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.

AN EXAMINATION OF HYDROXYL RADICAL: OUR CURRENT UNDERSTANDING OF THE OXIDATIVE CAPACITY OF THE TROPOSPHERE THROUGH EMPIRICAL, BOX, AND GLOBAL MODELING APPROACHES

Hydroxyl radical (OH) is the primary oxidant in the troposphere, initiating the removal of numerous atmospheric species including greenhouse gases, pollutants that are detrimental to human health, and ozone-depleting substances. Because of the complexity of OH chemistry, models vary widely in their OH chemistry schemes and resulting methane (CH4) lifetimes. The current state of knowledge concerning global OH abundances is often contradictory. This body of work encompasses three projects that investigate tropospheric OH from a modeling perspective, with the goal of improving the tropospheric community’s knowledge of the atmospheric lifetime of CH4. First, measurements taken during the airborne CONvective TRansport of Active Species in the Tropics (CONTRAST) field campaign are used to evaluate OH in global models. A box model constrained to measured variables is utilized to infer concentrations of OH along the flight track. Results are used to evaluate global model performance, suggest against the existence of a proposed “OH Hole” in the tropical Western Pacific, and investigate implications of high O3/low H2O filaments on chemical transport to the stratosphere. While methyl chloroform-based estimates of global mean OH suggest that models are overestimating OH, we report evidence that these models are actually underestimating OH in the tropical Western Pacific. The second project examines OH within global models to diagnose differences in CH4 lifetime. I developed an approach to quantify the roles of OH precursor field differences (O3, H2O, CO, NOx, etc.) using a neural network method. This technique enables us to approximate the change in CH4 lifetime resulting from variations in individual precursor fields. The dominant factors driving CH4 lifetime differences between models are O3, CO, and J(O3-O1D). My third project evaluates the effect of climate change on global fields of OH using an empirical model. Observations of H2O and O3 from satellite instruments are combined with a simulation of tropical expansion to derive changes in global mean OH over the past 25 years. We find that increasing H2O and increasing width of the tropics tend to increase global mean OH, countering the increasing CH4 sink and resulting in well-buffered global tropospheric OH concentrations.

Harmonization of Life Cycle Climate Performance and Its Improvements for Heat Pump Applications

Life Cycle Climate Performance (LCCP) is an evaluation method by which heating, ventilation, air conditioning and refrigeration systems can be evaluated for their global warming impact over the course of their complete life cycle. LCCP is more inclusive than previous metrics such as Total Equivalent Warming Impact. It is calculated as the sum of direct and indirect emissions generated over the lifetime of the system “from cradle to grave”. Direct emissions include all effects from the release of refrigerants into the atmosphere during the lifetime of the system. This includes annual leakage and losses during the disposal of the unit. The indirect emissions include emissions from the energy consumption during manufacturing process, lifetime operation, and disposal of the system. This thesis proposes a standardized approach to the use of LCCP and traceable data sources for all aspects of the calculation. An equation is proposed that unifies the efforts of previous researchers. Data sources are recommended for average values for all LCCP inputs. A residential heat pump sample problem is presented illustrating the methodology. The heat pump is evaluated at five U.S. locations in different climate zones. An excel tool was developed for residential heat pumps using the proposed method. The primary factor in the LCCP calculation is the energy consumption of the system. The effects of advanced vapor compression cycles are then investigated for heat pump applications. Advanced cycle options attempt to reduce the energy consumption in various ways. There are three categories of advanced cycle options: subcooling cycles, expansion loss recovery cycles and multi-stage cycles. The cycles selected for research are the suction line heat exchanger cycle, the expander cycle, the ejector cycle, and the vapor injection cycle. The cycles are modeled using Engineering Equation Solver and the results are applied to the LCCP methodology. The expander cycle, ejector cycle and vapor injection cycle are effective in reducing LCCP of a residential heat pump by 5.6%, 8.2% and 10.5%, respectively in Phoenix, AZ. The advanced cycles are evaluated with the use of low GWP refrigerants and are capable of reducing the LCCP of a residential heat by 13.7%, 16.3% and 18.6% using a refrigerant with a GWP of 10. To meet the U.S. Department of Energy’s goal of reducing residential energy use by 40% by 2025 with a proportional reduction in all other categories of residential energy consumption, a reduction in the energy consumption of a residential heat pump of 34.8% with a refrigerant GWP of 10 for Phoenix, AZ is necessary. A combination of advanced cycle, control options and low GWP refrigerants are necessary to meet this goal.

Contactless Spectral-Dependent Measurement of Bulk Lifetime and Surface Recombination Velocity in Silicon Photovoltaic Materials

Charge carrier lifetime measurements in bulk or unfinished photovoltaic (PV) materials allow for a more accurate estimate of power conversion efficiency in completed solar cells. In this work, carrier lifetimes in PV- grade silicon wafers are obtained by way of quasi-steady state photoconductance measurements. These measurements use a contactless RF system coupled with varying narrow spectrum input LEDs, ranging in wavelength from 460 nm to 1030 nm. Spectral dependent lifetime measurements allow for determination of bulk and surface properties of the material, including the intrinsic bulk lifetime and the surface recombination velocity. The effective lifetimes are fit to an analytical physics-based model to determine the desired parameters. Passivated and non-passivated samples are both studied and are shown to have good agreement with the theoretical model.