"Figures, tables and the appendices appear in the volume II". / Bibliography: leaves 130-152. / 2 v. (152 leaves, [5] leaves of plates; [75] leaves) : ill. (some col.), col. maps ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Botany, 2001

Thesis (M.S.)--University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file viewed on (February 6, 2007) Includes bibliographical references.

Ice cores are considered the gold standard for recording past climate and biogeochemical changes. However, gas records derived from ice core analysis have until now been largely limited to centennial and longer timescales because sufficient temporal resolution and analytical precision have been lacking, except during rare times when atmospheric concentrations changed rapidly. In this thesis I used a newly developed methane measurement line to make high-resolution, high-precision measurements of methane during the late Holocene (2800 years BP to present). This new measurement line is capable of an analytical precision of < 3 ppb using ~120 g samples whereas the previous highest resolution measurements attained a precision of ± 4.1 ppb using 500-1500g samples [MacFarling Meure et al., 2006]. The reduced sample size requirements as well as automation of a significant portion of the analysis process have enabled me to make >1500 discrete ice core methane measurements and construct the highest resolution records of methane available over the late Holocene. Ice core samples came from the recently completed West Antarctic Ice Sheet (WAIS) Divide ice core which has as one of its primary scientific objectives to produce the highest resolution records of greenhouse gases, and from the Greenland Ice Sheet Project (GISP2) ice core which is a proven paleoclimate archive. My thesis has the following three components. I first used a shallow ice core from WAIS Divide (WDC05A) to produce a 1000 year long methane record with a ~9 year temporal resolution. This record confirmed the existence of multidecadal scale variations that were first observed in the Law Dome, Antarctica ice core. I then explored a range of paleoclimate archives for possible mechanistic connections with methane concentrations on multidecadal timescales. In addition, I present a detailed description of the analytical methods used to obtain high-precision measurements of methane including the effects of solubility and a new chronology for the WDC05A ice core. I found that, in general, the correlations with paleoclimate proxies for temperature and precipitation were low over a range of geographic regions. Of these, the highest correlations were found from 1400-1600 C.E. during the onset of the Little Ice Age and with a drought index in the headwater region of the major East Asian rivers. Large population losses in Asia and the Americas are also coincident with methane concentration decreases indicating that anthropogenic activities may have been impacting multidecadal scale methane variability. In the second component I extended the WAIS Divide record back to 2800 years B.P. and also measured methane from GISP2D over this time interval. These records allowed me to examine the methane Inter-Polar Difference (IPD) which is created by greater northern hemispheric sources. The IPD provides an important constraint on changes in the latitudinal distribution of sources. We used this constraint and an 8-box global methane chemical transport model to examine the Early Anthropogenic Hypothesis which posits that humans began influencing climate thousands of years ago by increasing greenhouse gas emissions and preventing the onset of the next ice age. I found that most of the increase in methane sources over this time came from tropical regions with a smaller contribution coming from the extratropical northern hemisphere. Based on previous modeling estimates of natural methane source changes, I found that the increase in the southern hemisphere tropical methane emissions was likely natural and that the northern hemispheric increase in methane emissions was likely due to anthropogenic activities. These results also provide new constraints on the total magnitude of pre-industrial anthropogenic methane emissions, which I found to be between the high and low estimates that have been previously published in the literature. For the final component of my thesis I assembled a coalition of scientists to investigate the effects of layering on the process of air enclosure in ice at WAIS Divide. Air bubbles are trapped in ice 60-100m below the surface of an ice sheet as snow compacts into solid ice in a region that is known as the Lock-In Zone (LIZ). The details of this process are not known and in the absence of direct measurements previous researchers have assumed it to be a smooth process. This project utilized high-resolution methane and air content measurements as well as density of ice, δ¹⁵N of N₂, and bubble number density measurements to show that air entrapment is affected by high frequency (mm scale) layering in the density of ice within the LIZ. I show that previous parameterizations of the bubble closure process in firn models have not accounted for this variability and present a new parameterization which does. This has implications for interpreting rapid changes in trace gases measured in ice cores since variable bubble closure will impact the smoothing of those records. In particular it is essential to understand the details of this process as new high resolution ice core records from Antarctica and Greenland examine the relative timing between greenhouse gases and rapid climate changes. / Graduation date: 2013

