PM2.5 pH estimation in Seoul during the KORUS-AQ campaign using different thermodynamic models

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.