In the late spring of 2008, the Chevron-led Gulf of Mexico Gas Hydrate Joint Industry Project (JIP) expects to conduct an exploratory drilling and logging campaign to better understand gas hydrate-bearing sands in the deepwater Gulf of Mexico. The JIP Site Selection team selected three areas to test alternative geological models and geophysical interpretations supporting the existence of potential high gas hydrate saturations in reservoir-quality sands. The three sites are near existing drill holes which provide geological and geophysical constraints in Alaminos Canyon (AC) lease block 818, Green Canyon (GC) 955, and Walker Ridge (WR) 313. At the AC818 site, gas hydrate is interpreted to occur within the Oligocene Frio volcaniclastic sand at the crest of a fold that is shallow enough to be in the hydrate stability zone. Drilling at GC955 will sample a faulted, buried Pleistocene channel-levee system in an area characterized by seafloor fluid expulsion features, structural closure associated with uplifted salt, and abundant seismic evidence for upward migration of fluids and gas into the sand-rich parts of the sedimentary section. Drilling at WR313 targets ponded sheet sands and associated channel/levee deposits within a minibasin, making this a non-structural play. The potential for gas hydrate occurrence at WR313 is supported by shingled phase reversals consistent with the transition from gas-charged sand to overlying gas-hydrate saturated sand. Drilling locations have been selected at each site to 1) test geological methods and models used to infer the occurrence of gas hydrate in sand reservoirs in different settings in the northern Gulf of Mexico; 2) calibrate geophysical models used to detect gas hydrate sands, map reservoir thicknesses, and estimate the degree of gas hydrate saturation; and 3) delineate potential locations for subsequent JIP drilling and coring operations that will collect samples for comprehensive physical property, geochemical and other analyses

Gas hydrate investigations are converging on a suite of common techniques for hydrate observation and quantification. Samples retrieved and analyzed at full in situ pressures are the ”gold standard” with which the physical and chemical analysis of conventional cores, as well as the interpretation of geophysical data, are calibrated and groundtruthed. Methane mass balance calculations from depressurization of pressure cores provide the benchmark for gas hydrate concentration assessment. Nondestructive measurements of pressure cores have removed errors in the estimation of pore volume, making this methane mass balance technique accurate and robust. Data from methane mass balance used to confirm chlorinity baselines makes porewater freshening analysis more accurate. High-resolution nondestructive analysis of gas-hydratebearing cores at in situ pressures and temperatures also provides detailed information on the in situ nature and morphology of gas hydrate in sediments, allowing better interpretation of conventional core thermal images as well as downhole electrical resistivity logs. The detailed profiles of density and Vp, together with spot measurements of Vs, electrical resistivity, and hardness, provide background data essential for modeling the behavior of the formation on a larger scale. X-ray images show the detailed hydrate morphology, which provides clues to the mechanism of deposit formation and data for modeling the kinetics of deposit dissociation. Gashydrate- bearing pressure cores subjected to X-ray tomographic reconstruction provide evidence that gas hydrate morphology in many natural sedimentary environments is particularly complex and impossible to replicate in the laboratory. Even when only a small percentage of the sediment column is sampled with pressure cores, these detailed measurements greatly enhance the understanding and interpretation of the more continuous data sets collected by conventional coring and downhole logging. Pressure core analysis has become the keystone that links these data sets together and is an essential component of modern gas hydrate investigations.