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The increased level of greenhouse gases due to human activity is the main factor for climate change. CO2 is the main constitute among these gases. Subsurface storage of CO2 in geological systems such as coal reservoirs is considered as one of the promising perspectives. Coal can be safely and effectively utilized to both store CO2 and recover CH4. By injecting CO2 into the coal beds, methane is released with CO2 adsorption in the coal matrix and this process is known as enhanced coal bed methane recovery (ECBM). Zonguldak Coal Basin is one of the Turkey&amp / #8217 / s important coal resources. Since the coal seams in Bartin-Amasra field are found relatively deeper parts of the basin comparing to other places, this basin was not studied detailed enough yet. Bartin-Amasra basin was found convenient for enhanced coalbed methane recovery. The lithologic information taken from the Turkish Hard Coal Enterprise (TTK) was examined and the depths of the coal seams and the locations of the wells were visualized to perform a reliable correlation between seams existed in the area. According to the correlations, 63 continuous coal layers were found. A statistical reserve estimation of each coal layer for methane was made by using Monte Carlo simulation method. Uncertainty is an important parameter in risk analysis, for this reason the results were determined at probabilities of P10, P50 and P90. Enhanced coalbed methane recovery was simulated with CMG-GEM module using Coal Layer #26 which has more initial gas in place. The effects of adsorption, cleat spacing, compressibility, density, permeability, permeability anisotropy, porosity and water saturation parameters were examined in enhanced coalbed methane recovery by the simulation runs. The initial methane in place found in all these coal layers both in free and adsorbed states were estimated using probabilistic calculations resulted in possible reserve (P10) of 72.97 billion scf, probable reserve (P50) of 47.74 billion scf and proven reserves (P90) of 30.46 billion scf. Since the Amasra coal reservoir is not saturated with water, almost 10% of the total gas in place was found to be in the cleats as free gas. Coal layer #26 has an area of 4099 acres, average thickness of 6.23 ft and depth of 545 m (Karadon formation). P50 reserve estimation was 6.47 billion scf in matrix and 0.645 billion scf in fracture. Although the decrease in cleat porosity was less when shrinkage and swelling effects included, the decrease in cleat permeability as a function of porosity diminished the methane production. Cumulative methane production was enhanced with the injection of carbon dioxide (ECBM) approximately 23% than that of CBM recovery. Although closing the wells to production because of CO2 breakthrough had a negative effect on methane production initially, there was no difference between ultimate methane productions whether the wells remained open or closed, but more carbon dioxide was sequestered when the production ceased at the wells. Injected carbon dioxide amount of 5192 tonnes/year in base case was only capable to sequester only 0.3% of the yearly carbon dioxide emission of Zonguldak &Ccedil / atalagzi Power Plant nearby. Considering the gas in place capacity of the coal layer #26 as 15% of the resource area-A, it can be said that the project aiming ECBM recovery rather than carbon dioxide sequestration would be successful. In spite of water saturated coal reservoirs where the water production is required initially, it can be possible to start immediately the injection of CO2 with methane production for a dry coal reservoir. Cleat permeability being one of the most crucial parameter in the coal reservoir affected the rate of methane production. The more free gas was found in higher porosity cleat systems. Although the cumulative methane production was increased when the cleat porosity rose, methane recovery percentages were remained almost constant. The lower the cleat spacing the higher the rate of transfer between fracture and matrix was observed. The rate of gas desorption from the coal matrix and subsequent diffusion to both butt and face cleats was higher than the rate of flow in the face cleats, then production was flow-limited, pressure-driven and was defined by Darcy&amp / #8217 / s Law. The cumulative CH4 production was higher when the coal was denser. The change in coal compressibility affected slightly the cleat porosity and therefore the cleat permeability due to the change in reservoir pressure. Langmuir volume is defined as maximum adsorption capacity. Kozlu formation (deeper than Karadon formation) having lower Langmuir volume resulted in higher ultimate recovery because of lower Langmuir pressure than that of Karadon formation. In base case (Karadon formation), although the higher Langmuir volume was used, less methane production was observed. Permeability anisotropy generated the CO2-CH4 front in elliptic shape.

Title from PDF of title page. / Document formatted into pages; contains 70 pages. / Thesis (M.Ch.E.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: SiC is a hard man-made material and has emerged as an excellent material for a wide range of applications which are exposed to extreme conditions such as high temperatures and harsh chemical environments. These applications range from SiC being used as an abrasive, to a refractory material, to a semiconductor material for high power and high frequency electronic devices. The properties of the material for each application is different, with the semiconductor grade material for electronic devices being the most refined. SiC, with its excellent thermal properties and high resistance to harsh chemical environments, lends itself to being an ideal support for catalyst systems. / ABSTRACT: Various characterisation & analysis techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography (GC) are used in this thesis to investigate the suitability of single crystal SiC for high temperature catalytic systems. Low temperature oxidation of methane was used to investigate the catalytic activity of: - Porous and standard 4H-SiC with and without Pd - Porous and Standard 6H-SiC with and without Pd. - Nanocrystalline Beta-SiC powder with and without Pd. Part of the samples were impregnated with Pd using Palladium Nitrate (Pd (NO3)2) which is a common precursor for Pd. Activation treatments which were investigated were oxidation and reduction. Oxidation was generally better in activating the catalyst, as was expected, since the PdO phase is known to be more active in oxidising methane. / ABSTRACT: A mixed set of Pd and PdO were observed by SEM and EDS which were the main characterisation techniques used to analyze the structure of the catalysts before and after the reaction. The Beta-SiC showed by far the best activity which could be attributed to the micro-crystalline powder format in which it was used, where as all other catalysts studied here were derived from crushed wafer pieces. Type II porous 4H-SiC was another of the samples which registered impressive results, vis-à-vis catalytic activity. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

