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Submarine landslides are prevalent on the modern-day seafloor, yet an elusive problem is constraining the timing of slope failure. Herein, we present a novel technique for constraining the age of submarine landslides without sediment core dating. Underneath a submarine landslide in the Orca Basin, Gulf of Mexico, in 3D seismic data we map an irregular bottom simulating reflection (BSR), which mimics the geometry of the pre-slide seafloor rather than the modern bathymetry. Based on the observed BSR, we suggest that the gas hydrate stability zone (GHSZ) is currently adjusting to the post-slide sediment temperature perturbations. We apply transient conductive heat flow modeling to constrain the response of the GHSZ to the slope failure, which yields a most likely age of ~8 ka demonstrating that gas hydrate systems can respond to slope failures even on the millennia timescales. We also provide an analytical approach to rapidly determine the age of submarine slides at any location.

Slow (8–15 day), stepwise, degassing of synthesized methane hydrate-bearing sand packs was used to determine in situ salinity to within 0.5 wt%. Rebounds in pressure during shut-in intervals between degassing steps record gradual hydrate dissociation. During successive dissociation steps and pressure rebounds, the pressure decreases more than predicted for a sample with homogenous salinity and temperature at thermodynamic equilibrium. We interpret that hydrate dissociation is limited by local pore water freshening and endothermic cooling around the dissociating hydrate. These results suggest that during production, hydrate dissociation in a reservoir will occur along the freshwater phase boundary even though the bulk salinity of the system may be higher. Pore pressure rebound during shut-in is more rapid in freshwater experiments than in brine experiments, which indicates that salt diffusion plays a role in limiting recovery to homogenous bulk equilibrium during hydrate dissociation. We demonstrate that it is possible to interpret the in-situ salinity from the temperature and pressure at the onset of dissociation. This approach can be applied to actual hydrate-bearing pressure core samples and the results will assist our understanding of how these hydrates form. Depressurization experiments with controlled shut-in periods provide insight into the role of salt and heat diffusion on dissociation in coarse-grained sediments, particularly relevant to pauses in production and in regions of a hydrate reservoir near the hydrate phase boundary.

Highlights • Code comparisons build confidence in simulators to model interdependent processes. • International hydrate reservoir simulators are compared over five complex problems. • Geomechanical processes significantly impact response of gas hydrate reservoirs. • Simulators yielded comparable results, however many differences are noted. • Equivalent constitutive models are required to achieve agreement across simulators. Geologic reservoirs containing gas hydrate occur beneath permafrost environments and within marine continental slope sediments, representing a potentially vast natural gas source. Numerical simulators provide scientists and engineers with tools for understanding how production efficiency depends on the numerous, interdependent (coupled) processes associated with potential production strategies for these gas hydrate reservoirs. Confidence in the modeling and forecasting abilities of these gas hydrate reservoir simulators (GHRSs) grows with successful comparisons against laboratory and field test results, but such results are rare, particularly in natural settings. The hydrate community recognized another approach to building confidence in the GHRS: comparing simulation results between independently developed and executed computer codes on structured problems specifically tailored to the interdependent processes relevant for gas hydrate-bearing systems. The United States Department of Energy, National Energy Technology Laboratory, (DOE/NETL), sponsored the first international gas hydrate code comparison study, IGHCCS1, in the early 2000s. IGHCCS1 focused on coupled thermal and hydrologic processes associated with producing gas hydrates from geologic reservoirs via depressurization and thermal stimulation. Subsequently, GHRSs have advanced to model more complex production technologies and incorporate geomechanical processes into the existing framework of coupled thermal and hydrologic modeling. This paper contributes to the validation of these recent GHRS developments by providing results from a second GHRS code comparison study, IGHCCS2, also sponsored by DOE/NETL. IGHCCS2 includes participants from an international collection of universities, research institutes, industry, national laboratories, and national geologic surveys. Study participants developed a series of five benchmark problems principally involving gas hydrate processes with geomechanical components. The five problems range from simple geometries with analytical solutions to a representation of the world's first offshore production test of methane hydrates, which was conducted with the depressurization method off the coast of Japan. To identify strengths and limitations in the various GHRSs, study participants submitted solutions for the benchmark problems and discussed differing results via teleconferences. The GHRSs evolved over the course of IGHCCS2 as researchers modified their simulators to reflect new insights, lessons learned, and suggested performance enhancements. The five benchmark problems, final sample solutions, and lessons learned that are presented here document the study outcomes and serve as a reference guide for developing and testing gas hydrate reservoir simulators.

A new generation of models, laboratory, and field studies is helping scientists answer important questions about this mysterious substance.

Author(s): Meyer, DW; Flemings, PB; DiCarlo, D; You, K; Phillips, SC; Kneafsey, TJ | Abstract: We form methane hydrate by injecting methane gas into a brine-saturated, coarse-grained sample under hydrate-stable thermodynamic conditions. Hydrate forms to a saturation of 11%, which is much lower than that predicted assuming three-phase (gas-hydrate-brine) thermodynamic equilibrium (67%). During hydrate formation, there are temporary flow blockages. We interpret that a hydrate skin forms a physical barrier at the gas-brine interface. The skin fails periodically when the pressure differential exceeds the skin strength. Once the skin is present, further hydrate formation is limited by the rate that methane can diffuse through the solid skin. This process produces distinct thermodynamic states on either side of the skin that allows gas to flow through the sample. This study illuminates how gas can be transported through the hydrate stability zone and thus provides a mechanism for the formation of concentrated hydrate deposits in sand reservoirs. It also illustrates that models that assume local equilibrium at the core-scale and larger may not capture the fundamental behaviors of these gas flow and hydrate formation processes.