The past decade has witnessed dramatic changes in the oil and gas industry with the drilling and production extending into progressively deeper waters and higher operating pressures, therefore making it essential to gain a better understanding of the behaviour of gas hydrate at high pressure conditions. New experimental 3-phase H−LW−V (Hydrate−Liquid Water−Vapour) equilibrium data for nitrogen and H−LW−V (Hydrate−Liquid Water−Vapour) and H−LW−LHC (Hydrate−Liquid Water−Liquid Hydrocarbon) data for ethane and propane simple clathrate hydrates were generated by a reliable fixed-volume, isochoric, step-heating technique. The accuracy and reliability of the experimental measurements are demonstrated by comparing measurements with reliable literature data from different researchers. Additional experimental data up to high pressure (200 MPa when available) for CH4, C2H6, C3H8, i-C4H10, N2, Ar, Kr, Xe, H2S, O2, CO and CO2 clathrates have been gathered from literature. The Valderrama modification of the Patel-Teja (VPT) equation of state combined with non-density-dependent (NDD) mixing rules is used to model the fluid phases with previously reported binary interaction parameters. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. Langmuir constants have been calculated by both Kihara potential as well as direct techniques. Model predictions are validated against independent experimental data and a good agreement between predictions and experimental data is observed, supporting the reliability of the developed model.

In order to evaluate a methane gas productivity of methane hydrate reservoirs, it is necessary to develop a numeric simulator predicting gas production behavior. For precise assessment of long-term gas productivity, it is important to develop a mathematical model which describes mechanical behaviors of methane hydrate reservoirs in consideration of their time-dependent properties and to introduce it into the numeric simulator. In this study, based on previous experimental results of triaxial compression tests of Toyoura sand containing synthetic methane hydrate, stress-strain relationships were formulated by variable-compliance-type constitutive model. The suggested model takes into account the time-dependent property obtained from laboratory investigation that time dependency of methane hydrate bearing sediment is influenced by methane hydrate saturation and effective confining pressure. Validity of the suggested model should be verified by other laboratory experiments on time-dependent behaviors of methane hydrate bearing sediment.

Gashydrate sind natürlich vorkommende feste Verbindungen aus Wasser und Gas, deren Erschließung als zukünftige Energiequelle von Interesse ist. Für die bohrtechnische Erschließung mariner Gashydratlagerstätten ist eine leistungsfähige Bohrspülung notwendig. Das vom Bohrmeißel gelockerte Sediment und darin enthaltenes Gashydrat werden durch die Bohrspülung nach übertage transportiert. Die Gashydratpartikel verlassen beim Aufsteigen im Ringraum in ca. 300 m Wassertiefe ihren Stabilitätsbereich und dissoziieren in Wasser und Gas. Um eine Verdünnung und eine Dichteerniedrigung der Bohrspülung zu verhindern, soll das Gashydratbohrklein stabilisiert werden. Gleichzeitig darf sich in der Bohrspülung bei Anwesenheit von freiem Gas in der Lagerstätte kein neues Gashydrat bilden. Die Arbeit beschäftigt sich mit der Suche nach Additiven, welche die Gashydratneubildung und -dissoziation gleichzeitig hemmen. Es wurde ein Schüttelautoklav genutzt, um die Dissoziationstemperatur von Methanhydrat bei ca. 85 bar zu ermitteln und die Verzögerung des Hydratzerfalls bei Anwesenheit verschiedener Additive zu vergleichen. Es konnte ein Additiv gefunden werden, das diese Anforderungen erfüllt. Des Weiteren wurden neue rheologische Untersuchungsprogramme für verschiedene Spülungstypen erarbeitet, die eine detaillierte Charakterisierung der Fließfähigkeit, Thixotropie und Geleigenschaften von Bohrspülungen erlauben.

