Lifetime and distribution of ozone and related pollutants in the eastern United States

Most major cities in the eastern United States have air quality deemed unhealthy by the EPA under a set of regulations known as the National Ambient Air Quality Standards (NAAQS). The worst air quality in Maryland is measured in Edgewood, MD, a small community located along the Chesapeake Bay and generally downwind of Baltimore during hot, summertime days. Direct measurements and numerical simulations were used to investigate how meteorology and chemistry conspire to create adverse levels of photochemical smog especially at this coastal location. Ozone (O3) and oxidized reactive nitrogen (NOy), a family of ozone precursors, were measured over the Chesapeake Bay during a ten day experiment in July 2011 to better understand the formation of ozone over the Bay and its impact on coastal communities such as Edgewood. Ozone over the Bay during the afternoon was 10% to 20% higher than the closest upwind ground sites. A combination of complex boundary layer dynamics, deposition rates, and unaccounted marine emissions play an integral role in the regional maximum of ozone over the Bay. The CAMx regional air quality model was assessed and enhanced through comparison with data from NASA’s 2011 DISCOVER-AQ field campaign. Comparisons show a model overestimate of NOy by +86.2% and a model underestimate of formaldehyde (HCHO) by –28.3%. I present a revised model framework that better captures these observations and the response of ozone to reductions of precursor emissions. Incremental controls on electricity generating stations will produce greater benefits for surface ozone while additional controls on mobile sources may yield less benefit because cars emit less pollution than expected. Model results also indicate that as ozone concentrations improve with decreasing anthropogenic emissions, the photochemical lifetime of tropospheric ozone increases. The lifetime of ozone lengthens because the two primary gas-phase sinks for odd oxygen (Ox ≈ NO2 + O3) – attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate – weaken with decreasing pollutant emissions. This unintended consequence of air quality regulation causes pollutants to persist longer in the atmosphere, and indicates that pollutant transport between states and countries will likely play a greater role in the future.

THE DISTRIBUTION AND FUNCTION OF DENITRIFICATION GENES: EXPLORING AGRICULTURAL MANAGEMENT AND SOIL CHEMICAL IMPLICATIONS

Denitrification is a microbially-mediated process that converts nitrate (NO3-) to dinitrogen (N2) gas and has implications for soil fertility, climate change, and water quality. Using PCR, qPCR, and T-RFLP, the effects of environmental drivers and land management on the abundance and composition of functional genes were investigated. Environmental variables affecting gene abundance were soil type, soil depth, nitrogen concentrations, soil moisture, and pH, although each gene was unique in its spatial distribution and controlling factors. The inclusion of microbial variables, specifically genotype and gene abundance, improved denitrification models and highlights the benefit of including microbial data in modeling denitrification. Along with some evidence of niche selection, I show that nirS is a good predictor of denitrification enzyme activity (DEA) and N2O:N2 ratio, especially in alkaline and wetland soils. nirK was correlated to N2O production and became a stronger predictor of DEA in acidic soils, indicating that nirK and nirS are not ecologically redundant.