Contribution of Organic Nitrates to Organic Aerosol over South Korea during KORUS-AQ.

The role of anthropogenic NOx emissions in secondary organic aerosol (SOA) production is not fully understood but is important for understanding the contribution of emissions to air quality. Here, we examine the role of organic nitrates (RONO2) in SOA formation over the Korean Peninsula during the Korea-United States Air Quality field study in Spring 2016 as a model for RONO2 aerosol in cities worldwide. We use aircraft-based measurements of the particle phase and total (gas + particle) RONO2 to explore RONO2 phase partitioning. These measurements show that, on average, one-fourth of RONO2 are in the condensed phase, and we estimate that ≈15% of the organic aerosol (OA) mass can be attributed to RONO2. Furthermore, we observe that the fraction of RONO2 in the condensed phase increases with OA concentration, evidencing that equilibrium absorptive partitioning controls the RONO2 phase distribution. Lastly, we model RONO2 chemistry and phase partitioning in the Community Multiscale Air Quality modeling system. We find that known chemistry can account for one-third of the observed RONO2, but there is a large missing source of semivolatile, anthropogenically derived RONO2. We propose that this missing source may result from the oxidation of semi- and intermediate-volatility organic compounds and/or from anthropogenic molecules that undergo autoxidation or multiple generations of OH-initiated oxidation.

Recent changes of trans-boundary air pollution over the Yellow Sea: Implications for future air quality in South Korea.

The influence of air pollutants originating from the Chinese region on air quality over South Korea has been a major concern for policymakers. To investigate the inter-annual trends of the long-distance transport of air pollutants from China to South Korea, multi-year trend analysis was carried out for Aerosol Optical Depth (AOD, as a proxy of particulate matter), and CO (a water-insoluble air pollutant) and SO2 (a partially water-soluble air pollutant), over three regions in Northeast Asia. Air pollutants are typically long-range transported from the highly polluted parts of China to South Korea through the Yellow Sea. Taking advantage of this geographical merit, we carried out the multi-year trend analysis with a special focus on the Yellow Sea region. Decreasing trends of about 5-10%, 13-17% and 55-61% during the last decade were observed in surface CO, AOD and tropospheric SO2 columns over the North China Plain (NCP), Yellow Sea (YS), and South Korea (SK), respectively. Such decreasing trends were also found consistently during the last three, five, and seven years, indicating that the changes in pollution levels are likely in response to recent policy measures taken by the Chinese and Korean governments to improve air quality over the regions. Due to these efforts, the amounts of air pollutants transported from China to South Korea are expected to decrease in future years, to the likely rates of 1.50 ppb yr-1, 0.05 DU yr-1, and 0.56 µg m-3 yr-1 over the YS region for CO, SO2, and PM2.5, respectively. Given the ambitious plans recently announced by the Chinese government for the 21st meeting of Conference of Parties (COP21) and its co-control effects, the suggested percentage rates may even be conservative numbers. This analysis is expected to provide South Korean policymakers with valuable information to establish new air pollution policies in South Korea.

Development of a Reactive Plume Model for the Consideration of Power-Plant Plume Photochemistry and Its Applications.

A reactive plume model (RPM) was developed to comprehensively consider power-plant plume photochemistry with 255 condensed photochemical reactions. The RPM can simulate two main components of power-plant plumes: turbulent dispersion of plumes and compositional changes of plumes via photochemical reactions. In order to evaluate the performance of the RPM developed in the present study, two sets of observational data obtained from the TexAQS II 2006 (Texas Air Quality Study II 2006) campaign were compared with RPM-simulated data. Comparison shows that the RPM produces relatively accurate concentrations for major primary and secondary in-plume species such as NO2, SO2, ozone, and H2SO4. Statistical analyses show good correlation, with correlation coefficients (R) ranging from 0.61 to 0.92, and good agreement with the Index of Agreement (IOA) ranging from 0.76 to 0.95. Following evaluation of the performance of the RPM, a demonstration was also carried out to show the applicability of the RPM. The RPM can calculate NOx photochemical lifetimes inside the two plumes (Monticello and Welsh power plants). Further applicability and possible uses of the RPM are also discussed together with some limitations of the current version of the RPM.

