.

A new method for the concurrent treatment of Cr(VI)-contaminated wastewater and production of the useful I2 chemical was developed. The method is based on the redox reaction between Cr(VI) and I- that occurs when an aqueous wastewater solution containing Cr(VI) and I- is frozen, producing I2 and allowing for the effective removal of Cr. The redox reaction occurs primarily because of the accumulation of Cr(VI), I-, and protons in the ice grain boundaries formed during freezing (i.e., the freeze concentration effect). This effect was verified by confocal Raman spectroscopy and the experiments varying I- concentration and pH. The reduction of Cr(VI) (20 µM) was near complete after freezing at I- concentrations ≥ 100 µM, pH ≤ 3.0, and temperatures ≤ -10 °C. The freezing method (liquid cooling vs air cooling) had little effect on the final Cr(VI) reduction efficiency but had a significant effect on the Cr(VI) reduction rate. The freezing method was also tested with Cr(VI)-contaminated electroplating wastewater samples, and simultaneous Cr(VI) reduction and I2 production proceeded rapidly in a frozen solution but was not observed in an aqueous solution. Additionally, other substances in electroplating wastewater did not reduce the rate and final efficiency of Cr(VI) reduction and I2 production. Therefore, the freezing/Cr(VI)/I- system can be considered a feasible approach to water-energy nexus technology for simultaneous I2 production and Cr(VI)-contaminated wastewater treatment.

Isoprene photochemistry over the Amazon rainforest.

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets.

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

Isoprene Emission Response to Drought and the Impact on Global Atmospheric Chemistry.

Biogenic isoprene emissions play a very important role in atmospheric chemistry. These emissions are strongly dependent on various environmental conditions, such as temperature, solar radiation, plant water stress, ambient ozone and CO2 concentrations, and soil moisture. Current biogenic emission models (i.e., Model of Emissions of Gases and Aerosols from Nature, MEGAN) can simulate emission responses to some of the major driving variables, such as short-term variations in temperature and solar radiation, but the other factors are either missing or poorly represented. In this paper, we propose a new modeling approach that considers the physiological effects of drought stress on plant photosynthesis and isoprene emissions for use in the MEGAN3 biogenic emission model. We test the MEGAN3 approach by integrating the algorithm into the existing MEGAN2.1 biogenic emission model framework embedded into the global Community Land Model of the Community Earth System Model (CLM4.5/CESM1.2). Single-point simulations are compared against available field measurements at the Missouri Ozarks AmeriFlux (MOFLUX) field site. The modeling results show that the MEGAN3 approach of using of a photosynthesis parameter (Vcmax) and soil wetness factor (ßt) to determine the drought activity factor leads to better simulated isoprene emissions in non-drought and drought periods. The global simulation with the MEGAN3 approach predicts a 17% reduction in global annual isoprene emissions, in comparison to the value predicted using the default CLM4.5/MEGAN2.1 without any drought effect. This reduction leads to changes in surface ozone and oxidants in the areas where the reduction of isoprene emissions is observed. Based on the results presented in this study, we conclude that it is important to simulate the drought-induced response of biogenic isoprene emission accurately in the coupled Earth System model.

OH reactivity in urban and suburban regions in Seoul, South Korea - an East Asian megacity in a rapid transition.

South Korea has recently achieved developed country status with the second largest megacity in the world, the Seoul Metropolitan Area (SMA). This study provides insights into future changes in air quality for rapidly emerging megacities in the East Asian region. We present total OH reactivity observations in the SMA conducted at an urban Seoul site (May-June, 2015) and a suburban forest site (Sep, 2015). The total OH reactivity in an urban site during the daytime was observed at similar levels (∼15 s(-1)) to those previously reported from other East Asian megacity studies. Trace gas observations indicate that OH reactivity is largely accounted for by NOX (∼50%) followed by volatile organic compounds (VOCs) (∼35%). Isoprene accounts for a substantial fraction of OH reactivity among the comprehensive VOC observational dataset (25-47%). In general, observed total OH reactivity can be accounted for by the observed trace gas dataset. However, observed total OH reactivity in the suburban forest area cannot be largely accounted for (∼70%) by the trace gas measurements. The importance of biogenic VOC (BVOCs) emissions and oxidations used to evaluate the impacts of East Asian megacity outflows for the regional air quality and climate contexts are highlighted in this study.

Ecosystem-scale volatile organic compound fluxes during an extreme drought in a broadleaf temperate forest of the Missouri Ozarks (central USA).

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m(-2)  h(-1) at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The meganv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.

Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

Optimizing an airborne mass-balance methodology for accurate emission rate quantification of industrial facilities: A case study of industrial facilities in South Korea.

