DISSOLVED AND GASEOUS FLUXES OF CARBON AND NITROGEN FROM URBAN WATERSHEDS OF THE CHESAPEAKE BAY

Carbon and nitrogen loading to streams and rivers contributes to eutrophication as well as greenhouse gas (GHG) production in streams, rivers and estuaries. My dissertation consists of three research chapters, which examine interactions and potential trade-offs between water quality and greenhouse gas production in urban streams of the Chesapeake Bay watershed. My first research project focused on drivers of carbon export and quality in an urbanized river. I found that watershed carbon sources (soils and leaves) contributed more than in-stream production to overall carbon export, but that periods of high in-stream productivity were important over seasonal and daily timescales. My second research chapter examined the influence of urban storm-water and sanitary infrastructure on dissolved and gaseous carbon and nitrogen concentrations in headwater streams. Gases (CO2, CH4, and N2O) were consistently super-saturated throughout the course of a year. N2O concentrations in streams draining septic systems were within the high range of previously published values. Total dissolved nitrogen concentration was positively correlated with CO2 and N2O and negatively correlated with CH4. My third research chapter examined a long-term (15-year) record of GHG emissions from soils in rural forests, urban forest, and urban lawns in Baltimore, MD. CO2, CH4, and N2O emissions showed positive correlations with temperature at each site. Lawns were a net source of CH4 + N2O, whereas forests were net sinks. Gross CO2 fluxes were also highest in lawns, in part due to elevated growing-season temperatures. While land cover influences GHG emissions from soils, the overall role of land cover on this flux is very small (< 0.5%) compared with gases released from anthropogenic sources, according to a recent GHG budget of the Baltimore metropolitan area, where this study took place.

Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content

Incorporation of carbon nanostructures in metals is desirable to combine the strongly bonded electrons in the metal and the free electrons in carbon nanostructures that give rise to high ampacity and high conductivity, respectively. Carbon in copper has the potential to impact industries such as: building construction, power generation and transmission, and microelectronics. This thesis focuses on the structure and properties of bulk and thin films of a new material, Cu covetic, that contains carbon in concentrations up to 16 at.%. X-ray photoelectron spectroscopy (XPS) shows C 1s peak with both sp2 and sp3 bonded C measuring up to 3.5 wt.% (16 at.%). High resolution transmission electron microscopy and electron diffraction of bulk covetic samples show a modulated structure of ≈ 1.6 nm along several crystallographic directions in regions that have high C content suggesting that the carbon incorporates into the copper lattice forming a network. Electron energy loss spectra (EELS) from covetics reveal that the level of graphitization from the source material, activated carbon, is maintained in the covetic structure. Bulk Cu covetics have a slight increase in the lattice constant, as well as <111> texturing, or possibly a different structure, compared to pure Cu. Density functional theory calculations predict bonding between C and Cu at the edges and defects of graphene sheets. The electrical resistivity of bulk covetics first increases and then decreases with increasing C content. Cu covetic films were deposited using e-beam and pulsed laser deposition (PLD) at different temperatures. No copper oxide or any allotropes of carbon are present in the films. The e-beam films show enhanced electrical and optical properties when compared to pure Cu films of the same thickness even though no carbon was detected by XPS or EELS. They also have slightly higher ampacity than Cu metal films. EELS analysis of the C-K-edge in the PLD films indicate that graphitic carbon is transferred from the bulk into the films with uniform carbon distribution. PLD films exhibit flatter and higher transmittance curves and sheet resistance two orders of magnitude lower than e-beam films leading to a high figure of merit as transparent conductors.