No description available.

Extreme environments created through natural and anthropogenic processes harbor microbes with diverse physiologies capable of catalyzing chemical reactions which are environmentally beneficial on local and global scales. This work focused on two unique environments, the Gulf of Mexico (GoM) submarine mud volcano systems and the subsurface soils at the Department of Energy s (DOE) Field Research Center (FRC) located in the Oak Ridge National Laboratory Reservation (Oak Ridge, TN). In addition to the physical and chemical extremes present within mud volcano sediments and FRC subsurface soils, these environments are sources of greenhouse gases as well as metal/radionuclide contaminants, respectively. Within the previously uncharacterized mud volcano cold seep sediments, culture-independent analyses of microbial community structure via DNA and RNA clone libraries indicated Gammaproteobacteria and anaerobic methane oxidizing Archaea as the dominant methane oxidizing taxa. Culture-dependent studies of FRC subsurface Arthrobacter and Bacillus isolates demonstrated extensive lateral gene transfer of the PIB-type ATPase metal resistance genes. Additionally, FRC Bacillus and Rahnella isolates demonstrated U(VI) sequestration capabilities as up to 95% soluble U(VI) was immobilization via biogenic phosphate mineral production resulting from constitutive nonspecific phosphohydrolase activity. Findings from these studies identify the prokaryotic diversity within aquatic and terrestrial sediments that contribute to the geochemical cycling of carbon, metals, and radionuclides.

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2007. / Härtill 4 uppsatser.

Natural gas is stored as compressed natural gas (CNG) in heavy steel cylinders under pressures of 200-250 atm. However, such a method of storage has certain disadvantages which include multistage compression costs, limited driving range and safety aspects. Hence, alternative methods of storage such as adsorbed natural gas (ANG) which involve adsorbing natural gas at moderate pressures and room temperatures in a suitable nanoporous material are currently being explored. In this thesis, we have isolated model carbon nanostructures and defect geometries most likely to be found in these materials and investigated their specific interactions with methane. The thesis is concerned with ab-initio density functional theory calculations on these various model carbon nanostructures in order to identify the potential candidates that enhance methane adsorption. The adsorption energies of methane on graphite and graphene sheets were similar, with a value of 12.3 kJ/mol for graphene. The Stone-Wales defect in graphene was found to increase the methane adsorption energy to 37.2 kJ/mol, and small surface undulations on the graphene sheet resulted in a smaller increase (16 kJ/mol) in the adsorption energy relative to graphene. The presence of an interstitial carbon was found to significantly reduce the adsorption energy to 5.2 kJ/mol. The enhanced adsorption energy in the case of the Stone-Wales defect was attributed to the significant charge redistribution in the vicinity of the defect. A variety of functional groups such as carboxylic acid (COOH), carbonyl (CO), phenol (OH), pyran (-O-), phenone (=O), peroxide (OOH) and amine (NH2) groups have been observed on carbon surfaces. Extensive density functional calculations of methane adsorbed on various chemically functionalized graphene nanoribbons were carried out to evaluate their methane adsorption energies. A significant finding in this study, is the increased adsorption energies (relative to graphene) that occur for the functional groups containing the OH moiety. The adsorption energies for edge functionalized graphene nanoribbons are 27.6 and 69.7 kJ/mol for COOH and OOH functionalization. Additional computations reveal a strong correlation between the induced dipole moment on methane and the strength of the adsorption energies obtained for the extended nanoribbons. Adsorption isotherms for methane were obtained using grand canonical Monte Carlo simulations for slit-like graphitic pores with and without functional groups. For both OH and COOH functionalized graphite, we observe more than a 40 % increase in the volumetric loading over bare graphite for the highest weight % of the functional group and smallest pore width considered. The maximum volumetric loading decreases with a decrease in the wt% of the functional groups and with an increase in the pore width.