Accurate estimation of emissions from industrial point sources is crucial in understanding the effectiveness of reduction efforts and establishing reliable emission inventories. In this study, we employ an airborne Chemical Ionization Mass Spectrometry (CIMS) instrument to quantify sulfur dioxide (SO2) emissions from prominent industrial facilities in South Korea, including power plants, a steel mill, and a petrochemical facility. Our analysis utilizes the box mass balance technique to derive SO2 emissions and associated uncertainty. We evaluate the interpolation methods between 2D kriging and 3D radial basis function. The results demonstrate that the total uncertainty of the box mass balance technique ranges from 5 % to 28 %, with an average of 20 %. Mixing ratio ground extrapolation from the lowest altitude of the airborne sampling to the ground emerges as the dominant source of uncertainty, followed by the determination of the boundary layer height. Adequate sampling at multiple altitudes is found to be essential in reducing the overall uncertainty by capturing the full extent of the plume. Furthermore, we assess the uncertainty of the single-height transect mass balance method commonly employed in previous studies. Our findings reveal an average precision of 47 % for this method, with the potential for overestimating emissions by up to 206 %. Samplings at fewer altitudes or with larger altitude gaps increase the risk of under-sampling and elevate method uncertainties. Therefore, this study provides a quantitative basis to evaluate previously airborne observational emission constraints.

Airborne estimation of SO2 emissions rates from a coal-fired power plant using two top-down methods: A mass balance model and Gaussian footprint approach.

In this study, two top-down methods-mass balance and Gaussian footprint-were used to determine SO2 emissions rates via three airborne sampling studies over Korea's largest coal power plant in October 2019 and 2020. During the first two flights in October 2019, mass balance approaches significantly underestimated the SO2 emissions rates by 75 % and 28 %, respectively, as obtained from the real-time stack monitoring system. Notably, this large discrepancy accounted for the insufficient number of transects altitudes and high levels of background SO2 along the upwind side. Alternatively, the estimated SO2 emissions rates of the third flight (October 2020) displayed a difference of <10 % from rea-time monitoring data (630 vs. 690 kg·hr-1), owing to the enhanced vertical resolution with increased transects and lower background SO2 levels. In contrast to the mass balance method, Gaussian footprints offered significantly improved accuracy (relative error: 41 %, 32 %, and 2 % for Flights 1, 2, and 3, respectively). This relatively good performance was attributed to prior emissions knowledge via the Clean Air Policy Support System (CAPSS) emissions inventory and its unique ability to accurately estimate stack-level SO2 emissions rates. Theoretically, the Gaussian footprint was less prone to sparse transects and upwind background levels. However, it can be substantially influenced by atmospheric stability and consequently by effective stack heights and dispersion parameters; basically, all factors with minimal-to-no influence on the mass balance approach. Conversely, the mass balance method was the only plausible approach to estimate unidentified source emissions rates when well-defined prior emission information was unknown. Here, the footprint approach supplemented the mass balance method when the emission inventories were known, and employing both strategies approaches greatly enhanced the integrity of top-down emissions inventories from the power plant sources, thus, supporting their potential for ensuring operational compliance with SO2 emissions regulation.

Interpretation of the effects of anthropogenic chlorine on nitrate formation over northeast Asia during KORUS-AQ 2016.

The Weather Research and Forecasting-Community Multiscale Air Quality (WRF-CMAQ) model, implemented with anthropogenic chlorine (Cl) emissions, was evaluated against ground and NASA DC-8 aircraft measurements during the Korea-United States Air Quality (KORUS-AQ) 2016 campaign. The latest anthropogenic Cl emissions, including gaseous HCl and particulate chloride (pCl-) emissions from the Anthropogenic Chlorine Emissions Inventory of China (ACEIC-2014) (over China) and a global emissions inventory (Zhang et al., 2022) (over outer China), were used to examine the impacts of Cl emissions and the role of nitryl chloride (ClNO2) chemistry in N2O5 heterogeneous reactions on secondary nitrate (NO3-) formation across the Korean Peninsula. The model results against aircraft measurements clearly showed significant Cl- underestimations due mainly to the high gas-particle (G/P) partitioning ratios at aircraft measurement altitudes such as 700-850 hPa, but the ClNO2 simulations were reasonable. Several simulations of CMAQ-based sensitivity experiments against ground measurements indicated that although addition of Cl emission did not significantly alter NO3- formation, the activated ClNO2 chemistry with Cl emissions showed the best model performance with the reduced normalized mean bias (NMB) of 18.7 % compared to a value of 21.1 % for the Cl emissions-free case. In our model evaluation, ClNO2 accumulated during the night but quickly produced Cl radical due to ClNO2 photolysis at sunrise, which modulated other oxidation radicals (e.g., ozone [O3] and hydrogen oxide radicals [HOx]) in the early morning. In the morning hours (0800-1000 LST), the HOx were the dominant oxidants, contributing 86.6 % of the total oxidation capacity (sum of major oxidants such as O3 and HOx species), while oxidability was enhanced by up to ∼6.4 % (increase in 1 h HOx average of 2.89 × 106 molecules·cm-3) in the early morning mainly due to the changes in OH (+7.2 %), hydroperoxyl radical (HO2)(+10.0 %), and O3 (+4.2 %) over the Seoul Metropolitan Area, during the KORUS-AQ campaign. Our results improve understanding of the atmospheric changes in the PM2.5 formation pathway caused by ClNO2 chemistry and Cl emissions over northeast Asia.

