Shallow methane hydrate system controls ongoing, downslope sediment transport in a low-velocity active submarine landslide complex, Hikurangi Margin, New Zealand

NASA Astrophysics Data System (ADS)

Mountjoy, Joshu J.; Pecher, Ingo; Henrys, Stuart; Crutchley, Gareth; Barnes, Philip M.; Plaza-Faverola, Andreia

2014-11-01

Morphological and seismic data from a submarine landslide complex east of New Zealand indicate flow-like deformation within gas hydrate-bearing sediment. This "creeping" deformation occurs immediately downslope of where the base of gas hydrate stability reaches the seafloor, suggesting involvement of gas hydrates. We present evidence that, contrary to conventional views, gas hydrates can directly destabilize the seafloor. Three mechanisms could explain how the shallow gas hydrate system could control these landslides. (1) Gas hydrate dissociation could result in excess pore pressure within the upper reaches of the landslide. (2) Overpressure below low-permeability gas hydrate-bearing sediments could cause hydrofracturing in the gas hydrate zone valving excess pore pressure into the landslide body. (3) Gas hydrate-bearing sediment could exhibit time-dependent plastic deformation enabling glacial-style deformation. We favor the final hypothesis that the landslides are actually creeping seafloor glaciers. The viability of rheologically controlled deformation of a hydrate sediment mix is supported by recent laboratory observations of time-dependent deformation behavior of gas hydrate-bearing sands. The controlling hydrate is likely to be strongly dependent on formation controls and intersediment hydrate morphology. Our results constitute a paradigm shift for evaluating the effect of gas hydrates on seafloor strength which, given the widespread occurrence of gas hydrates in the submarine environment, may require a reevaluation of slope stability following future climate-forced variation in bottom-water temperature.

[Progress in Raman spectroscopic measurement of methane hydrate].

PubMed

Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun

2009-09-01

Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

Controls on the physical properties of gas-hydrate-bearing sediments because of the interaction between gas hydrate and porous media

USGS Publications Warehouse

Lee, Myung W.; Collett, Timothy S.

2005-01-01

Physical properties of gas-hydrate-bearing sediments depend on the pore-scale interaction between gas hydrate and porous media as well as the amount of gas hydrate present. Well log measurements such as proton nuclear magnetic resonance (NMR) relaxation and electromagnetic propagation tool (EPT) techniques depend primarily on the bulk volume of gas hydrate in the pore space irrespective of the pore-scale interaction. However, elastic velocities or permeability depend on how gas hydrate is distributed in the pore space as well as the amount of gas hydrate. Gas-hydrate saturations estimated from NMR and EPT measurements are free of adjustable parameters; thus, the estimations are unbiased estimates of gas hydrate if the measurement is accurate. However, the amount of gas hydrate estimated from elastic velocities or electrical resistivities depends on many adjustable parameters and models related to the interaction of gas hydrate and porous media, so these estimates are model dependent and biased. NMR, EPT, elastic-wave velocity, electrical resistivity, and permeability measurements acquired in the Mallik 5L-38 well in the Mackenzie Delta, Canada, show that all of the well log evaluation techniques considered provide comparable gas-hydrate saturations in clean (low shale content) sandstone intervals with high gas-hydrate saturations. However, in shaly intervals, estimates from log measurement depending on the pore-scale interaction between gas hydrate and host sediments are higher than those estimates from measurements depending on the bulk volume of gas hydrate.

Characterization of Gas-Hydrate Sediment: In Situ Evaluation of Hydrate Saturation in Pores of Pressured Sedimental Samples

NASA Astrophysics Data System (ADS)

Jin, Y.; Konno, Y.; Kida, M.; Nagao, J.

2014-12-01

Hydrate saturation of gas-hydrate bearing sediment is a key of gas production from natural gas-hydrate reservoir. Developable natural gas-hydrates by conventional gas/oil production apparatus almost exist in unconsolidated sedimental layer. Generally, hydrate saturations of sedimental samples are directly estimated by volume of gas generated from dissociation of gas hydrates in pore spaces, porosity data and volume of the sediments. Furthermore, hydrate saturation can be also assessed using velocity of P-wave through sedimental samples. Nevertheless, hydrate saturation would be changed by morphological variations (grain-coating, cementing and pore-filling model) of gas hydrates in pore spaces. Jin et al.[1,2] recently observed the O-H stretching bands of H2O molecules of methane hydrate in porous media using an attenuated total reflection IR (ATR-IR) spectra. They observed in situ hydrate formation/dissociation process in sandy samples (Tohoku Keisya number 8, grain size of ca. 110 μm). In this presentation, we present IR spectroscopy approach to in situ evaluation of hydrate saturation of pressured gas-hydrate sediments. This work was supported by funding from the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by the Ministry of Economy, Trade and Industry (METI), Japan. [1] Jin, Y.; Konno, Y.; Nagao, J. Energy Fules, 2012, 26, 2242-2247. [2] Jin, Y.; Oyama, H.; Nagao, J. Jpn. J. Appl. Phys. 2009, 48, No. 108001.

Methane hydrate formation in partially water-saturated Ottawa sand

USGS Publications Warehouse

Waite, W.F.; Winters, W.J.; Mason, D.H.

2004-01-01

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.

Hydrate-Bearing Clayey Sediments: Morphology, Physical Properties, Production and Engineering/Geological Implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Santamarina, J. Carlos

Fine-grained sediments host more than 90 percent of global gas hydrate accumulation. However, hydrate formation in clay-dominated sediments is less understood and characterized than other types of hydrate occurrence. There is an inadequate understanding of hydrate formation mechanisms, segregation structures, hydrate lens topology, system connectivity, and physical macro-scale properties of clay-dominated hydrate-bearing sediments. This situation hinders further analyses of the global carbon budget as well as engineering challenges/solutions related to hydrate instability and production. This project studies hydrate-bearing clay-dominated sediments with emphasis on the enhanced fundamental understanding of hydrate formation and resulting morphology, the development laboratory techniques to emulate naturalmore » hydrate formations, the assessment of analytical tools to predict physical properties, the evaluation of engineering and geological implications, and the advanced understanding of gas production potential from finegrained sediments.« less

Evaluation of Gas Hydrate at Alaminos Canyon 810, Northern Gulf of Mexico Slope

NASA Astrophysics Data System (ADS)

Yang, C.; Cook, A.; Sawyer, D.; Hillman, J. I. T.

2016-12-01

We characterize the gas hydrate reservoir in Alaminos Canyon Block 810 (AC810) on the northern Gulf of Mexico slope, approximately 400 km southeast of Houston, Texas, USA. Three-dimensional seismic data shows a bottom-simulating-reflection (BSR), over 30 km2, which suggests that a significant gas hydrate accumulation may occur at AC810. Furthermore, logging while drilling (LWD) data acquired from a Statoil well located that penetrated the BSR near the crest of the regional anticline indicates two possible gas hydrate units (Hydrate Unit A and Hydrate Unit B). LWD data in this interval are limited to gamma ray and resistivity only. Resistivity curve separations are observed in Hydrate Unit A (131 to 253 mbsf) suggesting hydrate-filled fractures in marine mud. A spiky high resistivity response in Hydrate Unit B (308 to 354 mbsf) could either be a marine mud or a sand-prone interval. The abrupt decrease (from 7 to 1 Ωm) in resistivity logs at 357 mbsf generally corresponds with the interpreted base of hydrate stability, as the BSR is observed near 350 mbsf on the seismic data. To further investigate the formation characteristics, we generate synthetic traces using general velocity and density trends for marine sediments to match the seismic trace extracted at the Statoil well. We consider models with 1) free gas and 2) water only below the base of hydrate stability. In our free gas-below models, we find the velocity of Hydrate Unit A and Hydrate Unit B is generally low and does not deviate significantly from the general velocity trends, suggesting that gas hydrate is present in a marine mud. In the water-below model, the compressional velocity of Hydrate Unit B ranges from 2450 m/s to 3150 m/s. This velocity is similar to the velocity of high hydrate saturation in sand; typically greater than 2500 m/s. This may indicate that Hydrate Unit B is sand with high hydrate saturation; however, to achieve a suitable match between the water-below synthetic seismogram and the trace, a high velocity layer was required below the base of hydrate stability, which is not indicated by the well logs. Our models indicate that at AC810, Hydrate Unit A probably contains hydrate filled fractures in a marine mud. For Hydrate Unit B, our models suggest hydrate may occur in a sand-prone interval, but is more likely to be gas hydrate filled fractures in marine mud.

Ab initio investigation of the first hydration shell of protonated glycine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Zhichao; Chen, Dong, E-mail: dongchen@henu.edu.cn, E-mail: boliu@henu.edu.cn; Zhao, Huiling

2014-02-28

The first hydration shell of the protonated glycine is built up using Monte Carlo multiple minimum conformational search analysis with the MMFFs force field. The potential energy surfaces of the protonated glycine and its hydration complexes with up to eight water molecules have been scanned and the energy-minimized structures are predicted using the ab initio calculations. First, three favorable structures of protonated glycine were determined, and the micro-hydration processes showed that water can significantly stabilize the unstable conformers, and then their first hydration shells were established. Finally, we found that seven water molecules are required to fully hydrate the firstmore » hydration shell for the most stable conformer of protonated glycine. In order to analyse the hydration process, the dominant hydration sites located around the ammonium and carboxyl groups are studied carefully and systemically. The results indicate that, water molecules hydrate the protonated glycine in an alternative dynamic hydration process which is driven by the competition between different hydration sites. The first three water molecules are strongly attached by the ammonium group, while only the fourth water molecule is attached by the carboxyl group in the ultimate first hydration shell of the protonated glycine. In addition, the first hydration shell model has predicted most identical structures and a reasonable accord in hydration energy and vibrational frequencies of the most stable conformer with the conductor-like polarizable continuum model.« less

Microstructural characteristics of natural gas hydrates hosted in various sand sediments.

PubMed

Zhao, Jiafei; Yang, Lei; Liu, Yu; Song, Yongchen

2015-09-21

Natural gas hydrates have aroused worldwide interest due to their energy potential and possible impact on climate. The occurrence of natural gas hydrates hosted in the pores of sediments governs the seismic exploration, resource assessment, stability of deposits, and gas production from natural gas hydrate reserves. In order to investigate the microstructure of natural gas hydrates occurring in pores, natural gas hydrate-bearing sediments were visualized using microfocus X-ray computed tomography (CT). Various types of sands with different grain sizes and wettability were used to study the effect of porous materials on the occurrence of natural gas hydrates. Spatial distributions of methane gas, natural gas hydrates, water, and sands were directly identified. This work indicates that natural gas hydrates tend to reside mainly within pore spaces and do not come in contact with adjacent sands. Such an occurring model of natural gas hydrates is termed the floating model. Furthermore, natural gas hydrates were observed to nucleate at gas-water interfaces as lens-shaped clusters. Smaller sand grain sizes contribute to higher hydrate saturation. The wetting behavior of various sands had little effect on the occurrence of natural gas hydrates within pores. Additionally, geometric properties of the sediments were collected through CT image reconstructions. These findings will be instructive for understanding the microstructure of natural gas hydrates within major global reserves and for future resource utilization of natural gas hydrates.

Thermodynamic properties of methane hydrate in quartz powder.

PubMed

Voronov, Vitaly P; Gorodetskii, Evgeny E; Safonov, Sergey S

2007-10-04

Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.

Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

USGS Publications Warehouse

Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

2007-01-01

The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

Development of hydrate risk quantification in oil and gas production

NASA Astrophysics Data System (ADS)

Chaudhari, Piyush N.

Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in order to reduce the parametric study that may require a long duration of time using The Colorado School of Mines Hydrate Kinetic Model (CSMHyK). The evolution of the hydrate plugging risk along flowline-riser systems is modeled for steady state and transient operations considering the effect of several critical parameters such as oil-hydrate slip, duration of shut-in, and water droplet size on a subsea tieback system. This research presents a novel platform for quantification of the hydrate plugging risk, which in-turn will play an important role in improving and optimizing current hydrate management strategies. The predictive strength of the hydrate risk quantification and hydrate prediction models will have a significant impact on flow assurance engineering and design with respect to building safe and efficient hydrate management techniques for future deep-water developments.

Methane hydrate induced permeability modification for multiphase flow in unsaturated porous media

NASA Astrophysics Data System (ADS)

Seol, Yongkoo; Kneafsey, Timothy J.

2011-08-01

An experimental study was performed using X-ray computed tomography (CT) scanning to capture three-dimensional (3-D) methane hydrate distributions and potential discrete flow pathways in a sand pack sample. A numerical study was also performed to develop and analyze empirical relations that describe the impacts of hydrate accumulation habits within pore space (e.g., pore filling or grain cementing) on multiphase fluid migration. In the experimental study, water was injected into a hydrate-bearing sand sample that was monitored using an X-ray CT scanner. The CT images were converted into numerical grid elements, providing intrinsic sample data including porosity and phase saturations. The impacts of hydrate accumulation were examined by adapting empirical relations into the flow simulations as additional relations governing the evolution of absolute permeability of hydrate bearing sediment with hydrate deposition. The impacts of pore space hydrate accumulation habits on fluid migration were examined by comparing numerical predictions with experimentally measured water saturation distributions and breakthrough curves. A model case with 3-D heterogeneous initial conditions (hydrate saturation, porosity, and water saturation) and pore body-preferred hydrate accumulations best captured water migration behavior through the hydrate-bearing sample observed in the experiment. In the best matching model, absolute permeability in the hydrate bearing sample does not decrease significantly with increasing hydrate saturation until hydrate saturation reaches about 40%, after which it drops rapidly, and complete blockage of flow through the sample can occur as hydrate accumulations approach 70%. The result highlights the importance of permeability modification due to hydrate accumulation habits when predicting multiphase flow through high-saturation, reservoir quality hydrate-bearing sediments.

Elastic properties of gas hydrate-bearing sediments

USGS Publications Warehouse

Lee, M.W.; Collett, T.S.

2001-01-01

Downhole-measured compressional- and shear-wave velocities acquired in the Mallik 2L-38 gas hydrate research well, northwestern Canada, reveal that the dominant effect of gas hydrate on the elastic properties of gas hydrate-bearing sediments is as a pore-filling constituent. As opposed to high elastic velocities predicted from a cementation theory, whereby a small amount of gas hydrate in the pore space significantly increases the elastic velocities, the velocity increase from gas hydrate saturation in the sediment pore space is small. Both the effective medium theory and a weighted equation predict a slight increase of velocities from gas hydrate concentration, similar to the field-observed velocities; however, the weighted equation more accurately describes the compressional- and shear-wave velocities of gas hydrate-bearing sediments. A decrease of Poisson's ratio with an increase in the gas hydrate concentration is similar to a decrease of Poisson's ratio with a decrease in the sediment porosity. Poisson's ratios greater than 0.33 for gas hydrate-bearing sediments imply the unconsolidated nature of gas hydrate-bearing sediments at this well site. The seismic characteristics of gas hydrate-bearing sediments at this site can be used to compare and evaluate other gas hydrate-bearing sediments in the Arctic.

Impact of Compound Hydrate Dynamics on Phase Boundary Changes

NASA Astrophysics Data System (ADS)

Osegovic, J. P.; Max, M. D.

2006-12-01

Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed systems include pipeline blockages and natural hydrate concentrations associated with upwelling fluids in marine sediments. 3) In open systems, mass can either flow into or out of a system. In such situations compound hydrate will form or decompose to re-establish chemical equilibrium. This is accomplished by 1) loading/consuming a preferred hydrate former to/from the surroundings, 2) lowering/raising the temperature of the system, and 3) increasing the local pressure. Examples of this type of system include hydrate produced for low pressure transport, depressurized or superheated hydrate settings (pipeline remediation or energy recovery), or in an industrial process where formation of compound hydrates may be used to separate and concentrate gases from a mixture. The relationship between composition and the phase boundary is as important as pressure and temperature effects. Composition is less significant for simple hydrates where the hydrate behaves as a one-component mineral, but for compound hydrate, feedback between pressure, temperature, and composition can result in complex system behavior.

Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

USGS Publications Warehouse

Lorenson, T.D.

1999-01-01

Molecular and isotopic composition of gases from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well demonstrate that the in situ gases can be divided into three zones composed of mixtures of microbial and thermogenic gases. Sediments penetrated by the well are thermally immature; thus the sediments are probably not a source of thermogenic gas. Thermogenic gas likely migrated from depths below 5000 m. Higher concentrations of gas within and beneath the gas hydrate zone suggest that gas hydrate is a partial barrier to gas migration. Gas hydrate accumulations occur wholly within zone 3, below the base of permafrost. The gas in gas hydrate resembles, in part, the thermogenic gas in surrounding sediments and gas desorbed from lignite. Gas hydrate composition implies that the primary gas hydrate form is Structure I. However, Structure II stabilizing gases are more concentrated and isotopically partitioned in gas hydrate relative to the sediment hosting the gas hydrate, implying that Structure II gas hydrate may be present in small quantities.

Economic geology of natural gas hydrate

USGS Publications Warehouse

Max, M.D.; Johnson, A.H.; Dillon, William P.

2006-01-01

This is the first book that attempts to broadly integrate the most recent knowledge in the fields of hydrate nucleation and growth in permafrost regions and marine sediments. Gas hydrate reactant supply, growth models, and implications for pore fill by natural gas hydrate are discussed for both seawater precursors in marine sediments and for permafrost hydrate. These models for forming hydrate concentrations that will constitute targets for exploration are discussed, along with exploration methods. Thermodynamic models for the controlled conversion of hydrate to natural gas, which can be recovered using conventional industry practices, suggest that a number of different types of hydrate occurrence are likely to be practical sources of hydrate natural gas. Current progress in the various aspects of commercial development of hydrate gas deposits are discussed, along with the principal extractive issues that have yet to be resolved.

Energy resource potential of natural gas hydrates

USGS Publications Warehouse

Collett, T.S.

2002-01-01

The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

Methane hydrates in nature - Current knowledge and challenges

USGS Publications Warehouse

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance our understanding of methane hydrates in nature. COL assembled a Methane Hydrate Project Science Team with members from academia, industry, and government. This Science Team worked with COL and DOE to develop and host the Methane Hydrate Community Workshop, which surveyed a substantial cross section of the methane hydrate research community for input on the most important research developments in our understanding of methane hydrates in nature and their potential role as an energy resource, a geohazard, and/or as an agent of global climate change. Our understanding of how methane hydrates occur in nature is still growing and evolving, and it is known with certainty that field, laboratory, and modeling studies have contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information needed to advance our understanding of methane hydrates.

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations.

PubMed

Schicks, J M; Luzi, M; Beeskow-Strauch, B

2011-11-24

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need to match the arrangements of silanols to form more hydrogen bonds. At the end of the simulation, the hydrate solid is separated from the silica surface by liquid water, with only several cages forming hydrogen bonds with the silica surface, mainly due to the low CH 4 aqueous concentrations near the surface. To further explore hydrate formation between graphite surfaces, CH 4 /water homogeneous solution systems are also simulated. CH 4 molecules in the solution are adsorbed onto graphite and hydrate nucleation occurs in the bulk region. During hydrate growth, the adsorbed CH 4 molecules are gradually converted into hydrate solid. It is found that the hydrate-like ordering of interfacial water induced by graphite promotes the contact between hydrate solid and graphite. We reveal that the ability of silanol groups on silica to form strong hydrogen bonds to stabilize incipient hydrate solid, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

Molecular Dynamics Simulation of the Crystal Nucleation and Growth Behavior of Methane Hydrate in the Presence of the Surface and Nanopores of Porous Sediment.

PubMed

Yan, Ke-Feng; Li, Xiao-Sen; Chen, Zhao-Yang; Xia, Zhi-Ming; Xu, Chun-Gang; Zhang, Zhiqiang

2016-08-09

The behavior of hydrate formation in porous sediment has been widely studied because of its importance in the investigation of reservoirs and in the drilling of natural gas hydrate. However, it is difficult to understand the hydrate nucleation and growth mechanism on the surface and in the nanopores of porous media by experimental and numerical simulation methods. In this work, molecular dynamics simulations of the nucleation and growth of CH4 hydrate in the presence of the surface and nanopores of clay are carried out. The molecular configurations and microstructure properties are analyzed for systems containing one H2O hydrate layer (System A), three H2O hydrate layers (System B), and six H2O hydrate layers (System C) in both clay and the bulk solution. It is found that hydrate formation is more complex in porous media than in the pure bulk solution and that there is cooperativity between hydrate growth and molecular diffusion in clay nanopores. The hydroxylated edge sites of the clay surface could serve as a source of CH4 molecules to facilitate hydrate nucleation. The diffusion velocity of molecules is influenced by the growth of the hydrate that forms a block in the throats of the clay nanopore. Comparing hydrate growth in different clay pore sizes reveals that the pore size plays an important role in hydrate growth and molecular diffusion in clay. This simulation study provides the microscopic mechanism of hydrate nucleation and growth in porous media, which can be favorable for the investigation of the formation of natural gas hydrate in sediments.

The molecular mechanism of the inhibition effects of PVCaps on the growth of sI hydrate: an unstable adsorption mechanism.

PubMed

Xu, Jiafang; Li, Liwen; Liu, Jinxiang; Wang, Xiaopu; Yan, Youguo; Zhang, Jun

2018-03-28

The inhibition properties of kinetic hydrate inhibitor (KHI) molecules on the dynamic growth of a hydrate/water interface are investigated by using molecular dynamics simulations. The shape of the hydrate interface is transformed from laminar to funnel by PVCaps. Results indicate that the inhibition effects not only depend on the adsorption capacity which was believed to determine inhibition, but also on the fact that PVCaps must have some non-binding-hydrate sites that don't tend to combine with hydrate. By observing the time evolution of the distance between each component of PVCaps and hydrate, the heterocyclic ring of PVCaps mainly contributes to adsorption and can preferentially adjust itself to come into contact with a hydrate semi-large-cage. The distance between the amide of PVCaps and hydrate is about 4 Å and exceeds the range of a general hydrogen bond (3.5 Å), which proves that the non-binding-hydrate sites of PVCaps exist. On the other hand, the amide of PVCaps is at the intersection of the solid-liquid interface but has no adsorption affinity for hydrate, so this adsorption pattern indicates that the PVCaps at the hydrate interface are not stable. Due to this unstable adsorption, a repeated hydrate destruction phenomenon was revealed by the identification algorithm of hydrate and the calculation of the local number density of methane. The statistical evolution of water rings further proved the existence of non-binding-hydrate sites in PVCaps and the inhibition mechanism to destroy the hydrate cages by PVCaps. This unstable adsorption mechanism may shed light on the development of novel efficient KHIs.

Pore Effect on the Occurrence and Formation of Gas Hydrate in Permafrost of Qilian Mountain, Qinghai-Tibet Plateau, China

NASA Astrophysics Data System (ADS)

Gao, H.; Lu, H.; Lu, Z.

2014-12-01

Gas hydrates were found in the permafrost of Qilian Mountain, Qinghai- Tibet Plateau, China in 2008. It has been found that gas hydrates occur in Jurassic sedimentary rocks, and the hydrated gases are mainly thermogenic. Different from the gas hydrates existing in loose sands in Mallik, Mackenzie Delta, Canada and North Slope, Alaska, USA, the gas hydrates in Qilian Mountain occurred in hard rocks. For understanding the occurrence and formation mechanism of gas hydrate in hard rcok, extensive experimental investigations have been conducted to study the pore features and hydrate formation in the rocks recovered from the hydrate layers in Qilian Mountain. The structures of sedimentary rock were observed by high-resolution X-ray CT, and pore size distribution of a rock specimen was measured with the mercury-injection method. Methane hydrate was synthesized in water-saturated rocks, and the saturations of hydrate in sedimentary rocks of various types were estimated from the amount of gas released from certain volume of rock. X-ray CT observation revealed that fractures were developed in the rocks associated with faults, while those away from faults were generally with massive structure. The mercury-injection analysis of pore features found that the porosities of the hydrate-existing rocks were generally less than 3%, and the pore sizes were generally smaller than 100 nm. The synthesizing experiments found that the saturation of methane hydrate were generally lower than 6% of pore space in rocks, but up to 16% when fractures developed. The low hydrate saturation in Qilian sedimentary rocks has been found mainly due to the small pore size of rock. The low hydrate saturation in the rocks might be the reason for the failure of regional seismic and logging detections of gas hydrates in Qilian Mountain.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Chand, Shyam; Minshull, Tim A.; Priest, Jeff A.; Best, Angus I.; Clayton, Christopher R. I.; Waite, William F.

2006-08-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L-38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

USGS Publications Warehouse

Chand, S.; Minshull, T.A.; Priest, J.A.; Best, A.I.; Clayton, C.R.I.; Waite, W.F.

2006-01-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L–38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

Dielectric method of high-resolution gas hydrate estimation

NASA Astrophysics Data System (ADS)

Sun, Y. F.; Goldberg, D.

2005-02-01

In-situ dielectric properties of natural gas hydrate are measured for the first time in the Mallik 5L-38 Well in the Mackenzie Delta, Canada. The average dielectric constant of the hydrate zones is 9, ranging from 5 to 20. The average resistivity is >5 ohm.m in the hydrate zones, ranging from 2 to 10 ohm.m at a 1.1 GHz dielectric tool frequency. The dielectric logs show similar trends with sonic and induction resistivity logs, but exhibits inherently higher vertical resolution (<5 cm). The average in-situ hydrate saturation in the well is about 70%, ranging from 20% to 95%. The dielectric estimates are overall in agreement with induction estimates but the induction log tends to overestimate hydrate content up to 15%. Dielectric estimates could be used as a better proxy of in-situ hydrate saturation in modeling hydrate dynamics. The fine-scale structure in hydrate zones could help reveal hydrate formation history.

Properties of samples containing natural gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, determined using Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI)

USGS Publications Warehouse

Winters, W.J.

1999-01-01

As part of an ongoing laboratory study, preliminary acoustic, strength, and hydraulic conductivity results are presented from a suite of tests conducted on four natural-gas-hydrate-containing samples from the Mackenzie Delta JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The gas hydrate samples were preserved in pressure vessels during transport from the Northwest Territories to Woods Hole, Massachusetts, where multistep tests were performed using GHASTLI (Gas Hydrate And Sediment Test Laboratory Instrument), which recreates pressure and temperature conditions that are stable for gas hydrate. Properties and changes in sediment behaviour were measured before, during, and after controlled gas hydrate dissociation. Significant amounts of gas hydrate occupied the sample pores and substantially increased acoustic velocity and shear strength.

Surfactant process for promoting gas hydrate formation and application of the same

DOEpatents

Rogers, Rudy E.; Zhong, Yu

2002-01-01

This invention relates to a method of storing gas using gas hydrates comprising forming gas hydrates in the presence of a water-surfactant solution that comprises water and surfactant. The addition of minor amounts of surfactant increases the gas hydrate formation rate, increases packing density of the solid hydrate mass and simplifies the formation-storage-decomposition process of gas hydrates. The minor amounts of surfactant also enhance the potential of gas hydrates for industrial storage applications.

Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates.

PubMed

Holzammer, Christine; Schicks, Judith M; Will, Stefan; Braeuer, Andreas S

2017-09-07

We present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO 2 ) gas hydrates using Raman spectroscopy. The CO 2 hydrates were formed from sodium chloride/water solutions with salinities of 0-10 wt %, which were pressurized with liquid CO 2 in a stirred vessel at 6 MPa and a subcooling of 9.5 K. The formation of the CO 2 hydrate resulted in a hydrate gel where the solid hydrate can be considered as the continuous phase that includes small amounts of a dispersed liquid water-rich phase that has not been converted to hydrate. During the hydrate formation process we quantified the fraction of solid hydrate, x H , and the fraction of the dispersed liquid water-rich phase, x L , from the signature of the hydroxyl (OH)-stretching vibration of the hydrate gel. We found that the fraction of hydrate x H contained in the hydrate gel linearly depends on the salinity of the initial liquid water-rich phase. In addition, the ratio of CO 2 and water was analyzed in the liquid water-rich phase before hydrate formation, in the hydrate gel during growth and dissociation, and after its complete dissociation again in the liquid water-rich phase. We observed a supersaturation of CO 2 in the water-rich phase after complete dissociation of the hydrate gel and were able to show that the excess CO 2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. These residual nano- and microdroplets could be a possible explanation for the so-called memory effect.

Probing methane hydrate nucleation through the forward flux sampling method.

PubMed

Bi, Yuanfei; Li, Tianshu

2014-11-26

Understanding the nucleation of hydrate is the key to developing effective strategies for controlling methane hydrate formation. Here we present a computational study of methane hydrate nucleation, by combining the forward flux sampling (FFS) method and the coarse-grained water model mW. To facilitate the application of FFS in studying the formation of methane hydrate, we developed an effective order parameter λ on the basis of the topological analysis of the tetrahedral network. The order parameter capitalizes the signature of hydrate structure, i.e., polyhedral cages, and is capable of efficiently distinguishing hydrate from ice and liquid water while allowing the formation of different hydrate phases, i.e., sI, sII, and amorphous. Integration of the order parameter λ with FFS allows explicitly computing hydrate nucleation rates and obtaining an ensemble of nucleation trajectories under conditions where spontaneous hydrate nucleation becomes too slow to occur in direct simulation. The convergence of the obtained hydrate nucleation rate was found to depend crucially on the convergence of the spatial distribution for the spontaneously formed hydrate seeds obtained from the initial sampling of FFS. The validity of the approach is also verified by the agreement between the calculated nucleation rate and that inferred from the direct simulation. Analyzing the obtained large ensemble of hydrate nucleation trajectories, we show hydrate formation at 220 K and 500 bar is initiated by the nucleation events occurring in the vicinity of water-methane interface, and facilitated by a gradual transition from amorphous to crystalline structure. The latter provides the direct support to the proposed two-step nucleation mechanism of methane hydrate.

Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement.

PubMed

Thompson, Helen; Soper, Alan K; Buchanan, Piers; Aldiwan, Nawaf; Creek, Jefferson L; Koh, Carolyn A

2006-04-28

Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.

CO2 hydrate formation and dissociation in cooled porous media: a potential technology for CO2 capture and storage.

PubMed

Yang, Mingjun; Song, Yongchen; Jiang, Lanlan; Zhu, Ningjun; Liu, Yu; Zhao, Yuechao; Dou, Binlin; Li, Qingping

2013-09-03

The purpose of this study was to investigate the hydrate formation and dissociation with CO2 flowing through cooled porous media at different flow rates, pressures, temperatures, and flow directions. CO2 hydrate saturation was quantified using the mean intensity of water. The experimental results showed that the hydrate block appeared frequently, and it could be avoided by stopping CO2 flooding early. Hydrate formed rapidly as the temperature was set to 274.15 or 275.15 K, but the hydrate formation delayed when it was 276.15 K. The flow rate was an important parameter for hydrate formation; a too high or too low rate was not suitable for CO2 hydration formation. A low operating pressure was also unacceptable. The gravity made hydrate form easily in the vertically upward flow direction. The pore water of the second cycle converted to hydrate more completely than that of the first cycle, which was a proof of the hydrate "memory effect". When the pressure was equal to atmospheric pressure, hydrate did not dissociate rapidly and abundantly, and a long time or reduplicate depressurization should be used in industrial application.

Thermodynamic properties of hydrate phases immersed in ice phase

NASA Astrophysics Data System (ADS)

Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

2006-01-01

Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

Numerical analysis of wellbore instability in gas hydrate formation during deep-water drilling

NASA Astrophysics Data System (ADS)

Zhang, Huaiwen; Cheng, Yuanfang; Li, Qingchao; Yan, Chuanliang; Han, Xiuting

2018-02-01

Gas hydrate formation may be encountered during deep-water drilling because of the large amount and wide distribution of gas hydrates under the shallow seabed of the South China Sea. Hydrates are extremely sensitive to temperature and pressure changes, and drilling through gas hydrate formation may cause dissociation of hydrates, accompanied by changes in wellbore temperatures, pore pressures, and stress states, thereby leading to wellbore plastic yield and wellbore instability. Considering the coupling effect of seepage of drilling fluid into gas hydrate formation, heat conduction between drilling fluid and formation, hydrate dissociation, and transformation of the formation framework, this study established a multi-field coupling mathematical model of the wellbore in the hydrate formation. Furthermore, the influences of drilling fluid temperatures, densities, and soaking time on the instability of hydrate formation were calculated and analyzed. Results show that the greater the temperature difference between the drilling fluid and hydrate formation is, the faster the hydrate dissociates, the wider the plastic dissociation range is, and the greater the failure width becomes. When the temperature difference is greater than 7°C, the maximum rate of plastic deformation around the wellbore is more than 10%, which is along the direction of the minimum horizontal in-situ stress and associated with instability and damage on the surrounding rock. The hydrate dissociation is insensitive to the variation of drilling fluid density, thereby implying that the change of the density of drilling fluids has a minimal effect on the hydrate dissociation. Drilling fluids that are absorbed into the hydrate formation result in fast dissociation at the initial stage. As time elapses, the hydrate dissociation slows down, but the risk of wellbore instability is aggravated due to the prolonged submersion in drilling fluids. For the sake of the stability of the wellbore in deep-water drilling through hydrate formation, the drilling fluid with low temperatures should be given priority. The drilling process should be kept under balanced pressures, and the drilling time should be shortened.

Effect of Sodium Dodecyl Sulfate Surfactant on Methane Hydrate Formation: A Molecular Dynamics Study.

PubMed

Choudhary, Nilesh; Hande, Vrushali R; Roy, Sudip; Chakrabarty, Suman; Kumar, Rajnish

2018-06-28

In experimental studies, it has been observed that the presence of sodium dodecyl sulfate (SDS) significantly increases the kinetics of hydrate formation and the final water-to-hydrate conversion ratio. In this study, we intend to understand the molecular mechanism behind the effect of SDS on the formation of methane hydrate through molecular dynamics simulation. Hydrate formation conditions similar to that of laboratory experiments were chosen to study hydrate growth kinetics in 1 wt % SDS solution. We also investigate the effect of interactions with isolated SDS molecules on methane hydrate growth. It was observed that the hydrophobic tail part of the SDS molecule favorably interacts with the growing hydrate surface and may occupy the partial hydrate cages while the head groups remain exposed to water.

Estimating pore-space gas hydrate saturations from well log acoustic data

NASA Astrophysics Data System (ADS)

Lee, Myung W.; Waite, William F.

2008-07-01

Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate-bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

Equilibrium, Kinetics, and Spectroscopic Studies of SF6 Hydrate in NaCl Electrolyte Solution.

PubMed

Seo, Youngrok; Moon, Donghyun; Lee, Changho; Park, Jeong-Woo; Kim, Byeong-Soo; Lee, Gang-Woo; Dotel, Pratik; Lee, Jong-Won; Cha, Minjun; Yoon, Ji-Ho

2015-05-19

Many studies have focused on desalination via hydrate formation; however, for their potential application, knowledge pertaining to thermodynamic stability, formation kinetics, and guest occupation behavior in clathrate hydrates needs to be determined. Herein, the phase equilibria of SF6 hydrates in the presence of NaCl solutions (0, 2, 4, and 10 wt %) were monitored in the temperature range of 277-286 K and under pressures of up to 1.4 MPa. The formation kinetics of SF6 hydrates in the presence of NaCl solutions (0, 2, and 4 wt %) was also investigated. Gas consumption curves of SF6 hydrates showed that a pure SF6 hydrate system allowed fast hydrate growth as well as high conversion yield, whereas SF6 hydrate in the presence of NaCl solutions showed retarded hydrate growth rate as well as low conversion yield. In addition, structural identification of SF6 hydrates with and without NaCl solutions was performed using spectroscopic tools such as Raman spectroscopy and X-ray diffraction. The Raman spectrometer was also used to evaluate the temperature-dependent release behavior of guest molecules in SF6 and SF6 + 4 wt % NaCl hydrates. The results indicate that whereas SF6 hydrate starts to decompose at around 240 K, the escape of SF6 molecules in SF6 + 4 wt % NaCl hydrate is initiated rapidly at around 205 K. The results of this study can provide a better understanding of guest-host interaction in electrolyte-containing systems.

