Nonspherical large cages in structure I (sI) clathrates impose non-uniform motion of nonspherical guest molecules and anisotropic lineshapes in NMR spectra of the guest. In this work, we calculate the lineshape anisotropy of the linear CO2 molecule in large sI clathrate cages based on molecular dynamics simulations of this inclusion compound. The methodology is general and does not depend on the temperature and type of inclusion compound or guest species studied. The nonspherical shape of the sI clathrate hydrate large cages leads to preferential alignment of linear CO2 molecules in directions parallel to the two hexagonal faces of the cages. The angular distribution of the CO2 guests in terms of a polar angle θ and azimuth angle  and small amplitude vibrational motions in the large cage are characterized by molecular dynamics simulations at different temperatures in the stability range of the CO2 sI clathrate. These distributions are used to calculate the NMR powder spectrum of CO2 at different temperatures. The experimental 13C NMR lineshapes of CO2 guests in the large cages show a reversal of the skew between the low temperature (77 K) and the high temperature (238 K) limits of the stability of the clathrate. Good agreement between experimental lineshapes and calculated lineshapes is obtained. No assumptions regarding the nature of the guest motions in the cages are required.

The stability of hydrogen clathrate hydrate was investigated using a classical Molecular Dynamic (MD) calculation code “MXDTRICL” as a theoretical approach. Arranging hydrogen molecules one by one into host-frame of the hydrogen hydrates, the inclusion energy of their system was evaluated, where Lennard-Jones potential and two types of TIP4P potentials were adopted on the MD calculations as intermolecular potentials. From the result, it is concluded that multiple molecules are included in both large and small cages so that the storage density could attain higher than 6wt% for any potential. Observation of the movement of H2 molecules in the cage under various conditions revealed that H2 molecules are not stable in the cage and a few part of the H2 molecules come in and go out of the cage through the center hole between hexagons.

Methane hydrate has a unique structure that the host water framework forms two kinds of cages, which contain one methane molecule each. Therefore, it has been expected that there may exist three kinds of translational modes of a methane molecule and also the distortion of translational mode of host water molecules compared with normal ice. We need information of the host and guest molecular dynamics over the wide momentum and energy transfer region for studying such dynamics. In this study inelastic neutron measurements were carried under 40 K with MARI spectrometer at ISIS in UK, TAS at JRR-3 and CAT at KENS in Japan. For the methane molecular motion we could confirm its freelike rotation by complementary use of MARI and TAS spectra. After the subtraction of the scattering intensity of the rotation evaluated by the free rotation model from the experimental data, three kinds of translation modes were identified at first experimentally. On the experimental spectra there still remains the excess intensity which could not explain the single mode excitation. The libration mode of the water framework shows the different momentum and energy transfer dependence with those of normal ice. The feature of the libration mode is resemble to ice-IX, that could be considered as a proton ordering of the cage structure appeared in ice-II, VIII and IX.

In order to understand the response of authigenic minerals to the gas hydrate geo-system, various authigenic pyrites were picked out under Zeiss Microscope and their S isotopes were analyzed later from 652 sediments samples at intervals of about 1.5m recovered from all 5 sites of Integrated Ocean Drilling Program (IODP) Expedition 311 on Cascadia Margin, northeastern Pacific. SEM photos of picked pyrites exhibit various aggregation features mainly in forms of strawberry, pillar/rod and dumbbell in sizes from 200 m to 1000m. Typical cubic pyrite crystals could be seen under smaller scale SEM photos. Most δ34S values in Site U1325 at the west deeper water location of IODP 311 show negative values low to -33.964‰ CDT, distinctly contrasted to the δ34S in Site U1329 at the east shallower location having much more positive values up to 28.29‰ CDT. At the cold venting position assigned as Site U1328 the δ34S values show strong negative values in the upper part of sediments column above 135 mbsf (meter below sea floor), increasing gradually with the depth from -35.83‰ CDT to -1.32‰ CDT, and then display many positive excursions up to 32.49‰ CDT below 135 mbsf, which is significantly distinguished from the values in nearby non-cold venting Site U1327 having much less positive excursions in the lower part of column below 110 mbsf. In all sites a general negative δ34S excursion occur in the upper part of sediments columns above 30~35 mbsf except in Site U1328 having more depth, indicating the potential current sulfate methane interface (SMI) activity zones. Distinct positive δ34S excursions up to the highest δ34S value 53.65‰ CDT from strawberry pyrites aggregations might indicate that sulfide products by AOM probably inherit completely the sulfate having high δ34S value and no sulfate was left after AOM at a high methane flux under gas hydrate geological background.

