UMD Theses and Dissertations
Permanent URI for this collectionhttp://hdl.handle.net/1903/3
New submissions to the thesis/dissertation collections are added automatically as they are received from the Graduate School. Currently, the Graduate School deposits all theses and dissertations from a given semester after the official graduation date. This means that there may be up to a 4 month delay in the appearance of a given thesis/dissertation in DRUM.
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Item Optical Properties of Marine and Picocyanobacteria-derived Dissolved Organic Matter in the Atlantic, Pacific and during Long-term Incubation Experiments(2022) Lahm, Madeline Amelia; Gonsior, Michael; Marine-Estuarine-Environmental Sciences; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Marine dissolved organic matter (DOM) is a large, dynamic, and complex pool of carbon, comparable in size to the carbon dioxide pool in the atmosphere, yet it is arguably the least understood component of the global carbon cycle. DOM deriving from picocyanobacterial cells via situationally unique mechanisms, such as viral lysis and metazoan grazing, complicate the picture as the resident pool present reflects sequestration processes that occur at time scales ranging from days to hundreds of thousands of years. Recently virus induced cell lysis released from the globally distributed picocyanobacteria, such as Synechococcus and Prochlorococcus, have been shown to release optically active DOM known as Chromophoric DOM (CDOM) that closely matches the “humic-like” appearance of marine CDOM raising questions about our understanding of this carbon pool given the reliance on spectral measures to assess its composition. Hence, this thesis is seeking to understand CDOM released by lysed picocyanobacteria and to investigate the molecular chemical composition of picocyanobacteria-derived DOM in general. A special focus will be to confirm the refractory nature of chromophores released by lysed picocyanobacteria (Synechococcus) given the reliance on optical properties of recalcitrant DOM being used in the investigation of timescales of carbon storage and biological processing of carbon. As we consider the outcomes of the current global carbon inventory with a sizable error in flux, linking products of microbial processes to chromophore structures and spectrometry is a capstone in understanding the global carbon cycle for decades of research. This study offers a direct comparison of fluorescence signatures from the Bermuda Atlantic Time-Series (BATS) and the Hawai'i Ocean Time-series (HOT), observes optical and nutrient profiles tracking long-term incubation experiments of oligotrophic microbial communities amended with Synechococcus-derived DOM, and explores new techniques in DOM solid-phase extraction (SPE). This work is part of a National Science Foundation project - The Fate of Lysis Products of Picocyanobacteria Contributes to Marine Humic-like Chromophoric Dissolved Organic Matter – linking the accumulating evidence of picocyanobacterial-derived DOM to our understanding of marine organic carbon. Furthermore, we seek to understand how picocyanobacteria-derived DOM is degraded and what role changing heterotrophic microbial communities plays. This research is important to the concept of a microbial carbon pump that supplies a constrained and constant source of DOM which has important implications for the marine carbon cycle and its role in global climate.Item Soil microbial processes and community structure in natural and restored tidal freshwater wetlands of the Chesapeake Bay, Maryland, USA(2017) Maietta, Christine E.; Yarwood, Stephane A.; Baldwin, Andrew H.; Environmental Science and Technology; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Tidal freshwater wetlands are integral to downstream water quality because they capture, store, and transform nutrients. Unfortunately, anthropogenic stressors are negatively impacting these habitats. While wetland restoration is helping to reinstate their presence in the landscape, restored wetlands frequently differ physically, chemically, and biologically from their natural counterparts. This research examined plant, soil, and microbe relationships and how their interactions affect soil carbon (C) storage and cycling in natural and restored tidal freshwater wetlands of the Chesapeake Bay, MD, USA. This research yielded important findings regarding differences between natural and restored habitats. First, we discovered soil microbial community composition of an urban tidal freshwater wetland retained similar composition as their less disturbed, suburban counterpart, and wetland sites constructed using similar restoration methodology produced similar microbial community structure and soil function. Additional research revealed that a natural and a restored wetland store soil C quite differently: A majority of soil C in the natural site was associated with large macroaggregates (> 2000 μm) whereas most soil C in the restored site was associated with smaller macroaggregates (> 250 to < 2000 μm). The distributions of six chemical compound classes (i.e., carboxylics, cyclics, aliphatics, lignin derivatives, carbohydrates derivatives, N-containing compounds) were relatively similar across the five soil fractions from both sites, however. In the final study, anaerobic laboratory mesocosms were used to evaluate the effects of clay content (%) and leaf litter quality on soil C cycling processes over time. This study found restored soils, regardless of clay content, mineralized more C as carbon dioxide (CO2) and methane (CH4) compared to natural wetland soils. Natural soils respired approximately half the volume of gas as restored soils, suggesting the addition of high- or low-quality C substrates to low C systems elicit a greater response from the heterotrophic microbial community. The results of these three studies suggest site history and edaphic features of restored wetlands are important drivers of microbial communities and their function. We propose that practitioners and researchers work together to identify practices that will enhance soil functions, particularly C storage, in tidal freshwater wetlands of the Chesapeake Bay region.Item LAND USE AND LAND COVER CHANGE AS A DRIVER OF ECOSYSTEM DEGRADATION ACROSS