Gashydratlagerstätten sind in Permafrostgebieten und unter dem Meeresboden zu finden. Das energetische Potential der weltweiten Gashydratvorkommen, vor allem im submarinen Bereich, ist enorm. Derzeit existiert aber noch keine Technologie mit der sie kommerziell erschlossen werden können. Die größten Herausforderungen bei der bohrtechnischen Erschließung submariner Gashydratlagerstätten werden in der Richtbohrtechnik in geringverfestigten Sedimenten, der Bohrlochstabilität, der Einhaltung eines sehr engen Druckfensters sowie in der Vermeidung ungewollter Dissoziationsvorgänge während des Bohrprozesses gesehen. In der Arbeit werden mögliche Ansätze für die bohrtechnische Erschließung von submarinen Gashydratlagerstätten, speziell für das gerichtete Bohren in unkonsolidierten Formationen, zusammengetragen. Es werden verschiedene Erschließungskonzepte diskutiert und schließlich wird die Machbarkeit von zwei Bohrkonzepten untersucht. Das erste Konzept zielt in erster Linie auf die Herstellung vertikaler Bohrungen zu Produktionstestzwecken in Gashydratlagerstätten ab. Auf Grundlage eines vorhandenen Meeresbodenbohrgerätes wird eine neuartige Technologie entwickelt, mit der eine Tiefsee-Gashydratbohrung abgeteuft, verrohrt und komplettiert werden kann, ohne dass eine Bohrplattform oder ein Bohrschiff eingesetzt werden muss. Das zweite Konzept beinhaltet die Herstellung von horizontalen Produktionsbohrungen für eine kommerzielle Gashydratnutzung. Es wird untersucht, ob und unter welchen Bedingungen solche Bohrungen mit konventionellem Equipment machbar sind. Es wird aufgezeigt, dass die Herausforderungen gemeistert werden können und die bohrtechnische Erschließung submariner Gashydratlagestätten mit beiden Konzepten grundsätzlich machbar erscheint.

The study focuses mainly on two gas hydrate-related targets, located on the Northern Cascadia Margin, offshore Vancouver Island: (1) a recently identified 70-80-m high carbonate mound, Cucumber Ridge, located ~3.5-km west of Ocean Drilling Program (ODP) Site 889 and Integrated Ocean Drilling Program (IODP) Site U1327, and (2) a large cold vent, Bullseye vent, which is up to ~500 m in diameter and was drilled by IODP at Site U1328. The objective of this thesis is to analyze seismic data that provide indicators of locally focused fluid flow and characteristics of the gas hydrate occurrence associated with these two features. A grid of closely-spaced single channel seismic (SCS) data was collected at Cucumber Ridge in July/August 2001, and deep-towed multichannel seismic (MCS) lines were collected using Deep-towed Acoustics and Geophysics System (DTAGS) at the Bullseye vent area and at Cucumber Ridge in October 2002. The high-resolution SCS data, with a frequency bandpass of 40-150 Hz, recorded coherent reflectivity down to about 400 m beneath the seafloor, and provide excellent images of the subseafloor structure of Cucumber Ridge and of the gas hydrate bottom-simulating reflector (BSR) beneath it. Cucumber Ridge is interpreted to have developed as a structural topographic high in the hanging wall of a large reverse fault formed at the base of the current seaward slope. The fault zone provides pathways for fluids including gas to migrate to the seafloor where diagenetic carbonate forms and cements the near-surface sediments. Over the seismic grid, heat flow was derived from the depth of the BSR. A simple 2-D analytical correction for theoretical heat flow variations due to topography is applied to the data. Across the mound, most of the variability in heat flow is explained by topographic effects, including a local 6 mW/m2 negative anomaly over the central mound and a large 20 mW/m2 positive anomaly over the mound steep side slope. However, just south of the mound, there is a 6-7 mW/m2 positive anomaly in a 2-km-long band that has predominantly flat seafloor. Most of this anomaly is probably unrelated to topographic effects, but rather likely due to warm upward fluid flow along faults or fracture zones. Towed ~300 m above seafloor, the high frequency (220-1k Hz) DTAGS signal can provide high vertical resolution images with increased lateral resolution. The major problems of DTAGS are significant nonlinear variations of the source depths and receivers locations. New routines were developed for optimal DTAGS data processing, mainly including (1) cable geometry estimation by node depths, direct arrivals and seasurface reflections using a Genetic Algorithm inversion method, (2) acoustic image stitching based on accurate relative-source positioning by crosscorrelation of redundant data between two adjacent shots, and (3) velocity inversion of wide-angle traveltimes using a nonlinear global grid search method. The final processed DTAGS images resolve multiple seismic blanking zones and fine details of subseafloor features in the slope sediments. At Bullseye vent, where a 35-m-thick near-surface massive hydrate layer was drilled at U1328, the DTAGS data resolved the upper part of layer as a dipping diffraction zone, likely corresponding to a fracture zone. The inverted velocity structure in upper 100 m sediments successfully revealed a 17-m-thick layer of high velocity (~1650 m/s) just below seafloor, probably related to carbonate presence. A local high velocity zone, with a positive velocity anomaly of ~40-80 m/s in the upper 50 m beneath seafloor, was observed over the ~100-m wide region between U1328 and the deepest part of a seafloor depression; the high velocity zone is consistent with the dipping diffraction zone in the DTAGS image and with the massive hydrate drilled at U1328.

