This thesis studies the monohydrate, dihydrate and in some cases, trihydrate of five carboxylic acids, namely acetic acid, propanoic acid, T-difluoroacetic acid, Gdifluoroacetic acid and trifluoacetic acid using the technique of Fourier tranform microwave spectroscopy. The rotational and centrifugal distortion constants of these hydrates were determined with high accuracy. Ab initio calculations were also performed to locate the different conformational minima of the hydrates and to optimize their structures. Comparison of the ab initio predicted rotational and centrifugal distortion constants with the experimentally observed values allows us to determine the structures of the global minimum conformations of the various hydrates without ambiguity. Hydrogen-bonded ring structures are found to be the predominant feature in all observed hydrates. In this structural arrangement, all the hydrogen bonds formed are located in the same ring, and the cooperativity effect between them significantly strengthens each hydrogen bond, as suggested by the sharp increase of their binding energies in the larger hydrates. The fine and hyperfine splittings observed in the specrum were also successfully analyzed, which allows information on the dynamics of the intramolecular large amplitude tunnelling motions to be extracted explicitly. In the final part of this thesis, the equilibrium constants for the formation of monohydrates of the different carboxylic acids involved in this thesis, together with that of formic acid whose microwave spectrum has been analyzed elsewhere, were calculated to approximately derive their abundances under typical atmospheric conditions. It was found that about 2% of FMA, ACA and PPA will complex with one H2O molecule to form monohydrates in the low troposphere, while for TFA, the value increases to about 15%, mainly as a result of the larger binding energy of TFA–(H2O) due to fluorination on the end group.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Différentes études ont été réalisées depuis les années 1778 pour étudier la formation des clathrates hydrates de gaz, notamment dans des conditions de haute pression et de basse température pour reproduire les conditions de production pétrolière. Mon travail de thèse concerne principalement l’étude du comportement thermodynamique des hydrates d’hydrocarbures gazeux : CO2 CH4, C2H6, C3H8, et C4H10, pris purs ou bien en mélanges. Les résultats expérimentaux de ce travail, complétés des résultats expérimentaux de la littérature, ont été utilisé afin d’optimiser les paramètres interne du modèle thermodynamique lié à la base de données du logiciel GasHyDyn.Ce modèle optimise les paramètres de Kihara, et nous permet dans un deuxième temps de conserver, ou bien d’écarter tel ou tel jeu de données, considéré comme des points d’équilibres, ou bien des points hors équilibre.Nous discutons finalement de la raison de la nature hors équilibre de certains points, considérés pourtant par leurs auteurs comme des points d’équilibres. Cette nature nous semble liée à des considérations cinétiques d’une compétition entre les différents gaz pour intégrer la structure hydrate en cours de croissance. / Many studies have been conducted since 1778’s to study the formation of clathrate hydrates of gas, especially under conditions of high pressure and low temperature to reproduce the conditions of oil production. My thesis mainly concerns the study of the thermodynamic of gas hydrates in presence of hydrocarbon: CO2 CH4, C2H6, C3H8, and C4H10 pure or in gas mixtures. The experimental results of this work complete the literature experimental results, were used to optimize the internal parameters related to the thermodynamic model data base GasHyDyn software.This model optimizes the parameters of Kihara and allows us to retain a second time , or to exclude a particular data set, considered as points of equilibrium , or balance points out .We finally discuss the reason for non-equilibrium of certain points, however, considered by their authors as equilibrium points. This seems kind of kinetic considerations related to a competition between gas hydrate structure to integrate during growth .

