Reservoirs impound and store large volumes of water and flood land. The water is used for electricity generation, irrigation, industrial and municipal consumption, flood control and to improve navigation. The decomposition of flooded soil and vegetation creates greenhouse gases and thus reservoirs are a source of greenhouse gases. Reservoirs are not well studied for greenhouse gas flux from the water to the atmosphere. The FLooded Upland Dynamics EXperiment (FLUDEX) involves the creation of three experimental reservoirs in the upland boreal forest to study greenhouse gas and mercury dynamics. The balance of biological processes, decomposition, primary production, CH₄ oxidation and the nitrogen cycle in the reservoirs controls the greenhouse gas flux from the reservoir to the atmosphere. Understanding the importance and controlling factors of these processes is vital to understanding the sources and sinks of greenhouse gases within reservoirs. The carbon and oxygen dynamics near the sediment-water interface are very important to the entire reservoir because many processes occur in this area. Light and dark benthic chambers were deployed, side-by-side, to determine the benthic flux of DIC and CH₄ across the sediment-water interface and to determine the role of benthic photoautotrophs in benthic DIC, CH₄ and O₂ cycling. Benthic chambers have shown photoautotrophs use the decomposing soil, rocks and exposed bedrock as a physical substrate to colonize and the CO₂ produced by the decomposing soil as a carbon source since the delta¹³C-DIC value of the DIC added to light chambers is enriched relative to dark chambers and net photosynthesis rates are linked to community respiration. Benthic photoautotrophs consume 15-33% of the potential DIC flux into the water column. CH₄ produced by the decomposition of soils is partially oxidized by methanotrophs that use the photosynthetically produced oxygen. The delta¹³C-CH₄ values of the CH₄ added to light chambers is enriched relative to dark chambers and 15-88% of the potential CH₄ flux into the water column is oxidized. An isotope-mass budget for DIC and CH₄ is presented for each reservoir to identify the importance of processes on areservoir scale. Input of DIC to the reservoirs from overland flow can be important because concentration is greater and delta¹³C-DIC values are depleted relative to inflow from Roddy Lake. Estimates of total reservoir primary production indicate that 3-19% of the total DIC production from decomposition is removed by photoautotrophs. The carbon cycling in biofilm and the importance of periphytic primary production needs to be better understood. Dissolved delta¹³C-CH₄ values of CH₄ in reservoir outflow enriched 45-60permil, indicating that CH₄ oxidation was an important CH₄ sink within the reservoirs. Stable carbon isotope data indicates that the CH₄ in the bubbles is partially oxidized so the site of bubble formation is the upper portion of the flooded soil. The fraction of CH₄ converted to CO₂ in the FLUDEX reservoirs is similar to that of the wetland flooded for the Experimental Lakes Area Reservoir Project (ELARP). Approximately half of the dissolved CH₄ in the FLUDEX reservoirs was removedby CH₄ oxidation. The ebullitive flux of CH₄ from FLUDEX reservoirs is reduced 25-75% by CH₄ oxidation. The CH₄ flux to the atmosphere from peat surface of the ELARP reservoir became less oxidized after flooding: 91% to 85% oxidized. The floating peat islands of the ELARP reservoir were less oxidized than the peat surface. Similar to the CH₄ in the FLUDEX reservoirs, CH₄ in the ELARP peat islands was oxidized 56%. CH₄ oxidation is an important process because it reduces the global warming potential of the greenhouse gas flux since CO₂ is less radiatively active than CH₄.

Production of hydrogen is primarily achieved via catalytic steam reforming, partial oxidation,and auto-thermal reforming of natural gas. Although these processes are mature technologies, they are somewhat complex and CO is formed as a by-product, therefore requiring a separation process if a pure or hydrogen-rich stream is needed. As an alternative method, supported metal catalysts can be used to catalytically decompose hydrocarbons to produce hydrogen. The process is known as catalytic cracking of hydrocarbons. Methane, the hydrocarbon containing the highest percentage of hydrogen, can be used in such a process to produce a hydrogen-rich stream. The decomposition of methane occurs on the surface of the active metal to produce hydrogen and filamentous carbon. As a result, only hydrogen is produced as a gaseous product, which eliminates the need of further separation processes to separate CO2 or CO. Nickel is commonly used in research as a catalyst for methane cracking in the 500-700C temperature range. To conduct methane catalytic cracking in a continuous manner, regeneration of the deactivated catalyst is required and circulation of the catalysts between cracking and regeneration cycles must be achieved. Different reactor designs have been successfully used in cyclic operation, such as a set of parallel fixed-bed reactors alternating between cracking and regeneration, but catalyst agglomeration due to carbon deposition may lead to blockage of the reactor and elevated pressure drop through the fixed bed. Also poor heat transfer in the fixed bed may lead to elevated temperature during the regeneration step when carbon is burned in air, which may cause catalyst sintering. A fluidized bed reactor appears as a viable option for methane catalytic cracking, since it would permit cyclic operation by moving the catalyst between a cracker and a regenerator. In addition, there is the possibility of using fine catalyst particles, which improves catalyst effectiveness. The aims of this project were 1) to develop and characterize a suitable nickel-based catalyst and 2) to develop a model for thermal catalytic decomposition of methane in a fluidized bed.

Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.

Despite the spatial significance of Canadas boreal forest, there is very little known about greenhouse gas emissions within it. The primary objective of this project was to study the atmosphere-soil exchange of CH4 and N2O in the boreal forest of central Saskatchewan. In the summers of 2006 and 2007, greenhouse gas emissions were measured along transects in three different mature forest stands (trembling aspen, black spruce and jack pine) using a sealed chamber method. In addition, the gross rates of mineralization and nitrification, and the relative contribution of nitrification and denitrification to N2O emissions, were measured at the trembling aspen site using a stable isotope technique in which 15N-enriched nitrate and ammonium were injected into intact soil cores. The amount of 14N found in the labeled pools was used to measure the gross rates, and the amount of 15N found in the emitted N2O was used to determine the relative contribution of the different N pathways to total N2O emissions. Results indicated that the jack pine and black spruce sites were slight sinks of CH4 (-1.23 kg CH4-C ha-1 yr-1and -0.17 kg CH4-C ha-1 yr-1 respectively in 2006 and -0.95 kg CH4-C ha-1 yr-1and 0.45 kg CH4-C ha-1 yr-1 respectively in 2007), whereas the trembling aspen site was a net source (46.7 kg CH4-C ha-1 yr-1 in 2006 and 196.0 kg CH4-C ha-1 yr-1 in 2007). All three sites had very low cumulative N2O emissions, ranging from -0.02 to 0.14 kg N2O-N ha-1 yr-1 in both years. Of the environmental controls examined for CH4, consumption at the jack pine site was correlated positively with organic carbon and negatively with water-filled pore space. Black spruce CH4 emissions were correlated negatively with both organic carbon and clay content, and emissions at the trembling aspen site were positively correlated with soil temperature and organic carbon, while also related to the presence of standing water (2006 and 2007 had very high precipitation, causing a high water table and ponding in depressions). The N2O emissions were not correlated with any of the environmental parameters measured at the jack pine or black spruce sites, but clay content was positively related to emissions at the trembling aspen site. The 15N results indicated that N cycling at the trembling aspen site was very rapid, allowing little N to escape the system as N2O; the majority of emissions that did occur were due to a nitrification-related process.

A new shock tube targeting low temperature, high pressure, and long test times was designed and installed at the Turbomachinery Laboratory in December of 2008. The single-pulse shock tube uses either lexan diaphragms or die-scored aluminum disks of up to 4 mm in thickness. The modular design of the tube allows for optimum operation over a large range of thermodynamic conditions from 1 to 100 atm and between 600-4000 K behind the reflected shock wave. The new facility allows for ignition delay time, chemical kinetics, high-temperature spectroscopy, vaporization, atomization, and solid particulate experiments. An example series of ignition delay time experiments was made on mixtures of CH4/C2H6/O2/Ar at pressures from 1 to 30.7 atm, intermediate temperatures from 1082 to 2248 K, varying dilutions (between 75 and 98% diluent), and equivalence ratios ranging from fuel lean (0.5) to fuel rich (2.0) in this new facility. The percentage by volume variation and equivalence ratios for the mixtures studied were chosen to cover a wide parameter space not previously well studied. Results are then used to validate and improve a detailed kinetics mechanism which models the oxidation and ignition of methane and other higher order hydrocarbons, through C4, with interest in further developing reactions important to methane- and ethane-related chemistry.

