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Permanently sequestering carbon dioxide (CO2) in gas-bearing shale formations is beneficial in that it can mitigate greenhouse gas emissions as well as enhance gas recovery in production wells. This is possible due to the sorption properties of the organic material within shales and their greater affinity for CO2 over methane. The phenomenon of preferentially adsorbing CO2 while desorbing methane has been proven in coalbed reservoirs successfully, and is feasible for shale formations. The objective of this thesis is to explore the potential for enhanced gas recovery from gas-bearing shale formations by injecting CO2 into a targeted shale formation. With the advancement of technologies in horizontal drilling combined with hydraulic fracturing, shale gas has become a significant source of energy throughout the United States. With over 6,000 trillion cubic feet (Tcf) of theoretical gas-in-place, Appalachia has proven a major basin for gas production from organic shales. With its extensive shale reserves and lack of conventional reservoirs typically used for CO2 storage, Appalachia's unconventional reservoirs are favorable candidates for CO2 storage with enhanced gas recovery. Enhancing gas recovery not only increases reserves, but extends the life of mature wells and fields throughout the basin. As part of this research, 510 tons of CO2 were successfully injected into a horizontal production well completed in the Chattanooga shale formation, a late Devonian shale, in Morgan County, Tennessee. An extensive monitoring program was implemented during the pre-injection baseline, injection, soaking, and flowback phases of the test. Multiple fluorinated tracers were used to monitor for potential CO2 breakthrough at offset production wells and to help account for the CO2 once the well was flowed back. Results from this test, once the well was put back into normal production state, confirm the injectivity and storage potential of CO2 in shale formations, as well as an increase in gas production rate and quality of gas produced. / Master of Science

Since the MINER Act of 2006, the minimum static load of in-situ underground mine seals has been increased from 20-psi to either 50-psi if monitoring is conducted or 120-psi if left unmonitored. These minimum strength requirements in seals must be designed, built, and maintained throughout the lifetime of the seal. Due to this, it has become necessary to assess the effectiveness of non-destructive testing (NDT) technologies to determine seal integrity, which in this case, are explored using sonic waves and tracer gases. Through both small and large scale testing, two NDT methods were evaluated on their abilities to determine integrity of the seal. A sonic wave technique to observe a change in wave velocity to identify faults within the seal material. As a NDT method, tracer gases may be used as a potential indicator of a connection between both sides of the seal material through a series of faults and cracks within the material itself. This paper reviews the history of underground mine seals and discusses the overall assessment of sonic waves and tracer gases to serve as NDT methods for estimating the integrity of these seals. / Master of Science

Currently, techniques used to determine whether or not there is a concealed fire in an inaccessible area of a coal mine are not definitive. Inaccessible areas of coal mines include: 1. A mined-out area, such as a long-wall gob. 2. A mine area, or entire mine, that has been sealed to extinguish a fire. 3. The interior of pillars in a mine. 4. Abandoned mines. Mined-out areas — gobs — are particularly problematic. The standard practice is to obtain measurements for certain gas concentrations from an inaccessible area, and to apply certain rules to the obtained concentrations in order to try to decipher whether or not there is a fire in the area. Unfortunately, none of the gas measurements, and the associated rules that are applied, are free of potential problems. Therefore, there is always some degree of uncertainty in any decision that is based on the current methods. A more definitive method of determining whether or not a concealed fire exists would be valuable; perhaps avoiding unnecessary exposure of miners to risks, and unnecessary exposure of mining companies to economic loss. This study details the inadequacies of the current methods for determining the presence of a fire in an inaccessible area of a coal mine, and proposes two novel methods for overcoming the current inadequacies. The first method that was studied involves looking for the presence of the radioisotope carbon-fourteen in the carbon monoxide in the return airways of coal mines. For the vast majority of coal mines, if there is no fire anywhere in the coal mine, carbon monoxide should not have any carbon-fourteen in it. If there is a fire, the carbon monoxide should have carbon-fourteen in it. This method is based on the Boudouard Reaction, which documents a reaction between carbon, carbon monoxide, and carbon dioxide that only occurs at temperatures that only occur with a fire. Because of the very small amounts of carbon-fourteen in carbon dioxide in the atmosphere, and the small amount of carbon monoxide usually present in a coal mine atmosphere, there does not appear to be any way, currently, to implement this method. Instrumentation that may allow implementation of this method, in the future, is discussed. The second method, that was studied, involves introducing a select, gaseous, organic compound into an inaccessible area; and then using a gas chromatograph to test for the presence of definitive fire decomposition products of the initial organic compound in the atmosphere that is exiting the inaccessible area. Laboratory tests, conducted as part of this study, established the concept of this novel method of using select, organic compounds for definitively determining whether or not a concealed fire exists in an inaccessible part of a coal mine. Based on an initial screening of 5 different compounds, two compounds have been selected for use as 'fire indicator gases' with the acronym of 'FIGs.' These two compounds are: 1. C6-Perfluoroketone (CF3CF2C(=O)CF(CF3)2 ) 2. 1,1 Difluoroethane (CH3CHF2) This study provides suggestions as to how to look for other potential FIGs, and how to improve the testing of potential FIGs. Examples of all four of the types of inaccessible areas listed above are discussed, particularly from the viewpoint of how FIGs could be utilized in each case, and how FIGs could provide better information in each case. In addition, as a by-product of the experiments conducted for this work, this study identifies at least six gases that might be used simultaneously as tracer gases for complex ventilation studies in a mine, or elsewhere. / Ph. D.