Dans les gisements, en cours de production ou dans les conduites de transport, les gaz naturels se trouvent fréquemment au contact d'une phase aqueuse. Les conditions sont telles que les pressions peuvent atteindre de très haute valeur dans une large gamme de températures. La connaissance du comportement des systèmes "eau-hydrocarbures" est donc essentielle à la profession profession pétrolière ainsi que celles des systèmes "eau-hydrocarbures-inhibiteur thermodynamique " pour lesquelles les données sont rares. Des mesures de teneur en eau ont été réalisées dans les phases vapeurs de différents systèmes d'hydrocarbures: méthane et éthane, et dans un mélange d'hydrocarbures gazeux (méthane 94%, éthane 4%, n-butane 2%) dans des conditions proches de la formation d'hydrates (de 258.15 à 313.15 K et jusqu'à 34.5 MPa) en présence ou non d'inhibiteurs tels que le méthanol ou l'éthylène glycol. Des mesures de solubilités de gaz des principaux constituants du gaz naturel ont été effectuées dans une large gamme de pressions et de températures. Ces mesures ont été effectuées avec deux techniques expérimentales, une technique statique-analytique avec échantillonnage de phases et une technique synthétique avec cellule à volume variable. Pour réaliser le traitement des données un logiciel a été développé, ce logiciel a permis l'ajustement et le traitement des résultats expérimentaux.

The depth of the sulfate-methane transition (SMT) above gas hydrate systems is a direct proxy to interpret upward methane flux and hydrate saturation. However, two competing reaction pathways can potentially form the SMT. Moreover, the pore water profiles across the SMT in shallow sediment show broad variability leading to different interpretations for how carbon, including CH4, cycles within gas-charged sediment sequences over time. The amount and distribution of marine gas hydrate impacts the chemistry of several other dissolved pore water species such as the dissolved inorganic carbon (DIC). A one-dimensional (1-D) numerical model is developed to account for downhole changes in pore water constituents, and transient and steady-state profiles are generated for three distinct hydrate settings. The model explains how an upward flux of CH4 consumes most SO42- at a shallow SMT implying that anaerobic oxidation of methane (AOM) is the dominant SO42- reduction pathway, and how a large flux of 13C-enriched DIC enters the SMT from depth impacting chemical changes across the SMT. Crucially, neither the concentration nor the d13C of DIC can be used to interpret the chemical reaction causing the SMT. The overall thesis objective is to develop generalized models building on this 1-D framework to understand the primary controls on gas hydrate occurrence. Existing 1-D models can provide first-order insights on hydrate occurrence, but do not capture the complexity and heterogeneity observed in natural gas hydrate systems. In this study, a two-dimensional (2-D) model is developed to simulate multiphase flow through porous media to account for heterogeneous lithologic structures (e.g., fractures, sand layers) and to show how focused fluid flow within these structures governs local hydrate accumulation. These simulations emphasize the importance of local, vertical, fluid flux on local hydrate accumulation and distribution. Through analysis of the fluid fluxes in 2-D systems, it is shown that a local Peclet number characterizes the local hydrate and free gas saturations, just as the Peclet number characterizes hydrate saturations in 1-D, homogeneous systems. Effects of salinity on phase equilibrium and co-existence of hydrate and gas phases can also be investigated using these models. Finally, infinite slope stability analysis assesses the model to identify for potential subsea slope failure and associated risks due to hydrate formation and free gas accumulation. These generalized models can be adapted to specific field examples to evaluate the amount and distribution of hydrate and free gas and to identify conditions favorable for economic gas production.