BIOMES(2016) Noojipady, Praveen; Prince, Stephen D; Geography; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The expansion and intensification of agricultural production in human-dominated landscapes threaten efforts to sustain natural ecosystems and maintain agricultural production in a changing climate. Long-term use of agricultural lands, combined with conversion of natural ecosystems for agricultural production, can rapidly degrade the health of remaining natural ecosystems. The fundamental goal of this dissertation was to assess the impacts of anthropogenic degradation on stocks and sequestration of carbon. Although degradation alters a range of ecosystem services, case studies of ecosystem degradation in this dissertation focus on reductions in vegetation productivity, carbon stocks, and the extent of natural forest cover as a result of human activity. Time series of satellite remote sensing data were used to track forest and rangeland degradation in the southwestern United States, forest carbon emissions from cropland expansion in the Brazilian Cerrado, and fire-driven forest conversion for oil palm plantations in Southeast Asia. Three major themes link the regional case studies: expansion and intensification of agricultural production, market demand and certification, and agricultural management in response to climate variability. Conclusions from the dissertation underscore the widespread influence of land management on vegetation productivity and forest carbon stocks. In the Southwest United States, reductions in net primary production on managed lands were higher in forested landscapes than other cover types. In contrast, Native American Indian Reservations, often considered to be more degraded, actually had smaller absolute reductions in net primary productivity during 2000-2011. Multi-year droughts in the southwest present new challenges for managing forests and rangelands, and climate projections suggest dry conditions will intensify in the coming century. In Southeast Asia, industry-led efforts to certify sustainable palm oil production were evaluated using satellite data on fires and forest loss. Rates of fire-driven deforestation and total fire activity declined following certification, highlighting the potential for certification to reduce ignitions during El Niño years and protect remaining fragments of lowland and peat forest. Aligning certification criteria for sustainable palm oil with satellite monitoring capabilities may help accelerate compliance with environmental legislation and market demands for deforestation-free products. In Brazil, government and industry actions to limit Amazon deforestation have largely overlooked the neighboring Cerrado biome. Forest carbon emissions from deforestation for soy expansion in the Cerrado increased substantially after the implementation of the Soy Moratorium in the Brazilian Amazon, partially offsetting recent reductions in Amazon deforestation carbon emissions. The success of policies to support sustainable agricultural production therefore depends on efforts to minimize cross-biome leakage and the ability to monitor compliance and unintended consequences. Solutions for management must also confront the growing influence of climate variability. Time series of satellite data may allow early detection of degradation impacts and support efforts to mitigate the influence of sustained agricultural production on natural systems. Changes in vegetation carbon stocks from ecosystem degradation varied across case studies, underscoring the diverse nature of direct and indirect drivers of degradation across different land use systems. Direct human drivers of ecosystem degradation in the southwest United States from management of livestock grazing resulted in gradual changes in vegetation productivity, whereas mining and oil extraction areas showed large and permanent reductions. Forest carbon emissions from agriculture expansion in the Cerrado were a one-time process, as native vegetation is cleared for cropland expansion. In contrast, the carbon emissions from Southeast Asia’s forest and peatland conversion involve both sudden and gradual processes, as carbon accumulation in oil palm plantations partially compensates for emissions from forest conversion. Overall, this research made contributions to understanding of the regional impacts of human activity and the potential for climate change mitigation from sustainable land use practices in human-dominated landscapes.Item Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content(2016) Isaacs, Romaine Antonio; Salamanca-Riba, Lourdes G; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)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.Item DISSOLVED AND GASEOUS FLUXES OF CARBON AND NITROGEN FROM URBAN WATERSHEDS OF THE CHESAPEAKE BAY(2016) Smith, Rose Marie; Kaushal, Sujay S; Geology; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)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.Item Mechanical and electrical properties of metal-carbon connections for battery applications(2014) Bilger, Christopher John; Bruck, Hugh A; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Material selection and processing techniques were investigated to form carbon-metal bonds. Mechanical and electrical characterization was performed to more fully comprehend the bonding mechanisms and properties. Utilizing carbon fibers as a primary conduction medium, the specimens from the processes investigated were utilized with lithium-ion cells to further characterize the electrical performance. Electroplating nickel onto the ends of the carbon fibers provides a relatively simple processing technique which improves fiber adhesion to nickel tabs by over 4.7 times when compared to conductive silver epoxy and over 5 times greater than a 1 inch immersion of carbon fiber into a SAC305 solder ingot. Additionally, a reduction of electrical resistance by 0.7 times over the solder ingot is achieved with the electroplating technique. The results of the electroplating are achieved by using about 25% less available contact area than the solder ingot and are scalable for usage in electrical circuits.Item Carbon Sequestration and Agents of Woody Encroachment in Southeastern Arizona Semi-arid Grasslands(2014) O'Neal, Kelley; Justice, Christopher; Geography; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Woody