Ozone production efficiency of a ship-plume: ITCT 2K2 case study.

Ozone production efficiency (OPE) of ship plume was first evaluated in this study, based on ship-plume photochemical/dynamic model simulations and the ship-plume composition data measured during the ITCT 2K2 (Intercontinental Transport and Chemical Transformation 2002) aircraft campaign. The averaged instantaneous OPEs (OPE(i)‾) estimated via the ship-plume photochemical/dynamic modeling for the ITCT 2K2 ship-plume ranged between 4.61 and 18.92, showing that the values vary with the extent of chemical evolution (or chemical stage) of the ship plume and the stability classes of the marine boundary layer (MBL). Together with OPE(i)‾, the equivalent OPEs (OPE(e)‾) for the entire ITCT 2K2 ship-plume were also estimated. The OPE(e)‾ values varied between 9.73 (for the stable MBL) and 12.73 (for the moderately stable MBL), which agreed well with the OPE(e)‾ of 12.85 estimated based on the ITCT 2K2 ship-plume observations. It was also found that both the model-simulated and observation-based OPE(e)‾ inside the ship-plume were 0.29-0.38 times smaller than the OPE(e)‾ calculated/measured outside the ITCT 2K2 ship-plume. Such low OPEs insides the ship plume were due to the high levels of NO and non-liner ship-plume photochemistry. Possible implications of this ship-plume OPE study in the global chemistry-transport modeling are also discussed.

Estimation of surface-level PM concentration from satellite observation taking into account the aerosol vertical profiles and hygroscopicity.

Surface-level PM10 distribution was estimated from the satellite aerosol optical depth (AOD) products, taking the account of vertical profiles and hygroscopicity of aerosols over Jeju, Korea during March 2008 and October 2009. In this study, MODIS AOD data from the Terra and Aqua satellites were corrected with aerosol extinction profiles and relative humidity data. PBLH (Planetary Boundary Layer Height) was determined from MPLNET lidar-derived aerosol extinction coefficient profiles. Through statistical analysis, better agreement in correlation (R = 0.82) between the hourly PM10 concentration and hourly average Sunphotometer AOD was the obtained when vertical fraction method (VFM) considering Haze Layer Height (HLH) and hygroscopic growth factor f(RH) was used. The validity of the derived relationship between satellite AOD and surface PM10 concentration clearly demonstrates that satellite AOD data can be utilized for remote sensing of spatial distribution of regional PM10 concentration.

Mobile MAX-DOAS observation of NO2 and comparison with OMI satellite data in the western coastal areas of the Korean peninsula.

Ground-based MAX-DOAS measurements have been used to retrieve column densities of atmospheric absorbers such as NO2, SO2, HCHO, and O3. In this study, mobile MAX-DOAS measurements were conducted to map the 2-D distributions of atmospheric NO2 in the western coastal areas of the Korean peninsula. A Mini-MAX-DOAS instrument was mounted on the rooftop of a mobile lab vehicle with a telescope mounted parallel to the driving direction, pointing forward. The measurements were conducted from 21 to 24 December 2010 along the western coastal areas from Gomso harbor (35.59N, 126.61E) to Gunsan harbor (35.98N, 126.67E). During mobile MAX-DOAS observations, high elevation angles were used to avoid shades from nearby obstacles. For the determination of the tropospheric vertical column density (VCD), the air mass factor (AMF) was retrieved by the so-called geometric approximation. The NO2 VCDs from 20 and 45 degree elevation angles were retrieved from mobile MAX-DOAS measurements. The tropospheric NO2 VCDs derived from mobile MAX-DOAS measurements were compared directly to those retrieved by the OMI satellite observations. Mobile MAX-DOAS VCD was in good agreement with OMI tropospheric VCD on most days. However, OMI tropospheric VCD was much higher than that of mobile MAX-DOAS on 23 December 2010. One probable reason for this difference is that OMI retrieval might overestimate NO2 VCD under haze conditions, when a pollution plume was transported over the measurement site. The mobile MAX-DOAS observations reveal much finer spatial patterns of NO2 distributions, which can provide useful information for the validation of satellite observation of atmospheric trace gases.

