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At least 19 recordsLinked to original sources
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↗
USGS2003

CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

Structure I (sI) carbon dioxide (CO 2 ) hydrate exhibits markedly different dissociation behavior from sI methane (CH 4 ) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H 2 O melting point (273.15 K). The CO 2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO 2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO 2 ·nH 2 O = CO 2 (g) + nH 2 O(1 to s) is measurably distinct from the pure H 2 O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH 4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO 2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO 2 hydrate was synthesized from CO 2 liquid and H 2 O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 μm diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the hydrate structure are filled such that n ≈ 5.75.

Journal of Physical Chemistry B↗
USGS2004

The role of water in gas hydrate dissociation

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

Journal of Physical Chemistry B↗
USGS2005

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

The composition of methane hydrate, namely n w for CH 4 · n w H 2 O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but n w may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n w = 5.81−6.10 H 2 O describes the entire range of measured values, with an average composition of CH 4 ·5.99(±0.07)H 2 O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence.

Journal of Physical Chemistry B↗
USGS2006

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Journal of Physical Chemistry B↗
USGS1997

Measurement of clathrate hydrates via Raman spectroscopy

Raman spectra of clathrate hydrate guest molecules are presented for three known structures ( I ( sI ), II ( sII ), and H ( sH )) in the following systems: CH 4 ( sI ), CO 2 ( sI ), C 3 H 8 ( sII ), CH 4 + CO 2 ( sI ), CD 4 + C 3 H 8 ( sII ), CH 4 + N 2 ( sI ), CH 4 + THF- d 8 ( sII ), and CH 4 + C 7 D 14 ( sH ). Relative occupancy of CH 4 in the large and small cavities of sI were determined by deconvoluting the ν 1 symmetric bands, resulting in hydration numbers of 6.04 ± 0.03. The frequency of the ν 1 bands for CH 4 in structures I, II, and H differ statistically, so that Raman spectroscopy is a potential tool to identify hydrate crystal structure. Hydrate guest compositions were also measured for two vapor compositions of the CH 4 + CO 2 system, and they compared favorably with predictions. The large cavities were measured to be almost fully occupied by CH 4 and CO 2 , whereas only a small fraction of the small cavities are occupied by CH 4 . No CO 2 was found in the small cavities. Hydration numbers from 7.27 to 7.45 were calculated for the mixed hydrate.

Journal of Physical Chemistry B↗
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↗
USGS1969

Magnetic susceptibility and exchange coupling in the mineral ardennite

Ardennite, a rare silicate mineral, contains about 19 wt.% manganese. Some of the manganese atoms are in positions which are close enough to allow negative exchange and hence a reduction of the total magnetic susceptibility. It is shown that the susceptibility can be accounted for approximately by the treatment of Earnshaw and Lewis (1958) for S = 5 2 "> S =52 and a Hamiltonian H = −2 g μ H b −2 JS 1 · S 2 .

Journal of Physics and Chemistry of Solids↗
USGS1971

Magnetic susceptibility and triangular exchange coupling in the tourmaline mineral group

Magnetic susceptibilities of three iron-rich tourmaline crystals from Mexquitic (Mexico), Pierpont (New York), and Madagascar with different and known chemical compositions have been studied from 8° to 300°K. The iron atoms in the tourmaline crystal structure, space group R3m , a∼15·9, c∼7·2 , are situated at the three corners of an equilateral triangle and are close enough for magnetic exchange interaction. For buergerite, the Mexquitic sample, the susceptibility data lead to an exchange constant J/k of 7·5°K. Although the amount of aluminum would be sufficient to fill point position 18(c) exactly, the magnetic data are consistent with some substitution of ferric iron for aluminum, as previously determined from X-ray and neutron diffraction studies. Some aluminum thus replaces iron in position 9(b). Exchange constants were also estimated for the other two magnesium-iron specimens, of which the madagascar sample is aluminum deficient. The results agree with the evidence from optical spectra that there is considerable deviation from octahedral symmetry in the oxygen coordination polyhedra about the 9(b) and 18(c) point positions.

New York↗
USGS2012

Molecular dynamics simulation of nitric oxide in myoglobin

The infrared (IR) spectroscopy and ligand migration of photodissociated nitric oxide (NO) in and around the active sites in myoglobin (Mb) are investigated. A distributed multipolar model for open-shell systems is developed and used, which allows one to realistically describe the charge distribution around the diatomic probe molecule. The IR spectra were computed from the trajectories for two conformational substates at various temperatures. The lines are narrow (width of 3–7 cm –1 at 20–100 K), in agreement with the experimental observations where they have widths of 4–5 cm –1 at 4 K. It is found that within one conformational substate (B or C) the splitting of the spectrum can be correctly described compared with recent experiments. Similar to photodissociated CO in Mb, additional substates exist for NO in Mb, which are separated by barriers below 1 kcal/mol. Contrary to full quantum mechanical calculations, however, the force field and mixed QM/MM simulations do not correctly describe the relative shifts between the B- and C-states relative to gas-phase NO. Free energy simulations establish that NO preferably localizes in the distal site and the barrier for migration to the neighboring Xe4 pocket is Δ G B→C = 1.7–2.0 kcal/mol. The reverse barrier is Δ G B←C = 0.7 kcal/mol, which agrees well with the experimental value of 0.7 kcal/mol, estimated from kinetic data.