Micromechanical cohesion force between gas hydrate particles measured under high pressure and low temperature conditions.

PubMed

Lee, Bo Ram; Sum, Amadeu K

2015-04-07

To prevent hydrate plugging conditions in the transportation of oil/gas in multiphase flowlines, one of the key processes to control is the agglomeration/deposition of hydrate particles, which are determined by the cohesive/adhesive forces. Previous studies reporting measurements of the cohesive/adhesive force between hydrate particles used cyclopentane hydrate particles in a low-pressure micromechanical force apparatus. In this study, we report the cohesive forces of particles measured in a new high-pressure micromechanical force (MMF) apparatus for ice particles, mixed (methane/ethane, 74.7:25.3) hydrate particles (Structure II), and carbon dioxide hydrate particles (Structure I). The cohesive forces are measured as a function of the contact time, contact force, temperature, and pressure, and determined from pull-off measurements. For the measurements performed of the gas hydrate particles in the gas phase, the determined cohesive force is about 30-35 mN/m, about 8 times higher than the cohesive force of CyC5 hydrates in the liquid CyC5, which is about 4.3 mN/m. We show from our results that the hydrate structure (sI with CO2 hydrates and sII with CH4/C2H6 hydrates) has no influence on the cohesive force. These results are important in the deposition of a gas-dominated system, where the hydrate particles formed in the liquid phase can then stick to the hydrate deposited in the wall exposed to the gas phase.

The water retention curve and relative permeability for gas production from hydrate-bearing sediments: pore-network model simulation

NASA Astrophysics Data System (ADS)

Mahabadi, Nariman; Dai, Sheng; Seol, Yongkoo; Sup Yun, Tae; Jang, Jaewon

2016-08-01

The water retention curve and relative permeability are critical to predict gas and water production from hydrate-bearing sediments. However, values for key parameters that characterize gas and water flows during hydrate dissociation have not been identified due to experimental challenges. This study utilizes the combined techniques of micro-focus X-ray computed tomography (CT) and pore-network model simulation to identify proper values for those key parameters, such as gas entry pressure, residual water saturation, and curve fitting values. Hydrates with various saturation and morphology are realized in the pore-network that was extracted from micron-resolution CT images of sediments recovered from the hydrate deposit at the Mallik site, and then the processes of gas invasion, hydrate dissociation, gas expansion, and gas and water permeability are simulated. Results show that greater hydrate saturation in sediments lead to higher gas entry pressure, higher residual water saturation, and steeper water retention curve. An increase in hydrate saturation decreases gas permeability but has marginal effects on water permeability in sediments with uniformly distributed hydrate. Hydrate morphology has more significant impacts than hydrate saturation on relative permeability. Sediments with heterogeneously distributed hydrate tend to result in lower residual water saturation and higher gas and water permeability. In this sense, the Brooks-Corey model that uses two fitting parameters individually for gas and water permeability properly capture the effect of hydrate saturation and morphology on gas and water flows in hydrate-bearing sediments.

Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

NASA Astrophysics Data System (ADS)

Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

2014-05-01

The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase. Hence, it is possible to detect areas in the sediment sample where free gas is released due to hydrate dissociation and displaces the liquid phase. Combined with measurements and numerical simulation of the total two-phase fluxes from the sediment sample (see abstract Abendroth et al., this volume), the LARS experiments allow for detailed information on the dissociation process during hydrate production. Here we present the workflow and first results estimating local hydrate saturations and permeabilities during hydrate formation and the movement of liquid and gas phases during hydrate dissociation, respectively.

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Lu, H.; Lorenson, T.D.; Moudrakovski, I.L.; Ripmeester, J.A.; Collett, T.S.; Hunter, R.B.; Ratcliffe, C.I.

2011-01-01

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH4 gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state 13C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean ??13C=-48.6??? and ??D=-248??? for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage. ?? 2010 Elsevier Ltd.

Effect of Electric Field on Gas Hydrate Nucleation Kinetics: Evidence for the Enhanced Kinetics of Hydrate Nucleation by Negatively Charged Clay Surfaces.

PubMed

Park, Taehyung; Kwon, Tae-Hyuk

2018-03-06

Natural gas hydrates are found widely in oceanic clay-rich sediments, where clay-water interactions have a profound effect on the formation behavior of gas hydrates. However, it remains unclear why and how natural gas hydrates are formed in clay-rich sediments in spite of factors that limit gas hydrate formation, such as small pore size and high salinity. Herein, we show that polarized water molecules on clay surfaces clearly promote gas hydrate nucleation kinetics. When water molecules were polarized with an electric field of 10 4 V/m, gas hydrate nucleation occurred significantly faster with an induction time reduced by 5.8 times. Further, the presence of strongly polarized water layers at the water-gas interface hindered gas uptake and thus hydrate formation, when the electric field was applied prior to gas dissolution. Our findings expand our understanding of the formation habits of naturally occurring gas hydrates in clay-rich sedimentary deposits and provide insights into gas production from natural hydrate deposits.

Historical methane hydrate project review

USGS Publications Warehouse

Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

2013-01-01

In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated effort, the U.S. Congress enacted Public Law 106-­‐193, the Methane Hydrate Research and Development Act of 2000. This Act called for the Secretary of Energy to begin a methane hydrate research and development program in consultation with other U.S. federal agencies. At the same time a new methane hydrate research program had been launched in Japan by the Ministry of International Trade and Industry to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. Since this early start we have seen other countries including India, China, Canada, and the Republic of Korea establish large gas hydrate research and development programs. These national led efforts have also included the investment in a long list of important scientific research drilling expeditions and production test studies that have provided a wealth of information on the occurrence of methane hydrate in nature. The most notable expeditions and projects have including the following:-­‐Ocean Drilling Program Leg 164 (1995)-­‐Japan Nankai Trough Project (1999-­‐2000)-­‐Ocean Drilling Program Leg 204 (2004)-­‐Japan Tokai-­‐oki to Kumano-­‐nada Project (2004)-­‐Gulf of Mexico JIP Leg I (2005)-­‐Integrated Ocean Drilling Program Expedition 311 (2005)-­‐Malaysia Gumusut-­‐Kakap Project (2006)-­‐India NGHP Expedition 01 (2006)-­‐China GMGS Expedition 01 (2007)-­‐Republic of Korea UBGH Expedition 01 (2007)-­‐Gulf of Mexico JIP Leg II (2009)-­‐Republic of Korea UBGH Expedition 02 (2010)-­‐MH-­‐21 Nankai Trough Pre-­‐Production Expedition (2012-­‐2013)-­‐Mallik Gas Hydrate Testing Projects (1998/2002/2007-­‐2008)-­‐Alaska Mount Elbert Stratigraphic Test Well (2007)-­‐Alaska Iġnik Sikumi Methane Hydrate Production Test Well (2011-­‐2012)Research coring and seismic programs carried out by the Ocean Drilling Program (ODP) and Integrated Ocean Drilling Program (IODP), starting with the ODP Leg 164 drilling of the Blake Ridge in the Atlantic Ocean in 1995, have also contributed greatly to our understanding of the geologic controls on the formation, occurrence, and stability of gas hydrates in marine environments. For the most part methane hydrate research expeditions carried out by the ODP and IODP provided the foundation for our scientific understanding of gas hydrates. The methane hydrate research efforts under ODP-­‐IODP have mostly dealt with the assessment of the geologic controls on the occurrence of gas hydrate, with a specific goal to study the role methane hydrates may play in the global carbon cycle.Over the last 10 years, national led methane hydrate research programs, along with industry interest have led to the development and execution of major methane hydrate production field test programs. Two of the most important production field testing programs have been conducted at the Mallik site in the Mackenzie River Delta of Canada and in the Eileen methane hydrate accumulation on the North Slope of Alaska. Most recently we have also seen the completion of the world’s first marine methane hydrate production test in the Nankai Trough in the offshore of Japan. Industry interest in gas hydrates has also included important projects that have dealt with the assessment of geologic hazards associated with the presence of hydrates.The scientific drilling and associated coring, logging, and borehole monitoring technologies developed in the long list of methane hydrate related field studies are one of the most important developments and contributions associated with methane hydrate research and development activities. Methane hydrate drilling has been conducted from advanced scientific drilling platforms like the JOIDES Resolution and the D/V Chikyu, which feature highly advanced integrated core laboratories and borehole logging capabilities. Hydrate research drilling has also included the use of a wide array of industry, geotechnical and multi-­‐service ships. All of which have been effectively used to collect invaluable geologic and engineering data on the occurrence of methane hydrates throughout the world. Technologies designed specifically for the collection and analysis of undisturbed methane hydrate samples have included the development of a host of pressure core systems and associated specialty laboratory apparatus. The study and use of both wireline conveyed and logging-­‐while-­‐drilling technologies have also contributed greatly to our understanding of the in-­‐situ nature of hydrate-­‐bearing sediments. Recent developments in borehole instrumentation specifically designed to monitor changes associated with hydrates in nature through time or to evaluate the response of hydrate accumulations to production have also contributed greatly to our understanding of the complex nature and evolution of methane hydrate systems.Our understanding of how methane hydrates occur and behave in nature is still growing and evolving – we do not yet know if methane hydrates can be economically produced, nor do we know fully the role of hydrates as an agent of climate change or as a geologic hazard. But it is known for certain that scientific drilling has contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information to advance our understanding of methane hydrates.

Spatial and temporal dependencies of structure II to structure I methane hydrate transformation in porous media under moderate pressure and temperature conditions

NASA Astrophysics Data System (ADS)

Dong, T.; Lin, J. F.; Gu, J. T.; Polito, P. J.; O'Connell, J.; Flemings, P. B.

2017-12-01

We used Raman spectroscopy to monitor methane hydrates transforming from structure II to structure I at the pore scale as a function of space and time. It is well documented that structure I hydrate is the thermodynamically stable phase for pure methane hydrate (<100 MPa, < 20 °C), but due to kinetic limitation, initial methane hydrate formation produces a mixture of structure I and structure II hydrates. We observed that the structure transformation originated around the porous medium grains and over time slowly migrated into the pore space. We synthesized methane hydrates in spherical glass beads (210-297 µm in diameter) in a pressure cell with a sapphire window to integrate optical observations with Raman measurements. We injected CH4 vapor into the cell and supplied only deionized water thereafter to maintain a constant pressure of 14.6 MPa at 3.5 °C, with 14.5 °C subcooling. We used Raman spectroscopy to map the methane hydrates in pore spaces at 5-25 µm resolution, in order to monitor the occupancy ratio of CH4 in large cages to CH4 in small cages, by their Raman peak intensity ratio, i.e., I( 2905 cm-1)/I( 2915 cm-1). We identified 3 stages of hydrate formation at the pore scale: (1) after the initial hydrate formation, Raman mapping revealed that the occupancy ratio ranged from 0.5 to 3, indicating a mixture of structure I and II hydrates; (2) within 1 week, we observed that all structure I hydrates occurred on the glass bead surfaces and structure II hydrates occupied the pore spaces; (3) over the following 2 weeks, structure II hydrates gradually recrystallized into structure I hydrates from glass bead surfaces towards the pore space. These results imply that (1) due to kinetics, the formation of methane hydrate in porous media is more complex than previously thought, and (2) the bulk physical and chemical properties of laboratory-synthesized methane hydrates in porous media may drift over time, as methane hydrates recrystallize from a metastable phase (structure II) to the thermodynamically stable phase (structure I).

Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

2014-12-01

The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E, Haeckel M. Methane Production from Gas Hydrate Deposits through Injection of Supercritical CO2. Energies 2012:5(7): 2112-2140.

The impact of permafrost-associated microorganisms on hydrate formation kinetics

NASA Astrophysics Data System (ADS)

Luzi-Helbing, Manja; Liebner, Susanne; Spangenberg, Erik; Wagner, Dirk; Schicks, Judith M.

2016-04-01

The relationship between gas hydrates, microorganisms and the surrounding sediment is extremely complex: On the one hand, microorganisms producing methane provide the prerequisite for gas hydrate formation. As it is known most of the gas incorporated into natural gas hydrates originates from biogenic sources. On the other hand, as a result of microbial activity gas hydrates are surrounded by a great variety of organic compounds which are not incorporated into the hydrate structure but may influence the formation or degradation process. For gas hydrate samples from marine environments such as the Gulf of Mexico a direct association between microbes and gas hydrates was shown by Lanoil et al. 2001. It is further assumed that microorganisms living within the gas hydrate stability zone produce biosurfactants which were found to enhance the hydrate formation process significantly and act as nucleation centres (Roger et al. 2007). Another source of organic compounds is sediment organic matter (SOM) originating from plant material or animal remains which may also enhance hydrate growth. So far, the studies regarding this relationship were focused on a marine environment. The scope of this work is to extend the investigations to microbes originating from permafrost areas. To understand the influence of microbial activity in a permafrost environment on the methane hydrate formation process and the stability conditions of the resulting hydrate phase we will perform laboratory studies. Thereby, we mimic gas hydrate formation in the presence and absence of methanogenic archaea (e.g. Methanosarcina soligelidi) and other psychrophilic bacteria isolated from permafrost environments of the Arctic and Antarctic to investigate their impact on hydrate induction time and formation rates. Our results may contribute to understand and predict the occurrences and behaviour of potential gas hydrates within or adjacent to the permafrost. Lanoil BD, Sassen R, La Duc MT, Sweet ST, Nealson KH (2001). Bacteria and Archaea Physically Associated with Gulf of Mexico Gas Hydrates. Appl Environ Microbiol 67: 5143-5153. Rogers R, Zhang G, Dearman J, Woods C (2007). Investigations into surfactant/gas hydrate relationship. J Petrol Sci Eng 56: 82-88.

Gas hydrate hunting in China seas

NASA Astrophysics Data System (ADS)

Yang, J.; Zhang, X.; Chen, J.; Xiang, Q.; Ye, Y.; Gong, J.

2003-04-01

Gas hydrate research is a hotspot now in geosciences. Many countries have carried on gas hydrate survey and research for many years. China, as a country with large sea areas unfolded gas hydrate research work in its marine areas in 1999 and tries to keep pace with the advanced countries on gas hydrate study. Substantial funds were launched by various governmental and non-governmental funding agencies to support gas hydrate research. Many institutions on marine geosciences are involved in. China Geological Survey (CGS) has launched several research projects in the sea. So far, some fieldwork such as seismic survey, sampling, profiling, underwater video imaging have been done in South China Sea and East China Sea areas. Some preliminary results have been achieved. BSRs are found in many seismic profiles. Some potential gas hydrate bearing areas are marked and potential amount of gas hydrate resources is calculated. At the same time, gas hydrate laboratory was founded and successful experiments have been carried out to model the gas hydrate synthesis in accordance with the geological condition of the China seas. Now, gas hydrate detecting techniques such as sampling equipment (PCS), seismic data processing, interpretation and the formation mechanism study as well as environmental effect research are undergoing. Though China's gas hydrate research work is still at its initial stage, China is willing to be an active member in the international society of gas hydrate study and hopes to contribute its effort.

Natural gas hydrate in oceanic and permafrost environments

USGS Publications Warehouse

Max, Michael D.

2003-01-01

THE BEGINNINGS OF HYDRATE RESEARCH Until very recently, our understanding of hydrate in the natural environment and its impact on seafloor stability, its importance as a sequester of methane, and its potential as an important mechanism in the Earth's climate change system, was masked by our lack of appreciation of the vastness of the hydrate resource. Only a few publications on naturally occurring hydrate existed prior to 1975. The first published reference to oceanic gas hydrate (Bryan and Markl, 1966) and the first publication in the scientific literature (Stoll, et a1., 1971) show how recently it has been since the topic of naturally occurring hydrate has been raised. Recently, however, the number of hydrate publications has increased substantially, reflecting increased research into hydrate topics and the initiation of funding to support the researchers. Awareness of the existence of naturally occurring gas hydrate now has spread beyond the few scientific enthusiasts who pursued knowledge about the elusive hydrate because of simple interest and lurking suspicions that hydrate would prove to be an important topic. The first national conference on gas hydrate in the U.S. was held as recently as April, 1991 at the U.S. National Center of the U.s. Geological Survey in Reston Virginia (Max et al., 1991). The meeting was co-hosted by the U.s. Geological Survey, the Naval Research Laboratory, and the U.S.

Complex admixtures of clathrate hydrates in a water desalination method

DOEpatents

Simmons, Blake A [San Francisco, CA; Bradshaw, Robert W [Livermore, CA; Dedrick, Daniel E [Berkeley, CA; Anderson, David W [Riverbank, CA

2009-07-14

Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

Sedimentological Control on Hydrate Saturation Distribution in Arctic Gas-Hydrate-Bearing Deposits

NASA Astrophysics Data System (ADS)

Behseresht, J.; Peng, Y.; Bryant, S. L.

2010-12-01

Grain size variations along with the relative rates of fluid phases migrating into the zone of hydrate stability, plays an important role in gas-hydrate distribution and its morphologic characteristics. In the Arctic, strata several meters thick containing large saturations of gas hydrate are often separated by layers containing small but nonzero hydrate saturations. Examples are Mt. Elbert, Alaska and Mallik, NW Territories. We argue that this sandwich type hydrate saturation distribution is consistent with having a gas phase saturation within the sediment when the base of gas hydrate stability zone (BGHSZ) was located above the sediment package. The volume change during hydrate formation process derives movement of fluid phases into the GHSZ. We show that this fluid movement -which is mainly governed by characteristic relative permeability curves of the host sediment-, plays a crucial role in the amount of hydrate saturation in the zone of major hydrate saturation. We develop a mechanistic model that enables estimating the final hydrate saturation from an initial gas/water saturation in sediment with known relative permeability curves. The initial gas/water saturation is predicted using variation of capillary entry pressure with depth, which in turn depends on the variation in grain-size distribution. This model provides a mechanistic approach for explaining large hydrate saturations (60%-75%) observed in zones of major hydrate saturation considering the governing characteristic relative permeability curves of the host sediments. We applied the model on data from Mount Elbert well on the Alaskan North Slope. It is shown that, assuming a cocurrent flow of gas and water into the GHSZ, such large hydrate saturations (up to 75%) cannot result from large initial gas saturations (close to 1-Sw,irr) due to limitations on water flux imposed by typical relative permeability curves. They could however result from modest initial gas saturations (ca. 40%) at which we have reasonable phase mobility ratios required for appropriate relative rates of gas and water transporting into GHSZ to form large hydrate saturations. Nevertheless, from the profile of capillary entry pressure vs. depth, we expect large initial gas saturations and thus the final high hydrate saturation suggests another form of water flow: water moves down through accumulated hydrate from the unfrozen water above. For this to happen the water phase must remain connected within the hydrate-bearing sediment. This seems plausible in hydrate bearing sediments because hydrate formation will be stopped before water saturation gets to very low values (lower than Sw,irr) due to salinity build up. The location of small hydrate saturations (10-15%) is consistent with the location of the residual gas phase established during water imbibition into these locations while they serve as a gas source to the layers above.

Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

PubMed

Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

2015-08-03

We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling dynamic accumulation of gas hydrates in Shenhu area, northern South China Sea

NASA Astrophysics Data System (ADS)

Su, Z.; Cao, Y.; Wu, N.

2013-12-01

The accumulation of the hydrates in Shenhu area on northern continental slope of the South China Sea (SCS) could not be well quantified by the numerical models. The formation mechanism of the hydrate deposits remains an open question. Here, a conceptual model was applied for illustrating the formation pattern of hydrate accumulation in Shenhu area based on the studies of sedimentary and tectonic geologies. Our results indicated that the present hydrate deposits were a development of 'ancient hydrates' in the faulted sediment. The dynamic accumulation of the hydrates was further quantified by using a numerical model with two controlling parameters of seafloor sedimentation rate and water flow rate. The model results were testified with the hydrate saturations derived from the chloride abnormalities at site SH2 in Shenhu area. It suggested that the hydrate accumulation in Shenhu area had experienced two typical stages. In the first stage, the gas hydrates grew in the fractured sediment ~1.5 Ma. High permeability of the fractured sediment permitted rapid water flow that carrying methane gas toward the seafloor. Massive gas transformed to gas hydrate in the gas hydrate stability zone (GHSZ) at water flow rate of 50m/kyr within 40kyrs. The 'ancient hydrate' filled 20% volume of the sediment pores in the stage. The second stage was initiated after ending of the last faulting activity. The water flow rate dropped to 0.7m/kyr due to quick burial of fine-grained sediments. Inadequate gas supply could merely sustain hydrate growth slowly at the base of GHSZ, and ultimately yielded the current hydrate deposits in Shenhu area after a subsequent evolution of 1.5 Myrs.

Identifying the morphologies of gas hydrate distribution using P-wave velocity and density: a test from the GMGS2 expedition in the South China Sea

NASA Astrophysics Data System (ADS)

Liu, Tao; Liu, Xuewei

2018-06-01

Pore-filling and fracture-filling are two basic distribution morphologies of gas hydrates in nature. A clear knowledge of gas hydrate morphology is important for better resource evaluation and exploitation. Improper exploitation may cause seafloor instability and exacerbate the greenhouse effect. To identify the gas hydrate morphologies in sediments, we made a thorough analysis of the characteristics of gas hydrate bearing sediments (GHBS) based on rock physics modeling. With the accumulation of gas hydrate in sediments, both the velocities of two types of GHBS increase, and their densities decrease. Therefore, these two morphologies cannot be differentiated only by velocity or density. After a series of tests, we found the attribute ρ {{V}{{P}}}0.5 as a function of hydrate concentration show opposite trends for these two morphologies due to their different formation mechanisms. The morphology of gas hydrate can thus be identified by comparing the measured ρ {{V}{{P}}}0.5 with its background value, which means the ρ {{V}{{P}}}0.5 of the hydrate-free sediments. In 2013, China’s second gas hydrate expedition was conducted by Guangzhou Marine Geologic Survey to explore gas hydrate resources in the northern South China Sea, and both two hydrate morphologies were recovered. We applied this method to three sites, which include two pore-filling and three fracture-filling hydrate layers. The data points, that agree with the actual situations, account for 72% and 82% of the total for the two pore-filling hydrate layers, respectively, and 86%, 74%, and 69% for the three fracture-filling hydrate layers, respectively.

Regional Mapping and Resource Assessment of Shallow Gas Hydrates of Japan Sea - METI Launched 3 Years Project in 2013.

NASA Astrophysics Data System (ADS)

Matsumoto, R.

2014-12-01

Agency of Natural Resources and Energy of METI launched a 3 years shallow gas hydrate exploration project in 2013 to make a precise resource assessment of shallow gas hydrates in the eastern margin of Japan Sea and around Hokkaido. Shallow gas hydrates of Japan Sea occur in fine-grained muddy sediments of shallow subsurface of mounds and gas chimneys in the form of massive nodular to platy accumulation. Gas hydrate bearing mounds are often associated with active methane seeps, bacterial mats and carbonate concretions and pavements. Gases of gas hydrates are derived either from deep thermogenic, shallow microbial or from the mixed gases, contrasting with totally microbial deep-seated stratigraphically controlled hydrates. Shallow gas hydrates in Japan Sea have not been considered as energy resource due to its limited distribution in narrow Joetsu basin. However recently academic research surveys have demonstrated regional distribution of gas chimney and hydrate mound in a number of sedimentary basins along the eastern margin of Japan Sea. Regional mapping of gas chimney and hydrate mound by means of MBES and SBP surveys have confirmed that more than 200 gas chimneys exist in 100 km x 100 km area. ROV dives have identified dense accumulation of hydrates on the wall of half collapsed hydrate mound down to 30 mbsf. Sequential LWD and shallow coring campaign in the Summer of 2014, R/V Hakurei, which is equipped with Fugro Seacore R140 drilling rig, drilled through hydrate mounds and gas chimneys down to the BGHS (base of gas hydrate stability) level and successfully recovered massive gas hydrates bearing sediments from several horizons.

Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea

USGS Publications Warehouse

Wang, Xiujuan; Hutchinson, Deborah R.; Wu, Shiguo; Yang, Shengxiong; Guo, Yiqun

2011-01-01

Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190–221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone.

Micromechanical measurements of the effect of surfactants on cyclopentane hydrate shell properties.

PubMed

Brown, Erika P; Koh, Carolyn A

2016-01-07

Investigating the effect of surfactants on clathrate hydrate growth and morphology, especially particle shell strength and cohesion force, is critical to advancing new strategies to mitigate hydrate plug formation. In this study, dodecylbenzenesulfonic acid and polysorbate 80 surfactants were included during the growth of cyclopentane hydrates at several concentrations above and below the critical micelle concentration. A novel micromechanical method was applied to determine the force required to puncture the hydrate shell using a glass cantilever (with and without surfactants), with annealing times ranging from immediately after the hydrate nucleated to 90 minutes after formation. It was shown that the puncture force was decreased by the addition of both surfactants up to a maximum of 79%. Over the entire range of annealing times (0-90 minutes), the thickness of the hydrate shell was also measured. However, there was no clear change in shell thickness with the addition of surfactants. The growth rate of the hydrate shell was found to vary less than 15% with the addition of surfactants. The cohesive force between two hydrate particles was measured for each surfactant and found to be reduced by 28% to 78%. Interfacial tension measurements were also performed. Based on these results, microscopic changes to the hydrate shell morphology (due to the presence of surfactants) were proposed to cause the decrease in the force required to break the hydrate shell, since no macroscopic morphology changes were observed. Understanding the hydrate shell strength can be critical to reducing the capillary bridge interaction between hydrate particles or controlling the release of unconverted water from the interior of the hydrate particle, which can cause rapid hydrate conversion.

Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates

PubMed Central

2017-01-01

We present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO2) gas hydrates using Raman spectroscopy. The CO2 hydrates were formed from sodium chloride/water solutions with salinities of 0–10 wt %, which were pressurized with liquid CO2 in a stirred vessel at 6 MPa and a subcooling of 9.5 K. The formation of the CO2 hydrate resulted in a hydrate gel where the solid hydrate can be considered as the continuous phase that includes small amounts of a dispersed liquid water-rich phase that has not been converted to hydrate. During the hydrate formation process we quantified the fraction of solid hydrate, xH, and the fraction of the dispersed liquid water-rich phase, xL, from the signature of the hydroxyl (OH)-stretching vibration of the hydrate gel. We found that the fraction of hydrate xH contained in the hydrate gel linearly depends on the salinity of the initial liquid water-rich phase. In addition, the ratio of CO2 and water was analyzed in the liquid water-rich phase before hydrate formation, in the hydrate gel during growth and dissociation, and after its complete dissociation again in the liquid water-rich phase. We observed a supersaturation of CO2 in the water-rich phase after complete dissociation of the hydrate gel and were able to show that the excess CO2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. These residual nano- and microdroplets could be a possible explanation for the so-called memory effect. PMID:28817275

A molecular dynamics study of model SI clathrate hydrates: the effect of guest size and guest-water interaction on decomposition kinetics.

PubMed

Das, Subhadip; Baghel, Vikesh Singh; Roy, Sudip; Kumar, Rajnish

2015-04-14

One of the options suggested for methane recovery from natural gas hydrates is molecular replacement of methane by suitable guests like CO2 and N2. This approach has been found to be feasible through many experimental and molecular dynamics simulation studies. However, the long term stability of the resultant hydrate needs to be evaluated; the decomposition rate of these hydrates is expected to depend on the interaction between these guest and water molecules. In this work, molecular dynamics simulation has been performed to illustrate the effect of guest molecules with different sizes and interaction strengths with water on structure I (SI) hydrate decomposition and hence the stability. The van der Waals interaction between water of hydrate cages and guest molecules is defined by Lennard Jones potential parameters. A wide range of parameter spaces has been scanned by changing the guest molecules in the SI hydrate, which acts as a model gas for occupying the small and large cages of the SI hydrate. All atomistic simulation results show that the stability of the hydrate is sensitive to the size and interaction of the guest molecules with hydrate water. The increase in the interaction of guest molecules with water stabilizes the hydrate, which in turn shows a slower rate of hydrate decomposition. Similarly guest molecules with a reasonably small (similar to Helium) or large size increase the decomposition rate. The results were also analyzed by calculating the structural order parameter to understand the dynamics of crystal structure and correlated with the release rate of guest molecules from the solid hydrate phase. The results have been explained based on the calculation of potential energies felt by guest molecules in amorphous water, hydrate bulk and hydrate-water interface regions.

Well log characterization of natural gas hydrates

USGS Publications Warehouse

Collett, Timothy S.; Lee, Myung W.

2011-01-01

In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids (i.e., free-water along with clay and capillary bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate production schemes.

Unraveling Mixed Hydrate Formation: Microscopic Insights into Early Stage Behavior.

PubMed

Hall, Kyle Wm; Zhang, Zhengcai; Kusalik, Peter G

2016-12-29

The molecular-level details of mixed hydrate nucleation remain unclear despite the broad implications of this process for a variety of scientific domains. Through analysis of mixed hydrate nucleation in a prototypical CH 4 /H 2 S/H 2 O system, we demonstrate that high-level kinetic similarities between mixed hydrate systems and corresponding pure hydrate systems are not a reliable basis for estimating the composition of early stage mixed hydrate nuclei. Moreover, we show that solution compositions prior to and during nucleation are not necessarily effective proxies for the composition of early stage mixed hydrate nuclei. Rather, microscopic details, (e.g., guest-host interactions and previously neglected cage types) apparently play key roles in determining early stage behavior of mixed hydrates. This work thus provides key foundational concepts and insights for understanding mixed hydrate nucleation.

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

NASA Astrophysics Data System (ADS)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Numerical simulations of CO2 -assisted gas production from hydrate reservoirs

NASA Astrophysics Data System (ADS)

Sridhara, P.; Anderson, B. J.; Myshakin, E. M.

2015-12-01

A series of experimental studies over the last decade have reviewed the feasibility of using CO2 or CO2+N2 gas mixtures to recover CH4 gas from hydrates deposits. That technique would serve the dual purpose of CO2 sequestration and production of CH4 while maintaining the geo-mechanical stability of the reservoir. In order to analyze CH4 production process by means of CO2 or CO2+N2 injection into gas hydrate reservoirs, a new simulation tool, Mix3HydrateResSim (Mix3HRS)[1], was previously developed to account for the complex thermodynamics of multi-component hydrate phase and to predict the process of CH4 substitution by CO2 (and N2) in the hydrate lattice. In this work, Mix3HRS is used to simulate the CO2 injection into a Class 2 hydrate accumulation characterized by a mobile aqueous phase underneath a hydrate bearing sediment. That type of hydrate reservoir is broadly confirmed in permafrost and along seashore. The production technique implies a two-stage approach using a two-well design, one for an injector and one for a producer. First, the CO2 is injected into the mobile aqueous phase to convert it into immobile CO2 hydrate and to initiate CH4 release from gas hydrate across the hydrate-water boundary (generally designating the onset of a hydrate stability zone). Second, CH4 hydrate decomposition is induced by the depressurization method at a producer to estimate gas production potential over 30 years. The conversion of the free water phase into the CO2 hydrate significantly reduces competitive water production in the second stage, thereby improving the methane gas production. A base case using only the depressurization stage is conducted to compare with enhanced gas production predicted by the CO2-assisted technique. The approach also offers a possibility to permanently store carbon dioxide in the underground formation to greater extent comparing to a direct injection of CO2 into gas hydrate sediment. Numerical models are based on the hydrate formations at the Prudhoe Bay L-Pad region on the Alaska North Slope. References [1] N.Garapati, "Reservoir Simulation for Production of CH4 from Gas Hydrate Reservoirs Using CO2/CO2+N2 by HydrateResSim", Ph.D. thesis, West Virginia University, 2013.

Along - Strike Analysis of Contemporary Ocean Temperature Change on the Cascadia Margin and Implications to Upper Slope Hydrate Instability

NASA Astrophysics Data System (ADS)

Phrampus, B.; Harris, R. N.; Trehu, A. M.; Embley, R. W.; Merle, S. G.

2017-12-01

Gas hydrates are found globally on continental margins and due to the large amount of sequestered carbon in hydrate reservoirs, whether these deposits are dynamic or stable has significant implications for slope stability, ocean/atmosphere carbon budget, and deep-water energy exploration. Recent studies indicate that upper slope hydrate degradation may be relatively widespread on passive margins due to recent ocean temperature warming between 0.012 and 0.033 °C/yr (e.g. Svalbard, North Alaska, and US Atlantic margin). However, the potential and breadth of warming induced hydrate instability remains contentious based on multiple observations including: 1) seep locations not consistent with locations of hydrate dissociation, 2) a lack of hydrate in regions of warming, and 3) evidence for long-lived seepage in regions associated with contemporary warming-induced hydrate dissociation. At the Cascadia margin, a recent study suggests that contemporary warming of intermediate water intersects the hydrate stability zone leading to hydrate dissociation that feeds upper slope seeps. Here, we provide a systematic analysis of along-strike variations in hydrate distribution along the Cascadia margin combined with a multivariable regression of ocean temperatures to characterize the potential of upper slope hydrate instability. Preliminary seep locations reveal upper slope seeps and observed regions of hydrate are correlated spatially between 42.5 and 48.0 °N, outside this region there is a dearth of identified upper slope hydrate and seeps. Between 44.5 and 48.0 °N a contemporary warming trend is as large as 0.006 °C/yr and is collocated with upper slope hydrate and gas seepage. This warming rate is relatively small, 2-5x smaller than warming trends identified in the Arctic where temperature induced hydrate instability remains uncertain. Additionally, we identify a region between 42.5 and 44.5 °N with collocated upper slope seepage and hydrate but no evidence of ocean warming, suggesting upper slope seepage is not driven by temperature induced hydrate instability, but maybe driven by tectonic uplift. These results highlight the absence of temperature driven seepage and slope instability on the Cascadia margin and deemphasize the impact of lower latitude warming on global hydrate dynamics and carbon budget.

Hydrate Formation in Gas-Rich Marine Sediments: A Grain-Scale Model

NASA Astrophysics Data System (ADS)

Holtzman, R.; Juanes, R.

2009-12-01

We present a grain-scale model of marine sediment, which couples solid- and multiphase fluid-mechanics together with hydrate kinetics. The model is applied to investigate the spatial distribution of the different methane phases - gas and hydrate - within the hydrate stability zone. Sediment samples are generated from three-dimensional packs of spherical grains, mapping the void space into a pore network by tessellation. Gas invasion into the water-saturated sample is simulated by invasion-percolation, coupled with a discrete element method that resolves the grain mechanics. The coupled model accounts for forces exerted by the fluids, including cohesion associated with gas-brine surface tension. Hydrate growth is represented by a hydrate film along the gas-brine interface, which increases sediment cohesion by cementing the grain contacts. Our model of hydrate growth includes the possible rupture of the hydrate layer, which leads to the creation of new gas-water interface. In previous work, we have shown that fine-grained sediments (FGS) exhibit greater tendency to fracture, whereas capillary invasion is the preferred mode of methane gas transport in coarse-grained sediments (CGS). The gas invasion pattern has profound consequences on the hydrate distribution: a larger area-to-volume ratio of the gas cluster leads to a larger drop in gas pressure inside the growing hydrate shell, causing it to rupture. Repeated cycles of imbibition and hydrate growth accompanied by trapping of gas allow us to determine the distribution of hydrate and gas within the sediment as a function of time. Our pore-scale model suggests that, even when film rupture takes place, the conversion of gas to hydrate is slow. This explains two common field observations: the coexistence of gas and hydrate within the hydrate stability zone in CGS, and the high methane fluxes through fracture conduits in FGS. These results demonstrate the importance of accounting for the strong coupling among multiphase flow, sediment mechanics, and hydrate formation. Our model explains the remarkable differences in hydrate distribution and saturation between fine- and coarse-grained sediments, and promotes the quantitative understanding of the role of methane hydrate in seafloor stability and the global carbon cycle, including the size of the hydrate energy resource, and estimates of methane fluxes into the ocean and the atmosphere.

Nasogastric hydration versus intravenous hydration for infants with bronchiolitis: a randomised trial.