Numerous glacial advances over the past 2 million years have covered the entire Canadian and Fennoscandian Shield outcrop. During glacial advance and retreat, permafrost is expected to form in front of the glacier. The question of how permafrost and freezing impact the formation and evolution of brines in natural systems may be vital to understanding the chemistry of groundwater in crystalline rocks. Investigations of groundwater conditions beneath thick permafrost can provide valuable information that can be applied to assessing safety of deep, underground nuclear waste repositories and understanding analogues to potential life-bearing zones on Mars. However, very little scientific investigation of cryogenic processes and hydrogeology deep within crystalline systems has been published. The purpose of this research is to evaluate the impacts of thick permafrost (>300m) formation on groundwater chemical and flow system evolution in the crystalline rock environment over geologic timescales. A field investigation was conducted at the Lupin Mine in Nunavut, Canada, to characterize the physical and hydrogeochemical conditions within and beneath a thick permafrost layer. Taliks, or unfrozen channels within the permafrost, are found beneath large lakes in the field area, and provide potential hydraulic connections through the permafrost. Rock matrix waters are dilute and do not appear to affect groundwater salinity. Permafrost waters are Na-Cl and Na-Cl-SO4 type, and have been contaminated with chloride and nitrate by mining activities. Sulfide oxidation in the permafrost may be naturally occurring or is enhanced by mining activities. Basal permafrost waters (550 to 570 mbgs) are variably affected by mining. The less contaminated basal waters have medium sulfate concentrations and are Ca-Na dominated. This is similar to deeper, uncontaminated subpermafrost waters, which are Ca-Na-Cl or Na-Ca-Cl type with a wide range of salinities (2.6 to 40 g•L-1). The lower salinity subpermafrost waters are attributed to dissociation of methane hydrate and drawdown of dilute talik waters by the hydraulic gradient created by mine dewatering. This investigation was unable to determine the influence of talik waters to the subpermafrost zone in undisturbed conditions. Pressures are also highly variable, and do not correlate with salinity. Fracture infillings are scarce and calcite δ18O and δ13C values have a large range. Microthermometry indicates a large range in salinities and homogenization temperatures as well, indicative of a boiling system. In situ freezing of fluids and methane hydrate formation may have concentrated the remaining fluids. Field activities at the Lupin mine also provided an opportunity to study the nature of gases within crystalline rocks in a permafrost environment. Gases were generally methane-dominated (64 to 87), with methane δ13C and δ2H values varying between -56 and -42‰ VPDB and -349 to -181 ‰ VSMOW, respectively. The gases sampled within the Lupin mine have unique ranges of chemical and isotopic compositions compared with other Canadian and Fennoscandian Shield gases. The gases may be of thermogenic origin, mixed with some bacteriogenic gas. The generally low δ2H-CH4 ratios are somewhat problematic to this interpretation, but the geologic history of the site, a metaturbidite sequence, supports a thermogenic gas origin. The presence of gas hydrate in the rock surrounding Lupin was inferred, based on temperature measurements and hydrostatic pressures. Evidence also suggests fractures near the mine have been depressurized, likely due to mine de-watering, resulting in dissipation of methane hydrate near the mine. Modeling results indicate methane hydrates were stable throughout the Quaternary glacial-interglacial cycles, potentially limiting subglacial recharge. The effects of deep permafrost formation and dissipation during the Pleistocene glacial/interglacial cycle to deep groundwaters in the Canadian Shield were also investigated by compiling data from thirty-nine sites at twenty-four locations across the Canadian Shield. Impacts due to glacial meltwater recharge and surficial cryogenic concentration of fluids, which had been previously considered by others, and in situ freeze-out effects due to ice and/or methane hydrate formation were considered. At some Canadian Shield sites, there are indications that fresh, brackish, and saline groundwaters have been affected by one of these processes, but the data were not sufficient to differentiate between mixed, intruded glacial meltwaters, or residual waters resulting from either permafrost or methane hydrate formation. Physical and geochemical data do not support the cryogenic formation of Canadian Shield brines from seawater in glacial marginal troughs. The origin and evolution of Canadian and Fennoscandian Shield brines was explored with a survey of chlorine and bromine stable isotope ratios. The δ37Cl and δ81Br isotopic ratios varied between -0.78 ‰ and 1.52 ‰ (SMOC) and 0.01 ‰ and 1.52 ‰ (SMOB), respectively. Variability of chlorine and bromine isotope ratios decreases with increasing depth. Fennoscandian Shield groundwaters tend to be more enriched than Canadian Shield groundwaters for both 37Cl and 81Br. Other sources and processes which may affect δ37Cl and δ81Br composition are also explored. Primary processes such as magmatic and/or hydrothermal activity are thought to be responsible for the isotopic composition of the most concentrated fluids at each site. Positive correlations between δ81Br, and δ37Cl with δ2H-CH4 and δ13C-CH4 were noted. At this time the cause of the relationship is unclear, and may be a result of changing redox, pH, temperature, and/or pressure conditions during hydrothermal, metamorphic, or volcanogenic processes. The data suggest solute sources and fluid evolution at individual sites would be better constrained utilizing a multi-tracer investigation of δ37Cl, δ81Br, and 87Sr/86Sr ratios comparing fluids, rocks, and fracture filling minerals (including fluid inclusions).

