Understanding the formation conditions of seep carbonate is crucial to better constrain the dynamic fluid flow and chemical fluxes associate with cold seeps on the seafloor. Rare earth element (REE) in seep carbonates collected from modern cold seeps of Gulf of Mexico, Black Sea, Congo Fan, ancient seeps of Beauvoisin (Oxfordian, J3, Southeastern France) and Marmorito (Miocene, Northern Italy) were studied. Our focus has been on 5% HNO3-treated solution (authigenic carbonate minerals) of carbonates. Several crystalline forms of carbonate minerals have been selected for analysis. Total REE (ΣREE) contents in seep carbonates varies widely, from 0.068 to 43.655 ppm, but the common trend is that the ΣREE in microcrystalline phases is highest and lowest of in sparite, suggesting that the ΣREE of seep carbonates may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates show varied Ce anomalies across several seep sites and even within one site, suggesting that the formation condition of seep carbonate is variable and complex. Overall, our results show that apart from anoxic, oxic formation condition is also common at hydrocarbon seep environments.

Stable isotope of natural gas hydrates provides useful information of their gas sources. We investigated the isotopic fractionation of gas molecules during the formation of synthetic gas hydrates composed of methane and ethane. The gas hydrate samples were experimentally prepared in a pressure cell and isotopic compositions (δ13C and δD) of both residual and hydratebound gases were measured. δD of hydrate-bound molecules of methane and ethane hydrates was several per mil lower than that of residual gas molecules in the formation processes, while there was no difference in the case of δ13C. Effect of temperature on the isotopic fractionation was also investigated and it was found that the fractionation was effective at low temperature.

Enormous amount of latent heat generates/absorbs at the formation/dissociation process of gas hydrates and controlls their thermal condition themselves. In this paper we investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. It has been reported by researchers that a structure II gas hydrate appears in appropriate gas composition of methane and ethane. We confirmed by using Raman spectroscopy that our samples had the following three patterns: structure I only, structure II only and mixture of structures I and II. Dissociation heats of the mixed-gas hydrates were within the range between those of pure methane and ethane hydrates and increased with ethane concentration. In most cases two peaks of heat flow appeared and the dissociation process was divided into two parts. This can be understood in the following explanation that (1) the sample contained both crystal structures, and/or (2) ethane-rich gas hydrate formed simultaneously from dissociated gas and showed the second peak of heat flow.

Dissociation and specific heats of synthetic methane and ethane hydrates were measured under high-pressure condition by using a heat-flow type calorimeter to understand thermodynamic properties of gas hydrates under submarine/sublacustrine environments. Ice powder was put into the sample cell and pressurized by methane and ethane up to 5MPa and 2MPa, respectively. After the completion of gas hydrate formation, samples were heated from 263K to 288K at the rate of 0.01 K min-1. Large negative peaks of heat flow corresponded to the dissociation of gas hydrates were detected in a temperature range 279-282K at a pressure of 5MPa for methane hydrate and 283-286K at 2MPa for ethane hydrate, respectively. We also obtained the specific heats of gas hydrates in the range 264-276K for methane and 264-282K for ethane under pressure.

Natural gas hydrates occur on most continental margins in organic-rich sediments at water depths >450 m (in polar regions >150 m). Gas hydrate distribution and abundance, however, varies significantly from margin to margin and with tectonic environment. The National Gas Hydrate Program (NGHP) Expedition 01 cored 10 sites in the Krishna-Godawari (K-G) basin, located on the southeastern passive margin of India. The drilling at the K-G basin was comprehensive, providing an ideal location to address questions regarding processes that lead to variations in gas hydrate concentration and distribution in marine sediments. Pore fluids recovered from both pressurized and non-pressurized cores were analyzed for salinity, Cl-, SO4 2-, alkalinity, Ca2+, Mg2+, Sr2+, Ba2+, Na+, and Li+ concentrations, as well as 􀀂13C-DIC, 􀀂18O, and 87/86Sr isotope ratios. This comprehensive suite of pore fluid concentration and isotopic profiles places important constraints on the fluid/gas sources, transport pathways, and CH4 fluxes, and their impact on gas hydrate concentration and distribution. Based on the Cl- and 􀀂18􀀁 depth profiles, catwalk infrared images, pressure core CH4 concentrations, and direct gas hydrate sampling, we show that the occurrence and concentration of gas hydrate varies considerably between sites. Gas hydrate was detected at all 10 sites, and occurs between 50 mbsf and the base of the gas hydrate stability zone (BGHSZ). In all but three sites cored, gas hydrate is mainly disseminated within the pore space with typical pore space occupancies being 􀀁2%. Massive occurrences of gas hydrate are controlled by high-angle fractures in clay/silt sediments at three sites, and locally by lithology (sand/silt) at the more “diffuse” sites with a maximum pore space occupancy of ~67%. Though a majority of the sites cored contained sand/silt horizons, little gas hydrate was observed in most of these intervals. At two sites in the K-G basin, we observe higher than seawater Cl- concentrations between the sulfate-methane transition (SMT) and ~80 mbsf, suggesting active gas hydrate formation at rates faster than Cl- diffusion and pore fluid advection. The fluids sampled within this depth range are chemically distinct from the fluids sampled below, and likely have been advected from a different source depth. These geochemical results provide the framework for a regional gas hydrate reservoir model that links the geology, geochemistry, and subsurface hydrology of the basin, with implications for the lateral heterogeneity of gas hydrate occurrence in continental margins.

