William J. Winters

Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a “capillary pressure” in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This “freeze-drying” may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability.

Methane hydrate formation in partially water-saturated Ottawa sand

Abstract Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate

Abstract This paper presents results of shear strength and acoustic velocity (p-wave) measurements performed on: (1) samples containing natural gas hydrate from the Mallik 2L-38 well, Mackenzie Delta, Northwest Territories; (2) reconstituted Ottawa sand samples containing methane gas hydrate formed in the laboratory; and (3) ice-bearing sands. These measurements show that hydrate increases shear strength and p-wave velocity in natural and reconstituted samples. The proportion of this increase depends on (1) the amount and distribution of hydrate present, (2) differences in sediment properties, and (3) differences in test conditions. Stress-strain curves from the Mallik samples suggest that natural gas hydrate does not cement sediment grains. However, stress-strain curves from the Ottawa sand (containing laboratory-formed gas hydrate) do imply cementation is present. Acoustically, rock physics modeling shows that gas hydrate does not cement grains of natural Mackenzie Delta sediment. Natural gas hydrates are best modeled as part of the sediment frame. This finding is in contrast with direct observations and results of Ottawa sand containing laboratory-formed hydrate, which was found to cement grains (Waite et al. 2004). It therefore appears that the microscopic distribution of gas hydrates in sediment, and hence the effect of gas hydrate on sediment physical properties, differs between natural deposits and laboratory-formed samples. This difference may possibly be caused by the location of water molecules that are available to form hydrate. Models that use laboratory-derived properties to predict behavior of natural gas hydrate must account for these differences.

Critical pressure and multiphase flow in Blake Ridge gas hydrates

We use core porosity, consolidation experiments, pressure core sampler data, and capillary pressure measurements to predict water pressures that are 70% of the lithostatic stress, and gas pressures that equal the lithostatic stress beneath the methane hydrate layer at Ocean Drilling Program Site 997, Blake Ridge, offshore North Carolina. A 29-m-thick interconnected free-gas column is trapped beneath the low-permeability hydrate layer. We propose that lithostatic gas pressure is dilating fractures and gas is migrating through the methane hydrate layer. Overpressured gas and water within methane hydrate reservoirs limit the amount of free gas trapped and may rapidly export methane to the seafloor.

Physical property changes in hydrate‐bearing sediment due to depressurization and subsequent repressurization

Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization W.F. Waite 1 , T.J. Kneafsey 2 , W.J. Winters 1 , D.H. Mason 1 U.S. Geological Survey, 384 Woods Hole Road, Woods Hole, MA 02543, USA Lawrence Berkeley National Laboratory, 1 Cyclotron Rd., MS 90R1116, Berkeley, CA 94720, USA

Estimating thermal diffusivity and specific heat from needle probe thermal conductivity data

Thermal diffusivity and specific heat can be estimated from thermal conductivity measurements made using a standard needle probe and a suitably high data acquisition rate. Thermal properties are calculated from the measured temperature change in a sample subjected to heating by a needle probe. Accurate thermal conductivity measurements are obtained from a linear fit to many tens or hundreds of temperature change data points. In contrast, thermal diffusivity calculations require a nonlinear fit to the measured temperature change occurring in the first few tenths of a second of the measurement, resulting in a lower accuracy than that obtained for thermal conductivity. Specific heat is calculated from the ratio of thermal conductivity to diffusivity, and thus can have an uncertainty no better than that of the diffusivity estimate. Our thermal conductivity measurements of ice Ih and of tetrahydrofuran (THF) hydrate, made using a 1.6mm outer diameter needle probe and a data acquisition rate of 18.2points∕s, ag...

GHASTLI — Determining Physical Properties of Sediment Containing Natural and Laboratory-Formed Gas Hydrate

Gas-hydrate samples have been recovered at about 16 areas worldwide (Booth et al., 1996). However, gas hydrate is known to occur at about 50 locations on continental margins (Kvenvolden, 1993) and is certainly far more widespread so it may represent a potentially enormous energy resource (Kvenvolden, 1988). But adverse effects related to the presence of hydrate do occur. Gas hydrate appears to have caused slope instabilities along continental margins (Booth et al., 1994; Dillon et al., 1998; Mienert et al., 1998; Paull & Dillon, (Chapter 12; Twichell & Cooper, 2000) and it has also been responsible for drilling accidents (Yakushev and Collett, 1992). Uncontrolled release of methane could affect global climate (Chapter 11), because methane is 15–20 times more effective as a “greenhouse gas” than an equivalent concentration of carbon dioxide. Clearly, a knowledge of gas-hydrate properties is necessary to safely explore the possibility of energy recovery and to understand its past and future impact on the geosphere.

Major occurrences and reservoir concepts of marine clathrate hydrates: implications of field evidence

Abstract Questions concerning clathrate hydrate as an energy resource, as a factor in modifying global climate and as a triggering mechanism for mass movements invite consideration of what factors promote hydrate concentration, and what the quintessential hydrate-rich sediment may be. Gas hydrate field data, although limited, provide a starting point for identifying the environments and processes that lead to more massive concentrations. Gas hydrate zones are up to 30 m thick and the vertical range of occurrence at a site may exceed 200 m. Zones typically occur more than 100 m above the phase boundary. Thicker zones are overwhelmingly associated with structural features and tectonism, and often contain sand. It is unclear whether an apparent association between zone thickness and porosity represents a cause-and-effect relationship. The primary control on the thickness of a potential gas hydrate reservoir is the geological setting. Deep water and low geothermal gradients foster thick gas hydrate stability zones (GHSZs). The presence of faults, fractures, etc., can favour migration of gas-rich fluids. Geological processes, such as eustacy or subsidence, may alter the thickness of the GHSZ or affect hydrate concentration. Tectonic forces may promote injection of gas into the GHSZ. More porous and permeable sediment, as host sediment properties, increase storage capacity and fluid conductivity, and thus also enhance reservoir potential.

Wave Processes and Geologic Responses on the Floor of the Yellow Sea

From Shoreline to Abyss: Contributions in Marine Geology in Honor of Francis Parker Shepard - Francis P. Shepard left a rich scientific legacy including more than 230 published papers and books primarily addressed to the study of submarine canyons and turbidity currents, continental shelves and associated sediments, coastal processes and sediments and marine physiography and tectonics. He is best remembered for his work on submarine canyons; however, his broad range of scientific interests and his remarkable ability to break new ground in each of these disciplines have served as a model for at least four generations of ?Shepard? students. This new work from these Shepard students addresses problems in marine geology from the global scale to the local outcrop scale. Relationships among tectonics, eustacy and both siliciclastic and carbonate sedimentation create a unifying theme. Special topics include coastal processes, shelf and slope evolution, and submarine canyon and fan systems.

Formation of Natural Gas Hydrates in Marine Sediments: Gas Hydrate Growth and Stability Conditioned by Host Sediment Properties

Abstract: The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine‐grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.