Numerous glacial advances over the past 2 million years have covered the entire Canadian and Fennoscandian Shield outcrop. During glacial advance and retreat, permafrost is expected to form in front of the glacier. The question of how permafrost and freezing impact the formation and evolution of brines in natural systems may be vital to understanding the chemistry of groundwater in crystalline rocks. Investigations of groundwater conditions beneath thick permafrost can provide valuable information that can be applied to assessing safety of deep, underground nuclear waste repositories and understanding analogues to potential life-bearing zones on Mars. However, very little scientific investigation of cryogenic processes and hydrogeology deep within crystalline systems has been published. The purpose of this research is to evaluate the impacts of thick permafrost (>300m) formation on groundwater chemical and flow system evolution in the crystalline rock environment over geologic timescales. A field investigation was conducted at the Lupin Mine in Nunavut, Canada, to characterize the physical and hydrogeochemical conditions within and beneath a thick permafrost layer. Taliks, or unfrozen channels within the permafrost, are found beneath large lakes in the field area, and provide potential hydraulic connections through the permafrost. Rock matrix waters are dilute and do not appear to affect groundwater salinity. Permafrost waters are Na-Cl and Na-Cl-SO4 type, and have been contaminated with chloride and nitrate by mining activities. Sulfide oxidation in the permafrost may be naturally occurring or is enhanced by mining activities. Basal permafrost waters (550 to 570 mbgs) are variably affected by mining. The less contaminated basal waters have medium sulfate concentrations and are Ca-Na dominated. This is similar to deeper, uncontaminated subpermafrost waters, which are Ca-Na-Cl or Na-Ca-Cl type with a wide range of salinities (2.6 to 40 g•L-1). The lower salinity subpermafrost waters are attributed to dissociation of methane hydrate and drawdown of dilute talik waters by the hydraulic gradient created by mine dewatering. This investigation was unable to determine the influence of talik waters to the subpermafrost zone in undisturbed conditions. Pressures are also highly variable, and do not correlate with salinity. Fracture infillings are scarce and calcite δ18O and δ13C values have a large range. Microthermometry indicates a large range in salinities and homogenization temperatures as well, indicative of a boiling system. In situ freezing of fluids and methane hydrate formation may have concentrated the remaining fluids. Field activities at the Lupin mine also provided an opportunity to study the nature of gases within crystalline rocks in a permafrost environment. Gases were generally methane-dominated (64 to 87), with methane δ13C and δ2H values varying between -56 and -42‰ VPDB and -349 to -181 ‰ VSMOW, respectively. The gases sampled within the Lupin mine have unique ranges of chemical and isotopic compositions compared with other Canadian and Fennoscandian Shield gases. The gases may be of thermogenic origin, mixed with some bacteriogenic gas. The generally low δ2H-CH4 ratios are somewhat problematic to this interpretation, but the geologic history of the site, a metaturbidite sequence, supports a thermogenic gas origin. The presence of gas hydrate in the rock surrounding Lupin was inferred, based on temperature measurements and hydrostatic pressures. Evidence also suggests fractures near the mine have been depressurized, likely due to mine de-watering, resulting in dissipation of methane hydrate near the mine. Modeling results indicate methane hydrates were stable throughout the Quaternary glacial-interglacial cycles, potentially limiting subglacial recharge. The effects of deep permafrost formation and dissipation during the Pleistocene glacial/interglacial cycle to deep groundwaters in the Canadian Shield were also investigated by compiling data from thirty-nine sites at twenty-four locations across the Canadian Shield. Impacts due to glacial meltwater recharge and surficial cryogenic concentration