Photochemical air pollution is a common problem at urban and regional scales, with ground-level ozone (O3) being a key constituent. Exposure to ozone can lead to adverse effects on human health, crop yields and ecosystems. As a secondary pollutant, ozone is formed by photochemical reactions involving its precursors: nitrogen oxides (NOx) and volatile organic compounds (VOC). Driven by the complex nonlinear chemistry, ozone responses to precursor reductions can vary in magnitude and sign, depending on where and when emissions of which precursor are reduced.
To develop effective air quality management plans, atmospheric chemistry and transport models are commonly used to simulate the physical and chemical processes involved and to demonstrate the adequacy of proposed emission control plans in a brute-force manner. Integrated online sensitivity analysis techniques can better resolve relationships between air quality responses and changes in precursor emission sources, but these techniques are less commonly used. Forward (source-oriented) sensitivity analysis techniques are typically used to compute sensitivities of many air quality responses to a specified model input perturbation. A complementary technique involving the use of the adjoint method is particularly effective and well-suited for delineating impacts on air quality of changes in many input parameters (e.g., spatially and temporally resolved emission rates). As a backward (receptor-oriented) technique, the adjoint sensitivity analysis can efficiently compute sensitivities of specific air quality response of interest to a large number of (actually all) input parameters in a single model run.
In this dissertation, I use the adjoint of Community Multiscale Air Quality model (CMAQ adjoint) to study the control of photochemical air pollution in California’s San Joaquin Valley (SJV). Air quality metrics of interest are defined to represent urban- and regional-scale odd oxygen (Ox ≡ O3 + NO2) responses. By employing the adjoint modeling tool at 4 km spatial and hourly temporal resolution, I examine how air quality responds to spatially and temporally resolved changes in precursor emissions. The spatiotemporal variations in chemical regimes that limit ozone formation are thereby illustrated. Synergies and tradeoffs in achieving different urban- and regional air quality objectives are discussed. I also investigate dependences of first-order source-receptor relationships on prevailing emissions and meteorological conditions, which are effectively second-order sensitivity analysis questions. Emission reductions on decadal time scales are considered by including anthropogenic emission scenarios corresponding to years 2000, 2012, and 2022. The benefits of location-specific NOx control are evaluated in detail, and demonstrate increasing efficacy over time. Three summer season meteorological regimes – baseline, low-wind, and high-T – are identified from a cluster analysis, with all of these regimes conducive to high ozone levels in the SJV. By comparing sensitivity results, I separately evaluate the effects of stagnation and increased temperature on ozone formation. High-priority source locations to target for emission reductions that are consistent across meteorological regimes are also pinpointed.
Contributions to odd oxygen responses in the SJV originate from precursor sources located within the SJV itself and also from upwind air basins. Under 2012 conditions, upwind contributions from the San Francisco Bay (23–35%) and Sacramento Valley (20–28%) combined are of comparable magnitude to within-valley contributions (36–48%), for three urban receptors located in the northern, middle, and southern portions of the SJV. Upwind impacts are mainly attributable to emissions released on prior days. Sensitivities to same-day emissions are mostly associated with local SJV sources. Depending on source location, time, and receptor of interest, the preferred precursor to control can be either NOx or VOC. At local source locations, the most influential emissions occur during early afternoon (1–3 pm) and morning (9–11 am) hours for NOx and VOC, respectively. A consistent diurnal evolution toward more NOx-sensitive (or less VOC-sensitive) conditions is found across receptors. Opportunities to control pollution through shifts in precursor source location and timing are discussed.
Large reductions in ozone precursor emissions have been achieved over the past two decades, and a transition from VOC- to NOx-sensitive ozone chemistry occurred in the SJV between 2000 and 2022. As a result, the efficacy of NOx-focused emission control programs increases, and areas with negative sensitivities to NOx vanish. The preferred source locations to target NOx control have shifted over decadal timescales. Under present-day (2022) conditions, the identified high-priority locations are associated with 28% of the total SJV NOx emissions, but account for 60% of the impacts on its population-weighted odd oxygen response. These high-priority source locations are found to differ for individual city-level versus regionwide receptors of interest.
Meteorological impacts on air pollution were found to be as influential as the effects of decadal-scale emission changes. Under stagnant (low-wind) weather conditions, local emission contributions to SJV Ox increase to 62-71%, compared to a 32-48% contribution under baseline meteorological conditions. Influential emission source locations become more widespread spatially under stagnant conditions, due to enhanced within-valley recirculation. The chemistry shifts towards a more VOC-sensitive (or less NOx-sensitive) regime. Impacts of increased temperatures (high-T scenario), on the other hand, lead to overall increases in Ox sensitivities to both precursors. Exceptions occur near major cities and busy traffic corridors, where high-T conditions drive sensitivities to NOx and VOC to change in opposite directions.
This dissertation features a comprehensive analysis of source-receptor relationships for urban- and regional-scale air pollution. The combination of both spatial and temporal dimensions in the analysis reveals the coupled spatiotemporal complexity in source-receptor relationships in great detail. The consideration of decadal emission changes and multiple meteorological regimes allows me to capture higher-order dynamics and interactions, going beyond static representations of first-order source-receptor relationships. From a regulatory perspective, my research identifies new opportunities for optimizing the design of air pollution control strategies through spatial and temporal targeting of mandated emission reductions. The approach described in this research can also be applied to other vexing air pollution problems such as airborne fine particulate matter (PM2.5), or for multi-pollutant control.