PubMed

Oakley, Ed; Borland, Meredith; Neutze, Jocelyn; Acworth, Jason; Krieser, David; Dalziel, Stuart; Davidson, Andrew; Donath, Susan; Jachno, Kim; South, Mike; Theophilos, Theane; Babl, Franz E

2013-04-01

Bronchiolitis is the most common lower respiratory tract infection in infants and the leading cause of hospital admission. Hydration is a mainstay of treatment, but insufficient evidence exists to guide clinical practice. We aimed to assess whether intravenous hydration or nasogastric hydration is better for treatment of infants. In this multicentre, open, randomised trial, we enrolled infants aged 2-12 months admitted to hospitals in Australia and New Zealand with a clinical diagnosis of bronchiolitis during three bronchiolitis seasons (April 1-Oct 31, in 2009, 2010, and 2011). We randomly allocated infants to nasogastric hydration or intravenous hydration by use of a computer-generated sequence and opaque sealed envelopes, with three randomly assigned block sizes and stratified by hospital site and age group (2-<6 months vs 6-12 months). The primary outcome was length of hospital stay, assessed in all randomly assigned infants. Secondary outcomes included rates of intensive-care unit admission, adverse events, and success of insertion. This trial is registered with the Australian and New Zealand clinical trials registry, ACTRN12605000033640. Mean length of stay for 381 infants assigned nasogastric hydration was 86·6 h (SD 58·9) compared with 82·2 h (58·8) for 378 infants assigned intravenous hydration (absolute difference 4·5 h [95% CI -3·9 to 12·9]; p=0·30). Rates of admission to intensive-care units, need for ventilatory support, and adverse events did not differ between groups. At randomisation, seven infants assigned nasogastric hydration were switched to intravenous hydration and 56 infants assigned intravenous hydration were switched to nasogastric hydration because the study-assigned method was unable to be inserted. For those infants who had data available for successful insertion, 275 (85%) of 323 infants in the nasogastric hydration group and 165 (56%) of 294 infants in the intravenous hydration group required only one attempt for successful insertion. Intravenous hydration and nasogastric hydration are appropriate means to hydrate infants with bronchiolitis. Nasogastric insertion might require fewer attempts and have a higher success rate of insertion than intravenous hydration. Australian National Health and Medical Research Council, Samuel Nissen Charitable Foundation (Perpetual), Murdoch Children's Research Institute, Victorian Government. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching.

PubMed

Grim, R Gary; Kerkar, Prasad B; Sloan, E Dendy; Koh, Carolyn A; Sum, Amadeu K

2012-06-21

In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.

Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand

USGS Publications Warehouse

Waite, W.F.; deMartin, B.J.; Kirby, S.H.; Pinkston, J.; Ruppel, C.D.

2002-01-01

Using von Herzen and Maxwell's needle probe method, we measured thermal conductivity in four porous mixtures of quartz sand and methane gas hydrate, with hydrate composing 0, 33, 67 and 100% of the solid volume. Thermal conductivities were measured at a constant methane pore pressure of 24.8 MPa between -20 and +15??C, and at a constant temperature of -10??C between 3.5 and 27.6 MPa methane pore pressure. Thermal conductivity decreased with increasing temperature and increased with increasing methane pore pressure. Both dependencies weakened with increasing hydrate content. Despite the high thermal conductivity of quartz relative to methane hydrate, the largest thermal conductivity was measured in the mixture containing 33% hydrate rather than in hydrate-free sand. This suggests gas hydrate enhanced grain-to-grain heat transfer, perhaps due to intergranular contact growth during hydrate synthesis. These results for gas-filled porous mixtures can help constrain thermal conductivity estimates in porous, gas hydrate-bearing systems.

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

Kida, M.; Watanabe, M.; Konno, Y.; Yoneda, J.; Jin, Y.; Nagao, J.

2016-12-01

Naturally occurring gas hydrates in marine or permafrost environments can trap methane and heavier hydrocarbons within its host lattice structure built up with hydrogen-bonded water molecules. Naturally occurring gas hydrates have been expected as new natural gas resources. It is important to reveal the distribution of guest hydrocarbons in host hydrate framework from viewpoint of assessment of gas capacity. In this study, we assessed cage occupancies of guest hydrocarbons in host hydrate framework of synthetic and natural gas hydrates using solid-state 13C NMR technique. As synthetic samples, gas hydrates formed from gas mixtures including C1 to C5 were investigated. As a natural sample, the pore-space gas hydrate sample recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation was studied. As a result, it revealed that all heavier hydrocarbons than ethane are preferentially incorporated into the larger cage cavities in hydrate frameworks. We performed this study as a part of a Japanese National hydrate research program (MH21, funded by METI).

The U.S. Geological Survey’s Gas Hydrates Project

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

The Gas Hydrates Project at the U.S. Geological Survey (USGS) focuses on the study of methane hydrates in natural environments. The project is a collaboration between the USGS Energy Resources and the USGS Coastal and Marine Geology Programs and works closely with other U.S. Federal agencies, some State governments, outside research organizations, and international partners. The USGS studies the formation and distribution of gas hydrates in nature, the potential of hydrates as an energy resource, and the interaction between methane hydrates and the environment. The USGS Gas Hydrates Project carries out field programs and participates in drilling expeditions to study marine and terrestrial gas hydrates. USGS scientists also acquire new geophysical data and sample sediments, the water column, and the atmosphere in areas where gas hydrates occur. In addition, project personnel analyze datasets provided by partners and manage unique laboratories that supply state-of-the-art analytical capabilities to advance national and international priorities related to gas hydrates.

Failure Mechanism of Cemented Hydrate-bearing Sand at Microscales

NASA Astrophysics Data System (ADS)

Yoneda, J.; Jin, Y.; Katagiri, J.; Tenma, N.

2016-12-01

On the basis of hypothetical particle-level mechanisms, several constitutive models of hydrate-bearing sediments have been proposed previously for gas production. However, to the best of our knowledge, the microstructural large-strain behaviors of hydrate-bearing sediments has not been reported to date because of the experimental challenges posed by the high-pressure and low-temperature testing conditions. Herein, as a part of a Japanese National hydrate research program (MH21, funded by METI), a novel microtriaxial testing apparatus was developed, and the mechanical large strain behavior of hydrate-bearing sediments with various hydrate saturation values (Sh = 0%, 39%, and 62%) were analyzed using microfocus X-ray computed tomography. Patchy hydrates were observed in the sediments at Sh = 39%. The obtained stress-strain relationships indicated strengthening with increasing hydrate saturation and a brittle failure mode of the hydrate-bearing sand. Localized deformations were quantified via image processing at the submillimeter and micrometer scale. Shear planes and particle deformation and/or rotation were detected, and the shear band thickness decreased with increasing hydrate saturation.

New observations and insights into the morphology and growth kinetics of hydrate films.

PubMed

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K

2014-02-19

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6.

Physical Properties of Gas Hydrates: A Review

DOE PAGES

Gabitto, Jorge F.; Tsouris, Costas

2010-01-01

Memore » thane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 10 16   m 3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.« less

New Observations and Insights into the Morphology and Growth Kinetics of Hydrate Films

PubMed Central

Li, Sheng-Li; Sun, Chang-Yu; Liu, Bei; Li, Zhi-Yun; Chen, Guang-Jin; Sum, Amadeu K.

2014-01-01

The kinetics of film growth of hydrates of methane, ethane, and methane-ethane mixtures were studied by exposing a single gas bubble to water. The morphologies, lateral growth rates, and thicknesses of the hydrate films were measured for various gas compositions and degrees of subcooling. A variety of hydrate film textures was revealed. The kinetics of two-dimensional film growth was inferred from the lateral growth rate and initial thickness of the hydrate film. A clear relationship between the morphology and film growth kinetics was observed. The shape of the hydrate crystals was found to favour heat or mass transfer and favour further growth of the hydrate film. The quantitative results on the kinetics of film growth showed that for a given degree of subcooling, the initial film thicknesses of the double hydrates were larger than that of pure methane or ethane hydrate, whereas the thickest hydrate film and the lowest lateral growth rate occurred when the methane mole fraction was approximately 0.6. PMID:24549241

Hydration behaviour of food grains and modelling their moisture pick up as per Peleg's equation: Part I. Cereals.

PubMed

Vasudeva, Singh; Vishwanathan, K H; Aswathanarayana, K N; Indhudhara Swamy, Y M

2010-01-01

Cereals and millets generally hydrate at a moderate rate and their hydration behaviour differs in native and in processed state. The study was on the hydration of paddy, milled rice, parboiled rice, wheat, millets and equilibrium moisture content (EMC) on soaking at room temperature. Paddy hydrated very slowly, hydration rate was slow in brown rice but fast in milled rice and highest in waxy rice. In most of the rice varieties, maximum absorption occurred at the end of 30 min. In wheat hydration rate was slow and its EMC was highest (43%). Maize grits of big size hydrated slowly compared to small grits. In coarse cereals EMC varied from 28 to 38%. Foxtail millet hydration was slow whereas that of finger millet was fast. The data were tested on the Peleg's equation, which gave a reasonable fit to experimental data. Peleg's constants k1 and k2 were calculated for the above grains and their hydration behaviour has been predicted. The model fitted very well to milled rice hydration data where the coefficient of variance ranged from 0.9982 to 0.9995. With exception in some millet the hydration data fitted well with the Peleg's equation. Generalized equations have been formulated for prediction of moisture content of cereals and millets.

Screening and Characterization of Hydrate Forms of T-3256336, a Novel Inhibitor of Apoptosis (IAP) Protein Antagonist.

PubMed

Takeuchi, Shoko; Kojima, Takashi; Hashimoto, Kentaro; Saito, Bunnai; Sumi, Hiroyuki; Ishikawa, Tomoyasu; Ikeda, Yukihiro

2015-01-01

Different crystal packing of hydrates from anhydrate crystals leads to different physical properties, such as solubility and stability. Investigation of the potential of varied hydrate formation, and understanding the stability in an anhydrous/hydrate system, are crucial to prevent an undesired transition during the manufacturing process and storage. Only one anhydrous form of T-3256336, a novel inhibitor of apoptosis (IAP) protein antagonist, was discovered during synthesis, and no hydrate form has been identified. In this study, we conducted hydrate screening such as dynamic water vapor sorption/desorption (DVS), and the slurry experiment, and characterized the solid-state properties of anhydrous/hydrate forms to determine the most desirable crystalline form for development. New hydrate forms, both mono-hydrate and hemi-hydrate forms, were discovered as a result of this hydrate screening. The characterization of two new hydrate forms was conducted, and the anhydrous form was determined to be the most desirable development form of T-3256336 in terms of solid-state stability. In addition, the stability of the anhydrous form was investigated using the water content and temperature controlled slurry experiment to obtain the desirable crystal form in the crystallization process. The water content regions of the stable phase of the desired form, the anhydrous form, were identified for the cooling crystallization process.

The interaction of climate change and methane hydrates

USGS Publications Warehouse

Ruppel, Carolyn D.; Kessler, John D.

2017-01-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

NASA Astrophysics Data System (ADS)

Ruppel, Carolyn D.; Kessler, John D.

2017-03-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

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

USGS Publications Warehouse

Winters, W.J.; Pecher, I.A.; Waite, W.F.; Mason, D.H.

2004-01-01

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.

The interaction of climate change and methane hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruppel, Carolyn D.; Kessler, John D.

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

The interaction of climate change and methane hydrates

DOE PAGES

Ruppel, Carolyn D.; Kessler, John D.

2016-12-14

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

Development of Carbon Sequestration Options by Studying Carbon Dioxide-Methane Exchange in Hydrates

NASA Astrophysics Data System (ADS)

Horvat, Kristine Nicole

Gas hydrates form naturally at high pressures (>4 MPa) and low temperatures (<4 °C) when a set number of water molecules form a cage in which small gas molecules can be entrapped as guests. It is estimated that about 700,000 trillion cubic feet (tcf) of methane (CH4) exist naturally as hydrates in marine and permafrost environments, which is more than any other natural sources combined as CH4 hydrates contain about 14 wt% CH4. However, a vast amount of gas hydrates exist in marine environments, which makes gas extraction an environmental challenge, both for potential gas losses during extraction and the potential impact of CH4 extraction on seafloor stability. From the climate change point of view, a 100 ppm increase in atmospheric carbon dioxide (CO2) levels over the past century is of urgent concern. A potential solution to both of these issues is to simultaneously exchange CH4 with CO 2 in natural hydrate reserves by forming more stable CO2 hydrates. This approach would minimize disturbances to the host sediment matrix of the seafloor while sequestering CO2. Understanding hydrate growth over time is imperative to prepare for large scale CH4 extraction coupled with CO2 sequestration. In this study, we performed macroscale experiments in a 200 mL high-pressure Jerguson cell that mimicked the pressure-temperature conditions of the seafloor. A total of 13 runs were performed under varying conditions. These included the formation of CH4 hydrates, followed by a CO2 gas injection and CO2 hydrate formation followed by a CH4 gas injection. Results demonstrated that once gas hydrates formed, they show "memory effect" in subsequent charges, irrespective of the two gases injected. This was borne out by the induction time data for hydrate formation that reduced from 96 hours for CH4 and 24 hours for CO2 to instant hydrate formation in both cases upon injection of a secondary gas. During the study of CH4-CO2 exchange where CH4 hydrates were first formed and CO2 gas was injected into the system, gas chromatographic (GC) analysis of the cell indicated a pure CH4 gas phase, i.e., all injected CO2 gas entered the hydrate phase and remained trapped in hydrate cages for several hours, though over time some CO2 did enter the gas phase. Alternatively, during the CH 4-CO2 exchange study where CO2 hydrates were first formed, the injected CH4 initially entered the hydrate phase, but quickly gaseous CO2 exchanged with CH4 in hydrates to form more stable CO2 hydrates. These results are consistent with the better thermodynamic stability of CO2 hydrates, and this appears to be a promising method to sequester CO2 in natural CH4 hydrate matrices. The macroscale study described above was complemented by a microscale study to visualize hydrate growth. This first-of-its-kind in-situ study utilized the x-ray computed microtomography (CMT) technique to visualize microscale CO2, CH4, and mixed CH 4-CO2 hydrate growth phenomenon in salt solutions in the presence or absence of porous media. The data showed that under the experimental conditions used, pure CH4 formed CH4 hydrates as mostly spheres, while pure CO2 hydrates were more dendritic branches. Additionally, varying ratios of mixed CH4-CO2 hydrates were also formed that had needle-like growth. In porous media, CO2 hydrates grew, consistent with known growth models in which the solution was the sediment wetting phase. When glass beads and Ottawa sand were used as a host, the system exhibited pore-filling hydrate growth, while the presence of liquid CO2 and possible CO2 hydrates in Ottawa sand initially were pore-filling that over time transformed into a grain-displacing morphology. The data appears promising to develop a method that would supplant our energy supply by extracting CH4 from naturally occurring hydrates while CO2 is sequestered in the same formations.

Effectiveness of oral hydration in preventing contrast-induced acute kidney injury in patients undergoing coronary angiography or intervention: a pairwise and network meta-analysis.

PubMed

Zhang, Weidai; Zhang, Jiawei; Yang, Baojun; Wu, Kefei; Lin, Hanfei; Wang, Yanping; Zhou, Lihong; Wang, Huatao; Zeng, Chujuan; Chen, Xiao; Wang, Zhixing; Zhu, Junxing; Songming, Chen

2018-06-01

The effectiveness of oral hydration in preventing contrast-induced acute kidney injury (CI-AKI) in patients undergoing coronary angiography or intervention has not been well established. This study aims to evaluate the efficacy of oral hydration compared with intravenous hydration and other frequently used hydration strategies. PubMed, Embase, Web of Science, and the Cochrane central register of controlled trials were searched from inception to 8 October 2017. To be eligible for analysis, studies had to evaluate the relative efficacy of different prophylactic hydration strategies. We selected and assessed the studies that fulfilled the inclusion criteria and carried out a pairwise and network meta-analysis using RevMan5.2 and Aggregate Data Drug Information System 1.16.8 software. A total of four studies (538 participants) were included in our pairwise meta-analysis and 1754 participants from eight studies with four frequently used hydration strategies were included in a network meta-analysis. Pairwise meta-analysis indicated that oral hydration was as effective as intravenous hydration for the prevention of CI-AKI (5.88 vs. 8.43%; odds ratio: 0.73; 95% confidence interval: 0.36-1.47; P>0.05), with no significant heterogeneity between studies. Network meta-analysis showed that there was no significant difference in the prevention of CI-AKI. However, the rank probability plot suggested that oral plus intravenous hydration had a higher probability (51%) of being the best strategy, followed by diuretic plus intravenous hydration (39%) and oral hydration alone (10%). Intravenous hydration alone was the strategy with the highest probability (70%) of being the worst hydration strategy. Our study shows that oral hydration is not inferior to intravenous hydration for the prevention of CI-AKI in patients with normal or mild-to-moderate renal dysfunction undergoing coronary angiography or intervention.

Thermal properties of methane gas hydrates

USGS Publications Warehouse

Waite, William F.

2007-01-01

Gas hydrates are crystalline solids in which molecules of a “guest” species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0°C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply “gas hydrates,” are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, λ: if λ is high, heat travels easily through the material. - Thermal diffusivity, κ: if κ is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to raise the temperature of the material.

Mechanical and electromagnetic properties of northern Gulf of Mexico sediments with and without THF hydrates

USGS Publications Warehouse

Lee, J.Y.; Santamarina, J.C.; Ruppel, C.

2008-01-01

Using an oedometer cell instrumented to measure the evolution of electromagnetic properties, small strain stiffness, and temperature, we conducted consolidation tests on sediments recovered during drilling in the northern Gulf of Mexico at the Atwater Valley and Keathley Canyon sites as part of the 2005 Chevron Joint Industry Project on Methane Hydrates. The tested specimens include both unremolded specimens (as recovered from the original core liner) and remolded sediments both without gas hydrate and with pore fluid exchanged to attain 100% synthetic (tetrahydrofuran) hydrate saturation at any stage of loading. Test results demonstrate the extent to which the electromagnetic and mechanical properties of hydrate-bearing marine sediments are governed by the vertical effective stress, stress history, porosity, hydrate saturation, fabric, ionic concentration of the pore fluid, and temperature. We also show how permittivity and electrical conductivity data can be used to estimate the evolution of hydrate volume fraction during formation. The gradual evolution of geophysical properties during hydrate formation probably reflects the slow increase in ionic concentration in the pore fluid due to ion exclusion in closed systems and the gradual decrease in average pore size in which the hydrate forms. During hydrate formation, the increase in S-wave velocity is delayed with respect to the decrease in permittivity, consistent with hydrate formation on mineral surfaces and subsequent crystal growth toward the pore space. No significant decementation/debonding occurred in 100% THF hydrate-saturated sediments during unloading, hence the probability of sampling hydrate-bearing sediments without disturbing the original sediment fabric is greatest for samples in which the gas hydrate is primarily responsible for maintaining the sediment fabric and for which the time between core retrieval and restoration of in situ effective stress in the laboratory is minimized. In evaluating the impact of core retrieval on specimen properties, it is also important to consider how far removed hydrate-bearing samples are from hydrate stability conditions. ?? 2008 Elsevier Ltd.

Well log characterization of natural gas-hydrates

USGS Publications Warehouse

Collett, Timothy S.; Lee, Myung W.

2012-01-01

In the last 25 years there have been significant advancements in the use of well-logging tools to acquire detailed information on the occurrence of gas hydrates in nature: whereas wireline electrical resistivity and acoustic logs were formerly used to identify gas-hydrate occurrences in wells drilled in Arctic permafrost environments, more advanced wireline and logging-while-drilling (LWD) tools are now routinely used to examine the petrophysical nature of gas-hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Resistivity- and acoustic-logging tools are the most widely used for estimating the gas-hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. Recent integrated sediment coring and well-log studies have confirmed that electrical-resistivity and acoustic-velocity data can yield accurate gas-hydrate saturations in sediment grain-supported (isotropic) systems such as sand reservoirs, but more advanced log-analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. New well-logging tools designed to make directionally oriented acoustic and propagation-resistivity log measurements provide the data needed to analyze the acoustic and electrical anisotropic properties of both highly interbedded and fracture-dominated gas-hydrate reservoirs. Advancements in nuclear magnetic resonance (NMR) logging and wireline formation testing (WFT) also allow for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids(i.e., free water along with clay- and capillary-bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas-hydrate reservoir properties (i.e., porosities and permeabilities) needed to accurately predict gas production rates for various gas-hydrate production schemes.

Complex Resistivity experiment of Methane Hydrate in Porous Media

NASA Astrophysics Data System (ADS)

Chen, Q.; Wang, C.

2017-12-01

Electric logging plays an important role in gas hydrate exploration and saturation estimation. However, due to the lack of specialized model, some classical models of petroleum industry were used to calculate the hydrate reserves such as Archie's law. But the widely used resistivity model is unable to characterize the electrical properties of hydrate bearing sediments comprehensively, while the complex resistivity method can reveal more details about the electric properties of gas hydrate porous media. In this paper, a series of electrochemical impedance spectroscope tests were carried out during methane hydrate formation and dissociation process in porous media with 3.5% brine. The hydrate saturation was controlled by decrease the pressure at certain temperature. At each saturation, complex resistivities with frequency of 0.1 Hz 1 MHz were acquired and the frequency dispersion characteristics were analyzed. Conclusion as below: 1. It exhibited remarkable frequency dispersion characteristics in hydrate porous media, especially when the frequency was below 10Hz. At certain hydrate saturation, the resistivity amplitude/real part/imaginary part decreased with frequency, but the resistivity variation trends were complicated with frequency: between 0.1- 2.3Hz, the resistivity amplitude and real part were decreased as hydrate saturation increasing; however when the frequency become higher, the resistivity were increased with hydrate saturation. 2. In the hydrate porous media test, the resistivity amplitude/real part/imaginary part didn't show a linear variation with hydrate saturation in the double logarithmic coordinate, so the Archie's law cannot get constant a, m parameters. Moreover, different frequency lead to different resistivity value at certain saturation, Archie's law parameters must be readjusted to certain logging method. 3. In this study the impedance spectroscopy of porous medium containing hydrate can be fitted through an equivalent circuit model with a resistor and capacitor in series, and the resultant complex resistivity model can be used to calculate the gas hydrate saturation which may provide a new way to predict hydrate reserves.

Numerical Simulations for Enhanced Methane Recovery from Gas Hydrate Accumulations by Utilizing CO2 Sequestration

NASA Astrophysics Data System (ADS)

Sridhara, Prathyusha

In 2013, the International Energy Outlook (EIA, 2013) projected that global energy demand will grow by 56% between 2010 and 2040. Despite strong growth in renewable energy supplies, much of this growth is expected to be met by fossil fuels. Concerns ranging from greenhouse gas emissions and energy security are spawning new interests for other sources of energy including renewable and unconventional fossil fuel such as shale gas and oil as well as gas hydrates. The production methods as well as long-term reservoir behavior of gas hydrate deposits have been under extensive investigation. Reservoir simulators can be used to predict the production potentials of hydrate formations and to determine which technique results in enhanced gas recovery. In this work, a new simulation tool, Mix3HydrateResSim (Mix3HRS), which accounts for complex thermodynamics of multi-component hydrate phase comprised of varying hydrate solid crystal structure, is used to perform the CO2-assisted production technique simulations from CH4 hydrate accumulations. The simulator is one among very few reservoir simulators which can simulate the process of CH4 substitution by CO2 (and N2 ) in the hydrate lattice. Natural gas hydrate deposits around the globe are categorized into three different classes based on the characteristics of the geological sediments present in contact with the hydrate bearing deposits. Amongst these, the Class 2 hydrate accumulations predominantly confirmed in the permafrost and along seashore, are characterized by a mobile aqueous phase underneath a hydrate bearing sediment. The exploitation of such gas hydrate deposits results in release of large amounts of water due to the presence of permeable water-saturated sediments encompassing the hydrate deposits, thus lowering the produced gas rates. In this study, a suite of numerical simulation scenarios with varied complexity are considered which aimed at understanding the underlying changes in physical, thermodynamic and transport properties with change in pressure and temperature due to the presence of the simple CO2-hydrate and mixed hydrates (mainly CH4-CO2 hydrate and CH4 -CO2-N2 hydrate) in the porous geologic media. These simulations on CO2/ CH4-CO2 hydrate reservoirs provided a basic insight to formulate and interpret a novel technological approach. This approach aims at prediction of enhanced gas production profiles from Class 2 hydrate accumulations by utilizing CO2 sequestration. The approach also offers a possibility to permanently store CO 2 in the geologic formation to a greater extent compared to a direct injection of CO2 into gas hydrate sediments. The production technique implies a three-stage approach using one vertical well design. In Stage I, the CO2 is injected into the underlying aquifer. In Stage II, the well is shut in and injected CO2 is allowed to be converted into immobile CO2 hydrate. Finally, during Stage III, decomposition of CH4 hydrate is induced by the depressurization method. The gas production potential is estimated over 15 years. The results reveal that methane production is increased together with simultaneous reduction of concomitant water production rate comparing to a conventional Class 2 reservoir production.

Indian National Gas Hydrate Program Expedition 01 report

USGS Publications Warehouse

Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.V.; ,

2015-01-01

The Indian National Gas Hydrate Program Expedition 01 was designed to study the gas-hydrate occurrences off the Indian Peninsula and along the Andaman convergent margin with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. During Indian National Gas Hydrate Program Expedition 01, dedicated gas-hydrate coring, drilling, and downhole logging operations were conducted from 28 April 2006 to 19 August 2006.

Physical properties of sediment containing methane gas hydrate

USGS Publications Warehouse

Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.

2005-01-01

A study conducted by the US Geological Survey (USGS) on the formation, behavior, and properties of mixtures of gas hydrate and sediment is presented. The results show that the properties of host material influence the type and quantity of hydrates formed. The presence of hydrate during mechanical shear tests affects the measured sediment pore pressure. Sediment shear strength may be increased more than 500 percent by intact hydrate, but greatly weakened if the hydrate dissociates.

Anisotropic Velocities of Gas Hydrate-Bearing Sediments in Fractured Reservoirs

USGS Publications Warehouse

Lee, Myung W.

2009-01-01

During the Indian National Gas Hydrate Program Expedition 01 (NGHP-01), one of the richest marine gas hydrate accumulations was discovered at drill site NGHP-01-10 in the Krishna-Godavari Basin, offshore of southeast India. The occurrence of concentrated gas hydrate at this site is primarily controlled by the presence of fractures. Gas hydrate saturations estimated from P- and S-wave velocities, assuming that gas hydrate-bearing sediments (GHBS) are isotropic, are much higher than those estimated from the pressure cores. To reconcile this difference, an anisotropic GHBS model is developed and applied to estimate gas hydrate saturations. Gas hydrate saturations estimated from the P-wave velocities, assuming high-angle fractures, agree well with saturations estimated from the cores. An anisotropic GHBS model assuming two-component laminated media - one component is fracture filled with 100-percent gas hydrate, and the other component is the isotropic water-saturated sediment - adequately predicts anisotropic velocities at the research site.

Hydration and Hot Yoga: Encouragement, Behaviors, and Outcomes.

PubMed

Mace Firebaugh, Casey J; Eggleston, Brandon

2017-01-01

Currently, the literature on hot yoga is lacking, and there is still much to understand regarding the safety of these practices. However, one point of safety often emphasized is hydration during the practice of hot yoga. The aim of this study was to examine hydration encouragement by hot yoga instructors and hydration behaviors and related outcomes by hot yoga participants. A cross-sectional study ( n = 700) collected self-report data on demographics, types and frequency of yoga practiced, hydration behaviors, and self-report measures of adverse outcomes experienced by participants during hot yoga. Associations between hydration encouragement, protective behaviors, and adverse outcomes were analyzed through Chi-square tests. Every protective hydration behavior was significantly associated with instructor encouragement ( P < 0.05). Hydration before or during hot yoga participation was associated with a lower occurrence of dehydration symptoms ( P < 0.05). Hot yoga instructors hold a key role in encouraging hydration and student safety outcomes.

Mechanical instability of monocrystalline and polycrystalline methane hydrates

PubMed Central

Wu, Jianyang; Ning, Fulong; Trinh, Thuat T.; Kjelstrup, Signe; Vlugt, Thijs J. H.; He, Jianying; Skallerud, Bjørn H.; Zhang, Zhiliang

2015-01-01

Despite observations of massive methane release and geohazards associated with gas hydrate instability in nature, as well as ductile flow accompanying hydrate dissociation in artificial polycrystalline methane hydrates in the laboratory, the destabilising mechanisms of gas hydrates under deformation and their grain-boundary structures have not yet been elucidated at the molecular level. Here we report direct molecular dynamics simulations of the material instability of monocrystalline and polycrystalline methane hydrates under mechanical loading. The results show dislocation-free brittle failure in monocrystalline hydrates and an unexpected crossover from strengthening to weakening in polycrystals. Upon uniaxial depressurisation, strain-induced hydrate dissociation accompanied by grain-boundary decohesion and sliding destabilises the polycrystals. In contrast, upon compression, appreciable solid-state structural transformation dominates the response. These findings provide molecular insight not only into the metastable structures of grain boundaries, but also into unusual ductile flow with hydrate dissociation as observed during macroscopic compression experiments. PMID:26522051

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

Ductile flow of methane hydrate

USGS Publications Warehouse

Durham, W.B.; Stern, L.A.; Kirby, S.H.

2003-01-01

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.

Water permeability in hydrate-bearing sediments: A pore-scale study

NASA Astrophysics Data System (ADS)

Dai, Sheng; Seol, Yongkoo

2014-06-01

Permeability is a critical parameter governing methane flux and fluid flow in hydrate-bearing sediments; however, limited valid data are available due to experimental challenges. Here we investigate the relationship between apparent water permeability (k') and hydrate saturation (Sh), accounting for hydrate pore-scale growth habit and meso-scale heterogeneity. Results from capillary tube models rely on cross-sectional tube shapes and hydrate pore habits, thus are appropriate only for sediments with uniform hydrate distribution and known hydrate pore character. Given our pore network modeling results showing that accumulating hydrate in sediments decreases sediment porosity and increases hydraulic tortuosity, we propose a modified Kozeny-Carman model to characterize water permeability in hydrate-bearing sediments. This model agrees well with experimental results and can be easily implemented in reservoir simulators with no empirical variables other than Sh. Results are also relevant to flow through other natural sediments that undergo diagenesis, salt precipitation, or bio-clogging.

X-Ray Micro-CT Observations of Hydrate Pore Habit and Lattice Boltzmann Simulations on Permeability Evolution in Hydrate Bearing Sediments (HBS)

NASA Astrophysics Data System (ADS)

Chen, X.; Espinoza, N.; Verma, R.; Prodanovic, M.

2017-12-01

We use X-ray micro-computed tomography (μCT) to observe xenon hydrate growth. During xenon hydrate formation in a single pore and a sandpack, we observe heterogeneous (patchy) hydrate distribution at both pore (10 μm) and core scales (10 cm). These results present similarities with earlier observations on naturally occurring and synthetic hydrate-bearing sediment (HBS). Based on image analyses of xenon hydrate in the single pore, we find that, under the quasi-isothermal condition, the xenon volumetric growth rate versus overpressurization curve fits an Arrhenius type equation. Using the μCT images of HBS, we are able to calculate the permeability of HBS using a lattice Boltzmann method. We find the reduced permeability versus hydrate saturation curve fits a simple Corey-type model as suggested by earlier studies. However, patchy distribution of hydrate does not permit a straightforward interpretation of the saturation exponent. This work provides fundamental observations of hydrate growth and pore habit in sediments and how hydrate habit affects the hydraulic conductivity of HBS. Further implications can be extended to the strength, seismic velocities and electrical properties of HBS.

Delineating the anti-cytotoxic and anti-genotoxic potentials of catechin hydrate against cadmium toxicity in human peripheral blood lymphocytes.

PubMed

Alshatwi, Ali A; Hasan, Tarique N; Alqahtani, Ali M; Syed, Naveed A; Shafi, Gowhar; Al-Assaf, Abdullah H; Al-Khalifa, Abdulrahmann S

2014-09-01

Catechins (flavan-3-ol) are a type of natural phenol and well-studied antioxidants. Catechin hydrate, also known as taxifolin; is non-mutagenic, low in toxicity compared to other immunomodulator antioxidants. We aimed to determine the potential of catechin hydrate to prevent the cyto-genotoxic effects of cadmium in lymphocytes; demonstrate the immuno-protective activity of catechin hydrate. Our previous study indicated that cadmium is apoptogenic. Lymphocytes were treated with catechin hydrate or cadmium and catechine hydrate combinations (range 0.1-100μM) to determine their effects on cell viability. Lymphocytes treated with 100μM catechin hydrate and 100μM cadmium showed cell viability 70.65±6.92% and 5.69±2.27%, respectively. In our previous study cadmium (10 and 20μM) induced apoptosis in 31.8% and 44.4% of lymphocytes, respectively. However, the percentage of apoptotic cells after treatment with the combination of cadmium and catechin hydrate was not significantly different from that of catechin hydrate (P>0.05). Only 7.3% and 10.5% of the lymphocytes were apoptotic after treatment with 10μM cadmium+10μM catechin hydrate and 20μM cadmium+20μM catechin hydrate, respectively. The anti-geno-cytotoxic and immuno-protective potential of catechin hydrate was also demonstrated by the non-significant expression of apoptosis-related genes after treatment with catechin hydrate. Copyright © 2014 Elsevier B.V. All rights reserved.

A new estimate of the volume and distribution of gas hydrate in the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Majumdar, U.; Cook, A.

2016-12-01

In spite of the wealth of information gained over the last several decades about gas hydrate in the northern Gulf of Mexico, there is still considerable uncertainty about the distribution and volume of gas hydrate. In our assessment we build a dataset of basin-wide gas hydrate distribution and thickness, as appraised from publicly available petroleum industry well logs within the gas hydrate stability zone (HSZ), and subsequently develop a Monte Carlo to determine the volumetric estimate of gas hydrate using the dataset. We evaluate the presence of gas hydrate from electrical resistivity well logs, and categorized possible reservoir type (either sand or clay) based on the gamma ray response and resistivity curve characteristics. Out of the 798 wells with resistivity well log data within the HSZ we analyzed, we found evidence of gas hydrate in 124 wells. In this research we present a new stochastic estimate of the gas hydrate volume in the northern Gulf of Mexico guided by our well log dataset. For our Monte Carlo simulation, we divided our assessment area of 200,000 km2 into 1 km2 grid cells. Our volume assessment model incorporates variables unique to our well log dataset such as the likelihood of gas hydrate occurrence, fraction of the HSZ occupied by gas hydrate, reservoir type, and gas hydrate saturation depending on the reservoir, in each grid cell, in addition to other basic variables such as HSZ thickness and porosity. Preliminary results from our model suggests that the total volume of gas at standard temperature and pressure in gas hydrate in the northern Gulf of Mexico is in the range of 430 trillion cubic feet (TCF) to 730 TCF, with a mean volume of 585 TCF. While the reservoir distribution from our well log dataset found gas hydrate in sand reservoirs in 30 wells out of the 124 wells with evidence of gas hydrate ( 24%), we find sand reservoirs contain over half of the total volume of gas hydrate in the Gulf of Mexico, as a result of the relatively high gas hydrate saturation in sand.

Comparison of the physical and geotechnical properties of gas-hydrate-bearing sediments from offshore India and other gas-hydrate-reservoir systems

USGS Publications Warehouse

Winters, William J.; Wilcox-Cline, R.W.; Long, P.; Dewri, S.K.; Kumar, P.; Stern, Laura A.; Kerr, Laura A.

