Understanding of the formation mechanisms of ozone and particulate matter at a fine scale over the southeastern U.S.: Process analyses and responses to future-year emissions

Abstract

Ozone (O3) and fine particle (PM2.5) formation over the southeastern U.S. are of a major concern due to high emissions of precursors and special weather conditions that are conducive to their formation. In this study, the Community Multiscale Air Quality (CMAQ) modeling system is applied to simulate the formation of major air pollutants over an area in the southeastern U.S. at a 4-km horizontal grid resolution for January, April, July, and October in 2002 and 2018. Model performance evaluation shows an overall satisfactory performance for O3 in all months and for PM2.5 in January and October at rural sites and in January, April, and October at urban sites. Large underpredictions in PM2.5 concentrations occur in April and July at rural sites and in July at urban sites, because of biases in meteorological predictions and underestimation of emissions of precursors. The model performance at 4-km in terms of O3, PM2.5 and PM2.5 components show some improvements but overall are not always better than that at 12-km. O3 chemistry is VOC-limited in urban areas and NOx-limited over the west of the mountain regions and the southern Georgia throughout the year, and VOC-limited over the rest of areas in January but NOx-limited in other months. Among all photochemical indicators examined, PH2O2/PHNO3 and O3/NOy are the most robust indicators. The domain is NH3-rich or neutral in all months, indicating a high potential for NH4NO3 formation and the sensitivity of PM2.5 formation to the emissions of SO2, NOx, and NH3. Surface O3 is accumulated primarily through vertical transport in urban, rural and coastal areas and both horizontal and vertical transport in mountain regions and produced via gas-phase chemistry at non-urban sites during daytime. The loss of O3 is attributed to gas-phase chemistry via NO titration in urban areas, and dry deposition and transport processes in rural and mountain areas. PM2.5 is produced by primary emissions and PM processes and lost through vertical and horizontal transport in urban areas. The combined effects of transport, emissions, and PM processes influence PM concentrations in other areas. The 2018 simulations project a decrease in PM2.5 concentrations and an improvement in visibility over almost the entire domain, slight decreases in O3 mixing ratios in urban areas in July and most non-urban areas in April and October but large increases in the rest of areas in other months, and a decrease in total N deposition fluxes in most areas except for central and eastern North Carolina and northern Georgia. The development of integrated emission control strategies should consider region-specific seasonality and differences in the responses of O3, PM2.5, visibility, and nitrogen deposition.