We extend a one-dimensional analytical solution by including buoyancy-driven flow to explore the impact of gravity on hydrate formation from gas injection into brine-saturated sediments within the hydrate stability zone. This solution includes the fully coupled gas and liquid phase flow and the associated advective transport in a homogeneous system. We obtain the saturations assuming Darcy flow under combined pressure and gravity gradients; capillary forces are neglected. At a high gas supply rate, the overpressure gradient (gradient of water pressure deviation from the hydrostatic pressure) dominates the gas flow, and the hydrate saturation is independent of the flow rate and flow direction. At a low gas supply rate, the buoyancy (the drive for gas flow induced by the density difference between gas and liquid) dominates the gas flow, and the hydrate saturation depends on the flow rate and flow direction. Hydrate saturation is highest for upward flow, and lowest for downward flow. Hydrate saturation decreases with flow rate for upward flow, and increases with flow rate for downward flow. In all cases, hydrate saturation is constant behind the hydrate solidification front. Gas saturation is homogeneous and close to the residual value for upward flow at a low rate; gas flows at the rate it is supplied. Gas saturation is much greater than the residual value, and decreases from the gas inlet to the hydrate solidification front for downward flow at a very low rate. The effect of gravity is usually negligible in laboratory experiments, yet is significant in natural hydrate systems.

We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation from gas injection into brine-saturated sediments within the hydrate stability zone. Our solution includes fully-coupled multiphase and multicomponent flow and the associated advective transport in a homogeneous system. Our solution shows that hydrate saturation is controlled by the initial thermodynamic state of the system, and changed by the gas fractional flow. Hydrate saturation in gas-rich systems can be estimated by 1−cl0clewhen Darcy flow dominates, where cl0 is the initial mass fraction of salt in brine, and cle is the mass fraction of salt in brine at three-phase (gas, liquid, and hydrate) equilibrium. Hydrate saturation is constant, gas saturation and gas flux decrease, and liquid saturation and liquid flux increase with the distance from the gas inlet to the hydrate solidification front. The total gas and liquid flux is constant from the gas inlet to the hydrate solidification front, and decreases abruptly at the hydrate solidification front due to gas inclusion into the hydrate phase. The advancing velocity of the hydrate solidification front decreases with hydrate saturation at a fixed gas inflow rate. This analytical solution illuminates how hydrate is formed by gas injection (methane, CO2, ethane, propane) at both the laboratory and field scales.

Methane hydrate formation and dissociation are buffered by salinity in a closed system. During hydrate formation, salt excluded from hydrate increases salinity, drives the system to three-phase (gas, water, and hydrate phases) equilibrium, and limits further hydrate formation and dissociation. We developed a zero-dimensional local thermodynamic equilibrium-based model to explain this concept. We demonstrated this concept by forming and melting methane hydrate from a partially brine-saturated sand sample in a controlled laboratory experiment by holding pressure constant (6.94 MPa) and changing temperature stepwise. The modeled methane gas consumptions and hydrate saturations agreed well with the experimental measurements after hydrate nucleation. Hydrate dissociation occurred synchronously with temperature increase. The exception to this behavior is that substantial subcooling (6.4°C in this study) was observed for hydrate nucleation. X-ray computed tomography scanning images showed that core-scale hydrate distribution was heterogeneous. This implied core-scale water and salt transport induced by hydrate formation. Bulk resistivity increased sharply with initial hydrate formation and then decreased as the hydrate ripened. This study reproduced the salinity-buffered hydrate behavior interpreted for natural gas-rich hydrate systems by allowing methane gas to freely enter/leave the sample in response to volume changes associated with hydrate formation and dissociation. It provides insights into observations made at the core scale and log scale of salinity elevation to three-phase equilibrium in natural hydrate systems.

The distribution of antimony (Sb) in topsoil and moss (Dicranum angustum) in disturbed and undisturbed areas, as well as coal and gangue, in Ny-Ålesund, Arctic was examined. Results show that the weathering of coal bed could not contribute to the increase of Sb concentrations in topsoil and moss in the study area. The distribution of Sb is partially associated with traffic and historical mining activities. The occurrence of the maximum Sb concentration is due to the contribution of human activities. In addition, the decrease of Sb content in topsoil near the coastline may be caused by the washing of seawater. Compared with topsoils, moss could be a useful tool for monitoring Sb in both highly and lightly polluted areas.

[1] Accurate description of induced gas flow in an unsaturated zone is indispensable for characterizing the unsaturated zone. Hantush's approximation and a finite difference approximation of the leakage term are frequently employed in modeling the induced gas flow in an unsaturated zone underlying a leaky confining layer. However, no studies have been conducted on the errors that result from these approximations. This study presents a physically more rigorous model based on mass conservation in both the upper leaky confining layer and the lower permeable layer (the unsaturated zone). Flow in the upper layer is assumed to be vertical, and in the lower layer, it is two-dimensionally axisymmetric, with gas pressure and flux continuity at the interface of the two layers. A new steady state solution for a well with a finite radius and two new transient solutions for a well with an infinitely small radius and with a finite radius are developed for this rigorous model. In addition, another new transient solution is derived using the finite difference approximation of the leakage term for the same problem. The developed solutions are compared with previous approximate solutions. Results indicate that Hantush's approximation overestimates the gas pressure at shallower depths and underestimates it at deeper depths under the condition of gas injection. This error changes with the hydrogeological parameters and well configurations. The finite difference approximation works reasonably well under the usual field conditions. Neglecting the well radius for a small radius well does not induce much error.