2014-01-01

The sediment characteristics of hydrate-bearing reservoirs profoundly affect the formation, distribution, and morphology of gas hydrate. The presence and type of gas, porewater chemistry, fluid migration, and subbottom temperature may govern the hydrate formation process, but it is the host sediment that commonly dictates final hydrate habit, and whether hydrate may be economically developed.In this paper, the physical properties of hydrate-bearing regions offshore eastern India (Krishna-Godavari and Mahanadi Basins) and the Andaman Islands, determined from Expedition NGHP-01 cores, are compared to each other, well logs, and published results of other hydrate reservoirs. Properties from the hydrate-free Kerala-Konkan basin off the west coast of India are also presented. Coarser-grained reservoirs (permafrost-related and marine) may contain high gas-hydrate-pore saturations, while finer-grained reservoirs may contain low-saturation disseminated or more complex gas-hydrates, including nodules, layers, and high-angle planar and rotational veins. However, even in these fine-grained sediments, gas hydrate preferentially forms in coarser sediment or fractures, when present. The presence of hydrate in conjunction with other geologic processes may be responsible for sediment porosity being nearly uniform for almost 500 m off the Andaman Islands.Properties of individual NGHP-01 wells and regional trends are discussed in detail. However, comparison of marine and permafrost-related Arctic reservoirs provides insight into the inter-relationships and common traits between physical properties and the morphology of gas-hydrate reservoirs regardless of location. Extrapolation of properties from one location to another also enhances our understanding of gas-hydrate reservoir systems. Grain size and porosity effects on permeability are critical, both locally to trap gas and regionally to provide fluid flow to hydrate reservoirs. Index properties corroborate more advanced consolidation and triaxial strength test results and can be used for predicting behavior in other NGHP-01 regions. Pseudo-overconsolidation is present near the seafloor and is underlain by underconsolidation at depth at some NGHP-01 locations.

Three-dimensional distribution of gas hydrate beneath southern Hydrate Ridge: Constraints from ODP Leg 204

USGS Publications Warehouse

Trehu, A.M.; Long, P.E.; Torres, M.E.; Bohrmann, G.; Rack, F.R.; Collett, T.S.; Goldberg, D.S.; Milkov, A.V.; Riedel, M.; Schultheiss, P.; Bangs, N.L.; Barr, S.R.; Borowski, W.S.; Claypool, G.E.; Delwiche, M.E.; Dickens, G.R.; Gracia, E.; Guerin, G.; Holland, M.; Johnson, J.E.; Lee, Y.-J.; Liu, C.-S.; Su, X.; Teichert, B.; Tomaru, H.; Vanneste, M.; Watanabe, M. E.; Weinberger, J.L.

2004-01-01

Large uncertainties about the energy resource potential and role in global climate change of gas hydrates result from uncertainty about how much hydrate is contained in marine sediments. During Leg 204 of the Ocean Drilling Program (ODP) to the accretionary complex of the Cascadia subduction zone, we sampled the gas hydrate stability zone (GHSZ) from the seafloor to its base in contrasting geological settings defined by a 3D seismic survey. By integrating results from different methods, including several new techniques developed for Leg 204, we overcome the problem of spatial under-sampling inherent in robust methods traditionally used for estimating the hydrate content of cores and obtain a high-resolution, quantitative estimate of the total amount and spatial variability of gas hydrate in this structural system. We conclude that high gas hydrate content (30-40% of pore space or 20-26% of total volume) is restricted to the upper tens of meters below the seafloor near the summit of the structure, where vigorous fluid venting occurs. Elsewhere, the average gas hydrate content of the sediments in the gas hydrate stability zone is generally <2% of the pore space, although this estimate may increase by a factor of 2 when patchy zones of locally higher gas hydrate content are included in the calculation. These patchy zones are structurally and stratigraphically controlled, contain up to 20% hydrate in the pore space when averaged over zones ???10 m thick, and may occur in up to ???20% of the region imaged by 3D seismic data. This heterogeneous gas hydrate distribution is an important constraint on models of gas hydrate formation in marine sediments and the response of the sediments to tectonic and environmental change. ?? 2004 Published by Elsevier B.V.

Volume change associated with formation and dissociation of hydrate in sediment

USGS Publications Warehouse

Ruppel, Carolyn D.; Lee, J.Y.; Santamarina, J. Carlos

2017-01-01

Gas hydrate formation and dissociation in sediments are accompanied by changes in the bulk volume of the sediment and can lead to changes in sediment properties, loss of integrity for boreholes, and possibly regional subsidence of the ground surface over areas where methane might be produced from gas hydrate in the future. Experiments on sand, silts, and clay subject to different effective stress and containing different saturations of hydrate formed from dissolved phase tetrahydrofuran are used to systematically investigate the impact of gas hydrate formation and dissociation on bulk sediment volume. Volume changes in low specific surface sediments (i.e., having a rigid sediment skeleton like sand) are much lower than those measured in high specific surface sediments (e.g., clay). Early hydrate formation is accompanied by contraction for all soils and most stress states in part because growing gas hydrate crystals buckle skeletal force chains. Dilation can occur at high hydrate saturations. Hydrate dissociation under drained, zero lateral strain conditions is always associated with some contraction, regardless of soil type, effective stress level, or hydrate saturation. Changes in void ratio during formation-dissociation decrease at high effective stress levels. The volumetric strain during dissociation under zero lateral strain scales with hydrate saturation and sediment compressibility. The volumetric strain during dissociation under high shear is a function of the initial volume average void ratio and the stress-dependent critical state void ratio of the sediment. Other contributions to volume reduction upon hydrate dissociation are related to segregated hydrate in lenses and nodules. For natural gas hydrates, some conditions (e.g., gas production driven by depressurization) might contribute to additional volume reduction by increasing the effective stress.

Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems: DIFFUSION-DRIVEN HYDRATE GROWTH IN SANDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nole, Michael; Daigle, Hugh; Cook, Ann E.

The goal of this study is to computationally determine the potential distribution patterns of diffusion-driven methane hydrate accumulations in coarse-grained marine sediments. Diffusion of dissolved methane in marine gas hydrate systems has been proposed as a potential transport mechanism through which large concentrations of hydrate can preferentially accumulate in coarse-grained sediments over geologic time. Using one-dimensional compositional reservoir simulations, we examine hydrate distribution patterns at the scale of individual sand layers (1 to 20 m thick) that are deposited between microbially active fine-grained material buried through the gas hydrate stability zone (GHSZ). We then extrapolate to two- dimensional and basin-scalemore » three-dimensional simulations, where we model dipping sands and multilayered systems. We find that properties of a sand layer including pore size distribution, layer thickness, dip, and proximity to other layers in multilayered systems all exert control on diffusive methane fluxes toward and within a sand, which in turn impact the distribution of hydrate throughout a sand unit. In all of these simulations, we incorporate data on physical properties and sand layer geometries from the Terrebonne Basin gas hydrate system in the Gulf of Mexico. We demonstrate that diffusion can generate high hydrate saturations (upward of 90%) at the edges of thin sands at shallow depths within the GHSZ, but that it is ineffective at producing high hydrate saturations throughout thick (greater than 10 m) sands buried deep within the GHSZ. As a result, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.« less

Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems: DIFFUSION-DRIVEN HYDRATE GROWTH IN SANDS

DOE PAGES

Nole, Michael; Daigle, Hugh; Cook, Ann E.; ...

2017-02-01

The goal of this study is to computationally determine the potential distribution patterns of diffusion-driven methane hydrate accumulations in coarse-grained marine sediments. Diffusion of dissolved methane in marine gas hydrate systems has been proposed as a potential transport mechanism through which large concentrations of hydrate can preferentially accumulate in coarse-grained sediments over geologic time. Using one-dimensional compositional reservoir simulations, we examine hydrate distribution patterns at the scale of individual sand layers (1 to 20 m thick) that are deposited between microbially active fine-grained material buried through the gas hydrate stability zone (GHSZ). We then extrapolate to two- dimensional and basin-scalemore » three-dimensional simulations, where we model dipping sands and multilayered systems. We find that properties of a sand layer including pore size distribution, layer thickness, dip, and proximity to other layers in multilayered systems all exert control on diffusive methane fluxes toward and within a sand, which in turn impact the distribution of hydrate throughout a sand unit. In all of these simulations, we incorporate data on physical properties and sand layer geometries from the Terrebonne Basin gas hydrate system in the Gulf of Mexico. We demonstrate that diffusion can generate high hydrate saturations (upward of 90%) at the edges of thin sands at shallow depths within the GHSZ, but that it is ineffective at producing high hydrate saturations throughout thick (greater than 10 m) sands buried deep within the GHSZ. As a result, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.« less

Adhesion force interactions between cyclopentane hydrate and physically and chemically modified surfaces.

PubMed

Aman, Zachary M; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2014-12-07

Interfacial interactions between liquid-solid and solid-solid phases/surfaces are of fundamental importance to the formation of hydrate deposits in oil and gas pipelines. This work establishes the effect of five categories of physical and chemical modification to steel on clathrate hydrate adhesive force: oleamide, graphite, citric acid ester, nonanedithiol, and Rain-X anti-wetting agent. Hydrate adhesive forces were measured using a micromechanical force apparatus, under both dry and water-wet surface conditions. The results show that the graphite coating reduced hydrate-steel adhesion force by 79%, due to an increase in the water wetting angle from 42 ± 8° to 154 ± 7°. Two chemical surface coatings (nonanedithiol and the citric acid ester) induced rapid hydrate growth in the hydrate particles; nonanedithiol increased hydrate adhesive force by 49% from the baseline, while the citric acid ester coating reduced hydrate adhesion force by 98%. This result suggests that crystal growth may enable a strong adhesive pathway between hydrate and other crystalline structures, however this effect may be negated in cases where water-hydrocarbon interfacial tension is minimised. When a liquid water droplet was placed on the modified steel surfaces, the graphite and citric acid ester became less effective at reducing adhesive force. In pipelines containing a free water phase wetting the steel surface, chemical or physical surface modifications alone may be insufficient to eliminate hydrate deposition risk. In further tests, the citric acid ester reduced hydrate cohesive forces by 50%, suggesting mild activity as a hybrid anti-agglomerant suppressing both hydrate deposition and particle agglomeration. These results demonstrate a new capability to develop polyfunctional surfactants, which simultaneously limit the capability for hydrate particles to aggregate and deposit on the pipeline wall.

Magnetic Tracking of Gas Hydrate Deposits.

NASA Astrophysics Data System (ADS)

Lowe, C.; Enkin, R. J.; Judith, B.; Dallimore, S. R.

2005-12-01

Analysis of recovered core from the Mallik gas hydrate field in the Mackenzie Delta, Northwest Territories, Canada demonstrates that the magnetic properties of hydrate-bearing strata differ significantly from those strata lacking gas hydrate. The recovered core, which extends from just above (885 m) to just below (1152 m) observed gas hydrate occurrences (891-1107 m), comprises a series of six stratigraphic units that are either sand or silt dominated. Gas hydrate is preferentially concentrated in the higher porosity, sand-dominated units. Although the sediment source region for the Mackenzie Delta is sufficiently large that silts and sands have similar primary mineralogy, their magnetic properties are distinct. Magnetite, apparent in silt units with porosities too low to accommodate significant gas hydrate deposits, is reduced to iron sulphide in the gas hydrate-bearing sand horizons. The degree of the observed magnetic reduction increases with increasing gas hydrate concentration. Furthermore, silts retain their primary magnetism, whereas sands are remagnetized. Two independent investigations of marine gas hydrate occurrences (Blake Ridge, offshore eastern USA and Cascadia, offshore western Canada) demonstrate similar magnetic reduction within known gas hydrate fields, and an even larger depletion of magnetic minerals in vent zones where methane is actively fluxing to surface. Collectively, the findings from these three regions indicate that porosity and structure are fundamental controls on methane pathways. Investigations are presently underway to determine the precise triggers and chemical pathways of the observed magnetic reductions. However, findings to date indicate that magnetic studies of host sediments in gas hydrate systems provide a powerful lithologic correlation tool, a window into the processes associated with gas hydrate formation, and form the basis of quantitative analysis of magnetic surveys over gas hydrate deposits.

Level of hydration and renal function in healthy humans.

PubMed

Anastasio, P; Cirillo, M; Spitali, L; Frangiosa, A; Pollastro, R M; De Santo, N G

2001-08-01

High hydration is commonly used in renal studies to improve the completeness of urine collection. The renal effects of hydration are not well defined. Renal function was studied under fasting conditions (baseline) and after a meat meal (2 g of protein/kg body weight) in 12 healthy adults on a low and high hydration regimen of 0.5 and 4 mL of oral water per kg body weight/30 min, respectively. Urine flow, urinary and plasma Na, K, urea, and osmolality were stably different on low and high hydration regimens. At baseline, there were significant or borderline significant correlations of plasma and urine osmolality with glomerular filtration rate (GFR; inulin clearance) only in the low hydration regimen. GFR was higher in the low than the high hydration regimen at all time points. The difference was significant at baseline (19.2%) and at 90 to 180 minutes after the meal (14.4%). After the meal, GFR increased significantly over baseline values only in the high hydration regimen (30.0% at peak time). Urinary excretion of Na, urea, and osmoles was lower in the low than the high hydration regimen at all time points: The difference was significant for Na (at baseline) and osmoles (all time points). Urinary K excretion was not different in the two regimens. After the meal, there were significant increases in urinary excretion of Na (in the low hydration regimen) and urea (90 to 180 min after the meal). In fasting adults, high hydration lowered GFR and increased natriuresis. After a meat meal, GFR increased only in the high hydration regimen and natriuresis only in the low hydration regimen. Hydration affects GFR and natriuresis under fasting conditions and after a meat meal.

Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

NASA Astrophysics Data System (ADS)

Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

2007-12-01

A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

Offshore gas hydrate sample database with an overview and preliminary analysis

USGS Publications Warehouse

Booth, James S.; Rowe, Mary M.; Fisher, Kathleen M.

1996-01-01

Synopsis -- A database of offshore gas hydrate samples was constructed from published observations and measurements. More than 90 samples from 15 distinct regions are represented in 13 data categories. This database has permitted preliminary description of gas hydrate (chiefly methane hydrate) tendencies and associations with respect to their geological environment. Gas hydrates have been recovered from offshore sediment worldwide and from total depths (water depth plus subseabed depth) ranging from 500 m to nearly 6,000 m. Samples have come from subbottom depths ranging from 0 to 400 m. Various physiographic provinces are represented in the data set including second order landforms such as continental margins and deep-sea trenches, and third order forms such as submarine canyons, continental slopes, continental margin ridges and intraslope basins. There is a clear association between fault zones and other manifestations of local, tectonic-related processes, and hydrate-bearing sediment. Samples of gas hydrate frequently consist of individual grains or particles. These types of hydrates are often further described as inclusions or disseminated in the sediment. Moreover, hydrates occur as a cement, as nodules, or as layers (mostly laminae) or in veins. The preponderance of hydrates that could be characterized as 2- dimensional (planar) were associated with fine sediment, either as intercalated layers or in fractures. Hydrate cements were commonly associated with coarser sediment. Hydrates have been found in association with grain sizes ranging from clay through gravel. More hydrates are associated with the more abundant finer-grained sediment than with coarser sediment, and many were discovered in the presence of both fine (silt and clay) and coarse sediment. The thickness of hydrate zones (i. e., sections of hydrate-bearing sediment) varies from a few centimeters to as much as 30 m. In contrast, the thickness of layers of pure hydrate or the dimensions of individual hydrate grains were most often characterized in terms of millimeters or centimeters, although a pure hydrate layer discovered in the Middle America Trench off Guatemala was as much as 3-4-m-thick. The data suggest that grains, or thin veins or laminae of pure gas hydrate may be ubiquitous in many hydrate zones but that typically they may only comprise a minor component of the thicker zones. In more than 80 percent of the hydrate samples the methane was of biogenic origin. The methane in the remainder was either classified as (or may be at least part) thermogenic. Each site where thermogenic gas was identified is characterized by faults or other manifestions of a dynamic geological environment (e.g., diapirs, mud volcanoes, gas seeps). Every sample in the database came from within the zone of theoretical methane hydrate stability, as determined on the basis of assumed regional pressure and temperature gradients. Most show that they were situated --- expressed in terms of depth --- well above the phase boundary and about 70% of the samples were located more than 100 m above the assumed regional position of that boundary. The calculated subseabed positions of the phase boundaries and the BSRs (bottom simulating reflector) are essentially identical. This may be taken as general corroboration of the regional phase boundary calculations and the concept of the BSR. Three provocative aspects of marine gas hydrates have been disclosed by the database: gas hydrates are frequently situated at much shallower subseabed depths than the assumed contemporary position of the regional phase boundary hydrates are often found in areas typified by faults or other indicators of a dynamic geological environment zones of gas hydrate-bearing sediment tend to be tens of centimeters to tens of meters thick but the hydrate within the thicker zones tends to be only a minor constituent. Whether existing as dispersed particles, cements, or pure layers or vein

Gas hydrate suspensions formation and transportation research

NASA Astrophysics Data System (ADS)

Gulkov, A. N.; Gulkova, S.; Zemenkov, Yu D.; Lapshin, V. D.

2018-05-01

An experimental unit for studying the formation of gas hydrate suspensions and their transport properties is considered. The scheme of installation and the basic processes, which can be studied, are described. The results of studies of gas hydrates and a gas hydrate suspension’ formation in an adiabatic process in a stream of seawater are given. The adiabatic method of obtaining gas hydrates and forming gas hydrate suspensions is offered to use. Directions for further research are outlined.

Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.

PubMed

Bagherzadeh, S Alireza; Englezos, Peter; Alavi, Saman; Ripmeester, John A

2012-03-15

We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase. © 2012 American Chemical Society

Apparatus investigates geological aspects of gas hydrates

USGS Publications Warehouse

Booth, J.S.; Winters, W.J.; Dillon, William P.

1999-01-01

The US Geological Survey (USGS), in response to potential geohazards, energy resource potential, and climate issues associated with marine gas hydrates, has developed a laboratory research system that permits hydrate genesis and dissociation under deep-sea conditions, employing user-selected sediment types and pore fluids.The apparatus, GHASTI (gas hydrate and sediment test laboratory instrument), provides a means to link field studies and theory and serves as a tool to improve gas hydrate recognition and assessment, using remote sensing techniques.GHASTLI's use was proven in an exploration well project led by the Geological Survey of Canada and the Japanese National Oil Corp., collaborating with Japan Petroleum Exploration Co. and the USGS. The site was in the Mackenzie Delta region of the Northwest Territories (Mallik 2L-38 drillsite).From tests on natural methane hydrate-bearing sand recovered at about 1,000 m subsurface, the in situ quantity of hydrate was estimated from acoustic properties, and a substantial increase in shear strength due to the presence of the hydrate was measured.1 2GHASTI can mimic a wide range of geologic settings and processes. Initial goals involve improved recognition and mapping of gas hydrate-bearing sediments, understanding factors that control the occurrence and concentration of gas hydrates, knowledge of hydrate's significance to slope failure and foundation problems, and analysis of gas hydrate's potential use as an energy resource.

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

USGS Publications Warehouse

Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

2013-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Three types of gas hydrate reservoirs in the Gulf of Mexico identified in LWD data

USGS Publications Warehouse

Lee, Myung Woong; Collett, Timothy S.

2011-01-01

High quality logging-while-drilling (LWD) well logs were acquired in seven wells drilled during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II in the spring of 2009. These data help to identify three distinct types of gas hydrate reservoirs: isotropic reservoirs in sands, vertical fractured reservoirs in shale, and horizontally layered reservoirs in silty shale. In general, most gas hydratebearing sand reservoirs exhibit isotropic elastic velocities and formation resistivities, and gas hydrate saturations estimated from the P-wave velocity agree well with those from the resistivity. However, in highly gas hydrate-saturated sands, resistivity-derived gas hydrate-saturation estimates appear to be systematically higher by about 5% over those estimated by P-wave velocity, possibly because of the uncertainty associated with the consolidation state of gas hydrate-bearing sands. Small quantities of gas hydrate were observed in vertical fractures in shale. These occurrences are characterized by high formation resistivities with P-wave velocities close to those of water-saturated sediment. Because the formation factor varies significantly with respect to the gas hydrate saturation for vertical fractures at low saturations, an isotropic analysis of formation factor highly overestimates the gas hydrate saturation. Small quantities of gas hydrate in horizontal layers in shale are characterized by moderate increase in P-wave velocities and formation resistivities and either measurement can be used to estimate gas hydrate saturations.

Gas hydrate property measurements in porous sediments with resonant ultrasound spectroscopy

NASA Astrophysics Data System (ADS)

McGrail, B. P.; Ahmed, S.; Schaef, H. T.; Owen, A. T.; Martin, P. F.; Zhu, T.

2007-05-01

Resonant ultrasound spectroscopy was used to characterize a natural geological core sample obtained from the Mallik 5L-38 gas hydrate research well at high pressure and subambient temperatures. Using deuterated methane gas to form gas hydrate in the core sample, it was discovered that resonance amplitudes are correlated with the fraction of the pore space occupied by the gas hydrate crystals. A pore water freezing model was developed that utilizes the known pore size distribution and pore water chemistry to predict gas hydrate saturation as a function of pressure and temperature. The model showed good agreement with the experimental measurements and demonstrated that pore water chemistry is the most important factor controlling equilibrium gas hydrate saturations in these sediments when gas hydrates are formed artificially in laboratory pressure vessels. With further development, the resonant ultrasound technique can provide a rapid, nondestructive, field portable means of measuring the equilibrium P-T properties and dissociation kinetics of gas hydrates in porous media, determining gas hydrate saturations, and may provide new insights into the nature of gas hydrate formation mechanisms in geologic materials.

Seismic- and well-log-inferred gas hydrate accumulations on Richards Island

USGS Publications Warehouse

Collett, T.S.

1999-01-01

The gas hydrate stability zone is areally extensive beneath most of the Mackenzie Delta-Beaufort Sea region, with the base of the gas hydrate stability zone more than 1000 m deep on Richards Island. In this study, gas hydrate has been inferred to occur in nine Richards Island exploratory wells on the basis of well-log responses calibrated to the response of the logs within the cored gas-hydrate-bearing intervals of the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The integration of the available well-log data with more than 240 km of industry-acquired reflection seismic data have allowed us to map the occurrence of four significant gas hydrate and associated free-gas accumulations in the Ivik-Mallik-Taglu area on Richards Island. The occurrence of gas hydrate on Richards Island is mostly restricted to the crest of large anticlinal features that cut across the base of the gas hydrate stability zone. Combined seismic and well-log data analysis indicate that the known and inferred gas hydrate accumulations on Richards Island may contain as much as 187 178106 m3 of gas.

Amount of gas hydrate estimated from compressional- and shear-wave velocities at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

USGS Publications Warehouse

Lee, M.W.

1999-01-01

The amount of in situ gas hydrate concentrated in the sediment pore space at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well was estimated by using compressional-wave (P-wave) and shear-wave (S-wave) downhole log measurements. A weighted equation developed for relating the amount of gas hydrate concentrated in the pore space of unconsolidated sediments to the increase of seismic velocities was applied to the acoustic logs with porosities derived from the formation density log. A weight of 1.56 (W=1.56) and the exponent of 1 (n=1) provided consistent estimates of gas hydrate concentration from the S-wave and the P-wave logs. Gas hydrate concentration is as much as 80% in the pore spaces, and the average gas hydrate concentration within the gas-hydrate-bearing section from 897 m to 1110 m (excluding zones where there is no gas hydrate) was calculated at 39.0% when using P-wave data and 37.8% when using S-wave data.

Implication of seismic attenuation for gas hydrate resource characterization, Mallik, Mackenzie Delta, Canada

NASA Astrophysics Data System (ADS)

Bellefleur, G.; Riedel, M.; Brent, T.; Wright, F.; Dallimore, S. R.

2007-10-01

Wave attenuation is an important physical property of hydrate-bearing sediments that is rarely taken into account in site characterization with seismic data. We present a field example showing improved images of hydrate-bearing sediments on seismic data after compensation of attenuation effects. Compressional quality factors estimated from zero-offset Vertical Seismic Profiling data acquired at Mallik, Northwest Territories, Canada, demonstrate significant wave attenuation for hydrate-bearing sediments. These results are in agreement with previous attenuation estimates obtained from sonic logs and crosshole data at different frequency intervals. The application of an inverse Q-filter to compensate attenuation effects of permafrost and hydrate-bearing sediments improved the resolution of surface 3D seismic data and its correlation with log data, particularly for the shallowest gas hydrate interval. Compensation of the attenuation effects of the permafrost likely explains most of the improvements for the shallow gas hydrate zone. Our results show that characterization of the Mallik gas hydrates with seismic data not corrected for attenuation would tend to overestimate thicknesses and lateral extent of hydrate-bearing strata and hence, the volume of hydrates in place.

Rapid gas hydrate formation processes: Will they work?

DOE PAGES

Brown, Thomas D.; Taylor, Charles E.; Bernardo, Mark P.

2010-06-07

Researchers at DOE’s National Energy Technology Laboratory (NETL) have been investigating the formation of synthetic gas hydrates, with an emphasis on rapid and continuous hydrate formation techniques. The investigations focused on unconventional methods to reduce dissolution, induction, nucleation and crystallization times associated with natural and synthetic hydrates studies conducted in the laboratory. Numerous experiments were conducted with various high-pressure cells equipped with instrumentation to study rapid and continuous hydrate formation. The cells ranged in size from 100 mL for screening studies to proof-of-concept studies with NETL’s 15-Liter Hydrate Cell. The results from this work demonstrate that the rapid and continuousmore » formation of methane hydrate is possible at predetermined temperatures and pressures within the stability zone of a Methane Hydrate Stability Curve.« less

Estimating pore-space gas hydrate saturations from well log acoustic data

USGS Publications Warehouse

Lee, Myung W.; Waite, William F.

2008-01-01

Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate–bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

Effects of hydration in contrast-induced acute kidney injury after primary angioplasty: a randomized, controlled trial.

PubMed

Maioli, Mauro; Toso, Anna; Leoncini, Mario; Micheletti, Carlo; Bellandi, Francesco

2011-10-01

Intravascular volume expansion represents a beneficial measure against contrast-induced acute kidney injury (CI-AKI) in patients undergoing elective angiographic procedures. However, the efficacy of this preventive strategy has not yet been established for patients with ST-elevation-myocardial infarction (STEMI), who are at higher risk of this complication after primary percutaneous coronary intervention (PCI). In this randomized study we investigated the possible beneficial role of periprocedural intravenous volume expansion and we compared the efficacy of 2 different hydration strategies in patients with STEMI undergoing primary PCI. We randomly assigned 450 STEMI patients to receive (1) preprocedure and postprocedure hydration of sodium bicarbonate (early hydration group), (2) postprocedure hydration of isotonic saline (late hydration group), or (3) no hydration (control group). The primary end point was the development of CI-AKI, defined as an increase in serum creatinine of ≥25% or 0.5 mg/dL over the baseline value within 3 days after administration of the contrast medium. Moreover, we evaluated a possible relationship between the occurrence of CI-AKI and total hydration volume administered. There were no significant differences in baseline clinical, biochemical, and procedural characteristics in the 3 groups. Overall, CI-AKI occurred in 93 patients (20.6%): the incidence was significantly lower in the early hydration group (12%) with respect to both the late hydration group (22.7%) and the control group (27.3%) (P for trend=0.001). In hydrated patients (early and late hydration groups), lower infused volumes were associated with a significant increase in CI-AKI incidence, and the optimal cutoff point of hydration volume that best discriminates patients at higher risk was ≤960 mL. Adequate intravenous volume expansion may prevent CI-AKI in patients undergoing primary PCI. A regimen of preprocedure and postprocedure hydration therapy with sodium bicarbonate appears to be more efficacious than postprocedure hydration only with isotonic saline.

Stability of CO2 hydrate under very high pressure and low temperature

NASA Astrophysics Data System (ADS)

Hirai, H.; Honda, M.; Kawamura, T.; Yamamoto, Y.; Yagi, T.

2009-12-01

CO2 hydrate is a clathrate compound and the crystal structure type is sI at low pressure. CO2-reduction in the atmosphere is one of the most urgent subjects for mankind. Some technical developments to seclude CO2 as CO2 hydrate in ocean floor have been proceeded. Looking around the solar system, existence of CO2 hydrate in and beneath Martian permafrost has been predicted from spacecraft probes and theoretical studies. Thus, its stability and properties under high pressures and low temperatures are of great interest for fundamental understanding of clathrate hydrate, for the ocean sequestration technology, and for planetary science. CO2 hydrate exhibits characteristic properties different from those of other gas hydrate such as methane hydrate. For example, phase boundary between hydrate and gas + water for many gas hydrates shows positive slope in pressure versus temperature field, and the gas hydrates are kept at pressures up to several GPa at room temperature. On the other hand, for CO2 hydrate, the phase boundary turns to negative slope from positive one at a certain critical point [Nakano et al., 1998], and it can exist only at low temperature regions. And, a theoretical study predicted that CO2 hydrate decompose at low temperature region [Longhi, 2005]. In this study, high pressure and low temperature experiments were performed to examine stability and phase changes of CO2 hydrate using diamond anvil cell in a pressure range from 0.1 to 2.5 GPa and a the temperature range from 65 to 265 K. X-ray diffractometry and Raman spectroscopy revealed that the known phase boundary was extended into lower temperature region, and that CO2 hydrate was kept at low temperature regions at least 65 K despite the theoretical prediction of decomposition. References [1] S. Nakano, M. Moritoki, K. Ohgaki, J. Chem. Eng. Data, 43, 807 (1998). [2] J. Longhi, Geochim. Cosmochim. Acta, 69, 529 (2005)

Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea

USGS Publications Warehouse

Wang, X.; Hutchinson, D.R.; Wu, S.; Yang, S.; Guo, Y.

2011-01-01

Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190-221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone. Copyright 2011 by the American Geophysical Union.

Grain-scale imaging and compositional characterization of cryo-preserved India NGHP 01 gas-hydrate-bearing cores

USGS Publications Warehouse

Stern, Laura A.; Lorenson, T.D.

2014-01-01

We report on grain-scale characteristics and gas analyses of gas-hydrate-bearing samples retrieved by NGHP Expedition 01 as part of a large-scale effort to study gas hydrate occurrences off the eastern-Indian Peninsula and along the Andaman convergent margin. Using cryogenic scanning electron microscopy, X-ray spectroscopy, and gas chromatography, we investigated gas hydrate grain morphology and distribution within sediments, gas hydrate composition, and methane isotopic composition of samples from Krishna–Godavari (KG) basin and Andaman back-arc basin borehole sites from depths ranging 26 to 525 mbsf. Gas hydrate in KG-basin samples commonly occurs as nodules or coarse veins with typical hydrate grain size of 30–80 μm, as small pods or thin veins 50 to several hundred microns in width, or disseminated in sediment. Nodules contain abundant and commonly isolated macropores, in some places suggesting the original presence of a free gas phase. Gas hydrate also occurs as faceted crystals lining the interiors of cavities. While these vug-like structures constitute a relatively minor mode of gas hydrate occurrence, they were observed in near-seafloor KG-basin samples as well as in those of deeper origin (>100 mbsf) and may be original formation features. Other samples exhibit gas hydrate grains rimmed by NaCl-bearing material, presumably produced by salt exclusion during original hydrate formation. Well-preserved microfossil and other biogenic detritus are also found within several samples, most abundantly in Andaman core material where gas hydrate fills microfossil crevices. The range of gas hydrate modes of occurrence observed in the full suite of samples suggests a range of formation processes were involved, as influenced by local in situconditions. The hydrate-forming gas is predominantly methane with trace quantities of higher molecular weight hydrocarbons of primarily microbial origin. The composition indicates the gas hydrate is Structure I.

Effects of Attenuation of Gas Hydrate-bearing Sediments on Seismic Data: Example from Mallik, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Bellefleur, G.; Riedel, M.; Brent, T.

2007-05-01

Wave attenuation is an important physical property of hydrate-bearing sediments that is rarely taken into account in site characterization with seismic data. We present a field example showing improved images of hydrate- bearing sediments on seismic data after compensation of attenuation effects. Compressional quality factors (Q) are estimated from zero-offset Vertical Seismic Profiling data acquired at Mallik, Northwest Territories, Canada. During the last 10 years, two internationally-partnered research drilling programs have intersected three major intervals of sub-permafrost gas hydrates at Mallik, and have successfully extracted core samples containing significant amount of gas hydrates. Individual gas hydrate intervals are up to 40m in thickness and are characterized by high in situ gas hydrate saturation, sometimes exceeding 80% of pore volume of unconsolidated clastic sediments having average porosities ranging from 25% to 40%. The Q-factors obtained from the VSP data demonstrate significant wave attenuation for permafrost and hydrate- bearing sediments. These results are in agreement with previous attenuation estimates from sonic logs and crosshole data at different frequency intervals. The Q-factors obtained from VSP data were used to compensate attenuation effects on surface 3D seismic data acquired over the Mallik gas hydrate research wells. Intervals of gas hydrate on surface seismic data are characterized by strong reflectivity and effects from attenuation are not perceptible from a simple visual inspection of the data. However, the application of an inverse Q-filter increases the resolution of the data and improves correlation with log data, particularly for the shallowest gas hydrate interval. Compensation of the attenuation effects of the permafrost likely explains most of the improvements for the shallow gas hydrate zone. Our results show that characterization of the Mallik gas hydrates with seismic data not corrected for attenuation would tend to overestimate thicknesses and lateral extent of hydrate-bearing strata and hence, the volume of hydrates in place.

Hydro-mechanical properties of pressure core sediments recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02

NASA Astrophysics Data System (ADS)

Yoneda, J.; Oshima, M.; Kida, M.; Kato, A.; Konno, Y.; Jin, Y.; Waite, W. F.; Jang, J.; Kumar, P.; Tenma, N.

2017-12-01

Pressure coring and analysis technology allows for gas hydrate to be recovered from the deep seabed, transferred to the laboratory and characterized while continuously maintaining gas hydrate stability. For this study, dozens of hydrate-bearing pressure core sediment subsections recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02 were tested with Pressure Core Non-destructive Analysis Tools (PNATs) through a collaboration between Japan and India. PNATs, originally developed by AIST as a part of the Japanese National hydrate research program (MH21, funded by METI) conducted permeability, compression and consolidation tests under various effective stress conditions, including the in situ stress state estimated from downhole bulk density measurements. At the in situ effective stress, gas hydrate-bearing sediments had an effective permeability range of 0.01-10mD even at pore-space hydrate saturations above 60%. Permeability increased by 10 to 100 times after hydrate dissociation at the same effective stress, but these post-dissociation gains were erased when effective stress was increased from in situ values ( 1 MPa) to 10MPa in a simulation of the depressurization method for methane extraction from hydrate. Vertical-to-horizontal permeability anisotropy was also investigated. First-ever multi-stage loading tests and strain-rate alternation compression tests were successfully conducted for evaluating sediment strengthening dependence on the rate and magnitude of effective confining stress changes. In addition, oedometer tests were performed up to 40MPa of consolidation stress to simulate the depressurization method in ultra-deep sea environments. Consolidation curves measured with and without gas hydrate were investigated over a wide range of effective confining stresses. Compression curves for gas hydrate-bearing sediments were convex downward due to high hydrate saturations. Consolidation tests show that, regardless of the consolidation history with hydrate in place, the consolidation behavior after dissociation will first return to, then follow, the original normal consolidation curve for the hydrate-free host sediment.

Estimation of potential distribution of gas hydrate in the northern South China Sea

NASA Astrophysics Data System (ADS)

Wang, Chunjuan; Du, Dewen; Zhu, Zhiwei; Liu, Yonggang; Yan, Shijuan; Yang, Gang

2010-05-01

Gas hydrate research has significant importance for securing world energy resources, and has the potential to produce considerable economic benefits. Previous studies have shown that the South China Sea is an area that harbors gas hydrates. However, there is a lack of systematic investigations and understanding on the distribution of gas hydrate throughout the region. In this paper, we applied mineral resource quantitative assessment techniques to forecast and estimate the potential distribution of gas hydrate resources in the northern South China Sea. However, current hydrate samples from the South China Sea are too few to produce models of occurrences. Thus, according to similarity and contrast principles of mineral outputs, we can use a similar hydrate-mining environment with sufficient gas hydrate data as a testing ground for modeling northern South China Sea gas hydrate conditions. We selected the Gulf of Mexico, which has extensively studied gas hydrates, to develop predictive models of gas hydrate distributions, and to test errors in the model. Then, we compared the existing northern South China Sea hydrate-mining data with the Gulf of Mexico characteristics, and collated the relevant data into the model. Subsequently, we applied the model to the northern South China Sea to obtain the potential gas hydrate distribution of the area, and to identify significant exploration targets. Finally, we evaluated the reliability of the predicted results. The south seabed area of Taiwan Bank is recommended as a priority exploration target. The Zhujiang Mouth, Southeast Hainan, and Southwest Taiwan Basins, including the South Bijia Basin, also are recommended as exploration target areas. In addition, the method in this paper can provide a useful predictive approach for gas hydrate resource assessment, which gives a scientific basis for construction and implementation of long-term planning for gas hydrate exploration and general exploitation of the seabed of China.