The Korea-United States Air Quality (KORUS-AQ) field study.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May-June 2016. The effort was jointly sponsored by the National Institute of Environmental Research of South Korea and the National Aeronautics and Space Administration of the United States. KORUS-AQ offered an unprecedented, multi-perspective view of air quality conditions in South Korea by employing observations from three aircraft, an extensive ground-based network, and three ships along with an array of air quality forecast models. Information gathered during the study is contributing to an improved understanding of the factors controlling air quality in South Korea. The study also provided a valuable test bed for future air quality-observing strategies involving geostationary satellite instruments being launched by both countries to examine air quality throughout the day over Asia and North America. This article presents details on the KORUS-AQ observational assets, study execution, data products, and air quality conditions observed during the study. High-level findings from companion papers in this special issue are also summarized and discussed in relation to the factors controlling fine particle and ozone pollution, current emissions and source apportionment, and expectations for the role of satellite observations in the future. Resulting policy recommendations and advice regarding plans going forward are summarized. These results provide an important update to early feedback previously provided in a Rapid Science Synthesis Report produced for South Korean policy makers in 2017 and form the basis for the Final Science Synthesis Report delivered in 2020.

Emerging investigator series: influence of marine emissions and atmospheric processing on individual particle composition of summertime Arctic aerosol over the Bering Strait and Chukchi Sea.

The Arctic is rapidly transforming due to sea ice loss, increasing shipping activity, and oil and gas development. Associated marine and combustion emissions influence atmospheric aerosol composition, impacting complex aerosol-cloud-climate feedbacks. To improve understanding of the sources and processes determining Arctic aerosol composition, atmospheric particles were collected aboard the Korean icebreaker R/V Araon cruising within the Bering Strait and Chukchi Sea during August 2016. Offline analyses of individual particles by microspectroscopic techniques, including scanning electron microscopy with energy dispersive X-ray spectroscopy and atomic force microscopy with infrared spectroscopy, provided information on particle size, morphology, and chemical composition. The most commonly observed particle types were sea spray aerosol (SSA), comprising ∼60-90%, by number, of supermicron particles, and organic aerosol (OA), comprising ∼50-90%, by number, of submicron particles. Sulfate and nitrate were internally mixed within both SSA and OA particles, consistent with particle multiphase reactions during atmospheric transport. Within the Bering Strait, SSA and OA particles were more aged, with greater number fractions of particles containing sulfate and/or nitrate, compared to particles collected over the Chukchi Sea. This is indicative of greater pollution influence within the Bering Strait from coastal and inland sources, while the Chukchi Sea is primarily influenced by marine sources.

Source signatures from combined isotopic analyses of PM2.5 carbonaceous and nitrogen aerosols at the peri-urban Taehwa Research Forest, South Korea in summer and fall.

Isotopes are essential tools to apportion major sources of aerosols. We measured the radiocarbon, stable carbon, and stable nitrogen isotopic composition of PM2.5 at Taehwa Research Forest (TRF) near Seoul Metropolitan Area (SMA) during August-October 2014. PM2.5, TC, and TN concentrations were 19.4 ±â€¯10.1 µg m-3, 2.6 ±â€¯0.8 µg C m-3, and 1.4 ±â€¯1.4 µg N m-3, respectively. The δ13C of TC and the δ15N of TN were - 25.4 ±â€¯0.7‰ and 14.6 ±â€¯3.8‰, respectively. EC was dominated by fossil-fuel sources with Fff (EC) of 78 ±â€¯7%. In contrast, contemporary sources were dominant for TC with Fc (TC) of 76 ±â€¯7%, revealing the significant contribution of contemporary sources to OC during the growing season. The isotopic signature carries more detailed information on sources depending on air mass trajectories. The urban influence was dominant under stagnant condition, which was in reasonable agreement with the estimated δ15N of NH4+. The low δ15N (7.0 ±â€¯0.2‰) with high TN concentration was apparent in air masses from Shandong province, indicating fossil fuel combustion as major emission source. In contrast, the high δ15N (16.1 ±â€¯3.2‰) with enhanced TC/TN ratio reveals the impact of biomass burning in the air transported from the far eastern border region of China and Russia. Our findings highlight that the multi-isotopic composition is a useful tool to identify emission sources and to trace regional sources of carbonaceous and nitrogen aerosols.

Taehwa Research Forest: A receptor site for severe domestic pollution events in Korea during 2016.

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.

Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.