Gas hydrates occur naturally around the world in the shallow-marine geosphere, and have received diverse attention, crossing many disciplines, ranging from interest as a drilling hazard in the petroleum industry through to their role in the carbon cycle, and their possible contribution in past and present climate change. Carbon dioxide (CO2) hydrates also occur naturally on Earth in the Okinawa Trough, offshore Japan, and they could exist elsewhere in the solar system. Additionally, CO2 hydrates are being investigated for their potential to store large volumes of CO2 to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. Although research into hydrates has rapidly gained pace in more recent years their mineralogy and formation processes are still relatively poorly understood. Various imaging techniques have been used to study gas hydrates, such as Nuclear Magnetic Resonance; Magnetic Resonance Imaging; X-ray Computed Tomography and Scanning Electron Microscopy (SEM). We have investigated CO2 hydrates formed within the BGS laboratories, using a cryogenic-SEM. This investigation has produced various different hydrate morphologies resulting from different formation conditions. Morphologies range from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. Cryogenic-SEM of these hydrates has yielded a wealth of information, and with further investigation of hydrate formed within different formation conditions we may begin to comprehend the complex growth mechanisms involved.

The presence of structure H (sH) methane hydrate in natural environments, in addition to the well-known structure-I (sI) and II (sII) hydrates, has recently been documented. Methane in the presence of condensates (C5-C7) forms sH hydrate at lower pressure than the sI hydrate. Thus, the occurrence of sH methane hydrate is likely to have both beneficial and negative practical implications. On the negative side, in the presence of condensate, sH hydrate may form and plug gas transmission pipelines at lower pressures than sI hydrate. On the other hand, sH hydrate can be synthesized at lower pressures and exploited to store methane. The existence of natural hydrates containing sH hydrate may also be expected in shallow offshore areas. There are at least 26 large guest molecules known as sH hydrate formers and each of them produces a sH hydrates with different properties. The hydrate stability, the cage occupancies and the rates of hydrate formation depend on the type of large molecule selected. Consequently, it is essential to understand how the host and the guest molecules interact. Studies at the molecular-level are therefore indispensable in providing information that is not obtainable from experiments or too costly to acquire. Free energy calculations are performed to determine the relative stability among different sH hydrate systems and the preferable cage occupancy. The latter would give indications of how much methane gas can be stored in the hydrate. The interaction of guest molecule inside the hydrate cage is also investigated. The results are related to the physical and chemical properties of gas hydrates observed from the experiments or reported in the literature.

One of the new approaches for capturing carbon dioxide from treated flue gas (post-combustion capture) and fuel gas (pre-combustion capture) is based on gas hydrate crystallization. The presence of small amount of tetrahydrofuran (THF) substantially reduces the hydrate formation pressure from a flue (CO2/N2) gas mixture and offers the possibility to capture CO2 at medium pressures [1]. A conceptual flow sheet for a medium pressure hydrate process for pre-combustion capture from a fuel gas (CO2/H2) was also developed and presented. In order to test the hydrate-based separation processes for pre and post combustion capture of CO2 at a larger scale a new apparatus that can operate with different gas/water contact modes is set up and presented.

In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually be a commercial resource yet technical and economic hurdles have historically made gas hydrate development a distant goal rather than a near-term possibility. This view began to change over the past five years with the realization that this unconventional resource could be developed in conjunction with conventional gas fields. The most significant development was gas hydrate production testing conducted at the Mallik site in Canada’s Mackenzie Delta in 2002. The Mallik 2002 Gas Hydrate Production Research Well Program yielded the first modern, fully integrated field study and production test of a natural gas hydrate accumulation. More recently, BP Exploration (Alaska) Inc. with the U.S. Department of Energy and the U.S. Geological Survey have successfully cored, logged, and tested a gas hydrate accumulation on the North Slope of Alaska know as the Mount Elbert Prospect. The Mallik 2002 project along with the Mount Elbert effort has for the first time allowed the rational assessment of the production response of a gas hydrate accumulation.

The presence of gas hydrates offshore of eastern Canada has long been inferred from estimated stability zone calculations, but the physical evidence is yet to be discovered. While geophysical evidence derived from seismic and borehole logging data provides indications of hydrate occurrence in a number of areas, the results are not regionally comprehensive and, in some cases, are inconsistent. In this study, the results of systematic seismic mapping along the Scotian and Newfoundland margins are documented. An extensive set of 2-D and 3-D, single and multi-channel, seismic reflection data comprising ~45,000 line-km was analyzed for possible evidence of hydrate. Bottom simulating reflectors (including one double BSR) were identified at five different sites, ranging between 300 and 600 m below the seafloor and in water depths of 1000 to 2900 m. The combined area of the five BSRs is 1720 km2, which comprises a small proportion of the theoretical stability zone area along the Scotian and Newfoundland margins (~635,000 km2). The apparent paucity of BSRs may relate to the rarity of gas hydrates on the margin or may be simply due to geophysical limitations in detecting hydrate.