Global occurrences of gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Lorenson, T.D.

2001-01-01

Natural gas hydrate is found worldwide in sediments of outer continental margins of all oceans and in polar areas with continuous permafrost. There are currently 77 localities identified globally where geophysical, geochemical and/or geological evidence indicates the presence of gas hydrate. Details concerning individual gas-hydrate occurrences are compiled at a new world-wide-web (www) site (http://walrus.wr.usgs.gov/globalhydrate). This site has been created to facilitate global gas-hydrate research by providing information on each of the localities where there is evidence for gas hydrate. Also considered are the implications of gas hydrate as a potential (1) energy resource, (2) factor in global climate change, and (3) geohazard.

Kinetics of formation and dissociation of gas hydrates

NASA Astrophysics Data System (ADS)

Manakov, A. Yu; Penkov, N. V.; Rodionova, T. V.; Nesterov, A. N.; Fesenko, E. E., Jr.

2017-09-01

The review covers a wide range of issues related to the nucleation, growth and dissociation of gas hydrates. The attention is focused on publications of the last 10-15 years. Along with the mathematical models used to describe these processes, the results of relevant experimental studies are surveyed. Particular sections are devoted to the gas hydrate self-preservation effect, the water memory effect in the hydrate formation, development of catalysts for hydrate formation and the effect of substances dissolved in the aqueous phase on the formation of hydrates. The main experimental techniques used to study gas hydrates are briefly considered. The bibliography includes 230 references.

Determination of pore-scale hydrate phase equilibria in sediments using lab-on-a-chip technology.

PubMed

Almenningen, Stian; Flatlandsmo, Josef; Kovscek, Anthony R; Ersland, Geir; Fernø, Martin A

2017-11-21

We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.

Gas hydrate drilling transect across northern Cascadia margin - IODP Expedition 311

USGS Publications Warehouse

Riedel, M.; Collett, T.; Malone, M.J.; Collett, T.S.; Mitchell, M.; Guerin, G.; Akiba, F.; Blanc-Valleron, M.; Ellis, M.; Hashimoto, Y.; Heuer, V.; Higashi, Y.; Holland, M.; Jackson, P.D.; Kaneko, M.; Kastner, M.; Kim, J.-H.; Kitajima, H.; Long, P.E.; Malinverno, A.; Myers, Gwen E.; Palekar, L.D.; Pohlman, J.; Schultheiss, P.; Teichert, B.; Torres, M.E.; Trehu, A.M.; Wang, Jingyuan; Worthmann, U.G.; Yoshioka, H.

2009-01-01

A transect of four sites (U1325, U1326, U1327 and U1329) across the northern Cascadia margin was established during Integrated Ocean Drilling Program Expedition 311 to study the occurrence and formation of gas hydrate in accretionary complexes. In addition to the transect sites, a fifth site (U1328) was established at a cold vent with active fluid flow. The four transect sites represent different typical geological environments of gas hydrate occurrence across the northern Cascadia margin from the earliest occurrence on the westernmost first accreted ridge (Site U1326) to the eastward limit of the gas hydrate occurrence in shallower water (Site U1329). Expedition 311 complements previous gas hydrate studies along the Cascadia accretionary complex, especially ODP Leg 146 and Leg 204 by extending the aperture of the transect sampled and introducing new tools to systematically quantify the gas hydrate content of the sediments. Among the most significant findings of the expedition was the occurrence of up to 20 m thick sand-rich turbidite intervals with gas hydrate concentrations locally exceeding 50% of the pore space at Sites U1326 and U1327. Moreover, these anomalous gas hydrate intervals occur at unexpectedly shallow depths of 50-120 metres below seafloor, which is the opposite of what was expected from previous models of gas hydrate formation in accretionary complexes, where gas hydrate was predicted to be more concentrated near the base of the gas hydrate stability zone just above the bottom-simulating reflector. Gas hydrate appears to be mainly concentrated in turbidite sand layers. During Expedition 311, the visual correlation of gas hydrate with sand layers was clearly and repeatedly documented, strongly supporting the importance of grain size in controlling gas hydrate occurrence. The results from the transect sites provide evidence for a structurally complex, lithology-controlled gas hydrate environment on the northern Cascadia margin. Local shallow occurrences of high gas hydrate concentrations contradict the previous model of gas hydrate formation at an accretionary prism. However, long-lived fluid flow (part of the old model) is still required to explain the shallow high gas hydrate concentrations, although it is most likely not pervasive throughout the entire accretionary prism, but rather localized and focused by the tectonic processes. Differences in the fluid flow regime across all of the transect drill sites indicate site-specific and probably disconnected (compartmented) deeper fluid sources in the various parts of the accretionary prism. The data and future analyses will yield a better understanding of the geologic controls, evolution and ultimate fate of gas hydrate in an accretionary prism as an important contribution to the role of gas hydrate methane gas in slope stability and possibly in climate change. ?? The Geological Society of London 2009.

Natural gas hydrate in sediments imaged by cryogenic SEM: Insights from lab experiments on synthetic hydrates as interpretive guides.

NASA Astrophysics Data System (ADS)

Stern, L. A.; Kirby, S. H.

2006-12-01

In the investigation of natural gas hydrates, distinguishing in situ grain textures and microstructures from artifacts produced during retrieval, storage, and examination can be quite challenging. Using cryogenic scanning electron microscopy, we investigated the physical states of gas hydrates produced in our lab as well as of those in drill core of hydrate-bearing sediment from marine and Arctic permafrost environments. Here, we compare grain and pore structures observed in samples from the Cascadia margin (courtesy IODP Expedition 311), McKenzie River Delta (Mallik Well 5L-38), and Gulf of Mexico (RSV Marion Dufresne 2002), with those present in hydrocarbon hydrates grown in our laboratory and subjected to controlled P-T conditions. The following trends are apparent for the natural gas hydrates imaged to-date: (1) Samples typically contain massive domains of polycrystalline gas hydrate that in turn contain isolated gas-filled pores that are sometimes lined with euhedral hydrate crystals. Pores are typically 5 50 microns in diameter and occupy roughly 10-30 percent of the domain. Grain sizes, where visible, are commonly 20 to 50 microns. (2) Hydrate grain boundaries, particularly near the exposed sample surface, are often replaced by a nanoporous material. Based on its location and behavior, this material is presumed to be gas-charged porous ice produced by hydrate decomposition along grain surfaces. In some samples, grains are instead bounded by a framework of dense, tabular material embedded within the sample, best revealed upon sublimation of the hydrate. Their composition is yet unknown but may be salt or carbonate-bearing minerals. (3) Where hydrate grows into clayey sediments, the clays typically arrange with platelets subparallel around the pods or veins of hydrate. (4) Domains of nano-to-micro- porous water ice are also seen in all recovered natural samples, presumed to be hydrate decomposition product produced during drill-core retrieval and handling. Based on lab experiments, we believe the initial liquid product is frozen as a result of the local temperature reduction accompanying the endothermic dissociation reaction. The porous texture is then preserved by liquid nitrogen quenching. (5) Samples from both marine and permafrost environments also display closely juxtaposed regions of dense and porous hydrate and ice. Although the close association of these regions remains puzzling, lab tests verify that dense hydrate can exhibit such porous appearance along it's surface after even minor decomposition at cold conditions (below 273 K). In turn, companion experiments show that nanoporous hydrate anneals to a densely crystalline habit at conditions within the hydrate stability region above 273 K, suggesting that nanoporous gas hydrate is not stable at most in situ natural conditions.

Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane

NASA Astrophysics Data System (ADS)

Cai, W.; Lu, H.; Huang, X.

2016-12-01

In natural gas hydrates, some heavy hydrocarbons are always detected in addition to methane. However, it is still not well understood how the trace amount of heavy gas affect the hydrate properties. Intensive studies have been carried out to study the thermodynamic properties and structure types of mixed gases hydrates, but comparatively few investigations have been carried out on the cage occupancies of guest molecules in mixed gases hydrates. For understanding how trace amount of propane affects the formation of mixed methane-propane hydrates, X-ray diffraction, Raman spectroscopy, and gas chromatography were applied to the synthesized mixed methane-propane hydrate specimens, to get their structural characteristics (structure type, structural parameters, cage occupancy, etc.) and gas compositions. The mixed methane-propane hydrates were prepared by reacting fine ice powders with various gas mixtures of methane and propane. When the propane content was below 0.4%, the hydrates synthesized were found containing both sI methane hydrate and sII methane-propane hydrate; while the hydrates were found always sII when propane was over certain content. Detail studies about the cage occupancies of propane and methane in sII hydrate revealed that: 1) with the increase in propane content of methane-propane mixture, the occupancy of propane in large cage increased as accompanied with the decrease in methane occupancy in large cage, however the occupancy of methane in small cage didn't experience significant change; 2) temperature and pressure seemed no obvious influence on cage occupancy.

Natural gas hydrate occurrence and issues

USGS Publications Warehouse

Kvenvolden, K.A.

1994-01-01

Naturally occurring gas hydrate is found in sediment of two regions: (1) continental, including continental shelves, at high latitudes where surface temperatures are very cold, and (2) submarine outer continental margins where pressures are very high and bottom-water temperatures are near 0??C. Continental gas hydrate is found in association with onshore and offshore permafrost. Submarine gas hydrate is found in sediment of continental slopes and rises. The amount of methane present in gas hydrate is thought to be very large, but the estimates that have been made are more speculative than real. Nevertheless, at the present time there has been a convergence of ideas regarding the amount of methane in gas hydrate deposits worldwide at about 2 x 1016 m3 or 7 x 1017 ft3 = 7 x 105 Tcf [Tcf = trillion (1012) ft3]. The potentially large amount of methane in gas hydrate and the shallow depth of gas hydrate deposits are two of the principal factors driving research concerning this substance. Such a large amount of methane, if it could be commercially produced, provides a potential energy resource for the future. Because gas hydrate is metastable, changes of surface pressure and temperature affect its stability. Destabilized gas hydrate beneath the sea floor leads to geologic hazards such as submarine mass movements. Examples of submarine slope failures attributed to gas hydrate are found worldwide. The metastability of gas hydrate may also have an effect on climate. The release of methane, a 'greenhouse' gas, from destabilized gas hydrate may contribute to global warming and be a factor in global climate change.

Observed correlation between the depth to base and top of gas hydrate occurrence from review of global drilling data

NASA Astrophysics Data System (ADS)

Riedel, M.; Collett, T. S.

2017-07-01

A global inventory of data from gas hydrate drilling expeditions is used to develop relationships between the base of structure I gas hydrate stability, top of gas hydrate occurrence, sulfate-methane transition depth, pressure (water depth), and geothermal gradients. The motivation of this study is to provide first-order estimates of the top of gas hydrate occurrence and associated thickness of the gas hydrate occurrence zone for climate-change scenarios, global carbon budget analyses, or gas hydrate resource assessments. Results from publically available drilling campaigns (21 expeditions and 52 drill sites) off Cascadia, Blake Ridge, India, Korea, South China Sea, Japan, Chile, Peru, Costa Rica, Gulf of Mexico, and Borneo reveal a first-order linear relationship between the depth to the top and base of gas hydrate occurrence. The reason for these nearly linear relationships is believed to be the strong pressure and temperature dependence of methane solubility in the absence of large difference in thermal gradients between the various sites assessed. In addition, a statistically robust relationship was defined between the thickness of the gas hydrate occurrence zone and the base of gas hydrate stability (in meters below seafloor). The relationship developed is able to predict the depth of the top of gas hydrate occurrence zone using observed depths of the base of gas hydrate stability within less than 50 m at most locations examined in this study. No clear correlation of the depth to the top and base of gas hydrate occurrences with geothermal gradient and sulfate-methane transition depth was identified.

Thermal conductivity of hydrate-bearing sediments

USGS Publications Warehouse

Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn D.

2009-01-01

A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

[Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

PubMed

Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

2015-11-01

Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

Observed correlation between the depth to base and top of gas hydrate occurrence from review of global drilling data

USGS Publications Warehouse

Riedel, Michael; Collett, Timothy S.

2017-01-01

A global inventory of data from gas hydrate drilling expeditions is used to develop relationships between the base of structure I gas hydrate stability, top of gas hydrate occurrence, sulfate-methane transition depth, pressure (water depth), and geothermal gradients. The motivation of this study is to provide first-order estimates of the top of gas hydrate occurrence and associated thickness of the gas hydrate occurrence zone for climate-change scenarios, global carbon budget analyses, or gas hydrate resource assessments. Results from publically available drilling campaigns (21 expeditions and 52 drill sites) off Cascadia, Blake Ridge, India, Korea, South China Sea, Japan, Chile, Peru, Costa Rica, Gulf of Mexico, and Borneo reveal a first-order linear relationship between the depth to the top and base of gas hydrate occurrence. The reason for these nearly linear relationships is believed to be the strong pressure and temperature dependence of methane solubility in the absence of large difference in thermal gradients between the various sites assessed. In addition, a statistically robust relationship was defined between the thickness of the gas hydrate occurrence zone and the base of gas hydrate stability (in meters below seafloor). The relationship developed is able to predict the depth of the top of gas hydrate occurrence zone using observed depths of the base of gas hydrate stability within less than 50 m at most locations examined in this study. No clear correlation of the depth to the top and base of gas hydrate occurrences with geothermal gradient and sulfate-methane transition depth was identified.

Overview: Nucleation of clathrate hydrates

NASA Astrophysics Data System (ADS)

Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

2016-12-01

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

The structural response of the cornea to changes in stromal hydration

PubMed Central

White, Tomas; Boote, Craig; Kamma-Lorger, Christina S.; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M.

2017-01-01

The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas (p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration (H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations (p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. PMID:28592658

Communication: Quantitative Fourier-transform infrared data for competitive loading of small cages during all-vapor instantaneous formation of gas-hydrate aerosols

NASA Astrophysics Data System (ADS)

Uras-Aytemiz, Nevin; Abrrey Monreal, I.; Devlin, J. Paul

2011-10-01

A simple method has been developed for the measurement of high quality FTIR spectra of aerosols of gas-hydrate nanoparticles. The application of this method enables quantitative observation of gas hydrates that form on subsecond timescales using our all-vapor approach that includes an ether catalyst rather than high pressures to promote hydrate formation. The sampling method is versatile allowing routine studies at temperatures ranging from 120 to 210 K of either a single gas or the competitive uptake of different gas molecules in small cages of the hydrates. The present study emphasizes hydrate aerosols formed by pulsing vapor mixtures into a cold chamber held at 160 or 180 K. We emphasize aerosol spectra from 6 scans recorded an average of 8 s after "instantaneous" hydrate formation as well as of the gas hydrates as they evolve with time. Quantitative aerosol data are reported and analyzed for single small-cage guests and for mixed hydrates of CO2, CH4, C2H2, N2O, N2, and air. The approach, combined with the instant formation of gas hydrates from vapors only, offers promise with respect to optimization of methods for the formation and control of gas hydrates.

Towards understanding the role of amines in the SO2 hydration and the contribution of the hydrated product to new particle formation in the Earth's atmosphere.

PubMed

Lv, Guochun; Nadykto, Alexey B; Sun, Xiaomin; Zhang, Chenxi; Xu, Yisheng

2018-08-01

By theoretical calculations, the gas-phase SO 2 hydration reaction assisted by methylamine (MA) and dimethylamine (DMA) was investigated, and the potential contribution of the hydrated product to new particle formation (NPF) also was evaluated. The results show that the energy barrier for aliphatic amines (MA and DMA) assisted SO 2 hydration reaction is lower than the corresponding that of water and ammonia assisted SO 2 hydration. In these hydration reactions, nearly barrierless reaction (only a barrier of 0.1 kcal mol -1 ) can be found in the case of SO 2  + 2H 2 O + DMA. These lead us to conclude that the SO 2 hydration reaction assisted by MA and DMA is energetically facile. The temporal evolution for hydrated products (CH 3 NH 3 + -HSO 3 - -H 2 O or (CH 3 ) 2 NH 2 + -HSO 3 - -H 2 O) in molecular dynamics simulations indicates that these complexes can self-aggregate into bigger clusters and can absorb water and amine molecules, which means that these hydrated products formed by the hydration reaction may serve as a condensation nucleus to initiate the NPF. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiple stage multiple filter hydrate store

DOEpatents

Bjorkman, H.K. Jr.

1983-05-31

An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means for separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means. 7 figs.

Multiple stage multiple filter hydrate store

DOEpatents

Bjorkman, Jr., Harry K.

1983-05-31

An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means or separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means.

The inhibition of tetrahydrofuran clathrate-hydrate formation with antifreeze protein

NASA Astrophysics Data System (ADS)

Zeng, H.; Wilson, L. D.; Walker, V. K.; Ripmeester, J. A.

2003-01-01

The effect of Type I fish antifreeze protein (AFP) from the winter flounder, Pleuronectes americanus (Walbaum), (WfAFP) on the formation of tetrahydrofuran (THF) clathrate hydrate was studied by observing changes in THF crystal morphology and determining the induction time for nucleation. AFP retarded THF clathrate-hydrate growth at the tested temperatures and modified the THF clathrate-hydrate crystal morphology from octahedral to plate-like. AFP appears to be even more effective than the kinetic inhibitor, polyvinylpyrrolidone (PVP). Recombinant AFP from an insect, a spruce budworm, Choristoneura fumiferana (Clem.), moth, (Cf) was also tested for inhibition activity by observation of the THF-hydrate-crystal-growth habit. Like WfAFP, CfAFP appeared to show adsorption on multiple THF-hydrate-crystal faces. A protein with no antifreeze activity, cytochrome C, was used as a control and it neither changed the morphology of the THF clathrate-hydrate crystals, nor retarded the formation of the hydrate. Preliminary experiments on the inhibition activity of WfAFP on a natural gas hydrate assessed induction time and the amount of propane gas consumed. Similar to the observations for THF, the data indicated that WfAFP inhibited propane-hydrate growth. Taken together, these results support our hypothesis that AFPs can inhibit clathrate-hydrate growth and as well, offer promise for the understanding of the inhibition mechanism.

Overview: Nucleation of clathrate hydrates.

PubMed

Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

2016-12-07

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

The structural response of the cornea to changes in stromal hydration.

PubMed

Hayes, Sally; White, Tomas; Boote, Craig; Kamma-Lorger, Christina S; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M

2017-06-01

The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS 2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas ( p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration ( H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations ( p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. © 2017 The Authors.

An Analytical Solution and Numerical Modeling Study of Gas Hydrate Saturation Effects on Porosity and Permeability of Porous Media

NASA Astrophysics Data System (ADS)

Zerpa, L.; Gao, F.; Wang, S.

2017-12-01

There are two major types of natural gas hydrate distributions in porous media: pore filling and contact cementing. The difference between these two distribution types is related to hydrate nucleation and growth processes. In the pore filling distribution, hydrate nucleates from a gas-dissolved aqueous phase at the grain boundary and grows away from grain contacts and surfaces into the pore space. In the contact cementing distribution, hydrate nucleates and grows at the gas-water interface and at intergranular contacts. Previous attempts to correlate changes on porosity and permeability during hydrate formation/dissociation were based on the length difference between the pore body and pore throat, and only considered contact cementing hydrate distribution. This work consists of a study of mathematical models of permeability and porosity as a function of gas hydrate saturation during formation and dissociation of gas hydrates in porous media. In this work, first we derive the permeability equation for the pore filling hydrate deposition as a function of hydrate saturation. Then, a more comprehensive model considering both types of gas hydrate deposition is developed to represent changes in permeability and porosity during hydrate formation and dissociation. This resulted in a model that combines pore filling and contact cementing deposition types in the same reservoir. Finally, the TOUGH+Hydrate numerical reservoir simulator was modified to include these models to analyze the response of production and saturation during a depressurization process, considering different combinations of pore filling and contact cementing hydrate distributions. The empirical exponent used in the permeability adjustment factor model influences both production profile and saturation results. This empirical factor describes the permeability dependence to changes in porosity caused by solid phase formation in the porous medium. The use of the permeability exponent decreases the permeability of the system for a given hydrate saturation, which affects the hydraulic performance of the system. However, from published experimental work, there is only a rough estimation of this permeability exponent. This factor could be represented with an empirical equation if more laboratory and field data becomes available.

Investigating the Metastability of Clathrate Hydrates for Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koh, Carolyn Ann

2014-11-18

Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathratemore » hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate hydrate systems are pivotal in the fundamental understanding of crystalline clathrate hydrates and the discovery of new clathrate hydrate properties and novel materials for a broad spectrum of energy applications, including: energy storage (hydrogen, natural gas); carbon dioxide sequestration; controlling hydrate formation in oil/gas transportation in subsea pipelines. The Project has also enabled the training of undergraduate, graduate and postdoctoral students in computational methods, molecular spectroscopy and diffraction, and measurement methods at extreme conditions of high pressure and low temperature.« less

Simulation and Characterization of Methane Hydrate Formation

NASA Astrophysics Data System (ADS)

Dhakal, S.; Gupta, I.

2017-12-01

The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate saturation is followed by decrease in the porosity and permeability of the reservoir rock. Sensitivities on flow rates of gas and water are simulated, using different reservoir properties, fault angles and grid sizes to study the properties of hydrate formation and accumulation in the subsurface.

Gas Hydrate Petroleum System Analysis

NASA Astrophysics Data System (ADS)

Collett, T. S.

2012-12-01

In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is characterized by basal silt- to sand-rich clay dominated stratigraphic units. The upper most debris flow at Site UBGH2-5 extends into the overlying gas hydrate stability zone and IR core scans indicate that this section contains some amount of gas hydrate. The UBGH2 LWD and coring program also confirmed the occurrence of numerous volcaniclastic and siliciclastic sand reservoirs that were deposited as part of local to basin-wide turbidite events. Gas hydrate saturations within the turbidite sands ranged between 60-80 percent. In 2009, the Gulf of Mexico (GOM) Joint Industry Project (JIP) drilled seven wells at three sites, finding gas hydrate at high concentration in sands in four wells, with suspected gas hydrate at low to moderate saturations in two other wells. In the northern GOM, high sedimentation rates in conjunction with salt tectonism, has promoted the formation of complex seafloor topography. As a result, coarse-grained deposition can occur as gravity-driven sedimentation traversing the slope within intra-slope "ponded" accommodation spaces.

Strengthening mechanism of cemented hydrate-bearing sand at microscales

NASA Astrophysics Data System (ADS)

Yoneda, Jun; Jin, Yusuke; Katagiri, Jun; Tenma, Norio

2016-07-01

On the basis of hypothetical particle-level mechanisms, several constitutive models of hydrate-bearing sediments have been proposed previously for gas production. However, to the best of our knowledge, the microstructural large-strain behaviors of hydrate-bearing sediments have not been reported to date because of the experimental challenges posed by the high-pressure and low-temperature testing conditions. Herein, a novel microtriaxial testing apparatus was developed, and the mechanical large-strain behavior of hydrate-bearing sediments with various hydrate saturation values (Sh = 0%, 39%, and 62%) was analyzed using microfocus X-ray computed tomography. Patchy hydrates were observed in the sediments at Sh = 39%. The obtained stress-strain relationships indicated strengthening with increasing hydrate saturation and a brittle failure mode of the hydrate-bearing sand. Localized deformations were quantified via image processing at the submillimeter and micrometer scale. Shear planes and particle deformation and/or rotation were detected, and the shear band thickness decreased with increasing hydrate saturation.

Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collett, Tim; Bahk, Jang-Jun; Frye, Matt

2013-12-31

This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, butmore » these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.« less

Oil & Natural Gas Technology A new approach to understanding the occurrence and volume of natural gas hydrate in the northern Gulf of Mexico using petroleum industry well logs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Ann; Majumdar, Urmi

The northern Gulf of Mexico has been the target for the petroleum industry for exploration of conventional energy resource for decades. We have used the rich existing petroleum industry well logs to find the occurrences of natural gas hydrate in the northern Gulf of Mexico. We have identified 798 wells with well log data within the gas hydrate stability zone. Out of those 798 wells, we have found evidence of gas hydrate in well logs in 124 wells (15% of wells). We have built a dataset of gas hydrate providing information such as location, interval of hydrate occurrence (if any)more » and the overall quality of probable gas hydrate. Our dataset provides a wide, new perspective on the overall distribution of gas hydrate in the northern Gulf of Mexico and will be the key to future gas hydrate research and prospecting in the area.« less

Mineralogical Study of Hydrated IDPs: X-Ray Diffraction and Transmission Electron Microscopy

NASA Technical Reports Server (NTRS)

Nakamura, K.; Keller, L. P.; Nakamura, T.; Noguchi, T.; Zolensky, M. E.

2004-01-01

Chondritic hydrated interplanetary dust particles (IDPs) comprise up to 50% of all IDPs collected in the stratosphere [1]. Hydrated IDPs are generally believed to be derived from asteroidal sources that have undergone aqueous alteration. However, the high C contents of hydrated IDPs (by 2 to 6X CI levels [2,3]) indicate that they are probably not derived from the same parent bodies sampled by the known chondritic meteorites. Some hydrated IDPs exhibit large deuterium enrichments [4] similar to those observed in anhydrous IDPs. Both anhydrous and hydrated IDPs contain a variety of anhydrous minerals such as silicates, sulfides, oxides, and carbonates. Controversies on hydrated IDPs still exist regarding their formation, history, and relationship to other primitive solar system materials, because of the lack of a systematic series of analysis on individual hydrated IDPs. In this study, we combine our observations of the bulk mineralogy, mineral/ organic chemistry in order to derive a more complete picture of hydrated IDPs.

Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

NASA Astrophysics Data System (ADS)

Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

2017-12-01

Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

Preliminary Experimental Examination Of Controls On Methane Expulsion During Melting Of Natural Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Flemings, P. B.; Bryant, S. L.; You, K.; Polito, P. J.

2013-12-01

Global climate change will cause warming of the oceans and land. This will affect the occurrence, behavior, and location of subseafloor and subterranean methane hydrate deposits. We suggest that in many natural systems local salinity, elevated by hydrate formation or freshened by hydrate dissociation, may control gas transport through the hydrate stability zone. We are performing experiments and modeling the experiments to explore this behavior for different warming scenarios. Initially, we are exploring hydrate association/dissociation in saline systems with constant water mass. We compare experiments run with saline (3.5 wt. %) water vs. distilled water in a sand mixture at an initial water saturation of ~0.5. We increase the pore fluid (methane) pressure to 1050 psig. We then stepwise cool the sample into the hydrate stability field (~3 degrees C), allowing methane gas to enter as hydrate forms. We measure resistivity and the mass of methane consumed. We are currently running these experiments and we predict our results from equilibrium thermodynamics. In the fresh water case, the modeled final hydrate saturation is 63% and all water is consumed. In the saline case, the modeled final hydrate saturation is 47%, the salinity is 12.4 wt. %, and final water saturation is 13%. The fresh water system is water-limited: all the water is converted to hydrate. In the saline system, pore water salinity is elevated and salt is excluded from the hydrate structure during hydrate formation until the salinity drives the system to three phase equilibrium (liquid, gas, hydrate) and no further hydrate forms. In our laboratory we can impose temperature gradients within the column, and we will use this to investigate equilibrium conditions in large samples subjected to temperature gradients and changing temperature. In these tests, we will quantify the hydrate saturation and salinity over our meter-long sample using spatially distributed temperature sensors, spatially distributed resistivity probes, compressional wave velocities, and X-ray computed tomography scanning. Modeling of hydrate formation and dissociation for these conditions indicates that the transport of bulk fluid phases (gas and water) plays a crucial role in the overall behavior, and we will explore open-system boundary conditions in the experiments to test this prediction.

Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

NASA Astrophysics Data System (ADS)

Burchwell, A.; Cook, A.

2015-12-01

Characterizing gas hydrate in a reservoir typically involves a full suite of geophysical well logs. The most common method involves using resistivity measurements to quantify the decrease in electrically conductive water when replaced with gas hydrate. Compressional velocity measurements are also used because the gas hydrate significantly strengthens the moduli of the sediment. At many gas hydrate sites, nuclear well logs, which include the photoelectric effect, formation sigma, carbon/oxygen ratio and neutron porosity, are also collected but often not used. In fact, the nuclear response of a gas hydrate reservoir is not known. In this research we will focus on the nuclear log response in gas hydrate reservoirs at the Mallik Field at the Mackenzie Delta, Northwest Territories, Canada, and the Gas Hydrate Joint Industry Project Leg 2 sites in the northern Gulf of Mexico. Nuclear logs may add increased robustness to the investigation into the properties of gas hydrates and some types of logs may offer an opportunity to distinguish between gas hydrate and permafrost. For example, a true formation sigma log measures the thermal neutron capture cross section of a formation and pore constituents; it is especially sensitive to hydrogen and chlorine in the pore space. Chlorine has a high absorption potential, and is used to determine the amount of saline water within pore spaces. Gas hydrate offers a difference in elemental composition compared to water-saturated intervals. Thus, in permafrost areas, the carbon/oxygen ratio may vary between gas hydrate and permafrost, due to the increase of carbon in gas hydrate accumulations. At the Mallik site, we observe a hydrate-bearing sand (1085-1107 m) above a water-bearing sand (1107-1140 m), which was confirmed through core samples and mud gas analysis. We observe a decrease in the photoelectric absorption of ~0.5 barnes/e-, as well as an increase in the formation sigma readings of ~5 capture units in the water-bearing sand as compared to the hydrate sand interval. This is further correlated with the carbon/oxygen ratio showing a decrease of 20% in the water sand compared to the hydrate sand above. In future research, we will quantify the effect of gas hydrate on the nuclear logs at the Mallik well and compare it to wells in the Gulf of Mexico.

In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

NASA Astrophysics Data System (ADS)

Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

2004-12-01

During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in concentrations too low to be detected by the current DORISS instrument. In situ analyses of the hydrates show them to be structure I hydrates with methane as the primary guest molecule; the data compare well to laboratory data.

Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myers, Greg

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Projectmore » Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.« less

Gas hydrate and humans

USGS Publications Warehouse

Kvenvolden, K.A.

2000-01-01

The potential effects of naturally occurring gas hydrate on humans are not understood with certainty, but enough information has been acquired over the past 30 years to make preliminary assessments possible. Three major issues are gas hydrate as (1) a potential energy resource, (2) a factor in global climate change, and (3) a submarine geohazard. The methane content is estimated to be between 1015 to 1017 m3 at STP and the worldwide distribution in outer continental margins of oceans and in polar regions are significant features of gas hydrate. However, its immediate development as an energy resource is not likely because there are various geological constraints and difficult technological problems that must be solved before economic recovery of methane from hydrate can be achieved. The role of gas hydrate in global climate change is uncertain. For hydrate methane to be an effective greenhouse gas, it must reach the atmosphere. Yet there are many obstacles to the transfer of methane from hydrate to the atmosphere. Rates of gas hydrate dissociation and the integrated rates of release and destruction of the methane in the geo/hydro/atmosphere are not adequately understood. Gas hydrate as a submarine geohazard, however, is of immediate and increasing importance to humans as our industrial society moves to exploit seabed resources at ever-greater depths in the waters of our coastal oceans. Human activities and installations in regions of gas-hydrate occurrence must take into account the presence of gas hydrate and deal with the consequences of its presence.

In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Lee, M.W.; Collett, T.S.

2011-01-01

In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

Simulating the effect of hydrate dissociation on wellhead stability during oil and gas development in deepwater

NASA Astrophysics Data System (ADS)

Li, Qingchao; Cheng, Yuanfang; Zhang, Huaiwen; Yan, Chuanliang; Liu, Yuwen

2018-02-01

It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development (OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.

Natural Gas Hydrates Estimation Using Seismic Inversion and Rock Physics

NASA Astrophysics Data System (ADS)

Dutta, N.; Dai, J.; Kleinberg, R.; Xu, H.

2005-05-01

Gas hydrate drilling worldwide indicates that the formation of gas hydrates in shallow sediments tends to increase P- and S-wave velocities of the hosting rocks. Rock physics models of gas hydrates provide the links between velocity anomalies and gas hydrate concentration. In this abstract, we evaluate the numerical predictions of some of the major rock physics models of gas hydrates and validate those with well log data from the Mallik and Blake Ridge wells. We find that a model in which the gas hydrate is a part of the rock framework produces results that are consistent with well log data. To enhance the accuracy of seismic estimation, we adopt a five-step, integrated workflow that enables us to identify and quantify gas hydrates in the deepwater Gulf of Mexico (GOM). It includes: 1) Reprocessing conventional 3D seismic data at high resolution using an amplitude-preserving flow with prestack time migration, 2) A detailed stratigraphic evaluation to identify potential hydrate zones, 3) Seismic attribute analysis to further delineate anomalous zones, 4) Full waveform prestack inversion to characterize acoustic properties of gas hydrates in 1D (Mallick, 1995; Mallick, 1999) and map in 3D using hybrid inversion techniques (Dutta, 2002; Mallick and Dutta, 2002), and 5) Quantitative estimation of gas hydrate saturation using rock property models. We illustrate the procedure using 3D seismic data, and estimate gas hydrate saturation in the study area in the GOM.

Combustion of Methane Hydrate

NASA Astrophysics Data System (ADS)

Roshandell, Melika

A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and methane release, some of the water from the dissociated zone needs to be drained. The results are consistent with the experimental observations. The understanding derived from the experiments and the numerical model permitted a brief exploration into the potential effects of pressure on the combustion of methane hydrates. The prediction is that combustion should improve under high pressure conditions because the evaporation of water is suppressed allowing more energy into the dissociation. Future experiments are needed to validate these initial findings.

Relict gas hydrates as possible reason of gas emission from shallow permafrost at the northern part of West Siberia

NASA Astrophysics Data System (ADS)

Chuvilin, Evgeny; Bukhanov, Boris; Tumskoy, Vladimir; Istomin, Vladimir; Tipenko, Gennady

2017-04-01

Intra-permafrost gas (mostly methane) is represent a serious geological hazards during exploration and development of oil and gas fields. Special danger is posed by large methane accumulations which usually confined to sandy and silty sand horizons and overlying in the frozen strata on the depth up to 200 meters. Such methane accumulations are widely spread in a number of gas fields in the northern part of Western Siberia. According to indirect indicators this accumulations can be relic gas hydrates, that formed earlier during favorable conditions for hydrate accumulation (1, 2). Until now, they could be preserved in the frozen sediments due to geological manifestation of the self-preservation effect of gas hydrates at temperatures below zero. These gas hydrate formations, which are lying above the gas hydrate stability zone today, are in a metastable state and are very sensitive to various anthropogenic impacts. During drilling and operation of production wells in the areas where the relic of gas hydrates can occur, there are active gas emission and gas explosion, that can lead to various technical complications up to the accident. Mathematical and experimental simulations were were conducted to evaluate the possibility of existence of relic gas hydrates in the northern part of West Siberia. The results of math simulations revealed stages of geological history when the gas hydrate stability zone began virtually from the ground surface and saturated in shallow permafrost horizons. Later permafrost is not completely thaw. Experimental simulations of porous gas hydrate dissociation in frozen soils and evaluation of self-preservation manifestation of gas hydrates at negative temperatures were carried out for identification conditions for relic gas hydrates existence in permafrost of northern part of West Siberia. Sandy and silty sand sediments were used in experimental investigations. These sediments are typical of most gas-seeping (above the gas hydrate stability zone) permafrost horizons. The results show that all investigated frozen hydrate-bearing sandy and silty sand samples in the temperature range from -16 °C to -2 °C are characterized by not complete decomposition of pore hydrate at relieving pressure below the equilibrium. It was observed that at typical north Western Siberian permafrost temperature of -6 ° C the safety of pore hydrate in frozen samples can reach 60% at the pressure reducing below the equilibrium. In was found that with increasing temperature and particle size (dispersity) the efficiency of pore hydrate self-preservation is decreased, but even at the temperature of -2 °C there is residual pore methane hydrate content in non-saline sandy samples. All this suggests about high preservation of methane hydrates in frozen sediments at non-equilibrium thermobaric conditions, close to reservoir conditions. Based on the results of mathematical and experimental simulations about the possibility of relic gas hydrates existence on permafrost depth up to 200 m in the northern part of Western Siberia on the less than 200 m due to geological manifestation of the self-preservation effect of gas hydrates. References. 1.Chuvilin EM, Yakushev VS, Perlova EV. Gas and gas hydrates in the permafrost of Bovanenkovo gas field, Yamal Peninsula, West Siberia. // Polarforschung 68: 215-219, 1998. (erschienen 2000). 2.Yakushev V.S., Chuvilin E.M. 2000. Natural gas and hydrate accumulation within permafrost in Russia. Cold Regions Science and Technology. 31: 189-197. These researches are supported by grant RSF №16-17-00051.

