Geology topics

L.A. Stern

Publications and source records attributed to L.A. Stern.

At least 37 records · Page 2Linked to original sources

USGS2003

Temperature, pressure, and compositional effects on anomalous or "self" preservation of gas hydrates

We previously reported on a thermal regime where pure, polycrystalline methane hydrate is preserved metastably in bulk at up to 75 K above its nominal temperature stability limit of 193 K at 0.1 MPa, following rapid release of the sample pore pressure. Large fractions (>50 vol.%) of methane hydrate can be preserved for 2-3 weeks by this method, reflecting the greatly suppressed rates of dissociation that characterize this "anomalous preservation" regime. This behavior contrasts that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) isothermal test conditions, where dissociation rates increase monotonically with increasing temperature. Here, we report on recent experiments that further investigate the effects of temperature, pressure, and composition on anomalous preservation behavior. All tests conducted on sI methane hydrate yielded self-consistent results that confirm the highly temperature-sensitive but reproducible nature of anomalous preservation behavior. Temperature-stepping experiments conducted between 250 and 268 K corroborate the relative rates measured previously in isothermal preservation tests, and elevated pore-pressure tests showed that, as expected, dissociation rates are further reduced with increasing pressure. Surprisingly, sII methane-ethane hydrate was found to exhibit no comparable preservation effect when rapidly depressurized at 268 K, even though it is thermodynamically stable at higher temperatures and lower pressures than sI methane hydrate. These results, coupled with SEM imaging of quenched sample material from a variety of dissociation tests, strongly support our earlier arguments that ice-"shielding" effects provided by partial dissociation along hydrate grain surfaces do not serve as the primary mechanism for anomalous preservation. The underlying physical-chemistry mechanism(s) of anomalous preservation remains elusive, but appears to be based more on textural or morphological changes within the hydrate material itself, rather than on compositional zoning or ice-rind development.

Canadian Journal of Physics↗

USGS2003

Neutron powder diffraction studies as a function of temperature of structure II hydrate formed from propane

Neutron powder diffraction data confirm that hydrate samples synthesized with propane crystallize as structure type II hydrate. The structure has been modeled using rigid-body constraints to describe C3H8 molecules located in the eight larger polyhedral cavities of a deuterated host lattice. Data were collected at 12, 40, 100, 130, 160, 190, 220, and 250 K and used to calculate the thermal expansivity from the temperature dependence of the lattice parameters. The data collected allowed for full structural refinement of atomic coordinates and the atomic-displacement parameters.

Canadian Journal of Physics↗

USGS2003

Ductile flow of methane hydrate

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

Canadian Journal of Physics↗

USGS2003

The strength and rheology of methane clathrate hydrate

Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

Journal of Geophysical Research B: Solid Earth↗

USGS2002

X-ray Computed Tomography Observation of Methane Hydrate Dissociation

Deposits of naturally occurring methane hydrate have been identified in permafrost and deep oceanic environments with global reserves estimated to be twice the total amount of energy stored in fossil fuels. The fundamental behavior of methane hydrate in natural formations, while poorly understood, is of critical importance if the economic recovery of methane from hydrates is to be accomplished. In this study, computed X-ray tomography (CT) scanning is used to image an advancing dissociation front in a heterogeneous gas hydrate/sand sample at 0.1 MPa. The cylindrical methane hydrate and sand aggregate, 2.54 cm in diameter and 6.3 cm long, was contained in a PVC sample holder that was insulated on all but one end. At the uninsulated end, the dissociated gas was captured and the volume of gas monitored. The sample was initially imaged axially using X-ray CT scanning within the methane hydrate stability zone by keeping the sample temperature at 77??K. Subsequently, as the sample warmed through the methane hydrate dissociation point at 194??K and room pressure, gas was produced and the temperature at the bottom of the sample plug was monitored while CT images were acquired. The experiment showed that CT imaging can resolve the reduction in density (as seen by a reduction in beam attenuation) of the hydrate/sand aggregate due to the dissociation of methane hydrate. In addition, a comparison of CT images with gas flow and temperature measurements reveals that the CT scanner is able to resolve accurately and spatially the advancing dissociation front. Future experiments designed to better understand the thermodynamics of hydrate dissociation are planned to take advantage of the temporal and spatial resolution that the CT scanner provides.