Ship-plume sulfur chemistry: ITCT 2K2 case study.

The ship-plume sulfur chemistry was investigated for the ITCT 2K2 (Intercontinental Transport and Chemical Transformation 2002) ship-plume experiment, using the ship-plume photochemical/dynamic model developed in this study. In order to evaluate the performance of the model, the model-predicted mixing ratios of SO2 and H2SO4 were compared with those observed. From these comparisons, it was found that the model-predicted levels were in reasonable agreements with those observed (0.56≤R≤0.71), when the pH of sea-salt particles (pHss) was ≤~6.5. The ship-plume equivalent lifetimes of SO2 (τ(eq)(SO(2))) were also estimated/investigated for this particular ship-plume case. The magnitudes of τ(eq)(SO(2)) were found to be controlled by two main factors: (i) the mixing ratios of in-plume hydroxyl radicals (OH) and (ii) pHss. The former is governed primarily by stability conditions of the marine boundary layer (MBL), when the ship NOx emission rate is fixed. The latter determines if the heterogeneous oxidation of dissolved SO2 occurs via reaction with hydrogen peroxide (H2O2, when pHss<6.5) or with ozone (O3, when pHss>6.5). According to the multiple ship-plume photochemical/dynamic model simulations, the estimated τ(eq)(SO(2)) over the entire ship plumes ranged from 10.32 to 14.32 h under moderately stable (E) to stable (F) MBL conditions. These values were clearly shorter than the background SO2 lifetime (τ(b)(SO(2))) of 15.18-23.20 h. In contrast, τ(eq)(SO(2)) was estimated to be 0.33 h when the pHss remained at ~8.0 (a rather unlikely case). In addition, the SO2 loss budget was further analyzed to estimate the influences of the two main factors on the ship-plume sulfur chemistry. The changes in the loss budget with pHss clearly showed a shift in the dominant SO2 loss processes from heterogeneous SO2 conversion (when pHss>~6.5) to the gas-phase oxidation of SO2 by OH (when pHss<~6.5).

Estimation of the contributions of long range transported aerosol in East Asia to carbonaceous aerosol and PM concentrations in Seoul, Korea using highly time resolved measurements: a PSCF model approach.

The contributions of long range transported aerosol in East Asia to carbonaceous aerosol and particulate matter (PM) concentrations in Seoul, Korea were estimated with potential source contribution function (PSCF) calculations. Carbonaceous aerosol (organic carbon (OC) and elemental carbon (EC)), PM(2.5), and PM(10) concentrations were measured from April 2007 to March 2008 in Seoul, Korea. The PSCF and concentration weighted trajectory (CWT) receptor models were used to identify the spatial source distributions of OC, EC, PM(2.5), and coarse particles. Heavily industrialized areas in Northeast China such as Harbin and Changchun and East China including the Pearl River Delta region, the Yangtze River Delta region, and the Beijing-Tianjin region were identified as high OC, EC and PM(2.5) source areas. The conditional PSCF analysis was introduced so as to distinguish the influence of aerosol transported from heavily polluted source areas on a receptor site from that transported from relatively clean areas. The source contributions estimated using the conditional PSCF analysis account for not only the aerosol concentrations of long range transported aerosols but also the number of transport days effective on the measurement site. Based on the proposed algorithm, the condition of airmass pathways was classified into two types: one condition where airmass passed over the source region (PS) and another condition where airmass did not pass over the source region (NPS). For most of the seasons during the measurement period, 249.5-366.2% higher OC, EC, PM(2.5), and coarse particle concentrations were observed at the measurement site under PS conditions than under NPS conditions. Seasonal variations in the concentrations of OC, EC, PM(2.5), and coarse particles under PS, NPS, and background aerosol conditions were quantified. The contributions of long range transported aerosols on the OC, EC, PM(2.5), and coarse particle concentrations during several Asian dust events were also estimated. We also investigated the performance of the PSCF results obtained from combining highly time resolved measurement data and backward trajectory calculations via comparison with those from data in low resolutions. Reduced tailing effects and the larger coverage over the area of interest were observed in the PSCF results obtained from using the highly time resolved data and trajectories.