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.

Plant Migrations Impact on Potential Vegetation and Carbon Redistribution in Northern North America from Climate Change

Forests have a prominent role in carbon storage and sequestration. Anthropogenic forcing has the potential to accelerate climate change and alter the distribution of forests. How forests redistribute spatially and temporally in response to climate change can alter their carbon sequestration potential. The driving question for this research was: How does plant migration from climate change impact vegetation distribution and carbon sequestration potential over continental scales? Large-scale simulation of the equilibrium response of vegetation and carbon from future climate change has shown relatively modest net gains in sequestration potential, but studies of the transient response has been limited to the sub-continent or landscape scale. The transient response depends on fine scale processes such as competition, disturbance, landscape characteristics, dispersal, and other factors, which makes it computational prohibitive at large domain sizes. To address this, this research used an advanced mechanistic model (Ecosystem Demography Model, ED) that is individually based, but pseudo-spatial, that reduces computational intensity while maintaining the fine scale processes that drive the transient response. First, the model was validated against remote sensing data for current plant functional type distribution in northern North America with a current climatology, and then a future climatology was used to predict the potential equilibrium redistribution of vegetation and carbon from future climate change. Next, to enable transient calculations, a method was developed to simulate the spatially explicit process of dispersal in pseudo-spatial modeling frameworks. Finally, the new dispersal sub-model was implemented in the mechanistic ecosystem model, and a model experimental design was designed and completed to estimate the transient response of vegetation and carbon to climate change. The potential equilibrium forest response to future climate change was found to be large, with large gross changes in distribution of plant functional types and comparatively smaller changes in net carbon sequestration potential for the region. However, the transient response was found to be on the order of centuries, and to depend strongly on disturbance rates and dispersal distances. Future work should explore the impact of species-specific disturbance and dispersal rates, landscape fragmentation, and other processes that influence migration rates and have been simulated at the sub-continent scale, but now at continental scales, and explore a range of alternative future climate scenarios as they continue to be developed.