Photochemical Formation and Cost-Efficient Abatement of Ozone: High-Order Sensitivity Analysis

Abstract

The abatement of ground-level ozone has been a priority of air pollution policy because of its harmful effects on human health, ecosystems, and climate. The responsiveness of ozone to emissions of its principal precursors, nitrogen oxides (NOx) and volatile organic compounds (VOCs), is known to depend nonlinearly on spatially and temporally variable factors. Given this variability, scientific understanding of ozone formation processes can facilitate the development of sensible control policies. This thesis applies a high-order sensitivity analysis technique, the Decoupled Direct Method in Three Dimensions (HDDM-3D), to examine ozone response to precursor emissions during summertime air pollution episodes in the southeastern United States. HDDM-3D is shown to accurately capture ozone response within an underlying air quality model, even over large ranges of emission perturbations. Nonlinearity of response is quantified, and nonlinear terms are applied to examine how estimates of sensitivity and source attribution respond to uncertainty in an emissions inventory. Ozone production regime is assessed using both HDDM-3D and species indicator ratios and found to be primarily NOx-limited outside urban centers. However, ozone response to region-wide emissions does not necessarily correspond to its sensitivity to local controls, hindering the usefulness of bipartite ozone regime classification. Significant heterogeneity of ozone response to NOx is found even over small spatial scales of emission origin, a potential complication often ignored in atmospheric modeling and emissions trading mechanisms. Atmospheric sensitivity analysis is linked with a comprehensive menu of potential control measures to demonstrate potential integration of scientific and economic considerations for control strategy formulation. Cost-optimized strategies are identified for attainment of federal ozone standards in Macon, Georgia, and for minimizing potential population exposure to unhealthful concentrations of ozone.