Journal of Physical Chemistry↗
USGS1999

A hydrometric and geochemical approach to test the transmissivity feedback hypothesis during snowmelt

To test the transmissivity feedback hypothesis of runoff generation, surface and subsurface waters were monitored and sampled during the 1996 snowmelt at various topographic positions in a 41 ha forested headwater catchment at Sleepers River, Vermont. Two conditions that promote transmissivity feedback existed in the catchment during the melt period. First, saturated hydraulic conductivity increased toward land surface, from a geometric mean of 3.6 mm h-1 in glacial till to 25.6 mm h-1 in deep soil to 54.0 mm h-1 in shallow soil. Second, groundwater levels rose to within 0.3 m of land surface at all riparian sites and most hillslope sites at peak melt. The importance of transmissivity feedback to streamflow generation was tested at the catchment scale by examination of physical and chemical patterns of groundwater in near-stream (discharge) and hillslope (recharge/lateral flow) zones, and within a geomorphic hollow (convergent flow). The presence of transmissivity feedback was supported by the abrupt increase in streamflow as the water table rose into the surficial, transmissive zone; a flattening of the groundwater level vs. streamflow curve occurred at most sites. This relation had a clockwise hysteresis (higher groundwater level for given discharge on rising limb than at same discharge on falling limb) at riparian sites, suggesting that the riparian zone was the dominant source area during the rising limb of the melt hydrograph. Hysteresis was counterclockwise at hillslope sites, suggesting that hillslope drainage controlled the snowmelt recession. End member mixing analysis using Ca, Mg, Na, dissolved organic carbon (DOC), and Si showed that stream chemistry could be explained as a two-component mixture of groundwater high in base cations and an O-horizon/overland flow water high in DOC. The dominance of shallow flow paths during events was indicated by the high positive correlation of DOC with streamflow (r2 = 0.82). Despite the occurrence of transmissivity feedback, hillslope till and soil water were ruled out as end members primarily because their distinctive high-Si composition had little or no effect on streamwater composition. Till water from the geomorphic hollow had a chemistry very close to streamwater base flow, and may represent the base flow end member better than the more concentrated riparian groundwater. During snowmelt, streamwater composition shifted as this base flow was diluted - not by shallow groundwater from the hillslope, but rather by a more surficial O-horizon/overland flow water.Surface and subsurface waters were analyzed to test the transmissivity feedback of runoff generation during the 1996 snowmelt in a catchment at Sleepers River, Vermont. The importance of transmissivity feedback to stream flow generation was tested by examination of physical and chemical patterns of groundwater in near-stream and hillslope zones within a geomorphic hollow. End member mixing analysis of Ca, Mg, Na, dissolved organic carbon (DOC), and Si showed that stream chemistry could be explained as a two-component mixture of groundwater high in base cations and an O-horizon/overland flow water high in DOC. The dominance of shallow water paths during the events was indicated by the high positive correlation of DOC with streamflow (r2 = 0.82).

Journal of Hydrology↗
USGS2011

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Wyoming↗
USGS2019

India National Gas Hydrate Program Expedition-02: Operational and technical summary

The India National Gas Hydrate Program is being steered by the government of India's Ministry of Petroleum and Natural Gas (MoPNG) with participation of Directorate General of Hydrocarbons (DGH), Oil and Natural Gas Corporation Limited (ONGC), and the National Oil Companies and Research Institutes of India. The India National Gas Hydrate Program Expedition 01 (NGHP-01) established the presence of gas hydrate in the Krishna Godavari (KG) and Mahanadi Basins and in the offshore area of the Andaman Sea Basin. However, the gas hydrates discovered during NGHP-01 were mainly distributed as fracture-filling material in fine-grained clay-rich sediments. The India National Gas Hydrate Program Expedition 02 (NGHP-02) was carried out with an objective to discover gas hydrate in sand-rich sediment along the eastern offshore margin of India. ONGC planned and executed NGHP-02 on the behalf of the MoPNG. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) tools and an additional 17 holes were then drilled and/or cored with conventional coring tools (HPCS/ESCS) or pressure coring tools (PCTB). Wireline logging was conducted in 10 holes and formation tests using a dual packer Modular Formation Dynamics Tester (MDT) tool were carried out in two holes. The onboard science team used the laboratory facilities on the D/V Chikyu to examine and analyse the physical properties, geochemistry, and sedimentology of all the cores collected during the expedition. Core samples were also analysed in additional post-expedition shore-based studies conducted in numerous domestic and international gas hydrate research laboratories. The NGHP-02 sediment cores were archived at the National Gas Hydrate Core Repository in Mumbai (India), which is associated with the ONGC Gas Hydrate Research and Technology Centre (GHRTC). The necessary data for characterizing the occurrence of gas hydrate, such as interstitial water chlorinities, core-derived gas chemistry, physical and sedimentological properties, thermal images of the recovered cores, pressure core and downhole measured logging data (LWD and/or conventional wireline log data), were obtained from most of the drill sites established during NGHP-02. Almost all the drill sites yielded evidence for the occurrence of gas hydrate; however, the inferred in situ concentration of gas hydrate varied substantially from site to site. For the most part, the interpretation of downhole logging data, core thermal images, interstitial water analyses, and pressure core images from the sites established during NGHP-02 indicate that the occurrence of concentrated gas hydrate is mostly associated with coarser grained (sand-rich) sediments. This paper presents the operational and technical summary of NGHP-02. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) to