This paper presents results of a seismic tomography experiment carried out at the Bullseye cold vent site offshore Vancouver Island. In the experiment, a seismic air gun survey was recorded on an array of five ocean bottom seismometers (OBS) deployed around the vent. The locations of the shots and the OBSs were determined to high accuracy by an inversion based on the shot travel times. A three-dimensional tomographic inversion was then carried out to determine the velocity structure around the vent, using the localized source and receiver positions. The inversion indicates a relatively uniform velocity field around and inside the vent. The velocities are close to the values expected for sediments containing no hydrate, which supports previous claims that the bulk concentrations of gas hydrates are low at the site. However, the largest resolved velocity anomalies of + 25 m/s are spatially within the limits of the acoustic blank zone seen in multichannel seismic data near the Bullseye vent. The velocity inversion is consistent with zones of high concentration (15-20 % of the pore space) in the top 50-100 m of sediment.

The aim of this work is to model the thermal evolution inside a hydrate forming system which is submitted to an imposed steady cooling. The study system is a cylindrical thin film of aqueous solution at 19 Mpa, the methane is the hydrate forming molecule and it is assumed that methane is homogeneously dissolved in the aqueous phase. The model in this work takes into account two factors involved in the hydrate crystallization: 1) the stochastic nature of crystallization that causes sub-cooling and 2) the heat source term due to the exothermic enthalpy of hydrate formation. The model equation is based on the resolution of the continuity equation in terms of a heat balance. The crystallization of the methane hydrate occurs at supercooling conditions (Tcryst < TF), besides, the heat released during crystallization interferes with the imposed condition of steady decrease of temperature around the system. Thus, the inclusion of the heat source term has to be considered in order to take into account the influence of crystallization. The rate of heat released during the crystallization is governed by the probability of nucleation J(T ). The results provided by the model equation subjected to boundary conditions allow depict the evolution of temperature in the dispersed phase. The most singular point in the temperature–time curve is the onset time of hydrate crystallization. Three time intervals characterize the temperature evolution during the steady cooling: (1) linear cooling, (2) hydrate formation with a release of heat, (3) a last interval of steady cooling.

In this study, Tetrahydrofuran (THF) hydrates were formed in-situ in the Zetasizer Nano ZS90. With various concentrations of SDS, we attempted to characterize the SDS adsorption on the surface of the hydrate particles. In doing so, we tried to correlate the adsorption of SDS to THF hydrate induction times with respect to SDS concentration (0 – 3.47 mM), to determine whether the fast nucleation of THF hydrates is due to the adsorption of SDS. The measured ζ-potential for pure THF hydrates was -100 ± 10 mV, indicating anion adsorption. An adsorption curve was observed where there is saturation leveling. Correlating this data to the hydrate induction times, we see that when the saturation level is reached, a significant reduction in induction time can be seen.

An approach to predictions of position and size of hydrate plugs inside gas wells has been proposed. It is based on the mathematical model of steady non-isothermal flow of real gas in tubes and an algorithm of calculation of equilibrium conditions of hydrate formation. The proposed approach includes the following steps. 1) Numerically solve the system of ordinary differential equations to find the distributions of pressure and temperature along a particular well. 2) Represent the results of calculations as connection between pressure and temperature. 3) Find the intersection of this function with the calculated or experimental equilibrium curve for a particular natural gas. 4) Find the depth of well from the results of numerical solution.

Gas hydrates are crystalline solids (clathrates) in which gas molecules are encaged within lattices of hydrogen bonded water molecules. Hydrates are stable at low temperatures and high pressures; and dissociation takes place at temperatures and pressures outside the stability zone. Modeling the dissociation behavior of hydrates in porous soil media requires attention be paid to the geomechanics of hydrate dissociation. This paper addresses the issue of coupling the hydrate dissociation problem with the soil deformation problem and constructs the mathematical framework. Thermally stimulated dissociation process under undrained conditions is considered with conduction heat transfer.

The experimental formation of natural gas hydrate on pendant water droplet exposed to natural gas was conducted and visually observed under the pressures from 3.86MPa to 6.05MPa. The temperature was set at 274.75K and 273.35K. The diameter of the pendant water droplet was around 4mm. The nucleation and growth of hydrate film on the pendant water drop exhibited a generalized trend. The film initially generated at the boundary between the water drop and suspension tube, and afterwards grew laterally and longitudinally on the surface of the water drop. The phenomenon of the two layers of hydrate films growing on the pendant water drop distinguished from the experiments on the sessile water drop. The effect of the driving force that resulted from the overpressure from the three equilibrium pressure on the hydrate nucleation and growth was investigated. It was found that the elevation of the driving force reduced the nucleation time and shortened the process of the hydrate growth on the pendant water drop. The crystals on the hydrate shell became coarser with the increase of the driving force. The mechanism for the hydrate film formation and growth on static pedant water droplet included four stages, such as nucleation, generation of the hydrate film, growth of the hydrate film, and hydration below the hydrate shell.