encroachment and proliferation within dryland ecosystems is potentially the second largest portion of the North American carbon sink and one of the largest areas of uncertainty. This dissertation examines a semi-arid grassland located in southeastern Arizona to better understand woody encroachment, agents of change, and the resultant carbon storage from 1984-2008. The objectives were to quantify changes in woody cover, rank agent importance, estimate carbon density, and calculate voluntary market value. The first objective of mapping changes in woody cover was addressed using a Landsat time-series to measure woody cover and calculate the change, rate of change, and change relative to initial cover over the 25-year time period. Results show the change in woody cover varies spatially and ranges from approximately -2 to 11% with most areas experiencing a 5% increase and 92% relative increase over initial cover, indicating woody cover nearly doubled in the region. The second objective of ranking the importance of agents was achieved using an ensemble classifier. Agents examined included grazing, number of times burned, soil texture, soil productivity, elevation, slope, aspect, and initial woody cover. Initial woody cover, number of times burned, elevation, and grazing were ranked as the most important agents of woody encroachment, indicating the importance of historical land management and disturbance, frequent fire, topography and correlated precipitation, and land use. The third objective of producing carbon estimates and calculating economic opportunity in the voluntary carbon markets was accomplished by applying cover to biomass, root:shoot, and carbon equations to the final woody plant cover maps to calculate carbon stocks, carbon density, and voluntary market value. Results show very low carbon density in the study area relative to similar ecosystems and other ecosystems in general. Given the insignificant annual accumulation of carbon on the small ownership parcels, current low carbon trading prices, and high beef prices, management for storage is not economically viable in the study area at this time.Item A TOOL FOR QUANTIFYING THE CARBON FOOTPRINT OF CONSTRUCTION PROJECTS IN THE TRANSPORTATION SECTOR(2010) Melanta, Suvish; Hooks, Elise M; Civil Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The U.S. construction industry ranks third in the nation in its production of carbon dioxide emissions. Increasing global pressure towards developing emissions reduction strategies is bound to affect the construction industry. The objective of this thesis was to develop a tool to estimate the carbon footprint of construction projects associated with transportation infrastructure. The tool determines emissions from an inventory of equipment, construction processes, and credits efforts to reduce emissions, while incorporating recent and future greenhouse gas (GHG) policies on quantifying emissions. This tool will enable construction companies to identify sources and reduce emissions, while also allowing state agencies to monitor these companies in accordance with GHG laws. The tool was applied to data associated with the construction of the Intercounty Connector, a new roadway that will connect counties in Maryland. Application of the tool to this case study showed its utility and highlighted the need for reduction strategies.Item Processing-Structure-Microstructure-Property Relationships in Polymer Nanocomposites(2008-01-31) Kota, Arun Kumar; Bruck, Hugh A; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The optimal development of polymer nanocomposites using carbon nanotube (CNTs) and carbon nanofiber (CNFs) fillers requires a complete understanding of processing-structure-property relationships. The purpose of this understanding is to determine the optimal approach for processing polymer nanocomposites with engineered microstructures and enhanced material properties. In this research, two processing techniques were investigated: solvent processing and twin screw extrusion. The former is a batch process which employs mixing a polymer solution with a filler suspension using long mixing times and low levels of shear mixing. The latter is a continuous process that mixes polymer melts with solid nanoscale ingredients using high levels of shear mixing for a short mixing time. Previous studies conducted on polymer-CNT/CNF using these processes have focused mainly on processing-microstructure and structure-property relationships using one technique or the other. This research focuses on understanding the processing-property relationships by comparing the structure-property relationships resulting from the two processes. Furthermore, the effect of ingredients and processing parameters within each process on microstructure and structure-property relationships was investigated. The microstructural features, namely, distribution of agglomerates, dispersion, alignment, and aspect ratio of the filler were studied using optical, scanning electron, confocal and transmission electron microscopy, respectively. The composition of the filler was determined using thermogravimetric analysis. The electrical, rheological, thermo-oxidative and mechanical properties of the composites were also investigated. Many significant insights related to processing-structure-property relationships were obtained including: (a) deagglomeration is a critical combination of the magnitude of shear rate and the residence time, (b) the structure-property relationships can be modeled using a new methodology based on the degree of percolation by representing the material as an interpenetrating phase composite, (c) annealing can re-establish interconnectivity and improve electrical properties, (d) the degree of dispersion can be resolved using thermogravimetric analysis, and (e) increasing extrusion speed inhibits thermal decomposition and begins to asymptotically increase strength and stiffness through reduction in aspect ratio and size of agglomerates. Finally, a new combinatorial approach was developed for rapidly determining processing-structure relationships of polymer nanocomposites. This dissertation has broad implications in the processing of high performance and multifunctional polymer nanocomposites, combinatorial materials science, and histopathology.