Assessing the feasibility of hydrate deposition on pipeline walls--adhesion force measurements of clathrate hydrate particles on carbon steel.

PubMed

Nicholas, Joseph W; Dieker, Laura E; Sloan, E Dendy; Koh, Carolyn A

2009-03-15

Adhesive forces between cyclopentane (CyC5) hydrates and carbon steel (CS) were measured. These forces were found to be substantially lower than CyC5 hydrate-CyC5 hydrate particle measurements and were also lower than ice-CS measurements. The measured adhesive forces were used in a force balance to predict particle removal from the pipeline wall, assuming no free water was present. The force balance predicted entrained hydrate particles of 3 microns and larger diameter would be removed at typical operating flow rates in offshore oil and gas pipelines. These predictions also suggest that hydrate deposition will not occur in stabilized (cold) flow practices.

Gas hydrate in nature

USGS Publications Warehouse

Ruppel, Carolyn D.

2018-01-17

Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

Laboratory formation of non-cementing, methane hydrate-bearing sands

USGS Publications Warehouse

Waite, William F.; Bratton, Peter M.; Mason, David H.

2011-01-01

Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

ERIC Educational Resources Information Center

Barlag, Rebecca; Nyasulu, Frazier

2011-01-01

The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

Observations of mass fractionation of noble gases in synthetic methane hydrate

USGS Publications Warehouse

Hunt, Andrew G.; Pohlman, John; Stern, Laura A.; Ruppel, Carolyn D.; Moscati, Richard J.; Landis, Gary P.; Pinkston, John C.

2011-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings are presently dissociating and releasing methane and other gases to the oceanatmosphere system. A key challenge in assessing the susceptibility of gas hydrates to warming climate is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sublake and subseafloor sediments, coalbeds, and other sources. Carbon and deuterium stable isotopic data provide only a first-order characterization of methane sources, while gas hydrate can sequester any type of methane. Here, we investigate the possibility of exploiting the pattern of noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under careful laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

A method to predict equilibrium conditions of gas hydrate formation in porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clarke, M.A.; Pooladi-Darvish, M.; Bishnoi, P.R.

1999-06-01

In the petroleum industry, it is desirable to avoid the formation of gas hydrates. When gas hydrates form, they tend to agglomerate and block pipelines and process equipment. However, naturally occurring gas hydrates that form in the permafrost region or in deep oceans represent a vast untouched natural gas reserve. Although the exact amount of gas in the hydrate form is not known, it is believed to be comparable to the known amount of gas in the free state. Numerous methods for the recovery of natural gas from hydrate fields have been proposed. These techniques include thermal decomposition, depressurization, andmore » chemical injection. To fully exploit hydrate reserves, it will be necessary to know the decomposition/formation conditions of the gas hydrate in porous media. A predictive model has been developed to determine the incipient hydrate formation conditions in porous media. The only additional information that is needed to determine the incipient hydrate formation conditions is the pore radius, surface energy per unit area, and wetting angle. It was found that the model performed well in predicting the experimental data of Handa and Stupin.« less

Methane hydrate formation in turbidite sediments of northern Cascadia, IODP Expedition 311

USGS Publications Warehouse

Torres, M.E.; Trehu, A.M.; Cespedes, N.; Kastner, M.; Wortmann, U.G.; Kim, J.-H.; Long, P.; Malinverno, A.; Pohlman, J.W.; Riedel, M.; Collett, T.

2008-01-01

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8??km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49??mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23??cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63????m) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245??mbsf. ?? 2008 Elsevier B.V.

Gas hydrates of outer continental margins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kvenvolden, K.A.

1990-05-01

Gas hydrates are crystalline substances in which a rigid framework of water molecules traps molecules of gas, mainly methane. Gas-hydrate deposits are common in continental margin sediment in all major oceans at water depths greater than about 300 m. Thirty-three localities with evidence for gas-hydrate occurrence have been described worldwide. The presence of these gas hydrates has been inferred mainly from anomalous lacoustic reflectors seen on marine seismic records. Naturally occurring marine gas hydrates have been sampled and analyzed at about tensites in several regions including continental slope and rise sediment of the eastern Pacific Ocean and the Gulf ofmore » Mexico. Except for some Gulf of Mexico gas hydrate occurrences, the analyzed gas hydrates are composed almost exclusively of microbial methane. Evidence for the microbial origin of methane in gas hydrates includes (1) the inverse relation between methane occurence and sulfate concentration in the sediment, (2) the subparallel depth trends in carbon isotopic compositions of methane and bicarbonate in the interstitial water, and (3) the general range of {sup 13}C depletion ({delta}{sub PDB}{sup 13}C = {minus}90 to {minus}60 {per thousand}) in the methane. Analyses of gas hydrates from the Peruvian outer continental margin in particular illustrate this evidence for microbially generated methane. The total amount of methane in gas hydrates of continental margins is not known, but estimates of about 10{sup 16} m{sup 3} seem reasonable. Although this amount of methane is large, it is not yet clear whether methane hydrates of outer continental margins will ever be a significant energy resource; however, these gas hydrates will probably constitute a drilling hazard when outer continental margins are explored in the future.« less

Quality Improvement Initiative to Increase the Use of Nasogastric Hydration in Infants With Bronchiolitis.

PubMed

Srinivasan, Mythili; Pruitt, Cassandra; Casey, Erin; Dhaliwal, Keerat; DeSanto, Cori; Markus, Richard; Rosen, Ayelet

2017-08-01

Intravenous (IV) hydration is used primarily in children with bronchiolitis at our institution. Because nasogastric (NG) hydration can provide better nutrition, the goal of our quality improvement (QI) initiative was to increase the rate of NG hydration in eligible children 1 to 23 months old with bronchiolitis by 20% over 6 months. We used Plan-Do-Study-Act cycles to increase the use of NG hydration in eligible children. Interventions included educational and system-based changes and sharing parental feedback with providers. Chart reviews were performed to identify the rates of NG hydration, which were plotted over time in a statistical process control p chart. The balancing measure was the rate of complications in children with NG versus IV hydration. Two hundred and ninety-three children who were hospitalized with bronchiolitis needed supplemental hydration during the QI initiative (January 2016-April 2016). Ninety-one children were candidates for NG hydration, and 53 (58%) received NG hydration. The rates of NG hydration increased from a baseline of 0% pre-QI bronchiolitis season (January 2015-April 2015) to 58% during the initiative. There was no aspiration and no accidental placement of the NG tube into a child's airway. Nine patients (17%) in the NG group had a progression of disease requiring nil per os status, and 6 of these were transferred to the PICU whereas none of those in the IV group were transferred to the PICU. Post-QI initiative, the majority of nurses (63%) and physicians (95%) stated that they are more likely to consider NG hydration in children with bronchiolitis. We successfully increased the rates of NG hydration in eligible children with bronchiolitis by using educational and system-based interventions. Copyright © 2017 by the American Academy of Pediatrics.

Natural-gas hydrates: Resource of the twenty-first century?

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Although considerable uncertainty and disagreement prevail concerning the world's gas-hydrate resources, the estimated amount of gas in those gas-hydrate accumulations greatly exceeds the volume of known conventional gas reserves. However, the role that gas hydrates will play in contributing to the world's energy requirements will ultimately depend less on the volume of gas-hydrate resources than on the cost to extract them. Gas hydrates occur in sedimentary deposits under conditions of pressure and temperature present in permafrost regions and beneath the sea in outer continental margins. The combined information from arctic gas-hydrate studies shows that in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 m to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors (known as bottom-simulating reflectors) that have been mapped at depths below the seafloor ranging from approximately 100 m to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas-hydrate accumulations are in rough accord at about 20,000 trillion m3. Gas hydrate as an energy commodity is often grouped with other unconventional hydrocarbon resources. In most cases, the evolution of a nonproducible unconventional resource to a producible energy resource has relied on significant capital investment and technology development. To evaluate the energy-resource potential of gas hydrates will also require the support of sustained research and development programs. Despite the fact that relatively little is known about the ultimate resource potential of gas hydrates, it is certain that they are a vast storehouse of natural gas, and significant technical challenges will need to be met before this enormous resource can be considered an economically producible reserve.

Methane gas hydrate effect on sediment acoustic and strength properties

USGS Publications Warehouse

Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.; Pecher, I.A.

2007-01-01

To improve our understanding of the interaction of methane gas hydrate with host sediment, we studied: (1) the effects of gas hydrate and ice on acoustic velocity in different sediment types, (2) effect of different hydrate formation mechanisms on measured acoustic properties (3) dependence of shear strength on pore space contents, and (4) pore pressure effects during undrained shear.A wide range in acoustic p-wave velocities (Vp) were measured in coarse-grained sediment for different pore space occupants. Vp ranged from less than 1 km/s for gas-charged sediment to 1.77–1.94 km/s for water-saturated sediment, 2.91–4.00 km/s for sediment with varying degrees of hydrate saturation, and 3.88–4.33 km/s for frozen sediment. Vp measured in fine-grained sediment containing gas hydrate was substantially lower (1.97 km/s). Acoustic models based on measured Vp indicate that hydrate which formed in high gas flux environments can cement coarse-grained sediment, whereas hydrate formed from methane dissolved in the pore fluid may not.The presence of gas hydrate and other solid pore-filling material, such as ice, increased the sediment shear strength. The magnitude of that increase is related to the amount of hydrate in the pore space and cementation characteristics between the hydrate and sediment grains. We have found, that for consolidation stresses associated with the upper several hundred meters of sub-bottom depth, pore pressures decreased during shear in coarse-grained sediment containing gas hydrate, whereas pore pressure in fine-grained sediment typically increased during shear. The presence of free gas in pore spaces damped pore pressure response during shear and reduced the strengthening effect of gas hydrate in sands.

Gas hydrates (clathrates) causing pore-water freshening and oxygen isotope fractionation in deep-water sedimentary sections of terrigenous continental margins

USGS Publications Warehouse

Hesse, R.; Harrison, W.E.

1981-01-01

The occurrence of gas hydrates in deep-water sections of the continental margins predicted from anomalous acoustic reflectors on seismic profiles has been confirmed by recent deep-sea drilling results. On the Pacific continental slope off Guatemala gas hydrates were brought up for the first time from two holes (497, 498A) drilled during Leg 67 of the DSDP in water depths of 2360 and 5500 m, respectively. The hydrates occur in organic matter-rich Pleistocene to Miocene terrigenous sediments. In the hydrate-bearing zone a marked decrease in interstitial water chlorinities was observed starting at about 10-20 m subbottom depth. Pore waters at the bottom of the holes (near 400 m subbottom) have as little as half the chlorinity of seawater (i.e. 9???). Similar, but less pronounced, trends were observed during previous legs of the DSDP in other hydrate-prone segments of the continental margins where recharge of fresh water from the continent can be excluded (e.g. Leg 11). The crystallization of hydrates, like ice, excludes salt ions from the crystal structure. During burial the dissolved salts are separated from the solids. Subsidence results in a downward motion of the solids (including hydrates) relative to the pore fluids. Thawing of hydrates during recovery releases fresh water which is remixed with the pore fluid not involved in hydrate formation. The volume of the latter decreases downhole thus causing downward decreasing salinity (chlorinity). Hydrate formation is responsible for oxygen isotope fractionation with 18O-enrichment in the hydrate explaining increasingly more positive ??18O values in the pore fluids recovered (after hydrate dissociation) with depth. ?? 1981.

Effect of pH and temperature on the stability of UV-induced repairable pyrimidine hydrates in DNA.

PubMed

O'Donnell, R E; Boorstein, R J; Cunningham, R P; Teebor, G W

1994-08-23

UV irradiation of cytosine yields 6-hydroxy-5,6-dihydrocytosine (cytosine hydrate) whether the cytosine is in solution as base, nucleoside, or nucleotide or on the DNA backbone. Cytosine hydrate decomposes by elimination of water, yielding cytosine, or by irreversible deamination, yielding uracil hydrate, which, in turn, decomposes by dehydration yielding uracil. To determine how pH and temperature affect these decomposition reactions, alternating poly(dG-[3H]dC) copolymer was irradiated at 254 nm and incubated under different conditions of pH and temperature. The cytosine hydrate and uracil hydrate content of the DNA was determined by the use of Escherichia coli endonuclease III, which releases pyrimidine hydrates from DNA by virtue of its DNA glycosylase activity. Uracil content was determined by using uracil-DNA glycosylase. The rate of decomposition of cytosine hydrate to cytosine was determined at 4 temperatures at pH 3.1, 5.4, and 7.4. The Ea was determined from the rates by using the Arrhenius equation and proved to be the same at pH 5.4 and 7.4, although the decomposition rate at pH 5.4 was faster at all temperatures. At pH 3.1, the Ea was reduced. These results suggest that the dehydration reaction is affected by two discrete protonations, most probably of the N-3 and the OH group of C-6 of cytosine hydrate. The deamination of cytosine hydrate to uracil hydrate was maximal at pH 3.1 at all temperatures. The doubly protonated cytosine hydrate probably is the common intermediate for both competing decomposition reactions, explaining why cytosine hydrate is prone to deamination at acid pH.(ABSTRACT TRUNCATED AT 250 WORDS)

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

Reservoir controls on the occurrence and production of gas hydrates in nature

USGS Publications Warehouse

Collett, Timothy Scott

2014-01-01

modeling has shown that concentrated gas hydrate occurrences in sand reservoirs are conducive to existing well-based production technologies. The resource potential of gas hydrate accumulations in sand-dominated reservoirs have been assessed for several polar terrestrial basins. In 1995, the U.S. Geological Survey (USGS) assigned an in-place resource of 16.7 trillion cubic meters of gas for hydrates in sand-dominated reservoirs on the Alaska North Slope. In a more recent assessment, the USGS indicated that there are about 2.42 trillion cubic meters of technically recoverable gas resources within concentrated, sand-dominated, gas hydrate accumulations in northern Alaska. Estimates of the amount of in-place gas in the sand dominated gas hydrate accumulations of the Mackenzie Delta Beaufort Sea region of the Canadian arctic range from 1.0 to 10 trillion cubic meters of gas. Another prospective gas hydrate resources are those of moderate-to-high concentrations within sandstone reservoirs in marine environments. In 2008, the Bureau of Ocean Energy Management estimated that the Gulf of Mexico contains about 190 trillion cubic meters of gas in highly concentrated hydrate accumulations within sand reservoirs. In 2008, the Japan Oil, Gas and Metals National Corporation reported on a resource assessment of gas hydrates in which they estimated that the volume of gas within the hydrates of the eastern Nankai Trough at about 1.1 trillion cubic meters, with about half concentrated in sand reservoirs. Because conventional production technologies favor sand-dominated gas hydrate reservoirs, sand reservoirs are considered to be the most viable economic target for gas hydrate production and will be the prime focus of most future gas hydrate exploration and development projects.

The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

PubMed

Zhang, Zhengcai; Guo, Guang-Jun

2017-07-26

Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

A comparison of hydration effect on body fluid and temperature regulation between Malaysian and Japanese males exercising at mild dehydration in humid heat.

PubMed

Wakabayashi, Hitoshi; Wijayanto, Titis; Lee, Joo-Young; Hashiguchi, Nobuko; Saat, Mohamed; Tochihara, Yutaka

2014-02-04

This study investigated the effect of hydration differences on body fluid and temperature regulation between tropical and temperate indigenes exercising in the heat. Ten Japanese and ten Malaysian males with matched physical characteristics (height, body weight, and peak oxygen consumption) participated in this study. Participants performed exercise for 60 min at 55% peak oxygen uptake followed by a 30-min recovery at 32°C and 70% relative air humidity with hydration (4 times each, 3 mL per kg body weight, 37°C) or without hydration. Rectal temperature, skin temperature, heart rate, skin blood flow, and blood pressure were measured continuously. The percentage of body weight loss and total sweat loss were calculated from body weight measurements. The percentage change in plasma volume was estimated from hemoglobin concentration and hematocrit. Malaysian participants had a significantly lower rectal temperature, a smaller reduction in plasma volume, and a lower heart rate in the hydrated condition than in the non-hydrated condition at the end of exercise (P <0.05), whereas Japanese participants showed no difference between the two hydration conditions. Hydration induced a greater total sweat loss in both groups (P <0.05), and the percentage of body weight loss in hydrated Malaysians was significantly less than in hydrated Japanese (P <0.05). A significant interaction between groups and hydration conditions was observed for the percentage of mean cutaneous vascular conductance during exercise relative to baseline (P <0.05). The smaller reduction in plasma volume and percentage body weight loss in hydrated Malaysians indicated an advantage in body fluid regulation. This may enable Malaysians to reserve more blood for circulation and heat dissipation and thereby maintain lower rectal temperatures in a hydrated condition.

The characteristics of gas hydrates occurring in natural environment

NASA Astrophysics Data System (ADS)

Lu, H.; Moudrakovski, I.; Udachin, K.; Enright, G.; Ratcliffe, C.; Ripmeester, J.

2009-12-01

In the past few years, extensive analyses have been carried out for characterizing the natural gas hydrate samples from Cascadia, offshore Vancouver Island; Mallik, Mackenzie Delta; Mount Elbert, Alaska North Slope; Nankai Trough, offshore Japan; Japan Sea and offshore India. With the results obtained, it is possible to give a general picture of the characteristics of gas hydrates occurring in natural environment. Gas hydrate can occur in sediments of various types, from sands to clay, although it is preferentially enriched in sediments of certain types, for example coarse sands and fine volcanic ash. Most of the gas hydrates in sediments are invisible, occurring in the pores of the sediments, while some hydrates are visible, appearing as massive, nodular, planar, vein-like forms and occurring around the seafloor, in the fractures related to fault systems, or any other large spaces available in sediments. Although methane is the main component of most of the natural gas hydrates, C2 to C7 hydrocarbons have been recognized in hydrates, sometimes even in significant amounts. Shallow marine gas hydrates have been found generally to contain minor amounts of hydrogen sulfide. Gas hydrate samples with complex gas compositions have been found to have heterogeneous distributions in composition, which might reflect changes in the composition of the available gas in the surrounding environment. Depending on the gas compositions, the structure type of a natural gas hydrate can be structure I, II or H. For structure I methane hydrate, the large cages are almost fully occupied by methane molecules, while the small cages are only partly occupied. Methane hydrates occurring in different environments have been identified with almost the same crystallographic parameters.

Permafrost-associated natural gas hydrate occurrences on the Alaska North Slope

USGS Publications Warehouse

Collett, T.S.; Lee, M.W.; Agena, W.F.; Miller, J.J.; Lewis, K.A.; Zyrianova, M.V.; Boswell, R.; Inks, T.L.

2011-01-01

In the 1960s Russian scientists made what was then a bold assertion that gas hydrates should occur in abundance in nature. Since this early start, the scientific foundation has been built for the realization that gas hydrates are a global phenomenon, occurring in permafrost regions of the arctic and in deep water portions of most continental margins worldwide. In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually become a producible energy resource, yet technical and economic hurdles have historically made gas hydrate development a distant goal. This view began to change in recent years with the realization that this unconventional resource could be developed with existing conventional oil and gas production technology. One of the most significant developments was the completion of the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope, which along with the Mallik project in Canada, have for the first time allowed the rational assessment of gas hydrate production technology and concepts. Almost 40 years of gas hydrate research in northern Alaska has confirmed the occurrence of at least two large gas hydrate accumulations on the North Slope. We have also seen in Alaska the first ever assessment of how much gas could be technically recovered from gas hydrates. However, significant technical concerns need to be further resolved in order to assess the ultimate impact of gas hydrate energy resource development in northern Alaska. ?? 2009 Elsevier Ltd.

Pre- and post-drill comparison of the Mount Elbert gas hydrate prospect, Alaska North Slope

USGS Publications Warehouse

Lee, M.W.; Agena, W.F.; Collett, T.S.; Inks, T.L.

2011-01-01

In 2006, the United States Geological Survey (USGS) completed a detailed analysis and interpretation of available 2-D and 3-D seismic data, along with seismic modeling and correlation with specially processed downhole well log data for identifying potential gas hydrate accumulations on the North Slope of Alaska. A methodology was developed for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area. The study revealed a total of 14 gas hydrate prospects in this area.In order to validate the gas hydrate prospecting protocol of the USGS and to acquire critical reservoir data needed to develop a longer-term production testing program, a stratigraphic test well was drilled at the Mount Elbert prospect in the Milne Point area in early 2007. The drilling confirmed the presence of two prominent gas-hydrate-bearing units in the Mount Elbert prospect, and high quality well logs and core data were acquired. The post-drill results indicate pre-drill predictions of the reservoir thickness and the gas-hydrate saturations based on seismic and existing well data were 90% accurate for the upper unit (hydrate unit D) and 70% accurate for the lower unit (hydrate unit C), confirming the validity of the USGS approach to gas hydrate prospecting. The Mount Elbert prospect is the first gas hydrate accumulation on the North Slope of Alaska identified primarily on the basis of seismic attribute analysis and specially processed downhole log data. Post-drill well log data enabled a better constraint of the elastic model and the development of an improved approach to the gas hydrate prospecting using seismic attributes. ?? 2009.

Gulf of Mexico Gas Hydrate Joint Industry Project Leg II logging-while-drilling data acquisition and analysis

USGS Publications Warehouse

Collett, Timothy S.; Lee, Wyung W.; Zyrianova, Margarita V.; Mrozewski, Stefan A.; Guerin, Gilles; Cook, Ann E.; Goldberg, Dave S.

2012-01-01

One of the objectives of the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II (GOM JIP Leg II) was the collection of a comprehensive suite of logging-while-drilling (LWD) data within gas-hydrate-bearing sand reservoirs in order to make accurate estimates of the concentration of gas hydrates under various geologic conditions and to understand the geologic controls on the occurrence of gas hydrate at each of the sites drilled during this expedition. The LWD sensors just above the drill bit provided important information on the nature of the sediments and the occurrence of gas hydrate. There has been significant advancements in the use of downhole well-logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From using electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells to where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Recent integrated sediment coring and well-log studies have confirmed that electrical resistivity and acoustic velocity data can yield accurate gas hydrate saturations in sediment grain supported (isotropic) systems such as sand reservoirs, but more advanced log analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. In support of the GOM JIP Leg II effort, well-log data montages have been compiled and presented in this report which includes downhole logs obtained from all seven wells drilled during this expedition with a focus on identifying and characterizing the potential gas-hydrate-bearing sedimentary section in each of the wells. Also presented and reviewed in this report are the gas-hydrate saturation and sediment porosity logs for each of the wells as calculated from available downhole well logs.

Shifting Focus: From Hydration for Performance to Hydration for Health.

PubMed

Perrier, Erica T

2017-01-01

Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the relationships between water intake, hydration, vasopressin, and health outcomes. Thus, this emerging field represents an excellent opportunity, particularly for young researchers, to develop relevant and novel lines of research. © 2017 The Author(s) Published by S. Karger AG, Basel.

Methane Hydrate Formation in Thick Sand Reservoirs: Long-range Gas Transport or Short-range Methane Diffusion?

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2016-12-01

We developed two 2-D numerical models to simulate hydrate formation by long range methane gas transport and short-range methane diffusion. We interpret that methane hydrates in thick sands are most likely formed by long range gas transport where methane gas is transported upward into the hydrate stability zone (HSZ) under buoyancy and locally forms hydrate to its stability limit. In short-range methane diffusion, methane is generated locally by biodegradation of organic matter in mud and diffused into bounding sands where it forms hydrate. We could not simulate enough methane transport by diffusion to account for its observed concentration in thick sands. In our models, we include the capillary effect on dissolved methane solubility and on the hydrate phase boundary, sedimentation and different compaction in sand and mud, fracture generation as well as the fully coupled multiphase flow and multicomponent transport. We apply our models to a 12 meter-thick hydrate-bearing sand layer at Walker Ridge 313, Northern Gulf of Mexico. With the long-range gas transport, hydrate saturation is greater than 90% and salinity is increased from seawater to about 8 wt.% through the entire sand. With short-range diffusion, hydrate saturation is more than 90% at the sand base and is less than 10% in the overlying section; salinity is close to seawater when sand is deposited to 800 meter below seafloor by short-range methane diffusion. With short-range diffusion, the amount of hydrate formed is much less than that interpreted from the well log data. Two transient gas layers separated by a hydrate layer are formed from short-range diffusion caused by capillary effect. This could be interpreted as a double bottom simulating reflector. This study provides further insights into different hydrate formation mechanisms, and could serve as a base to confirm the hydrate formation mechanism in fields.

Basin-Wide Temperature Constraints On Gas Hydrate Stability In The Gulf Of Mexico

NASA Astrophysics Data System (ADS)

MacDonald, I. R.; Reagan, M. T.; Guinasso, N. L.; Garcia-Pineda, O. G.

2012-12-01

Gas hydrate deposits commonly occur at the seafloor-water interface on marine margins. They are especially prevalent in the Gulf of Mexico where they are associated with natural oil seeps. The stability of these deposits is potentially challenged by fluctuations in bottom water temperature, on an annual time-scale, and under the long-term influence of climate change. We mapped the locations of natural oil seeps where shallow gas hydrate deposits are known to occur across the entire Gulf of Mexico basin based on a comprehensive review of synthetic aperture radar (SAR) data (~200 images). We prepared a bottom water temperature map based on the archive of CTD casts from the Gulf (~6000 records). Comparing the distribution of gas hydrate deposits with predicted bottom water temperature, we find that a broad area of the upper slope lies above the theoretical stability horizon for structure 1 gas hydrate, while all sites where gas hydrate deposits occur are within the stability horizon for structure 2 gas hydrate. This is consistent with analytical results that structure 2 gas hydrates predominate on the upper slope (Klapp et al., 2010), where bottom water temperatures fluctuate over a 7 to 10 C range (approx. 600 m depth), while pure structure 1 hydrates are found at greater depths (approx. 3000 m). Where higher hydrocarbon gases are available, formation of structure 2 gas hydrate should significantly increase the resistance of shallow gas hydrate deposits to destabilizing effects variable or increasing bottom water temperature. Klapp, S.A., Bohrmann, G., Kuhs, W.F., Murshed, M.M., Pape, T., Klein, H., Techmer, K.S., Heeschen, K.U., and Abegg, F., 2010, Microstructures of structure I and II gas hydrates from the Gulf of Mexico: Marine and Petroleum Geology, v. 27, p. 116-125.Bottom temperature and pressure for Gulf of Mexico gas hydrate outcrops and stability horizons for sI and sII hydrate.

Concentration of Natural Gas Hydrate Beneath the Permafrost Zone: Implications for Geochemical and Hydrologic Investigations

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Namikawa, T.

2004-12-01

Gas hydrates are ice-like solids made of water molecules containing various gas molecules. The geological evaluations have suggested worldwide methane contents of gas hydrate beneath deep sea floors as well as permafrost-related zones to about twice the total reserves of conventional and unconventional hydrocarbon. Scientific and economic interests are increasing in gas hydrate as a new energy resource and a potential greenhouse gas. In 1998 and 2002 Mallik wells were drilled in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data, anomalies of chloride contents in pore waters, core temperature depression as well as visible gas hydrates have confirmed the highly saturated pore-space hydrate as intergranular pore filling within sandy layers, whose saturations are higher than 70% in pore volume. Muddy sediments scarcely contain gas hydrate. The Nankai Trough runs along the Japanese Island, where forearc basins and accretionary prisms developed extensively and BSRs (bottom simulating reflectors) have been recognized widely. The METI Nankai Trough wells in 2000 also revealed the presence of pore-space hydrate filling intergranular pore of sandy layers. It is remarked that there are many similar features in appearance and characteristics between the Mallik and Nankai Trough areas with observations of well-interconnected and highly saturated pore-space hydrate. It is necessary for evaluating subsurface fluid flow behaviors to know both porosity and permeability of gas hydrate-bearing sandy sediments, and measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sands revealed important geologic and sedimentologic controls on the formation and concentration of gas hydrate. It is suggested that the distribution of a porous and coarser-grained sandy sediments is one of the most important factors to control the occurrence of gas hydrates, as well as physicochemical conditions.

Experimental and Numerical Observations of Hydrate Reformation during Depressurization in a Core-Scale Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seol, Yongkoo; Myshakin, Evgeniy

2011-01-01

Gas hydrate has been predicted to reform around a wellbore during depressurization-based gas production from gas hydrate-bearing reservoirs. This process has an adverse effect on gas production rates and it requires time and sometimes special measures to resume gas flow to producing wells. Due to lack of applicable field data, laboratory scale experiments remain a valuable source of information to study hydrate reformation. In this work, we report laboratory experiments and complementary numerical simulations executed to investigate the hydrate reformation phenomenon. Gas production from a pressure vessel filled with hydrate-bearing sand was induced by depressurization with and without heat fluxmore » through the boundaries. Hydrate decomposition was monitored with a medical X-ray CT scanner and pressure and temperature measurements. CT images of the hydrate-bearing sample were processed to provide 3-dimensional data of heterogeneous porosity and phase saturations suitable for numerical simulations. In the experiments, gas hydrate reformation was observed only in the case of no-heat supply from surroundings, a finding consistent with numerical simulation. By allowing gas production on either side of the core, numerical simulations showed that initial hydrate distribution patterns affect gas distribution and flow inside the sample. This is a direct consequence of the heterogeneous pore network resulting in varying hydraulic properties of the hydrate-bearing sediment.« less

Structural study of the Fox-1 RRM protein hydration reveals a role for key water molecules in RRM-RNA recognition

PubMed Central

Blatter, Markus; Cléry, Antoine; Damberger, Fred F.

2017-01-01

Abstract The Fox-1 RNA recognition motif (RRM) domain is an important member of the RRM protein family. We report a 1.8 Å X-ray structure of the free Fox-1 containing six distinct monomers. We use this and the nuclear magnetic resonance (NMR) structure of the Fox-1 protein/RNA complex for molecular dynamics (MD) analyses of the structured hydration. The individual monomers of the X-ray structure show diverse hydration patterns, however, MD excellently reproduces the most occupied hydration sites. Simulations of the protein/RNA complex show hydration consistent with the isolated protein complemented by hydration sites specific to the protein/RNA interface. MD predicts intricate hydration sites with water-binding times extending up to hundreds of nanoseconds. We characterize two of them using NMR spectroscopy, RNA binding with switchSENSE and free-energy calculations of mutant proteins. Both hydration sites are experimentally confirmed and their abolishment reduces the binding free-energy. A quantitative agreement between theory and experiment is achieved for the S155A substitution but not for the S122A mutant. The S155 hydration site is evolutionarily conserved within the RRM domains. In conclusion, MD is an effective tool for predicting and interpreting the hydration patterns of protein/RNA complexes. Hydration is not easily detectable in NMR experiments but can affect stability of protein/RNA complexes. PMID:28505313

An experimental challenge: Unraveling the dependencies of ultrasonic and electrical properties of sandy sediments with pore-filling gas hydrates

NASA Astrophysics Data System (ADS)

Heeschen, Katja; Spangenberg, Erik; Seyberth, Karl; Priegnitz, Mike; Schicks, Judith M.

2016-04-01

The accuracy of gas hydrate quantification using seismic or electric measurements fundamentally depends on the knowledge of any factor describing the dependencies of physical properties on gas hydrate saturation. Commonly, these correlations are the result of laboratory measurements on artificially produced gas hydrates of exact saturation. Thus, the production of gas hydrates and accurate determination of gas hydrate concentrations or those of a substitute are a major concern. Here we present data of both, seismic and electric measurements on accurately quantified pore-filling ice as a substitute for natural gas hydrates. The method was validated using selected gas hydrate saturations in the same experimental set-up as well as literature data from glass bead samples [Spangenberg and Kulenkampff, 2006]. The environmental parameters were chosen to fit those of a possible gas hydrate reservoir in the Danube Delta, which is in the focus of models for joint inversions of seismic and electromagnetic data in the SUGAR III project. The small effective pressures present at this site proved to be yet another challenge for the experiments. Using a more powerful pulse generator and a 4 electrode electric measurement, respectively, models for a wide range of gas hydrate saturations between 20 - 90 % vol. could be established. Spangenberg, E. and Kulenkampff, J., Influence of methane hydrate content on electrical sediment properties. Geophysical Research Letters 2006, 33, (24).

Gas hydrate in seafloor sediments: Impact on future resources and drilling safety

USGS Publications Warehouse

Dillon, William P.; Max, Michael D.

2001-01-01

Gas hydrate concentrates methane and sometimes other gases in its crystal lattice and this gas can be released intentionally creating a resource or escape accidentally forming a hazard. The densest accumulations of gas hydrate tend to occur at sites where the base of the gas hydrate stability zone (commonly the upper several hundred m of the sedimentary section) is configured to trap gas, often as a broad arch. The gas may rise from below or form by bacterial activity at shallow depth, but gas commonly is concentrated near the base of the gas hydrate stability zone by recycling. This gas accumulates in presumably leaky traps, then enriches the hydrate above as it migrates upward by diffusion, fluid movement through sedimentary pores, or flow along fracture channelways. Analysis of seismic reflection profiles is beginning to identify such concentrations and the circumstances that create them. The first attempt to explore for gas hydrate off Japan by the Japanese National Oil Corporation produced quite favorable results, showing high gas hydrate contents in permeable sediments. Gas hydrate dissociation can be a safety concern in drilling and production. The volume of water and gas released in dissociation is often greater than the volume of the hydrate, so overpressures can be created. Furthermore, the gas hydrate can provide shallow seals, so the possibility of high-pressure flows or generation of slides is apparent. 

Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

NASA Astrophysics Data System (ADS)

Avdellidou, C.; Delbo', M.; Fienga, A.

2018-04-01

Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

Glacial Cycles Influence Marine Methane Hydrate Formation

NASA Astrophysics Data System (ADS)

Malinverno, A.; Cook, A. E.; Daigle, H.; Oryan, B.

2018-01-01

Methane hydrates in fine-grained continental slope sediments often occupy isolated depth intervals surrounded by hydrate-free sediments. As they are not connected to deep gas sources, these hydrate deposits have been interpreted as sourced by in situ microbial methane. We investigate here the hypothesis that these isolated hydrate accumulations form preferentially in sediments deposited during Pleistocene glacial lowstands that contain relatively large amounts of labile particulate organic carbon, leading to enhanced microbial methanogenesis. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent organic carbon deposition controlled by glacioeustatic sea level variations. In the model, hydrate forms in sediments with greater organic carbon content deposited during the penultimate glacial cycle ( 120-240 ka). The model predictions match hydrate-bearing intervals detected in three sites drilled on the northern Gulf of Mexico continental slope, supporting the hypothesis of hydrate formation driven by enhanced organic carbon burial during glacial lowstands.