Journal of Marine and Petroleum Geology↗
USGS2010

Mineralogy and chemistry of cobbles at Meridiani Planum, Mars, investigated by the Mars Exploration Rover Opportunity

Numerous loose rocks with dimensions of a few centimeters to tens of centimeters and with no obvious physical relationship to outcrop rocks have been observed along the traverse of the Mars Exploration Rover Opportunity. To date, about a dozen of these rocks have been analyzed with Opportunity's contact instruments, providing information about elemental chemistry (Alpha Particle X‐ray Spectrometer), iron mineralogy and oxidation states (Mössbauer Spectrometer) and texture (Microscopic Imager). These “cobbles” appear to be impact related, and three distinct groups can be identified on the basis of chemistry and mineralogy. The first group comprises bright fragments of the sulfate‐rich bedrock that are compositionally and texturally indistinguishable from outcrop rocks. All other cobbles are dark and are divided into two groups, referred to as the “Barberton group” and the “Arkansas group,” after the first specimen of each that was encountered by Opportunity. Barberton group cobbles are interpreted as meteorites with an overall chemistry and mineralogy consistent with a mesosiderite silicate clast composition. Arkansas group cobbles appear to be related to Meridiani outcrop and contain an additional basaltic component. They have brecciated textures, pointing to an impact‐related origin during which local bedrock and basaltic material were mixed.

Journal of Geophysical Research E: Planets↗
USGS2008

Veneers, rinds, and fracture fills: Relatively late alteration of sedimentary rocks at Meridiani Planum, Mars

Veneers and thicker rinds that coat outcrop surfaces and partially cemented fracture fills formed perpendicular to bedding document relatively late stage alteration of ancient sedimentary rocks at Meridiani Planum, Mars. The chemistry of submillimeter thick, buff-colored veneers reflects multiple processes at work since the establishment of the current plains surface. Veneer composition is dominated by the mixing of silicate-rich dust and sulfate-rich outcrop surface, but it has also been influenced by mineral precipitation, including NaCl, and possibly by limited physical or chemical weathering of sulfate minerals. Competing processes of chemical alteration (perhaps mediated by thin films of water or water vapor beneath blanketing soils) and sandblasting of exposed outcrop surfaces determine the current distribution of veneers. Dark-toned rinds several millimeters thick reflect more extensive surface alteration but also indicate combined dust admixture, halite precipitation, and possible minor sulfate removal. Cemented fracture fills that are differentially resistant to erosion occur along the margins of linear fracture systems possibly related to impact. These appear to reflect limited groundwater activity along the margins of fractures, cementing mechanically introduced fill derived principally from outcrop rocks. The limited thickness and spatial distribution of these three features suggest that aqueous activity has been rare and transient or has operated at exceedingly low rates during the protracted interval since outcropping Meridiani strata were exposed on the plains surface.

Journal of Geophysical Research E: Planets↗
USGS2015

Chemical variations in Yellowknife Bay formation sedimentary rocks analyzed by ChemCam on board the Curiosity rover on Mars

The Yellowknife Bay formation represents a ~5 m thick stratigraphic section of lithified fluvial and lacustrine sediments analyzed by the Curiosity rover in Gale crater, Mars. Previous works have mainly focused on the mudstones that were drilled by the rover at two locations. The present study focuses on the sedimentary rocks stratigraphically above the mudstones by studying their chemical variations in parallel with rock textures. Results show that differences in composition correlate with textures and both manifest subtle but significant variations through the stratigraphic column. Though the chemistry of the sediments does not vary much in the lower part of the stratigraphy, the variations in alkali elements indicate variations in the source material and/or physical sorting, as shown by the identification of alkali feldspars. The sandstones contain similar relative proportions of hydrogen to the mudstones below, suggesting the presence of hydrous minerals that may have contributed to their cementation. Slight variations in magnesium correlate with changes in textures suggesting that diagenesis through cementation and dissolution modified the initial rock composition and texture simultaneously. The upper part of the stratigraphy (~1 m thick) displays rocks with different compositions suggesting a strong change in the depositional system. The presence of float rocks with similar compositions found along the rover traverse suggests that some of these outcrops extend further away in the nearby hummocky plains.

Journal of Geophysical Research E: Planets↗