of fluids, which had been previously considered by others, and in situ freeze-out effects due to ice and/or methane hydrate formation were considered. At some Canadian Shield sites, there are indications that fresh, brackish, and saline groundwaters have been affected by one of these processes, but the data were not sufficient to differentiate between mixed, intruded glacial meltwaters, or residual waters resulting from either permafrost or methane hydrate formation. Physical and geochemical data do not support the cryogenic formation of Canadian Shield brines from seawater in glacial marginal troughs. The origin and evolution of Canadian and Fennoscandian Shield brines was explored with a survey of chlorine and bromine stable isotope ratios. The δ37Cl and δ81Br isotopic ratios varied between -0.78 ‰ and 1.52 ‰ (SMOC) and 0.01 ‰ and 1.52 ‰ (SMOB), respectively. Variability of chlorine and bromine isotope ratios decreases with increasing depth. Fennoscandian Shield groundwaters tend to be more enriched than Canadian Shield groundwaters for both 37Cl and 81Br. Other sources and processes which may affect δ37Cl and δ81Br composition are also explored. Primary processes such as magmatic and/or hydrothermal activity are thought to be responsible for the isotopic composition of the most concentrated fluids at each site. Positive correlations between δ81Br, and δ37Cl with δ2H-CH4 and δ13C-CH4 were noted. At this time the cause of the relationship is unclear, and may be a result of changing redox, pH, temperature, and/or pressure conditions during hydrothermal, metamorphic, or volcanogenic processes. The data suggest solute sources and fluid evolution at individual sites would be better constrained utilizing a multi-tracer investigation of δ37Cl, δ81Br, and 87Sr/86Sr ratios comparing fluids, rocks, and fracture filling minerals (including fluid inclusions).

The dependency on fossil fuels faces resource limitations and sustainability concerns. This situation requires new strategies for greenhouse gas emission management and the development of new sources of energy. This thesis explores fundamental concepts related to carbon geological storage, including CO2-CH4 replacement in hydrate-bearing sediments. In particular it addresses the following phenomena: - Interfacial tension and contact angle in CO2-water-mineral and CH4-water-mineral systems. These data are needed to upscale pore phenomena through the sediment porous network, to define multiphase flow characteristics in enhanced gas recovery operations, and to optimize the injection and storage CO2 in geological formations. - Coupled processes and potential geomechanical implications associated to CH4-CO2 replacement in hydrate bearing sediments. Results include physical monitoring data gathered for CH4 hydrate-bearing sediments during and after CO2 injection. - Performance of cap rocks as trapping structures for CO2 injection sites. This study focuses on clay-CO2-water systems and CO2 breakthrough through highly compacted fine-grained sediments. Long term experiments help evaluate different sediments according to their vulnerability to CO2, predict the likelihood and time-scale of breakthrough, and estimate consequent CO2 leaks.

No description available.

Studies of geologic and geophysical data from the offshore of India have revealed two geologically distinct areas with inferred gas hydrate occurrences: the passive continental margins of the Indian Peninsula and along the Andaman convergent margin. The Indian National Gas Hydrate Program (NGHP) Expedition 01 was designed to study the occurrence of gas hydrate off the Indian Peninsula and along the Andaman convergent margin with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. NGHP Expedition 01 established the presence of gas hydrates in Krishna- Godavari, Mahanadi and Andaman basins. The expedition discovered one of the richest gas hydrate accumulations yet documented (Site 10 in the Krishna-Godavari Basin), documented the thickest and deepest gas hydrate stability zone yet known (Site 17 in Andaman Sea), and established the existence of a fully-developed gas hydrate system in the Mahanadi Basin (Site 19).