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High concentrations of PM2.5 have become a serious environmental issue in South Korea, which ranked 1st or 2nd among OECD countries in terms of population exposure to PM2.5. Quantitative understanding of PM2.5 source attribution is thus crucial for developing efficient air quality mitigation strategies. Here we use a suite of extensive observations of PM2.5 and its precursors concentrations during the international KORea-US cooperative Air Quality field study in Korea (KORUS-AQ) in May–June 2016 to investigate source contributions to PM2.5 in South Korea under various meteorological conditions. For the quantitative analysis, we updated a 3-D chemical transport model, GEOS-Chem, and its adjoint with the latest regional emission inventory and other recent findings. The updated model is evaluated by comparing against observed daily PM2.5 and its component concentrations from six ground sites (Bangnyung, Bulkwang, Olympic park, Gwangju, Ulsan, and Jeju). Overall, simulated concentrations of daily PM2.5 and its components are in a good agreement with observations over the peninsula. We conduct an adjoint sensitivity analysis for simulated surface level PM2.5 concentrations at five ground sites (except for Bangnyung because of its small population) under four different meteorological conditions: dynamic weather, stagnant, extreme pollution, and blocking periods. Source contributions by regions vary greatly depending on synoptic meteorological conditions. Chinese contribution accounts for almost 68% of PM2.5 in surface air in South Korea during the extreme pollution period of the campaign, whereas an enhanced contribution from domestic sources (57%) occurs for the blocking period. Results from our sensitivity analysis suggest that the reduction of domestic anthropogenic NH3 emissions could be most effective in reducing population exposure to PM2.5 in South Korea (effectiveness = 14%) followed by anthropogenic SO2 emissions from Shandong region (effectiveness = 11%), domestic anthropogenic NOx emissions (effectiveness = 10%), anthropogenic NH3 emissions from Shandong region (effectiveness = 8%), anthropogenic NOx emissions from Shandong region (effectiveness = 7%), domestic anthropogenic OC emissions (effectiveness = 7%), and domestic anthropogenic BC emissions (effectiveness = 5%).

Despite its profound influence on air quality, the aerosol acidity, quantifiable by aerosol pH is poorly characterized in South Korea where high concentrations of fine particles have become a serious environmental issue. In this study, we estimated the pH values of PM2.5 using observations of inorganic species and precursor gases concentrations, ambient temperature and relative humidity (RH), measured at the Olympic Park in Seoul during the KORUS-AQ campaign (10 May to June 19, 2016). For the aerosol pH calculation, the ISORROPIA and E-AIM thermodynamic equilibrium models in forward mode were used, in which we found the phase state assumption, either stable (solid + liquid) or metastable (liquid only) had no significant impact on pH predictions. As reported previously, the unrealistic pH prediction of ∼7.6 by ISORROPIA, which largely misrepresents ammonia-rich aerosol contents in the Seoul atmosphere was mainly due to coding errors in the standard ISORROPIA model (i.e., forward mode with stable state assumption). Using the revised ISORROPIA, pH predictions obtained with stable assumption approached those obtained with the metastable state assumption. Following such amendment, fine particle samples were predicted to be acidic with pH values ranging from 1.5 to 4.0 as determined by both ISORROPIA and E-AIM calculations. These pH values were higher than those reported in the United States and Europe and lower than those reported in northern China. A comparison of ISORROPIA and E-AIM models revealed that the pH values obtained using ISORROPIA were consistently but only ∼0.4 pH unit higher than those obtained using E-AIM, demonstrating the precision and consistent utility of thermodynamic equilibrium model in the quantification of PM2.5 pH in Seoul.

Photolysis of nitrous acid (HONO) is recognized as an early-morning source of OH radicals in the urban air. During the Korea-US air quality (KORUS-AQ) campaign, HONO was measured using quantum cascade - tunable infrared laser differential absorption spectrometer (QC-TILDAS) at Olympic Park in Seoul from 17 May, 2016 to 14 June, 2016. The HONO concentration was in the range of 0.07-3.46 ppbv, with an average of 0.93 ppbv. Moreover, it remained high from 00:00-05:00 LST. During this time, the mean concentration was higher during the high-O3 episodes (1.82 ppbv) than the non-episodes (1.20 ppbv). In the morning, the OH radicals that were produced from HONO photolysis were 50% higher (0.95 pptv) during the high-O3 episodes than the non-episodes. Diurnal variations in HOx and O3 concentrations were simulated by the F0AM model, which revealed a difference of ~20 ppbv in the daily maximum O3 concentrations between the high-O3 episodes and non-episodes. Furthermore, the HONO concentration increased with an increase in relative humidity (RH) up to 80%; the highest HONO was associated with the top 10% NO2 in each RH group, confirming that NO2 is one of the main precursors of HONO. At night, the conversion ratio of NO2 to HONO was estimated to be 0.88×10-2 h-1; this ratio was found to increase with an increase in RH. The Aitken mode particles (30-120 nm), which act as catalyst surfaces, exhibited a similar tendency with a conversion ratio that increased along with RH, indicating the coupling of surfaces with HONO conversion. Using an artificial neural network (ANN) model, HONO concentrations were successfully simulated with measured variables (r2 = 0.66 as an average of five models). Among these variables, NOx, aerosol surface area, and RH were found to be the main factors affecting the ambient HONO concentrations. The results reveal that RH facilitates the conversion of NO2 to HONO by constraining the availability of aerosol surfaces. This study demonstrates the coupling of HONO with the HOx-O3 cycle in the Seoul Metropolitan Area (SMA) and provides practical evidence of the heterogeneous formation of HONO by employing the ANN model.