Conference Paper↗

USGS2001

Rheology of ice I at low stress and elevated confining pressure

Triaxial compression testing of pure, polycrystalline water ice I at conditions relevant to planetary interiors and near-surface environments (differential stresses 0.45 to 10 MPa, temperatures 200 to 250 K, confining pressure 50 MPa) reveals that a complex variety of rheologies and grain structures may exist for ice and that rheology of ice appears to depend strongly on the grain structures. The creep of polycrystalline ice I with average grain size of 0.25 mm and larger is consistent with previously published dislocation creep laws, which are now extended to strain rates as low as 2×10 −8 s −1 . When ice I is reduced to very fine and uniform grain size by rapid pressure release from the ice II stability field, the rheology changes dramatically. At 200 and 220 K the rheology matches the grain-size-sensitive rheology measured by Goldsby and Kohlstedt [1997, this issue] at 1 atm. This finding dispels concerns that the Goldsby and Kohlstedt results were influenced by mechanisms such as microfracturing and cavitation, processes not expected to operate at elevated pressures in planetary interiors. At 233 K and above, grain growth causes the fine-grained ice to become more creep resistant. Scanning electron microscopy investigation of some of these deformed samples shows that grains have markedly coarsened and the strain hardening can be modeled by normal grain growth and the Goldsby and Kohlstedt rheology. Several samples also displayed very heterogeneous grain sizes and high aspect ratio grain shapes. Grain-size-sensitive creep and dislocation creep coincidentally contribute roughly equal amounts of strain rate at conditions of stress, temperature, and grain size that are typical of terrestrial and planetary settings, so modeling ice dynamics in these settings must include both mechanisms.

Journal of Geophysical Research B: Solid Earth↗

USGS2001

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Journal of Physical Chemistry A↗

USGS2001

Preservation of methane hydrate at 1 atm

A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

Energy and Fuels↗

USGS2001

Anomalous preservation of pure methane hydrate at 1 atm

Direct measurement of decomposition rates of pure, polycrystalline methane hydrate reveals a thermal regime where methane hydrate metastably `preserves' in bulk by as much as 75 K above its nominal equilibrium temperature (193 K at 1 atm). Rapid release of the sample pore pressure at isothermal conditions between 242 and 271 K preserves up to 93% of the hydrate for at least 24 h, reflecting the greatly suppressed rates of dissociation that characterize this regime. Subsequent warming through the H2O ice point then induces rapid and complete dissociation, allowing controlled recovery of the total expected gas yield. This behavior is in marked contrast to that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) test conditions, where dissociation rates increase monotonically with increasing temperature. Anomalous preservation has potential application for successful retrieval of natural gas hydrate or hydrate-bearing sediments from remote settings, as well as for temporary low-pressure transport and storage of natural gas.

Journal of Physical Chemistry B↗

USGS2001

Measurement of gas yields and flow rates using a custom flowmeter

A simple gas collection apparatus based on the principles of a Torricelli tube has been designed and built to measure gas volume yields and flow rates. This instrument is routinely used to monitor and collect methane gas released during methane hydrate dissociation experiments. It is easily and inexpensively built, operates at ambient pressures and temperatures, and measures gas volumes of up to 7 L to a precision of about 15 ml (about 0.0025 mol). It is capable of measuring gas flow rates varying from more than 103 to less than 10-1 ml/min during gas evolution events that span minutes to several days. We have obtained a highly reproducible hydrate number of n=5.891 with a propagated uncertainty of ??0.020 for synthetic methane hydrate. ?? 2001 American Institute of Physics.

Review of Scientific Instruments↗

USGS2000

Transformations in methane hydrates

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Proceedings of the National Academy of Sciences of↗

USGS2000

Methane hydrate dissociation rates at 0.1 MPa and temperatures above 272 K

We performed rapid depressurization experiments on methane hydrate under isothermal conditions above 272 K to determine the amount and rate of methane evolution. Sample temperatures rapidly drop below 273 K and stabilize near 272.5 K during dissociation. This thermal anomaly and the persistence of methane hydrate are consistent with the reported recovery of partially dissociated methane hydrate from ocean drilling cores.

Conference Paper↗

USGS1998

Optical-cell evidence for superheated ice under gas-hydrate-forming conditions

We previously reported indirect but compelling evidence that fine-grained H 2 O ice under elevated CH 4 gas pressure can persist to temperatures well above its ordinary melting point while slowly reacting to form methane clathrate hydrate. This phenomenon has now been visually verified by duplicating these experiments in an optical cell while observing the very slow hydrate-forming process as the reactants were warmed from 250 to 290 K at methane pressures of 23 to 30 MPa. Limited hydrate growth occurred rapidly after initial exposure of the methane gas to the ice grains at temperatures well within the ice subsolidus region. No evidence for continued growth of the hydrate phase was observed until samples were warmed above the equilibrium H 2 O melting curve. With continued heating, no bulk melting of the ice grains or free liquid water was detected anywhere within the optical cell until hydrate dissociation conditions were reached (292 K at 30 MPa), even though full conversion of the ice grains to hydrate requires 6−8 h at temperatures approaching 290 K. In a separate experimental sequence, unreacted portions of H 2 O ice grains that had persisted to temperatures above their ordinary melting point were successfully induced to melt, without dissociating the coexisting hydrate in the sample tube, by reducing the pressure overstep of the equilibrium phase boundary and thereby reducing the rate of hydrate growth at the ice−hydrate interface. Results from similar tests using CO 2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH 4 −H 2 O system.

