Ozone response to emission reductions in the southeastern United States

Ozone (O-3) formation in the southeastern US is studied in relation to nitrogen oxide (NOx) emissions using long-term (1990s-2015) surface measurements of the Southeastern Aerosol Research and Characterization (SEARCH) network, U.S. Environmental Protection Agency (EPA) O-3 measurements, and EPA Clean Air Status and Trends Network (CASTNET) nitrate deposition data. Annual fourth-highest daily peak 8 h O-3 mixing ratios at EPA monitoring sites in Georgia, Alabama, and Mississippi exhibit statistically significant (p < 0.0001) linear correlations with annual NOx emissions in those states between 1996 and 2015. The annual fourth-highest daily peak 8 h O-3 mixing ratios declined toward values of similar to 45-50 ppbv and monthly O-3 maxima decreased at rates averaging similar to 1-1.5 ppbv yr(-1). Mean annual total oxidized nitrogen (NOy) mixing ratios at SEARCH sites declined in proportion to NOx emission reductions. CASTNET data show declining wet and dry nitrate deposition since the late 1990s, with total (wet plus dry) nitrate deposition fluxes decreasing linearly in proportion to reductions of NOx emissions by similar to 60% in Alabama and Georgia. Annual nitrate deposition rates at Georgia and Alabama CASTNET sites correspond to 30% of Georgia emission rates and 36% of Alabama emission rates, respectively. The fraction of NOx emissions lost to deposition has not changed. SEARCH and CASTNET sites exhibit downward trends in mean annual nitric acid (HNO3) concentrations. Observed relationships of O-3 to NOz (NOy-NOx) support past model predictions of increases in cycling of NO and increasing responsiveness of O-3 to NOx. The study data provide a long-term record that can be used to examine the accuracy of process relationships embedded in modeling efforts. Quantifying observed O-3 trends and relating them to reductions in ambient NOy species concentrations offers key insights into processes of general relevance to air quality management and provides important information supporting strategies for reducing O-3 mixing ratios.