This thesis work is directed at estimating gas hydrate and free gas distribution and saturation in local structures in the Ulleung Basin, East Sea offshore Korea. The estimates are obtained from a 2-D multi-channel seismic (MCS) reflection profile from the basin. Firstly, structures of locally focused upwelling fluid and gas flow were imaged using time-migrated sections and seismic attributes, and secondly seismic velocities were obtained to estimate gas hydrate and free gas saturations. The structures investigated are up to 1 km across, and are characterized by reduced reflectivity (‘blank zones’) and pulled-up sediment reflectors on the seismic sections. Throughout the study, a comparison is made between the blank zones and areas outside them where not much gas hydrate or gas is expected, to examine their peculiar characteristics as related to the formation of gas hydrate and underlying free gas. The regional depth of possible occurrence of gas hydrate and free gas is determined by predicting the base of the gas hydrate stability zone (BGHSZ) from sediment properties and heat flow estimates calibrated by a few bottom-simulating reflectors (BSRs) from outside the analyzed seismic section. A large number of normal moveout (stacking) velocity profiles were obtained within and outside the blank zones. Interval velocities were then derived by applying the commonly used unconstrained Dix equation as well as by applying constraints to inversion using regularized linear inversion and non-linear Bayesian inversion. The latter method fully explores the uncertainty of the interval velocity estimates. Compared to areas outside the blank zones, the velocities within the blank zones are up to 30% larger at about 30 m above the BGHSZ and up to 65% smaller immediately below the BGHSZ. The velocity increase implies a gas hydrate saturation of 10-40% of the pore space. The velocity decrease implies a free gas saturation of 1-4% of the pore space. Their detailed distribution within individual structures cannot be resolved. Reflector pull-up in time sections in the hydrate zone allows an independent velocity estimate, assuming the pull-up is solely a velocity effect. The implied velocity is much higher than the interval velocity estimates, so there also must be physical deformation. The heat flow estimated depth of the BGHSZ is in good agreement with the transition from gas hydrate to free gas as inferred from seismic velocities. The general conclusion of the thesis work is that a variety of careful analyses of MCS data that characterize the seismic signal and estimate the seismic velocity structure can provide insight into gas hydrate and free gas occurrences. The large amounts of gas hydrate and free gas associated with the blank zones inferred by this study should draw special attention to future energy and climate effects in this area and other similar regions.