Journal of Physical Chemistry B↗

USGS1998

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH 4 gas with granulated H 2 O ice, and then warming the reactants to promote the reaction CH 4 (g) + 6H 2 O(s→l) → CH 4 ·6H 2 O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H 2 O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H 2 O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, P c = 50−100 MPa, and ε = 10 - 4 −10 - 6 s - 1 . Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H 2 O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Energy and Fuels↗

USGS1997

Grain-size-induced weakening of H2O ices I and II and associated anisotropic recrystallization

Grain-size-dependent flow mechanisms tend to be favored over dislocation creep at low differential stresses and can potentially influence the rheology of low-stress, low-strain rate environments such as those of planetary interiors. We experimentally investigated the effect of reduced grain size on the solid-state flow of water ice I, a principal component of the asthenospheres of many icy moons of the outer solar system, using techniques new to studies of this deformation regime. We fabricated fully dense ice samples of approximate grain size 2±1 μm by transforming “standard” ice I samples of 250±50 μm grain size to the higher-pressure phase ice II, deforming them in the ice II field, and then rapidly releasing the pressure deep into the ice I stability field. At T ≤200 K, slow growth and rapid nucleation of ice I combine to produce a fine grain size. Constant-strain rate deformation tests conducted on these samples show that deformation rates are less stress sensitive than for standard ice and that the fine-grained material is markedly weaker than standard ice, particularly during the transient approach to steady state deformation. Scanning electron microscope examination of the deformed fine-grained ice samples revealed an unusual microstructure dominated by platelike grains that grew normal to the compression direction, with c axes preferentially oriented parallel to compression. In samples tested at T ≥220 K the elongation of the grains is so pronounced that the samples appear finely banded, with aspect ratios of grains approaching 50:1. The anisotropic growth of these crystallographically oriented neoblasts likely contributes to progressive work hardening observed during the transient stage of deformation. We have also documented remarkably similar microstructural development and weak mechanical behavior in fine-grained ice samples partially transformed and deformed in the ice II field.

Journal of Geophysical Research B: Solid Earth↗

USGS1997

Creep of water ices at planetary conditions: A compilation

Many constitutive laws for the flow of ice have been published since the advent of the Voyager explorations of the outer solar system. Conflicting data have occasionally come from different laboratories, and refinement of experimental techniques has led to the publication of laws that supersede earlier ones. In addition, there are unpublished data from ongoing research that also amend the constitutive laws. Here we compile the most current laboratory-derived flow laws for water ice phases I, II, III, V, and VI, and ice I mixtures with hard particulates. The rheology of interest is mainly that of steady state, and the conditions reviewed are the pressures and temperatures applicable to the surfaces and interiors of icy moons of the outer solar system. Advances in grain-size-dependent creep in ices I and II as well as in phase transformations and metastability under differential stress are also included in this compilation. At laboratory strain rates the several ice polymorphs are rheologically distinct in terms of their stress, temperature, and pressure dependencies but, with the exception of ice III, have fairly similar strengths. Hard particulates strengthen ice I significantly only at high particulate volume fractions. Ice III has the potential for significantly affecting mantle dynamics because it is much weaker than the other polymorphs and its region of stability, which may extend metastably well into what is nominally the ice II field, is located near likely geotherms of large icy moons.

Journal of Geophysical Research E: Planets↗

USGS1997

Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

ACS Division of Fuel Chemistry, Preprints↗

USGS1996

Rheology of water ices V and VI

We have measured the mechanical strength (σ) of pure water ices V and VI under steady state deformation conditions. Constant displacement rate compressional tests were conducted in a gas apparatus at confining pressures from 400 < P < 800 MPa, temperatures from 209 < T < 270 K, and strain rates 7 × 10 −7 < < 7 × 10 −4 s −1 . Most of the results fit to an empirical flow law of the form = A σ n exp {−( E * + PV *)/ RT }, where the four material constants A , n , E *, and V * are (for in inverse seconds and P and σ in megapascals) 10 23.0 , 6.0, 136 kJ/mol, and 29 cm 3 /mol, respectively, for ice V; and 10 6.7 , 4.5, 66 kJ/mol, and 11 cm 3 /mol, respectively, for ice VI. Ice VI may weaken to a mechanism of higher E * at T > 250 K. Ices V and VI are thus rheologically distinct but by coincidence have approximately the same strength under the conditions chosen for these experiments. To avoid misidentification, these tests are therefore accompanied by careful observations of the occurrences and characteristics of phase changes. One sample each of ice V and VI was quenched at pressure to metastably retain the high-pressure phase and the acquired deformation microstructures; X ray diffraction analysis of these samples confirmed the phase identification. Surface replicas of the deformed and quenched samples suggest that ice V probably deforms largely by dislocation creep, while ice VI deforms by a more complicated process involving substantial grain size reduction through recrystallization.

Journal of Geophysical Research B: Solid Earth↗