Photochemistry and transport of tropospheric ozone and its precursors in urban and remote environments

Tropospheric ozone (O3) adversely affects human health, reduces crop yields, and contributes to climate forcing. To limit these effects, the processes controlling O3 abundance as well as that of its precursor molecules must be fully characterized. Here, I examine three facets of O3 production, both in heavily polluted and remote environments. First, using in situ observations from the DISCOVER-AQ field campaign in the Baltimore/Washington region, I evaluate the emissions of the O3 precursors CO and NOx (NOx = NO + NO2) in the National Emissions Inventory (NEI). I find that CO/NOx emissions ratios derived from observations are 21% higher than those predicted by the NEI. Comparisons to output from the CMAQ model suggest that CO in the NEI is accurate within 15 ± 11%, while NOx emissions are overestimated by 51-70%, likely due to errors in mobile sources. These results imply that ambient ozone concentrations will respond more efficiently to NOx controls than current models suggest. I then investigate the source of high O3 and low H2O structures in the Tropical Western Pacific (TWP). A combination of in situ observations, satellite data, and models show that the high O3 results from photochemical production in biomass burning plumes from fires in tropical Southeast Asia and Central Africa; the low relative humidity results from large-scale descent in the tropics. Because these structures have frequently been attributed to mid-latitude pollution, biomass burning in the tropics likely contributes more to the radiative forcing of climate than previously believed. Finally, I evaluate the processes controlling formaldehyde (HCHO) in the TWP. Convective transport of near surface HCHO leads to a 33% increase in upper tropospheric HCHO mixing ratios; convection also likely increases upper tropospheric CH3OOH to ~230 pptv, enough to maintain background HCHO at ~75 pptv. The long-range transport of polluted air, with NO four times the convectively controlled background, intensifies the conversion of HO2 to OH, increasing OH by a factor of 1.4. Comparisons between the global chemistry model CAM-Chem and observations show that consistent underestimates of HCHO by CAM-Chem throughout the troposphere result from underestimates in both NO and acetaldehyde.

THE INFLUENCE OF URBAN FORM AT DIFFERENT GEOGRAPHICAL SCALES ON TRAVEL BEHAVIOR; EVIDENCE FROM U.S. CITIES

Suburban lifestyle is popular among American families, although it has been criticized for encouraging automobile use through longer commutes, causing heavy traffic congestion, and destroying open spaces (Handy, 2005). It is a serious concern that people living in low-density suburban areas suffer from high automobile dependency and lower rates of daily physical activity, both of which result in social, environmental and health-related costs. In response to such concerns, researchers have investigated the inter-relationships between urban land-use pattern and travel behavior within the last few decades and suggested that land-use planning can play a significant role in changing travel behavior in the long-term. However, debates regarding the magnitude and efficiency of the effects of land-use on travel patterns have been contentious over the years. Changes in built-environment patterns is potentially considered a long-term panacea for automobile dependency and traffic congestion, despite some researchers arguing that the effects of land-use on travel behavior are minor, if any. It is still not clear why the estimated impact is different in urban areas and how effective a proposed land-use change/policy is in changing certain travel behavior. This knowledge gap has made it difficult for decision-makers to evaluate land-use plans and policies. In addition, little is known about the influence of the large-scale built environment. In the present dissertation, advanced spatial-statistical tools have been employed to better understand and analyze these impacts at different scales, along with analyzing transit-oriented development policy at both small and large scales. The objective of this research is to: (1) develop scalable and consistent measures of the overall physical form of metropolitan areas; (2) re-examine the effects of built-environment factors at different hierarchical scales on travel behavior, and, in particular, on vehicle miles traveled (VMT) and car ownership; and (3) investigate the effects of transit-oriented development on travel behavior. The findings show that changes in built-environment at both local and regional levels could be very influential in changing travel behavior. Specifically, the promotion of compact, mixed-use built environment with well-connected street networks reduces VMT and car ownership, resulting in less traffic congestion, air pollution, and energy consumption.