Substantial amounts of methane are sequestered in naturally occurring ice-like formations known as gas hydrates. In particular, oceanic gas hydrates are globally distributed in complex heterogeneous ecosystems that typically occur at depths exceeding 300 m. Gas hydrates have received attention for their potential as an alternative energy resource, as marine geohazards, and their role in cycling of greenhouse gases. In addition, chemosynthetic communities often play a vital role in the cycling and sequestration of carbon emanating from cold hydrocarbon seeps surrounding hydrate sites. Research efforts are presently striving to better understand the significance and complexity of these ecosystems through the establishment of seafloor observatories capable of long-term monitoring with integrated sensor networks. In this thesis, infrared (IR) spectroscopy has been implemented for the investigation of molecular-specific signatures to monitor gas hydrate growth dynamics and evaluate carbonate minerals, which are intimately connected with complex chemosynthetic processes occurring in these harsh environments. The first fundamental principles and data evaluation strategies for monitoring and quantifying gas hydrate growth dynamics utilizing mid-infrared (MIR) fiber-optic evanescent field spectroscopy have been established by exploiting the state-responsive IR absorption behavior of water. This has been achieved by peak area evaluation of the O-H stretch, H-O-H bend, and libration modes and assessing peak shifts in the 3rd libration overtone and libration bands during the formation and dissociation of simple clathrate hydrates of methane, ethane, and propane formed from aqueous solution. Hydrate growth and monitoring was facilitated with a customized pressure cell enabling operation up to ~5.9 MPa with spectroscopic, temperature, pressure, and video monitoring capabilities. Furthermore, the initial feasibility for extending the developed IR spectroscopic hydrate monitoring strategies into oceanic gas hydrate ecosystems has been demonstrated through the evaluation of potential spectroscopic interferences from sediment matrices in samples collected from two hydrate sites in the Gulf of Mexico (GoM). With exception of the libration band, the primary IR absorption features of water are readily accessed within hydrated sediment samples. Additional consideration for potential long-term hydrate monitoring applications revealed that the collection of approx. 2 IR spectra per day should enable direct insight into the temporal dynamics of hydrates...

The current theoretical understanding of thermodynamics of clathrate hydrates is based on the van der Waals and Plattew (vdWP) theory developed using statistical thermodynamics approach. vdWP theory has been widely used to predict the phase equilibrium of clathrate hydrates over the decades. However, earlier studies have shown that this success could be due to the presence of a large number of parameters. In this thesis, a systematic and a rigorous analysis of vdWP theory is per-formed with the help of Monte Carlo molecular simulations for methane hydrate. The analysis revealed that long range guest-water interactions and guest-guest interactions are important, Monte Carlo integration to is superior to the spherical shell approximation for the Langmuir constant calculation and even after inclusion of all the interactions and using Monte Carlo integration for Langmuir constant, the vdWP theory still fails to regress parameters correctly. This failure of vdWP theory is attributed to the rigid water lattice approximation. To address the rigid water lattice approximation, a new method is proposed. In the proposed method, the Langmuir constant is computed in flexible water lattice, by considering the movement of water molecules. The occupancy values predicted using the proposed method are in excellent agreement with the values obtained from Monte Carlo molecular simulations for variety of hydrates, methane, ethane, carbon dioxide and tetrahydrofuran(THF) hydrates . In addition to small guest molecules like methane, ethane etc. which are mod- heled as rigid, the method is extended for large guest molecules like propane and isobutane, using configurationally bias Monte Carlo method. The phase equilib-rium and occupancy along the phase equilibrium predictions from vdWP theory are compared with the exact phase equilibrium computed from Monte Carlo molecular simulations. This comparison is done for a wide variety of hydrate systems, single hydrates , binary hydrates and quaternary hydrate. In all the cases, the vdWP theory with the flexible water lattice showed significant improvement over the rigid lattice model with significantly less absolute relative deviations in pressure. Guest-cavity interactions for hydrates are calculated using abinitio calculations. In general, these guest-cavity interaction from first principle calculations are used to develop classical force field parameters in alternative to Lorentz-Berthelot rule. In the study, comparison of guest-cavity interactions from MP2 and CCSD(T) methods revealed that less expensive MP2 method, which is generally used, is insouciant to capture the dispersion interactions accurately. These guest-cavity interactions using CCSD(T) method extrapolated to complete basis set are used to model the interaction parameters between cyclopropane and water. The potential parameters obtained from ab-initio calculations are used in the calculation of Langmuir constant using vdWP theory. Langmuir constant calculated using vdWP theory with flexible water lattice gave close agreement with the values obtained from experimental occupancy data. In addition, simulation methodology to calculate ternary hydrate phase equilibrium is extended for binary hydrates. Simulations have been successful in the prediction of sIsII and sII-sI structural transitions as observed in experiments. Predicted methane-ethane binary hydrate is also compared with the available experimental phase equilibrium data. The phase equilibrium obtained from simulations showed very good qualitative agreement with the experimental data.