Water retention curve for hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Dai, Sheng; Santamarina, J. Carlos

2013-11-01

water retention curve plays a central role in numerical algorithms that model hydrate dissociation in sediments. The determination of the water retention curve for hydrate-bearing sediments faces experimental difficulties, and most studies assume constant water retention curves regardless of hydrate saturation. This study employs network model simulation to investigate the water retention curve for hydrate-bearing sediments. Results show that (1) hydrate in pores shifts the curve to higher capillary pressures and the air entry pressure increases as a power function of hydrate saturation; (2) the air entry pressure is lower in sediments with patchy rather than distributed hydrate, with higher pore size variation and pore connectivity or with lower specimen slenderness along the flow direction; and (3) smaller specimens render higher variance in computed water retention curves, especially at high water saturation Sw > 0.7. Results are relevant to other sediment pore processes such as bioclogging and mineral precipitation.

Roles of Sodium Dodecyl Sulfate on Tetrahydrofuran-Assisted Methane Hydrate Formation.

PubMed

Siangsai, Atsadawuth; Inkong, Katipot; Kulprathipanja, Santi; Kitiyanan, Boonyarach; Rangsunvigit, Pramoch

2018-06-01

Sodium dodecyl sulfate (SDS) markedly improved tetrahydrofuran (THF) - assisted methane hydrate formation. Firstly, methane hydrate formation with different THF amount, 1, 3, and 5.56 mol%, was studied. SDS with 1, 4, and 8 mM was then investigated for its roles on the methane hydrate formation with and without THF. The experiments were conducted in a quiescent condition in a fixed volume crystallizer at 8 MPa and 4°C. The results showed that almost all studied THF and SDS concentrations enhanced the methane hydrate formation kinetics and methane consumption compared to that without the promoters, except 1 mol% THF. Although, with 1 mol% THF, there were no hydrates formed for 48 hours, the addition of just 1 mM SDS surprisingly promoted the hydrate formation with a significant increased in the kinetics. This prompts the use of methane hydrate technology for natural gas storage application with minimal promoters.

Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation

PubMed Central

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Park, Da-Hye; Han, Kunwoo; Lee, Kun-Hong

2013-01-01

As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media. PMID:23938301

Formation and decomposition of ethane, propane, and carbon dioxide hydrates in silica gel mesopores under high pressure.

PubMed

Aladko, E Ya; Dyadin, Yu A; Fenelonov, V B; Larionov, E G; Manakov, A Yu; Mel'gunov, M S; Zhurko, F V

2006-10-05

The experimental data on decomposition temperatures for the gas hydrates of ethane, propane, and carbon dioxide dispersed in silica gel mesopores are reported. The studies were performed at pressures up to 1 GPa. It is shown that the experimental dependence of hydrate decomposition temperature on the size of pores that limit the size of hydrate particles can be described on the basis of the Gibbs-Thomson equation only if one takes into account changes in the shape coefficient that is present in the equation; in turn, the value of this coefficient depends on a method of mesopore size determination. A mechanism of hydrate formation in mesoporous medium is proposed. Experimental data providing evidence of the possibility of the formation of hydrate compounds in hydrophobic matrixes under high pressure are reported. Decomposition temperature of those hydrate compounds is higher than that for the bulk hydrates of the corresponding gases.

Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Dan

Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydratesmore » and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.« less

Scanning electron microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Circone, S.; Durham, W.B.

2004-01-01

Scanning electron microscopy (SEM) was used to investigate grain texture and pore structure development within various compositions of pure sI and sII gas hydrates synthesized in the laboratory, as well as in natural samples retrieved from marine (Gulf of Mexico) and permafrost (NW Canada) settings. Several samples of methane hydrate were also quenched after various extents of partial reaction for assessment of mid-synthesis textural progression. All laboratory-synthesized hydrates were grown under relatively high-temperature and high-pressure conditions from rounded ice grains with geometrically simple pore shapes, yet all resulting samples displayed extensive recrystallization with complex pore geometry. Growth fronts of mesoporous methane hydrate advancing into dense ice reactant were prevalent in those samples quenched after limited reaction below and at the ice point. As temperatures transgress the ice point, grain surfaces continue to develop a discrete "rind" of hydrate, typically 5 to 30 ??m thick. The cores then commonly melt, with rind microfracturing allowing migration of the melt to adjacent grain boundaries where it also forms hydrate. As the reaction continues under progressively warmer conditions, the hydrate product anneals to form dense and relatively pore-free regions of hydrate grains, in which grain size is typically several tens of micrometers. The prevalence of hollow, spheroidal shells of hydrate, coupled with extensive redistribution of reactant and product phases throughout reaction, implies that a diffusion-controlled shrinking-core model is an inappropriate description of sustained hydrate growth from melting ice. Completion of reaction at peak synthesis conditions then produces exceptional faceting and euhedral crystal growth along exposed pore walls. Further recrystallization or regrowth can then accompany even short-term exposure of synthetic hydrates to natural ocean-floor conditions, such that the final textures may closely mimic those observed in natural samples of marine origin. Of particular note, both the mesoporous and highly faceted textures seen at different stages during synthetic hydrate growth were notably absent from all examined hydrates recovered from a natural marine-environment setting.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

Gas hydrate saturation from acoustic impedance and resistivity logs in the shenhu area, south china sea

USGS Publications Warehouse

Wang, X.; Wu, S.; Lee, M.; Guo, Y.; Yang, S.; Liang, J.

2011-01-01

During the China's first gas hydrate drilling expedition -1 (GMGS-1), gas hydrate was discovered in layers ranging from 10 to 25 m above the base of gas hydrate stability zone in the Shenhu area, South China Sea. Water chemistry, electrical resistivity logs, and acoustic impedance were used to estimate gas hydrate saturations. Gas hydrate saturations estimated from the chloride concentrations range from 0 to 43% of the pore space. The higher gas hydrate saturations were present in the depth from 152 to 177 m at site SH7 and from 190 to 225 m at site SH2, respectively. Gas hydrate saturations estimated from the resistivity using Archie equation have similar trends to those from chloride concentrations. To examine the variability of gas hydrate saturations away from the wells, acoustic impedances calculated from the 3 D seismic data using constrained sparse inversion method were used. Well logs acquired at site SH7 were incorporated into the inversion by establishing a relation between the water-filled porosity, calculated using gas hydrate saturations estimated from the resistivity logs, and the acoustic impedance, calculated from density and velocity logs. Gas hydrate saturations estimated from acoustic impedance of seismic data are ???10-23% of the pore space and are comparable to those estimated from the well logs. The uncertainties in estimated gas hydrate saturations from seismic acoustic impedances were mainly from uncertainties associated with inverted acoustic impedance, the empirical relation between the water-filled porosities and acoustic impedances, and assumed background resistivity. ?? 2011 Elsevier Ltd.

Theoretical modeling insights into elastic wave attenuation mechanisms in marine sediments with pore-filling methane hydrate

NASA Astrophysics Data System (ADS)

Marín-Moreno, H.; Sahoo, S. K.; Best, A. I.

2017-03-01

The majority of presently exploitable marine methane hydrate reservoirs are likely to host hydrate in disseminated form in coarse grain sediments. For hydrate concentrations below 25-40%, disseminated or pore-filling hydrate does not increase elastic frame moduli, thus making impotent traditional seismic velocity-based methods. Here, we present a theoretical model to calculate frequency-dependent P and S wave velocity and attenuation of an effective porous medium composed of solid mineral grains, methane hydrate, methane gas, and water. The model considers elastic wave energy losses caused by local viscous flow both (i) between fluid inclusions in hydrate and pores and (ii) between different aspect ratio pores (created when hydrate grows); the inertial motion of the frame with respect to the pore fluid (Biot's type fluid flow); and gas bubble damping. The sole presence of pore-filling hydrate in the sediment reduces the available porosity and intrinsic permeability of the sediment affecting Biot's type attenuation at high frequencies. Our model shows that attenuation maxima due to fluid inclusions in hydrate are possible over the entire frequency range of interest to exploration seismology (1-106 Hz), depending on the aspect ratio of the inclusions, whereas maxima due to different aspect ratio pores occur only at sonic to ultrasound frequencies (104-106 Hz). This frequency response imposes further constraints on possible hydrate saturations able to reproduce broadband elastic measurements of velocity and attenuation. Our results provide a physical basis for detecting the presence and amount of pore-filling hydrate in seafloor sediments using conventional seismic surveys.

Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

2017-12-01

A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

Brookian sequence well log correlation sections and occurrence of gas hydrates, north-central North Slope, Alaska

USGS Publications Warehouse

Lewis, Kristen A.; Collett, Timothy S.

2013-01-01

Gas hydrates are naturally occurring crystalline, ice-like substances that consist of natural gas molecules trapped in a solid-water lattice. Because of the compact nature of their structure, hydrates can effectively store large volumes of gas and, consequently, have been identified as a potential unconventional energy source. First recognized to exist geologically in the 1960s, significant accumulations of gas hydrate have been found throughout the world. Gas hydrate occurrence is limited to environments such as permafrost regions and subsea sediments because of the pressure and temperature conditions required for their formation and stability. Permafrost-associated gas hydrate accumulations have been discovered in many regions of the Arctic, including Russia, Canada, and the North Slope of Alaska. Gas hydrate research has a long history in northern Alaska. This research includes the drilling, coring, and well log evaluation of two gas hydrate stratigraphic test wells and two resource assessments of gas hydrates on the Alaska North Slope. Building upon these previous investigations, this report provides a summary of the pertinent well log, gas hydrate, and stratigraphic data for key wells related to gas hydrate occurrence in the north-central North Slope. The data are presented in nine well log correlation sections with 122 selected wells to provide a regional context for gas hydrate accumulations and the relation of the accumulations to key stratigraphic horizons and to the base of the ice-bearing permafrost. Also included is a well log database that lists the location, available well logs, depths, and other pertinent information for each of the wells on the correlation section.

Consequences of CO2 solubility for hydrate formation from carbon dioxide containing water and other impurities.

PubMed

Kvamme, Bjørn; Kuznetsova, Tatiana; Jensen, Bjørnar; Stensholt, Sigvat; Bauman, Jordan; Sjøblom, Sara; Nes Lervik, Kim

2014-05-14

Deciding on the upper bound of water content permissible in a stream of dense carbon dioxide under pipeline transport conditions without facing the risks of hydrate formation is a complex issue. In this work, we outline and analyze ten primary routes of hydrate formation inside a rusty pipeline, with hydrogen sulfide, methane, argon, and nitrogen as additional impurities. A comprehensive treatment of equilibrium absolute thermodynamics as applied to multiple hydrate phase transitions is provided. We also discuss in detail the implications of the Gibbs phase rule that make it necessary to consider non-equilibrium thermodynamics. The analysis of hydrate formation risk has been revised for the dominant routes, including the one traditionally considered in industrial practice and hydrate calculators. The application of absolute thermodynamics with parameters derived from atomistic simulations leads to several important conclusions regarding the impact of hydrogen sulfide. When present at studied concentrations below 5 mol%, the presence of hydrogen sulfide will only support the carbon-dioxide-dominated hydrate formation on the phase interface between liquid water and hydrate formers entering from the carbon dioxide phase. This is in contrast to a homogeneous hydrate nucleation and growth inside the aqueous solution bulk. Our case studies indicate that hydrogen sulfide at higher than 0.1 mol% concentration in carbon dioxide can lead to growth of multiple hydrate phases immediately adjacent to the adsorbed water layers. We conclude that hydrate formation via water adsorption on rusty pipeline walls will be the dominant contributor to the hydrate formation risk, with initial concentration of hydrogen sulfide being the critical factor.

Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

DOE PAGES

Calero, Carles; Stanley, H.; Franzese, Giancarlo

2016-04-27

Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs). We calculate the rotational and translational slowdown of the dynamics of water confinedmore » in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i) to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii) to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii) to the higher probability of water–lipid HBs as the hydration decreases. Lastly, our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.« less

Geomechanical Modeling of Gas Hydrate Bearing Sediments

NASA Astrophysics Data System (ADS)

Sanchez, M. J.; Gai, X., Sr.

2015-12-01

This contribution focuses on an advance geomechanical model for methane hydrate-bearing soils based on concepts of elasto-plasticity for strain hardening/softening soils and incorporates bonding and damage effects. The core of the proposed model includes: a hierarchical single surface critical state framework, sub-loading concepts for modeling the plastic strains generally observed inside the yield surface and a hydrate enhancement factor to account for the cementing effects provided by the presence of hydrates in sediments. The proposed framework has been validated against recently published experiments involving both, synthetic and natural hydrate soils, as well as different sediments types (i.e., different hydrate saturations, and different hydrates morphologies) and confinement conditions. The performance of the model in these different case studies was very satisfactory.

Fracturing Behavior of Methane-Hydrate-Bearing Sediment

NASA Astrophysics Data System (ADS)

Konno, Y.; Jin, Y.; Yoneda, J.; Uchiumi, T.; Shinjou, K.; Nagao, J.

2016-12-01

As a part of a Japanese national hydrate research program (MH21, funded by the Ministry of Economy, Trade, and Industry), we performed laboratory experiments of hydraulic fracturing in methane-hydrate-bearing sediment. Distilled water was injected into methane-hydrate-bearing sand which was artificially made in a tri-axial pressure cell. X-ray computed tomography revealed that tensile failure was occurred after a rapid drop in the injection pressure. It was found that generated fractures cause a significant increase in the effective water permeability of hydrate-bearing sand. The result contributes fundamental understanding of the accumulation mechanism of gas hydrates in sediments and shows that hydraulic fracturing is one of promising enhanced recovery methods for low-permeable gas hydrate reservoirs.

Effects of cyclic structure inhibitors on the morphology and growth of tetrahydrofuran hydrate crystals

NASA Astrophysics Data System (ADS)

Li, Sijia; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2013-08-01

Morphology and growth of hydrate crystals with cyclic structure inhibitors at a hydrate-liquid interface were directly observed through a microscopic manipulating apparatus. Tetrahydrofuran (THF) hydrate was employed as an objective. The effects of four kind of cyclic structure inhibitors, polyvinylpyrrolidone (PVP), poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine) (PVPP), poly(2-vinyl pyridine-co-N-vinylcaprolactam) (PVPC) and poly(N-vinylcaprolactam) (PVCap), were investigated. Morphological patterns between each hydrate crystal growth from hydrate-liquid interface into droplet were found differ significantly. Lamellar structure growth of hydrate crystal was observed without inhibitor, while with PVP was featheriness-like, PVPP was like long dendritic crystal, PVPC was Mimosa pudica leaf-like and PVCap was like weeds. The growth rate of hydrate crystal without inhibitor was 0.00498 mm3/s, while with PVPP, PVPC and PVCap, were 0.00339 mm3/s, 0.00350 mm3/s, 0.00386 mm3/s and 0.00426 mm3/s, respectively. Cyclic structure inhibitors can decrease the growth rate, degree of reduction in growth rate of hydrate crystals decrease with the increase of cylinder number.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mamontov, Eugene

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

A primer on the geological occurrence of gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.

1998-01-01

This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert).Natural gas hydrates occur world-wide in polar regions, usually associated with onshore and offshore permafrost, and in sediment of outer continental and insular margins. The total amount of methane in gas hydrates probably exceeds 1019 g of methane carbon. Three aspects of gas hydrates are important: their fossil fuel resource potential; their role as a submarine geohazard; and their effects on global climate change. Because gas hydrates represent a large amount of methane within 2000 m of the Earth's surface, they are considered to be an unconventional, unproven source of fossil fuel. Because gas hydrates are metastable, changes of pressure and temperature affect their stability. Destabilized gas hydrates beneath the sea floor lead to geological hazards such as submarine slumps and slides, examples of which are found world-wide. Destabilized gas hydrates may also affect climate through the release of methane, a 'greenhouse' gas, which may enhance global warming and be a factor in global climate change.

Gas hydrate inhibition by perturbation of liquid water structure

NASA Astrophysics Data System (ADS)

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

2015-06-01

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

Gas hydrate inhibition by perturbation of liquid water structure.

PubMed

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

2015-06-17

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311: indications for heterogeneous compositions in hydrate crystals.

PubMed

Schicks, J M; Ziemann, M A; Lu, H; Ripmeester, J A

2010-12-01

Natural gas hydrates usually are found in the form of structure I, encasing predominantly methane in the hydrate lattices as guest molecules, sometimes also minor amount of higher hydrocarbons, CO2 or H2S. Raman spectroscopy is an approved tool to determine the composition of the hydrate phase. Thus, in this study Raman spectroscopic analyses have been applied to hydrate samples obtained from Integrated Ocean Drilling Program (IODP) Expedition 311 in two different approaches: studying the samples randomly taken from the hydrate core, and--as a new application--mapping small areas on the surface of clear hydrate crystals. The results obtained imply that the gas composition of hydrate, in terms of relative concentrations of CH4 and H2S, is not homogeneous over a core or even within a crystal. The mapping method yielded results with very high lateral resolution, indicating the coexistence of different phases with the same structure but different compositions within a hydrate crystal. Copyright © 2010 Elsevier B.V. All rights reserved.

New hydrate formation methods in a liquid-gas medium

NASA Astrophysics Data System (ADS)

Chernov, A. A.; Pil'Nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

New hydrate formation methods in a liquid-gas medium.

PubMed

Chernov, A A; Pil'nik, A A; Elistratov, D S; Mezentsev, I V; Meleshkin, A V; Bartashevich, M V; Vlasenko, M G

2017-01-18

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

DOE PAGES

Mamontov, Eugene

2017-05-24

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

Gas Hydrate Estimation Using Rock Physics Modeling and Seismic Inversion

NASA Astrophysics Data System (ADS)

Dai, J.; Dutta, N.; Xu, H.

2006-05-01

ABSTRACT We conducted a theoretical study of the effects of gas hydrate saturation on the acoustic properties (P- and S- wave velocities, and bulk density) of host rocks, using wireline log data from the Mallik wells in the Mackenzie Delta in Northern Canada. We evaluated a number of gas hydrate rock physics models that correspond to different rock textures. Our study shows that, among the existing rock physics models, the one that treats gas hydrate as part of the solid matrix best fits the measured data. This model was also tested on gas hydrate hole 995B of ODP leg 164 drilling at Blake Ridge, which shows adequate match. Based on the understanding of rock models of gas hydrates and properties of shallow sediments, we define a procedure that quantifies gas hydrate using rock physics modeling and seismic inversion. The method allows us to estimate gas hydrate directly from seismic information only. This paper will show examples of gas hydrates quantification from both 1D profile and 3D volume in the deepwater of Gulf of Mexico.

Models for Gas Hydrate-Bearing Sediments Inferred from Hydraulic Permeability and Elastic Velocities

USGS Publications Warehouse

Lee, Myung W.

2008-01-01

Elastic velocities and hydraulic permeability of gas hydrate-bearing sediments strongly depend on how gas hydrate accumulates in pore spaces and various gas hydrate accumulation models are proposed to predict physical property changes due to gas hydrate concentrations. Elastic velocities and permeability predicted from a cementation model differ noticeably from those from a pore-filling model. A nuclear magnetic resonance (NMR) log provides in-situ water-filled porosity and hydraulic permeability of gas hydrate-bearing sediments. To test the two competing models, the NMR log along with conventional logs such as velocity and resistivity logs acquired at the Mallik 5L-38 well, Mackenzie Delta, Canada, were analyzed. When the clay content is less than about 12 percent, the NMR porosity is 'accurate' and the gas hydrate concentrations from the NMR log are comparable to those estimated from an electrical resistivity log. The variation of elastic velocities and relative permeability with respect to the gas hydrate concentration indicates that the dominant effect of gas hydrate in the pore space is the pore-filling characteristic.

New hydrate formation methods in a liquid-gas medium

PubMed Central

Chernov, A. A.; Pil’nik, A. A.; Elistratov, D. S.; Mezentsev, I. V.; Meleshkin, A. V.; Bartashevich, M. V.; Vlasenko, M. G.

2017-01-01

Conceptually new methods of hydrate formation are proposed. The first one is based on the shock wave impact on a water-bubble medium. It is shown that the hydrate formation rate in this process is typically very high. A gas hydrate of carbon dioxide was produced. The process was experimentally studied using various initial conditions, as well as different external action magnitudes. The obtained experimental data are in good agreement with the proposed model. Other methods are based on the process of boiling liquefied gas in an enclosed volume of water (explosive boiling of a hydrating agent and the organization of cyclic boiling-condensation process). The key features of the methods are the high hydrate formation rate combined with a comparatively low power consumption leading to a great expected efficiency of the technologies based on them. The set of experiments was carried out. Gas hydrates of refrigerant R134a, carbon dioxide and propane were produced. The investigation of decomposition of a generated gas hydrate sample was made. The criteria of intensification of the hydrate formation process are formulated. PMID:28098194

Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRH-Theory): three-dimensional PC validation

NASA Astrophysics Data System (ADS)

Kadyshevich, E. A.; Dzyabchenko, A. V.; Ostrovskii, V. E.

2014-04-01

Size compatibility of the CH4-hydrate structure II and multi-component DNA fragments is confirmed by three-dimensional simulation; it is validation of the Life Origination Hydrate Theory (LOH-Theory).

Natural gas hydrates; vast resource, uncertain future

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Gas hydrates are naturally occurring icelike solids in which water molecules trap gas molecules in a cagelike structure known as a clathrate. Although many gases form hydrates in nature, methane hydrate is by far the most common; methane is the most abundant natural gas. The volume of carbon contained in methane hydrates worldwide is estimated to be twice the amount contained in all fossil fuels on Earth, including coal.

Hydration reactivity of crystalline and vitrified diopside under hydrothermal conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grzeszczyk, S.; Szuba, J.

1990-07-01

Hydration reactivity of diopside in both the crystalline and amorphous (glassy) phase was studied under hydrothermal conditions. Samples were treated in an autoclave at 200{degrees}C in saturated vapor for 24 and 72 h. The progress of hydration was determined by X-ray powder diffractometry and IR spectroscopy. Results indicate that crystalline diopside possessed poor hydraulic activity. However, once vitrified it proved to be much more reactive. The principal hydration products found for the glassy diopside after 24 and 72 h of treatment were calcium silicate hydrate (xonotlite) and magnesium silicate hydrates (chrysotile and tremolite).

Gas hydrates from the continental slope, offshore Sakhalin Island, Okhotsk Sea

USGS Publications Warehouse

Ginsburg, G.D.; Soloviev, V.A.; Cranston, R.E.; Lorenson, T.D.; Kvenvolden, K.A.

1993-01-01

Ten gas-vent fields were discovered in the Okhotsk Sea on the northeast continental slope offshore from Sakhalin Island in water depths of 620-1040 m. At one vent field, estimated to be more than 250 m across, gas hydrates, containing mainly microbial methane (??13C = -64.3???), were recovered from subbottom depths of 0.3-1.2 m. The sediment, having lenses and bedded layers of gas hydrate, contained 30-40% hydrate per volume of wet sediment. Although gas hydrates were not recovered at other fields, geochemical and thermal measurements suggest that gas hydrates are present. ?? 1993 Springer-Verlag.

Results at Mallik highlight progress in gas hydrate energy resource research and development

USGS Publications Warehouse

Collett, T.S.

2005-01-01

The recent studies that project the role of gas hydrates in the future energy resource management are reviewed. Researchers have long speculated that gas hydrates could eventually be a commercial resource for the future. A Joint Industry Project led by ChevronTexaco and the US Department of Energy is designed to characterize gas hydrates in the Gulf of Mexico. Countries including Japan, canada, and India have established large gas hydrate research and development projects, while China, Korea and Mexico are investigating the viability of forming government-sponsored gas hydrate research projects.

The analysis of magnesium oxide hydration in three-phase reaction system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Xiaojia; Guo, Lin; Chen, Chen

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phasemore » system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.« less

Quantitative assessment of combination bathing and moisturizing regimens on skin hydration in atopic dermatitis.

PubMed

Chiang, Charles; Eichenfield, Lawrence F

2009-01-01

Standard recommendations for skin care for patients with atopic dermatitis stress the importance of skin hydration and the application of moisturizers. However, objective data to guide recommendations regarding the optimal practice methods of bathing and emollient application are scarce. This study quantified cutaneous hydration status after various combination bathing and moisturizing regimens. Four bathing/moisturizer regimens were evaluated in 10 subjects, five pediatric subjects with atopic dermatitis and five subjects with healthy skin. The regimens consisted of bathing alone without emollient application, bathing and immediate emollient application, bathing and delayed application, and emollient application alone. Each regimen was evaluated in all subjects, utilizing a crossover design. Skin hydration was assessed with standard capacitance measurements. In atopic dermatitis subjects, emollient alone yielded a significantly (p < 0.05) greater mean hydration over 90 minutes (206.2% baseline hydration) than bathing with immediate emollient (141.6%), bathing and delayed emollient (141%), and bathing alone (91.4%). The combination bathing and emollient application regimens demonstrated hydration values at 90 minutes not significantly greater than baseline. Atopic dermatitis subjects had a decreased mean hydration benefit compared with normal skin subjects. Bathing without moisturizer may compromise skin hydration. Bathing followed by moisturizer application provides modest hydration benefits, though less than that of simply applying moisturizer alone.

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

PubMed

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Modeling of acoustic wave dissipation in gas hydrate-bearing sediments

NASA Astrophysics Data System (ADS)

Guerin, Gilles; Goldberg, David

2005-07-01

Recent sonic and seismic data in gas hydrate-bearing sediments have indicated strong waveform attenuation associated with a velocity increase, in apparent contradiction with conventional wave propagation theory. Understanding the reasons for such energy dissipation could help constrain the distribution and the amounts of gas hydrate worldwide from the identification of low amplitudes in seismic surveys. A review of existing models for wave propagation in frozen porous media, all based on Biot's theory, shows that previous formulations fail to predict any significant attenuation with increasing hydrate content. By adding physically based components to these models, such as cementation by elastic shear coupling, friction between the solid phases, and squirt flow, we are able to predict an attenuation increase associated with gas hydrate formation. The results of the model agree well with the sonic logging data recorded in the Mallik 5L-38 Gas Hydrate Research Well. Cementation between gas hydrate and the sediment grains is responsible for the increase in shear velocity. The primary mode of energy dissipation is found to be friction between gas hydrate and the sediment matrix, combined with an absence of inertial coupling between gas hydrate and the pore fluid. These results predict similar attenuation increase in hydrate-bearing formations over most of the sonic and seismic frequency range.

Occurrence and structural characterization of gas hydrates associated with a cold vent field, offshore Vancouver Island

NASA Astrophysics Data System (ADS)

Lu, Hailong; Moudrakovski, Igor; Riedel, Michael; Spence, George; Dutrisac, Regent; Ripmeester, John; Wright, Fred; Dallimore, Scott

2005-10-01

Gas hydrate samples recovered from a cold vent field offshore Vancouver Island were studied in detail both by macroscopic observations and instrumental methods (powder X-ray diffraction method (PXRD), nuclear magnetic resonance (NMR), and Raman spectroscopy). It was found that gas hydrates were massive from 2.64 to 2.94 m below seafloor (mbsf), elongated, nodular and tabular from 4.60 to 4.81 mbsf, and vein-like from 5.48 to 5.68 mbsf, showing a trend of decreasing hydrate content with increasing depth. All samples were determined to be structure I hydrate from PXRD, NMR, and Raman spectroscopies. The hydration numbers were estimated to be 6.1 ± 0.2 on average as determined from the methane distribution over the cage sites from NMR and Raman analytical results. Estimates of conversion levels indicated that ˜78% of the water in the massive samples was hydrate, down to a low value of ˜0.4% for the pore hydrate samples. The results are compared with measurements on synthetic hydrates and samples recovered from below the permafrost on the Mallik site. Differences in methane content and lattice parameters for synthetic and natural samples are relatively minor. Additional work is needed to address the presence of minor gas components and the heterogeneity of natural hydrate samples.

Visual observation of gas hydrates nucleation and growth at a water - organic liquid interface

NASA Astrophysics Data System (ADS)

Stoporev, Andrey S.; Semenov, Anton P.; Medvedev, Vladimir I.; Sizikov, Artem A.; Gushchin, Pavel A.; Vinokurov, Vladimir A.; Manakov, Andrey Yu.

2018-03-01

Visual observation of nucleation sites of methane and methane-ethane-propane hydrates and their further growth in water - organic liquid - gas systems with/without surfactants was carried out. Sapphire Rocking Cell RCS6 with transparent sapphire cells was used. The experiments were conducted at the supercooling ΔTsub = 20.2 °C. Decane, toluene and crude oils were used as organics. Gas hydrate nucleation occurred on water - metal - gas and water - sapphire - organic liquid three-phase contact lines. At the initial stage of growth hydrate crystals rapidly covered the water - gas or water - organics interfaces (depending on the nucleation site). Further hydrate phase accrete on cell walls (sapphire surface) and into the organics volume. At this stage, growth was accompanied by water «drawing out» from under initial hydrate film formed at water - organic interface. Apparently, it takes place due to water capillary inflow in the reaction zone. It was shown that the hydrate crystal morphology depends on the organic phase composition. In the case of water-in-decane emulsion relay hydrate crystallization was observed in the whole sample, originating most likely due to the hydrate crystal intergrowth through decane. Contacts of such crystals with adjacent water droplets result in rapid hydrate crystallization on this droplet.

A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

PubMed Central

Jo, Byung-Wan; Chakraborty, Sumit

2015-01-01

To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

Experimental investigation of gas hydrate formation, plugging and transportability in partially dispersed and water continuous systems

NASA Astrophysics Data System (ADS)

Vijayamohan, Prithvi

As oil/gas subsea fields mature, the amount of water produced increases significantly due to the production methods employed to enhance the recovery of oil. This is true especially in the case of oil reservoirs. This increase in the water hold up increases the risk of hydrate plug formation in the pipelines, thereby resulting in higher inhibition cost strategies. A major industry concern is to reduce the severe safety risks associated with hydrate plug formation, and significantly extending subsea tieback distances by providing a cost effective flow assurance management/safety tool for mature fields. Developing fundamental understanding of the key mechanistic steps towards hydrate plug formation for different multiphase flow conditions is a key challenge to the flow assurance community. Such understanding can ultimately provide new insight and hydrate management guidelines to diminish the safety risks due to hydrate formation and accumulation in deepwater flowlines and facilities. The transportability of hydrates in pipelines is a function of the operating parameters, such as temperature, pressure, fluid mixture velocity, liquid loading, and fluid system characteristics. Specifically, the hydrate formation rate and plugging onset characteristics can be significantly different for water continuous, oil continuous, and partially dispersed systems. The latter is defined as a system containing oil/gas/water, where the water is present both as a free phase and partially dispersed in the oil phase (i.e., entrained water in the oil). Since hydrate formation from oil dispersed in water systems and partially dispersed water systems is an area which is poorly understood, this thesis aims to address some key questions in these systems. Selected experiments have been performed at the University of Tulsa flowloop to study the hydrate formation and plugging characteristics for the partially dispersed water/oil/gas systems as well as systems where the oil is completely dispersed in water. These experiments indicate that the partially dispersed systems tend to be problematic and are more severe cases with respect to flow assurance when compared to systems where the water is completely dispersed in oil. We have found that the partially dispersed systems are distinct, and are not an intermediate case between water dominated, and water-in-oil emulsified systems. Instead the experiments indicate that the hydrate formation and plugging mechanism for these systems are very complex. Hydrate growth is very rapid for such systems when compared to 100% water cut systems. The plugging mechanism for these systems is a combination of various phenomena (wall growth, agglomeration, bedding/settling, etc). Three different oils with different viscosities have been used to investigate the transportability of hydrates with respect to oil properties. The experiments indicate that the transportability of hydrates increases with increase in oil viscosity. The data from the tests performed provide the basis for a mechanistic model for hydrate formation and plugging in partially dispersed systems. It is found that in systems that were in stratified flow regime before hydrate onset, the hydrates eventually settled on the pipe walls thereby decreasing the flow area for the flow of fluids. In systems that were in the slug flow regime before hydrate formation, moving beds of hydrates were the main cause for plugging. In both the flow regimes, the systems studied entered a plugging regime beyond a certain hydrate concentration. This is termed as φplugging onset and can be used as an indicator to calculate the amount of hydrates that can be transported safely without requiring any additional treatment for a given set of flow characteristics. A correlation to calculate this hydrate concentration based on easily accessible parameters is developed in terms of flow characteristics and oil properties. The work performed in this thesis has enhanced the understanding of the hydrate plug mechanism in pipelines having high amounts of water. This work has also shown the effect of hydrate formation in different flow regimes thereby shedding light on the effects of hydrates on multiphase flow and vice versa. Lessons resulting from this work could be incorporated into flow assurance models, as well as operating company production strategies to reduce or mitigate hydrate plugging risks in complex multiphase systems.

Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2011-12-01

Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. This paper describes and demonstrates a numerical solution scheme for ternary hydrate systems that seeks a balance between accuracy and computational efficiency. This scheme uses a generalize cubic equation of state, functional forms for the hydrate equilibria and cage occupancies, variable switching scheme for phase transitions, and kinetic exchange of hydrate formers (i.e., CH4, CO2, and N2) between the mobile phases (i.e., aqueous, liquid CO2, and gas) and hydrate phase. Accuracy of the scheme will be evaluated by comparing property values and phase equilibria against experimental data. Computational efficiency of the scheme will be evaluated by comparing the base scheme against variants. The application of interest will the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

Detection and Production of Methane Hydrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

George Hirasaki; Walter Chapman; Gerald Dickens

This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remotemore » quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand processes that control production potential of hydrates in marine settings, Mallik was included because of the extensive data collected in a producible hydrate accumulation. To date, such a location had not been studied in the oceanic environment. The project worked closely with ongoing projects (e.g. GOM JIP and offshore India) that are actively investigating potentially economic hydrate accumulations in marine settings. The overall approach was fivefold: (1) collect key data concerning hydrocarbon fluxes which is currently missing at all locations to be included in the study, (2) use this and existing data to build numerical models that can explain gas hydrate variance at all four locations, (3) simulate how natural gas could be produced from each location with different production strategies, (4) collect new sediment property data at these locations that are required for constraining fluxes, production simulations and assessing sediment stability, and (5) develop a method for remotely quantifying heterogeneities in gas hydrate and free gas distributions. While we generally restricted our efforts to the locations where key parameters can be measured or constrained, our ultimate aim was to make our efforts universally applicable to any hydrate accumulation.« less

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

NASA Astrophysics Data System (ADS)

Braun, Doris E.; Griesser, Ulrich J.

2018-02-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4'-diaminodiphenyl sulfone, DDS) 0.33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and a stable anhydrate at room temperature (form III) differ only by approximately 1 kJ mol–1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study addresses the critical class of non-stoichiometric hydrates, highlighting that only a multidisciplinary investigation can unravel hydrate formation at a molecular level, knowledge which is a requirement in modern drug development.

Evaluation of the correlation between Scoring Feline Allergic Dermatitis and Feline Extent and Severity Index and skin hydration in atopic cats.

PubMed

Szczepanik, Marcin P; Wilkołek, Piotr M; Adamek, Łukasz R; Zając, Marcin; Gołyński, Marcin; Sitkowski, Wiesław; Taszkun, Iwona

2018-02-01

Evaluation of the severity of clinical signs of cats with allergic skin diseases has used two scoring systems: Scoring Feline Allergic Dermatitis (SCORFAD) and the Feline Extent and Severity Index (FeDESI). The integrity of the cutaneous barrier can also be evaluated by measuring skin hydration. A correlation between the clinical score and skin hydration has been observed in humans and dogs with atopic dermatitis (AD). To demonstrate a correlation between the clinical score and skin hydration of cats affected with presumed AD. European short hair cats (n = 18): 11 females and seven males with a confirmed diagnosis of AD. SCORFAD and FeDESI scores were calculated and the measurements of skin hydration were assessed from seven body sites using corneometry. The correlation between the SCORFAD and FeDESI systems and skin hydration of each site, and the average skin hydration was calculated. There was a positive correlation between the SCORFAD score and skin hydration for the axilla, thorax and forelimb; for FeDESI and axilla and lumbar sites. There was a negative correlation between the FeDESI and skin hydration for the pinna (r = -0.47). Measurements of skin hydration could be a useful tool for the evaluation of allergic cats. There is limited evidence of any useful correlation between clinical scoring systems and measurements of hydration. The pinna may be a suitable region for the assessment of skin barrier function in normal and allergic cats. © 2017 ESVD and ACVD.