The primary goal of this research concerns the synthesis of organic ligands in an effort to create metal-organic porous materials for the storage of gas molecules for alternative energy applications as well as other applications such as catalysis, molecular sensing, selective gas adsorption and separation. Initially, the focus of this work was on the synthesis of metal-organic polyhedra, yet the research has to date not progressed past the synthesis of ligands and the theoretical polyhedron that may form. Further efforts to obtain polyhedra from these ligands need to be explored. Concurrently, the search for a metal-organic framework that hopefully breaks the record for methane adsorption at low pressure and standard temperature was undertaken. A framework, PCN-80, was synthesized based off a newly synthesized extended bianthracene derivative, yet was unstable to the atmosphere. Hydrogen and methane adsorption capacities have been evaluated by molecular simulations; these adsorption isotherms indicated a gravimetric hydrogen uptake of 9.59 weight percent and a volumetric uptake of methane of 78.47 g/L. Following the synthesis of PCN-80, a comparison study involving the effect of the stepwise growth of the number of aromatic rings in the ligand of a MOF was pursued; the number of aromatic rings in the ligand was varied from one to eight while still maintaining a linear, ditopic moiety. The synthesis of another bianthracene-based ligand was used to complete the series of ligands and PCN-81, a two-dimensional framework with no noticeable porosity as evident by the simulated hydrogen uptake of 0.68 weight percent, was synthesized. All of these MOFs were synthesized from zinc salts to reduce the number of variables. No clear relationship was established in terms of the number of aromatic rings present in the ligand and the hydrogen adsorption capacity. However, it was confirmed that the density and hydrogen uptake in weight percent are inversely proportional. Further work needs to be done to determine what advantages are offered by these novel frameworks containing extended bianthracene derivatives. For example, with the highly fluorescent nature of the ligands from which they are composed, both PCN-80 and PCN-81 should be studied for the potential use in the application of fluorescent materials.

Numerical reservoir simulation has been used to describe mechanism of methane gas desorption process, diffusion process, and fluid flow in a coalbed methane reservoir. The reservoir simulation model reflects the response of a reservoir system and the relationship among coalbed methane reservoir properties, operation procedures, and gas production. This work presents a procedure to select the optimum well spacing scenario by using a reservoir simulation. This work uses a two-phase compositional simulator with a dual porosity model to investigate well-spacing effects on coalbed methane production performance and methane recovery. Because of reservoir parameters uncertainty, a sensitivity and parametric study are required to investigate the effects of parameter variability on coalbed methane reservoir production performance and methane recovery. This thesis includes a reservoir parameter screening procedures based on a sensitivity and parametric study. Considering the tremendous amounts of simulation runs required, this work uses a regression analysis to replace the numerical simulation model for each wellspacing scenario. A Monte Carlo simulation has been applied to present the probability function. Incorporated with the Monte Carlo simulation approach, this thesis proposes a well-spacing study procedure to determine the optimum coalbed methane development scenario. The study workflow is applied in a North America basin resulting in distinct Net Present Value predictions between each well-spacing design and an optimum range of well-spacing for a particular basin area.

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (leaves 260-285).

Thesis (M.S. in E.A.S.)--School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 2004. Directed by Daniel Lizarralde. / Includes bibliographical references (leaves 69-73).

Countries around the world face social, economic, and ecological damage from escalating natural disasters caused by climate change. In an effort to curtail climate change impacts, local and regional governments are beginning to employ green house gas (GHG) mitigation strategies to reduce their carbon footprint. These strategies work to eliminate a range of GHG emissions from entering the atmosphere. Apart from carbon dioxide (CO₂), the most prevalent GHG is methane. In terms of global warming, methane is approximately 21 times more harmful to the atmosphere than CO₂. Natural gas systems, coal mining, manure management, rice cultivation, wastewater treatment, and landfills all contribute to methane generation. According to the US Environmental Protection Agency's 2011 US GHG inventory, landfills generate 1.5% of total GHG emissions in carbon dioxide equivalents. Recognizing the global impacts of its policies and operations, municipalities are working to reduce their GHG emissions. Coalitions like the C40 Cities Climate Leadership Group were created to specifically address GHG reductions, which will result in a 248 million MT reduction in GHGs released to the atmosphere by 2020. Guided by existing literature, this Master's Report calculates methane generation and transport to determine the effectiveness of applying two methane mitigation alternatives--passive methane oxidation biocovers (PMOBs) and landfill gas to energy technologies (LFGTE)--at an inactive landfill site to reduce GHG emissions. LFGTE generates energy for direct use such as space heating or industrial processes or for electricity generation. Cost-saving strategies abound for landfills which utilize LFGTE. PMOBs optimize the landfill surface soil cover environment to promote microbial growth of bacteria, called methanotrophs, which convert methane into carbon dioxide. When employed, these mitigation alternatives are designed to significantly reduce methane emissions from landfills. The EPA has developed a computer modeling program (LANDGEM) to aid in the calculation of landfill gas generation. A hypothetical case study of a one million ton landfill was created and modeled for methane generation over a 35 year period. With methane generation rates calculated, assessment of potential LFGTE was performed and methane oxidation rate calculations were made to determine the impact of a PMOB and LFGTE on net GHG emissions at the landfill. The overall GHG reductions with these engineering controls were two-thirds of the level a landfill without controls would emit. These results indicate that implementing methane mitigation steps at closed landfills throughout the world would yield significant reductions in GHG emissions. / text