Efficacy of oral hydration in the prevention of contrast-induced acute kidney injury in patients undergoing coronary angiography or intervention.

PubMed

Akyuz, Sukru; Karaca, Mehmet; Kemaloglu Oz, Tugba; Altay, Servet; Gungor, Baris; Yaylak, Baris; Yazici, Selcuk; Ozden, Kivilcim; Karakus, Gultekin; Cam, Nese

2014-01-01

Efficacy of intravenous (IV) volume expansion in preventing contrast-induced acute kidney injury (CI-AKI) is well known. However, the role of oral hydration has not been well established. The aim of this work was to evaluate the efficacy of oral hydration in preventing CI-AKI. We prospectively randomized 225 patients undergoing coronary angiography and/or percutaneous coronary intervention in either oral hydration or IV hydration groups. Patients who have at least one of the high-risk factors for developing CI-AKI (advanced age, type 2 diabetes mellitus, anemia, hyperuricemia, a history of cardiac failure or systolic dysfunction) were included in the study. All patients had normal renal function or stage 1-2 chronic kidney disease. Patients in the oral hydration group were encouraged to drink unrestricted amounts of fluids freely whereas isotonic saline infusion was performed by the standard protocol in the IV hydration group. CI-AKI occurred in 8/116 patients (6.9%) in the oral hydration group and 8/109 patients (7.3%) in the IV hydration group (p = 0.89). There was also no statistically significant difference between the two groups when different CI-AKI definitions were taken into account. Oral hydration is as effective as IV hydration in preventing CI-AKI in patients with normal kidney function or stage 1-2 chronic kidney disease, and who also have at least one of the other high-risk factors for developing CI-AKI. © 2014 S. Karger AG, Basel.

Stress and Dilatancy Relation of Methane Hydrate Bearing Sand with Various Fines Content

NASA Astrophysics Data System (ADS)

Hyodo, M.

2016-12-01

This study presents an experimental and numerical study on the shear behaviour of methane hydrate bearing sand with variable confining pressures and methane hydrate saturations. A representative grading curve of Nankai Trough is selected as the grain size distribution of host sand to artificially produce the methane hydrate bearing sand. A shear strength estimation equation for methane hydrate bearing sand from test results is established. A simple constitutive model has been proposed to predict the stress-strain response of methane hydrate bearing sand based on a few well-known relationships. Experimental results indicate that the inclination of stress-dilatancy curve becomes steeper with a rise in methane hydrate saturation. A revised stress-dilatancy equation has been integrated with this simple model to consider the variance in the inclination of stress-dilatancy curve. The mean stress Pcr at critical state when the peak stress ratio reduces to the residual stress ratio increases with the level of methane hydrate saturation. The dilatancy parameter a tends to increase with the methane hydrate saturation. The shear deformability parameter A exhibits a decreasing tendency with the rise in methane hydrate saturation at each confining pressure. This model is capable of reasonably predicting the strength and stiffness enhancement and the dilation behaviour as methane hydrate saturation increases. The volumetric variation from contraction to expansion of MH bearing sand at a lower confining pressure and only pure volumetric contraction a higher confining pressure can be represented by this simple model.

Water-wetting surfaces as hydrate promoters during transport of carbon dioxide with impurities.

PubMed

Kuznetsova, Tatiana; Jensen, Bjørnar; Kvamme, Bjørn; Sjøblom, Sara

2015-05-21

Water condensing as liquid drops within the fluid bulk has traditionally been the only scenario accepted in the industrial analysis of hydrate risks. We have applied a combination of absolute thermodynamics and molecular dynamics modeling to analyze the five primary routes of hydrate formation in a rusty pipeline carrying dense carbon dioxide with methane, hydrogen sulfide, argon, and nitrogen as additional impurities. We have revised the risk analysis of all possible routes in accordance with the combination of the first and the second laws of thermodynamics to determine the highest permissible content of water. It was found that at concentrations lower than five percent, hydrogen sulfide will only support the formation of carbon dioxide-dominated hydrate from adsorbed water and hydrate formers from carbon dioxide phase rather than formation in the aqueous phase. Our results indicate that hydrogen sulfide leaving carbon dioxide for the aqueous phase will be able to create an additional hydrate phase in the aqueous region adjacent to the first adsorbed water layer. The growth of hydrate from different phases will decrease the induction time by substantially reducing the kinetically limiting mass transport across the hydrate films. Hydrate formation via adsorption of water on rusty walls will play the decisive role in hydrate formation risk, with the initial concentration of hydrogen sulfide being the critical factor. We concluded that the safest way to eliminate hydrate risks is to ensure that the water content of carbon dioxide is low enough to prevent water dropout via the adsorption mechanism.

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Daniel

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production. A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Legmore » II in 2009 and recently confirmed with coring in 2017. A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.« less

Sedimentological Properties of Natural Gas Hydrates-Bearing Sands in the Nankai Trough and Mallik Areas

NASA Astrophysics Data System (ADS)

Uchida, T.; Tsuji, T.; Waseda, A.

2009-12-01

The Nankai Trough parallels the Japanese Island, where extensive BSRs have been interpreted from seismic reflection records. High resolution seismic surveys have definitely indicated gas hydrate distributions, and drilling the MITI Nankai Trough wells in 2000 and the METI Tokai-oki to Kumano-nada wells in 2004 have revealed subsurface gas hydrate in the eastern part of Nankai Trough. In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that also clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. During the field operations, the LWD and wire-line well log data were continuously obtained and plenty of gas hydrate-bearing sand cores were recovered. Subsequence sedimentological and geochemical analyses performed on those core samples revealed the crucial geologic controls on the formation and preservation of natural gas hydrate in sediments. Pore-space gas hydrates reside in sandy sediments mostly filling intergranular porosity. Pore waters chloride anomalies, core temperature depression and core observations on visible gas hydrates confirm the presence of pore-space gas hydrates within moderate to thick sandy layers, typically 10 cm to a meter thick. Sediment porosities and pore-size distributions were obtained by mercury porosimetry, which indicate that porosities of gas hydrate-bearing sandy strata are approximately 45 %. According to grain size distribution curves, gas hydrate is dominant in fine- to very fine-grained sandy strata. Gas hydrate saturations are typically up to 80 % in pore volume throughout most of the hydrate-dominant sandy layers, which are estimated by well log analyses as well as pore water chloride anomalies. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicated that highly saturated sands should have permeability of 1 x 10-15 to 5 x 10-15 m2 (1 to 5 millidarcies). Most of gas hydrates fill the intergranular pore systems of sandy layers, which are derived from the sedimentary facies such as channels and crevasse splay/levee deposits. It is remarked that those sandy strata are usually composed of arenite sands with matrix-free intergranular pore systems. Gas hydrates are less frequently found in fine-grained sediments such as siltstone and mudstone from overbank deposits. Methane gas accumulation and original pore space large enough to occur within host sediments may be required for forming highly saturated gas hydrate in pore system. The distribution of a porous and coarser-grained host rock should be one of the important factors to control the occurrence of gas hydrate, as well as physicochemical conditions. This appears to be a similar mode for conventional oil and gas accumulations, and this knowledge is important to predicting the location of other hydrate deposits and their eventual energy resource. This study was performed as a part of the MH21 Research Consortium on methane hydrate in Japan.

21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate...

21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

Temporal Characterization of Hydrates System Dynamics beneath Seafloor Mounds. Integrating Time-Lapse Electrical Resistivity Methods and In Situ Observations of Multiple Oceanographic Parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lutken, Carol; Macelloni, Leonardo; D'Emidio, Marco

This study was designed to investigate temporal variations in hydrate system dynamics by measuring changes in volumes of hydrate beneath hydrate-bearing mounds on the continental slope of the northern Gulf of Mexico, the landward extreme of hydrate occurrence in this region. Direct Current Resistivity (DCR) measurements were made contemporaneously with measurements of oceanographic parameters at Woolsey Mound, a carbonate-hydrate complex on the mid-continental slope, where formation and dissociation of hydrates are most vulnerable to variations in oceanographic parameters affected by climate change, and where changes in hydrate stability can readily translate to loss of seafloor stability, impacts to benthic ecosystems,more » and venting of greenhouse gases to the water-column, and eventually, the atmosphere. We focused our study on hydrate within seafloor mounds because the structurally-focused methane flux at these sites likely causes hydrate formation and dissociation processes to occur at higher rates than at sites where the methane flux is less concentrated and we wanted to maximize our chances of witnessing association/dissociation of hydrates. We selected a particularly well-studied hydrate-bearing seafloor mound near the landward extent of the hydrate stability zone, Woolsey Mound (MC118). This mid-slope site has been studied extensively and the project was able to leverage considerable resources from the team’s research experience at MC118. The site exhibits seafloor features associated with gas expulsion, hydrates have been documented at the seafloor, and changes in the outcropping hydrates have been documented, photographically, to have occurred over a period of months. We conducted observatory-based, in situ measurements to 1) characterize, geophysically, the sub-bottom distribution of hydrate and its temporal variability, and 2) contemporaneously record relevant environmental parameters (temperature, pressure, salinity, turbidity, bottom currents) to detect short-term changes within the hydrates system, identify relationships/impacts of local oceanographic parameters on the hydrates system, and improve our understanding of how seafloor instability is affected by hydrates-driven changes. A 2009 DCR survey of MC118 demonstrated that we could image resistivity anomalies to a depth of 75m below the seafloor in water depths of 1km. We reconfigured this system to operate autonomously on the seafloor in a pre-programmed mode, for periods of months. We designed and built a novel seafloor lander and deployment capability that would allow us to investigate the seafloor at potential deployment sites and deploy instruments only when conditions met our criteria. This lander held the DCR system, controlling computers, and battery power supply, as well as instruments to record oceanographic parameters. During the first of two cruises to the study site, we conducted resistivity surveying, selected a monitoring site, and deployed the instrumented lander and DCR, centered on what appeared to be the most active locations within the site, programmed to collect a DCR profile, weekly. After a 4.5-month residence on the seafloor, the team recovered all equipment. Unfortunately, several equipment failures occurred prior to recovery of the instrument packages. Prior to the failures, however, two resistivity profiles were collected together with oceanographic data. Results show, unequivocally, that significant changes can occur in both hydrate volume and distribution during time periods as brief as one week. Occurrences appear to be controlled by both deep and near-surface structure. Results have been integrated with seismic data from the area and show correspondence in space of hydrate and structures, including faults and gas chimneys.« less

Sensitivity Studies on Productivity Performance from 3D Heterogeneous Reservoir Model Based on the L-Pad Gas Hydrate Accumulation in Prudhoe Bay Unit, North Slope Alaska

NASA Astrophysics Data System (ADS)

Myshakin, E. M.; Ajayi, T.; Seol, Y.; Boswell, R.

2016-12-01

Three-dimensional reservoir model of the "L-Pad" hydrate deposit located in the Prudhoe Bay region of the Alaska's North Slope was created including four stratigraphic units; silty shale overburden, hydrate-bearing D sand, inter-reservoir silty shale, hydrate-bearing C sand, and silty shale underburden. The model incorporates the actual geological settings, accounts for the presence of faults, reservoir dip, the hydrate-water contact in the C sand. Geostatistical porosity distributions in D and C sands conditioned to log data from 78 wells drilled in the vicinity of the Prudhoe Bay "L-pad" were developed providing vertical and lateral 3D heterogeneity in porosity and porosity-dependent hydrate saturation and intrinsic permeability. Gas production potential was estimated using a conventional vertical wellbore completion and a deviated toe-down wellbore perforated through both sand units to induce hydrate depressurization at a constant bottom-hole pressure. The results have shown the greater performance of the deviated well design over the vertical one. The scenarios involving simultaneous and sequential hydrate dissociation in sand units were explored and the effect of the underlying aquifer in the C sand was estimated. Sensitivity analysis has demonstrated that hydraulic communication with over- and underlying shale units affects production in the beginning of depressurization due to competitive water influx into producing mobile flow and could suppress efficient hydrate decomposition resulting in production lag. Another important factor greatly influencing the productivity performance is the effective permeability of hydrate-bearing sediment controlled by the relative permeability function. The results call for the necessity of thorough fundamental studies to understand multi-phase flow in hydrate-bearing sediments with different hydrate precipitation habits.

Gender- and hydration- associated differences in the physiological response to spinning.

PubMed

Ramos-Jiménez, Arnulfo; Hernández-Torres, Rosa Patricia; Wall-Medrano, Abraham; Torres-Durán, Patricia Victoria; Juárez-Oropeza, Marco Antonio; Viloria, María; Villalobos-Molina, Rafael

2014-03-01

There is scarce and inconsistent information about gender-related differences in the hydration of sports persons, as well as about the effects of hydration on performance, especially during indoor sports. To determine the physiological differences between genders during in indoor physical exercise, with and without hydration. 21 spinning sportspeople (12 men and 9 women) participated in three controlled, randomly assigned and non-sequential hydration protocols, including no fluid intake and hydration with plain water or a sports drink (volume adjusted to each individual every 15 min), during 90 min of spinning exercise. The response variables included body mass, body temperature, heart rate and blood pressure. During exercise without hydration, men and women lost ~2% of body mass, and showed higher body temperature (~0.2°C), blood pressure (~4 mmHg) and heart rate (~7 beats/min) compared to exercises with hydration. Body temperature and blood pressure were higher for men than for women during exercise without hydration, differences not observed during exercise with hydration. Between 42-99% of variance in body temperature, blood pressure and heart rate could be explained by the physical characteristics of subjects and the work done. During exercise with hydration (either with water or sport drink), the physiological response was similar for both genders. Exercise without hydration produced physical stress, which could be prevented with either of the fluids (plain water was sufficient). Gender differences in the physiological response to spinning (body temperature, mean blood pressure and heart rate) can be explained in part by the distinct physical characteristics of each individual. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

USGS Publications Warehouse

Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

2004-01-01

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

In Situ Raman Detection of Gas Hydrates Exposed on the Seafloor of the South China Sea

NASA Astrophysics Data System (ADS)

Zhang, Xin; Du, Zengfeng; Luan, Zhendong; Wang, Xiujuan; Xi, Shichuan; Wang, Bing; Li, Lianfu; Lian, Chao; Yan, Jun

2017-10-01

Gas hydrates are usually buried in sediments. Here we report the first discovery of gas hydrates exposed on the seafloor of the South China Sea. The in situ chemical compositions and cage structures of these hydrates were measured at the depth of 1,130 m below sea level using a Raman insertion probe (RiP-Gh) that was carried and controlled by a remotely operated vehicle (ROV) Faxian. This in situ analytical technique can avoid the physical and chemical changes associated with the transport of samples from the deep sea to the surface. Natural gas hydrate samples were analyzed at two sites. The in situ spectra suggest that the newly formed hydrate was Structure I but contains a small amount of C3H8 and H2S. Pure gas spectra of CH4, C3H8, and H2S were also observed at the SCS-SGH02 site. These data represent the first in situ proof that free gas can be trapped within the hydrate fabric during rapid hydrate formation. We provide the first in situ confirmation of the hydrate growth model for the early stages of formation of crystalline hydrates in a methane-rich seafloor environment. Our work demonstrates that natural hydrate deposits, particularly those in the early stages of formation, are not monolithic single structures but instead exhibit significant small-scale heterogeneities due to inclusions of free gas and the surrounding seawater, there inclusions also serve as indicators of the likely hydrate formation mechanism. These data also reinforce the importance of correlating visual and in situ measurements when characterizing a sampling site.

Seismic reflections identify finite differences in gas hydrate resources

USGS Publications Warehouse

Dillon, William P.; Max, M.

1999-01-01

Gas hydrate is a gas-bearing, ice-like crystalline solid. The substance's build ing blocks consist of a gas molecule (generally methane) sur-rounded by a cage of water molecules. The total amount of methane in hydrate in the world is immense - the most recent speculative estimate centers on values of 21x1015 cu meters. Thus, it may represent a future energy resource. This estimate was presented by Keith Kvenvolden at the International Symposium on Methane Hydrates, Resources in the Near Future, sponsor ed by Japanese National Oil Company (Tokyo, October, 1998).But, as with any natural resource, there is a need to find naturally occurring concentrations in order to effectively extract gas. We need to answer four basic questions:Do methane hydrate concentrations suitable for methane extraction exist?How can we recognize these concentrations?Where are concentrations located?What processes control methane hydrate concentrations?Gas hydrate occurs naturally at the pressure/ temperature/chemical conditions that are present within ocean floor sediments at water depths greater than about 500 meters. The gas hydrate stability zone (GHSZ) extends from the sea bottom downward to a depth where the natural increase in temperature causes the hydrate to melt (dissociate), even though the downward pressure increase is working to increase gas hydrate stability.Thus, the base of the GHSZ tends to parallel the seafloor at any given water depth (pressure), because the sub-seafloor isotherms (depths of constant temperature) generally parallel the seafloor. The layer at which gas hydrate is stable commonly extends from the sea floor to several hundred meters below it. The gas in most gas hydrates is methane, generated by bacteria in the sediments. In some cases, it can be higher carbon-number, thermogenic hydrocarbon gases that rise from greater depths.

HYDRATE v1.5 OPTION OF TOUGH+ v1.5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moridis, George

HYDRATE v1.5 is a numerical code that for the simulation of the behavior of hydrate-bearing geologic systems, and represents the third update of the code since its first release [Moridis et al., 2008]. It is an option of TOUGH+ v1.5 [Moridis and Pruess, 2014], a successor to the TOUGH2 [Pruess et al., 1999, 2012] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. HYDRATE v1.5 needs the TOUGH+ v1.5 core code in order to compile and execute. It is written in standard FORTRAN 95/2003, and can be run on any computational platformmore » (workstation, PC, Macintosh) for which such compilers are available. By solving the coupled equations of mass and heat balance, the fully operational TOUGH+HYDRATE code can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH 4-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.5 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH 4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects.« less

Free energy landscape and molecular pathways of gas hydrate nucleation.

PubMed

Bi, Yuanfei; Porras, Anna; Li, Tianshu

2016-12-07

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

Free energy landscape and molecular pathways of gas hydrate nucleation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bi, Yuanfei; Porras, Anna; Li, Tianshu, E-mail: tsli@gwu.edu

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p{sub B} histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage ordermore » parameter (H-COP) which we developed for driving FFS, through conducting the p{sub B} histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.« less

TOUGH+HYDRATE v1.2 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moridis, George J.; Kowalsky, Michael B.; Pruess, Karsten

TOUGH+HYDRATE v1.2 is a code for the simulation of the behavior of hydratebearing geologic systems, and represents the second update of the code since its first release [Moridis et al., 2008]. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH4-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy’s law is valid. TOUGH+HYDRATE v1.2 includes both an equilibrium and a kinetic modelmore » of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is a member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95/2003, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.« less

Numerical studies of gas production from several CH4 hydrate zones at the Mallik site, Mackenzie Delta, Canada

USGS Publications Warehouse

Moridis, G.J.; Collett, T.S.; Dallimore, S.R.; Satoh, T.; Hancock, S.; Weatherill, B.

2004-01-01

The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. A gas hydrate research well was drilled at the site in 1998. The objective of this study is the analysis of various gas production scenarios from five methane hydrate-bearing zones at the Mallik site. In Zone #1, numerical simulations using the EOSHYDR2 model indicated that gas production from hydrates at the Mallik site was possible by depressurizing a thin free gas zone at the base of the hydrate stability field. Horizontal wells appeared to have a slight advantage over vertical wells, while multiwell systems involving a combination of depressurization and thermal stimulation offered superior performance, especially when a hot noncondensible gas was injected. Zone #2, which involved a gas hydrate layer with an underlying aquifer, could yield significant amounts of gas originating entirely from gas hydrates, the volumes of which increased with the production rate. However, large amounts of water were also produced. Zones #3, #4 and #5 were lithologically isolated gas hydrate-bearing deposits with no underlying zones of mobile gas or water. In these zones, thermal stimulation by circulating hot water in the well was used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increased with the gas hydrate saturation, the initial formation temperature, the temperature of the circulating water in the well, and the formation thermal conductivity. Methane production appears to be less sensitive to the specific heat of the rock and of the hydrate, and to the permeability of the formation. ?? 2004 Published by Elsevier B.V.

Physical property studies in the USGS GHASTLI Laboratory

USGS Publications Warehouse

Winters, William J.; Waite, William F.; Hutchinson, Deborah R.; Mason, David H.

2008-01-01

One of the many challenges in studying methane hydrate is that it is unstable at typical surface pressure and temperature conditions. To enable methane hydrates and hydrate-bearing sediments to be formed, analyzed, and experimented with, the National Energy Technology Laboratory (NETL), and the U.S. Geological Survey (USGS) in Woods Hole, MA collaborated in the development of the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI). Over the past decade, the USGS has been operating GHASTLI and collaborating in the development of new sample handling tools and procedures, in an effort to improve our ability to analyze methane hydrate in the lab. These tools will enable hydrate researchers to more confidently link field studies (for example geophysics or drilling) with theoretical and predictive studies, leading to a better understanding of the geological conditions and processes that control the growth and concentration of natural gas hydrates, how hydrates affect the properties of the host sediments, and how the hydrate-sediment system changes when hydrate dissociates and releases the previously bound gas. To date, GHASTLI has been used to measure natural samples from ODP Leg 164 (Blake Ridge off the U.S. southeast Atlantic margin), Leg 204 (Hydrate Ridge off the Pacific Northwest margin) and the Mallik well (Mackenzie Delta in northwestern Canada). Additional samples in the queue for analysis are from the Chevron Joint Industry Project Experiment in the Gulf of Mexico and most recently, from IODP Leg 311 off Vancouver Island. Several foreign nations have asked whether GHASTLI will be available to analyze samples that might be recovered during national drilling programs. The ability to perform lab testing of hydrates within sediments is one of the unique capabilities of GHASTLI that separates it from other simulators at NETL and elsewhere.

The Dependence of Water Permeability in Quartz Sand on Gas Hydrate Saturation in the Pore Space

NASA Astrophysics Data System (ADS)

Kossel, E.; Deusner, C.; Bigalke, N.; Haeckel, M.

2018-02-01

Transport of fluids in gas hydrate bearing sediments is largely defined by the reduction of the permeability due to gas hydrate crystals in the pore space. Although the exact knowledge of the permeability behavior as a function of gas hydrate saturation is of crucial importance, state-of-the-art simulation codes for gas production scenarios use theoretically derived permeability equations that are hardly backed by experimental data. The reason for the insufficient validation of the model equations is the difficulty to create gas hydrate bearing sediments that have undergone formation mechanisms equivalent to the natural process and that have well-defined gas hydrate saturations. We formed methane hydrates in quartz sand from a methane-saturated aqueous solution and used magnetic resonance imaging to obtain time-resolved, three-dimensional maps of the gas hydrate saturation distribution. These maps were fed into 3-D finite element method simulations of the water flow. In our simulations, we tested the five most well-known permeability equations. All of the suitable permeability equations include the term (1-SH)n, where SH is the gas hydrate saturation and n is a parameter that needs to be constrained. The most basic equation describing the permeability behavior of water flow through gas hydrate bearing sand is k = k0 (1-SH)n. In our experiments, n was determined to be 11.4 (±0.3). Results from this study can be directly applied to bulk flow analysis under the assumption of homogeneous gas hydrate saturation and can be further used to derive effective permeability models for heterogeneous gas hydrate distributions at different scales.

Steps Towards Understanding Large-scale Deformation of Gas Hydrate-bearing Sediments

NASA Astrophysics Data System (ADS)

Gupta, S.; Deusner, C.; Haeckel, M.; Kossel, E.

2016-12-01

Marine sediments bearing gas hydrates are typically characterized by heterogeneity in the gas hydrate distribution and anisotropy in the sediment-gas hydrate fabric properties. Gas hydrates also contribute to the strength and stiffness of the marine sediment, and any disturbance in the thermodynamic stability of the gas hydrates is likely to affect the geomechanical stability of the sediment. Understanding mechanisms and triggers of large-strain deformation and failure of marine gas hydrate-bearing sediments is an area of extensive research, particularly in the context of marine slope-stability and industrial gas production. The ultimate objective is to predict severe deformation events such as regional-scale slope failure or excessive sand production by using numerical simulation tools. The development of such tools essentially requires a careful analysis of thermo-hydro-chemo-mechanical behavior of gas hydrate-bearing sediments at lab-scale, and its stepwise integration into reservoir-scale simulators through definition of effective variables, use of suitable constitutive relations, and application of scaling laws. One of the focus areas of our research is to understand the bulk coupled behavior of marine gas hydrate systems with contributions from micro-scale characteristics, transport-reaction dynamics, and structural heterogeneity through experimental flow-through studies using high-pressure triaxial test systems and advanced tomographical tools (CT, ERT, MRI). We combine these studies to develop mathematical model and numerical simulation tools which could be used to predict the coupled hydro-geomechanical behavior of marine gas hydrate reservoirs in a large-strain framework. Here we will present some of our recent results from closely co-ordinated experimental and numerical simulation studies with an objective to capture the large-deformation behavior relevant to different gas production scenarios. We will also report on a variety of mechanically relevant test scenarios focusing on effects of dynamic changes in gas hydrate saturation, highly uneven gas hydrate distributions, focused fluid migration and gas hydrate production through depressurization and CO2 injection.

Testing short-range migration of microbial methane as a hydrate formation mechanism: Results from Andaman Sea and Kumano Basin drill sites and global implications

NASA Astrophysics Data System (ADS)

Malinverno, Alberto; Goldberg, David S.

2015-07-01

Methane gas hydrates in marine sediments often concentrate in coarse-grained layers surrounded by fine-grained marine muds that are hydrate-free. Methane in these hydrate deposits is typically microbial, and must have migrated from its source as the coarse-grained sediments contain little or no organic matter. In "long-range" migration, fluid flow through permeable layers transports methane from deeper sources into the gas hydrate stability zone (GHSZ). In "short-range" migration, microbial methane is generated within the GHSZ in fine-grained sediments, where small pore sizes inhibit hydrate formation. Dissolved methane can then diffuse into adjacent sand layers, where pore size does not restrict hydrate formation and hydrates can accumulate. Short-range migration has been used to explain hydrate accumulations in sand layers observed in drill sites on the northern Cascadia margin and in the Gulf of Mexico. Here we test the feasibility of short-range migration in two additional locations, where gas hydrates have been found in coarse-grained volcanic ash layers (Site NGHP-01-17, Andaman Sea, Indian Ocean) and turbidite sand beds (Site IODP-C0002, Kumano forearc basin, Nankai Trough, western Pacific). We apply reaction-transport modeling to calculate dissolved methane concentration and gas hydrate amounts resulting from microbial methane generated within the GHSZ. Model results show that short-range migration of microbial methane can explain the overall amounts of methane hydrate observed at the two sites. Short-range migration has been shown to be feasible in diverse margin environments and is likely to be a widespread methane transport mechanism in gas hydrate systems. It only requires a small amount of organic carbon and sediment sequences consisting of thin coarse-grained layers that can concentrate microbial methane generated within thick fine-grained sediment beds; these conditions are common along continental margins around the globe.

A comparison of hydration effect on body fluid and temperature regulation between Malaysian and Japanese males exercising at mild dehydration in humid heat

PubMed Central

2014-01-01

Background This study investigated the effect of hydration differences on body fluid and temperature regulation between tropical and temperate indigenes exercising in the heat. Methods Ten Japanese and ten Malaysian males with matched physical characteristics (height, body weight, and peak oxygen consumption) participated in this study. Participants performed exercise for 60 min at 55% peak oxygen uptake followed by a 30-min recovery at 32°C and 70% relative air humidity with hydration (4 times each, 3 mL per kg body weight, 37°C) or without hydration. Rectal temperature, skin temperature, heart rate, skin blood flow, and blood pressure were measured continuously. The percentage of body weight loss and total sweat loss were calculated from body weight measurements. The percentage change in plasma volume was estimated from hemoglobin concentration and hematocrit. Results Malaysian participants had a significantly lower rectal temperature, a smaller reduction in plasma volume, and a lower heart rate in the hydrated condition than in the non-hydrated condition at the end of exercise (P <0.05), whereas Japanese participants showed no difference between the two hydration conditions. Hydration induced a greater total sweat loss in both groups (P <0.05), and the percentage of body weight loss in hydrated Malaysians was significantly less than in hydrated Japanese (P <0.05). A significant interaction between groups and hydration conditions was observed for the percentage of mean cutaneous vascular conductance during exercise relative to baseline (P <0.05). Conclusions The smaller reduction in plasma volume and percentage body weight loss in hydrated Malaysians indicated an advantage in body fluid regulation. This may enable Malaysians to reserve more blood for circulation and heat dissipation and thereby maintain lower rectal temperatures in a hydrated condition. PMID:24490869

Determining gas hydrate distribution in sands using integrated analysis of well log and seismic data in the Terrebonne Basin, Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hillman, Jess; Cook, Ann; Daigle, Hugh

The Terrebonne Basin is a salt bounded mini-basin in the northeast section of the Walker Ridge protraction area in the Gulf of Mexico, and the main site for an upcoming gas-hydrate focused International Ocean Discovery Program (IODP) cruise. The basin is infilled by an increasingly mud rich sedimentary sequence with several 5-15 meter gas-hydrate filled sand units of Miocene to Pliocene age overlying the up-domed salt. These gas-hydrate filled sand units can be identified in logging while drilling data from two existing wells in the Terrebonne Basin, drilled in 2009 by the Gas Hydrate Joint Industry Project (JIP) Leg 2.more » The sand units are cross cut by a distinct bottom-simulating reflector (BSR), and are clearly characterized by a polarity reversal in the sand units. The polarity reversal is caused by a positive gas-hydrate filled sand within the stability zone changing to negative gas-bearing sand. Using well data and calculated synthetic seismogram well ties we are able to identify several additional 1-4 meter gas-hydrate and water-saturated sand units associated with thick (100-200 m-thick), fine grained, hydrate bearing fractured units in the upper sedimentary sequence on the seismic data. Following on previous work, we propose that microbial generation of methane occurring within the fine-grained, fractured units acts as a source for gas hydrate formation in the thin sands. In contrast, it has been proposed that the gas hydrate in the 5-15 m-thick sands first discovered by the JIP was originates from a deeper thermogenic source. Through correlating hydrate occurrence in sands from well data, to amplitudes derived from the seismic data, we can estimate possible distribution of hydrate across the basin. Overall, we find the Terrebonne basin to be a complex gas hydrate system with multiple mechanisms of methane generation and migration.« less

Modeling the formation of methane hydrate-bearing intervals in fine-grained sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Sediment grain size exerts a fundamental control on how methane hydrates are distributed within the pore space. Fine-grained muds are the predominant sediments in continental margins, and hydrates in these sediments have often been observed in semi-vertical veins and fractures. In several instances, these hydrate veins/fractures are found in discrete depth intervals a few tens meters thick within the gas hydrate stability zone (GHSZ) surrounded by hydrate-free sediments above and below. As they are not obviously connected with free gas occurring beneath the base of the GHSZ, these isolated hydrate-bearing intervals have been interpreted as formed by microbial methane generatedmore » in situ. To investigate further the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, solute diffusion, and microbial methane generation. The microbial methane generation term depends on the amount of metabolizable organic carbon deposited at the seafloor, which is degraded at a prescribed rate resulting in methane formation beneath the sulfate reduction zone. In the model, methane hydrate precipitates once the dissolved methane concentration is greater than solubility, or hydrate dissolves if concentration goes below solubility. If the deposition of organic carbon at the seafloor is kept constant in time, we found that the predicted amounts of hydrate formed in discrete intervals within the GHSZ are much less than those estimated from observations. We then investigated the effect of temporal variations in the deposition of organic carbon. If greater amounts of organic carbon are deposited during some time interval, methane generation is enhanced during burial in the corresponding sediment interval. With variations in organic carbon deposition that are consistent with observations in continental margin sediments, we were able to reproduce the methane hydrate contents estimated in discrete depth intervals. Our results support the suggestion that in situ microbial methane generation is the source for hydrates within fine-grained sediments.« less

Magnetic Hysteresis Parameters and Day-Plot Analysis to Delineate Diagenetic Alteration in Gas Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Enkin, R. J.; Baker, J.; Nourgaliev, D.; Iassonov, P.

2005-12-01

Gas hydrates are naturally occurring cage structures of ice found in continental slope and permafrost sediments. They contain vast quantities of methane which is important both as a climate driver and an energy resource. Hydrate formation alters the redox potential of interstitial fluids which can in turn alter magnetic minerals. Thus magnetic methods can help delineate diagenetic pathways, provide a proxy method to map out past hydrate occurrences, and eventually lead to new remote sensing methods in prospecting for gas hydrates. We present data acquired using a J-Meter Coercivity Spectrometer. Induced and remanent magnetism are simultaneously measured on 1.5 cc samples as they spin on a 50 cm diameter disk, 20 times per second. The applied field ramps between ± 500 mT to produce a hysteresis loop in 7 minutes. Sub-second viscous decay is measured to provide a proxy for the amount of superparamagnetism present. The rapid and simple measurements made possible by this robust machine are ideal for core logging. Measurements made on frozen core from the Mallik permafrost gas hydrate field in Canada's Northwest Territories demonstrates that the magnetic properties are dependent on the concentration of gas hydrate present. Day-plots of magnetic hysteresis parameter ratios distinguish the magnetic carriers in gas hydrate rich sediments. The original magnetite is often reduced to sulphide when gas hydrate concentration exceeds 40%. In other high-concentration gas hydrate horizons, fine single-domain (SD) grains of magnetite apparently dissolve leaving nothing but large multi-domain (MD) magnetite grains. Independently measured superparamagnetism is shown to push hysteresis ratios off the hyperbola expected for SD-MD mixtures, as predicted by Dunlop [JGR, 10.10291/2001JB000486, 2002]. Magnetic study of host sediments in gas hydrate systems provides a powerful core-logging tool, offers a window into the processes of gas hydrate formation, and forms the basis for quantitative analysis of magnetic surveys over gas hydrate fields.

21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as safe...

A Wearable Hydration Sensor with Conformal Nanowire Electrodes.

PubMed

Yao, Shanshan; Myers, Amanda; Malhotra, Abhishek; Lin, Feiyan; Bozkurt, Alper; Muth, John F; Zhu, Yong

2017-03-01

A wearable skin hydration sensor in the form of a capacitor is demonstrated based on skin impedance measurement. The capacitor consists of two interdigitated or parallel electrodes that are made of silver nanowires (AgNWs) in a polydimethylsiloxane (PDMS) matrix. The flexible and stretchable nature of the AgNW/PDMS electrode allows conformal contact to the skin. The hydration sensor is insensitive to the external humidity change and is calibrated against a commercial skin hydration system on an artificial skin over a wide hydration range. The hydration sensor is packaged into a flexible wristband, together with a network analyzer chip, a button cell battery, and an ultralow power microprocessor with Bluetooth. In addition, a chest patch consisting of a strain sensor, three electrocardiography electrodes, and a skin hydration sensor is developed for multimodal sensing. The wearable wristband and chest patch may be used for low-cost, wireless, and continuous monitoring of skin hydration and other health parameters. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strength and acoustic properties of Ottawa sand containing laboratory-formed methane gas hydrate

USGS Publications Warehouse

Winters, William J.; Waite, William F.; Mason, David H.

2004-01-01

Although gas hydrate occurs in a wide variety of sediment types and is present and even pervasive at some locations on continental margins, little is known about how it forms naturally. Physical properties of the resultant gas hydrate-sediment mixtures, data needed for input into models that predict location and quantity of in situ hydrate are also lacking. Not only do properties of the host materials influence the type and quantity of hydrate formed and whether a particular deposit may be an economic resource or a geohazard, the properties of the natural sediment are also subsequently changed by the formation of gas hydrate in the pore space. The magnitude of the change is primarily related to the amount and the weighted inter-particle distribution of the hydrate deposits in relation to the actual sediment grains. Our goal is to understand the interaction between natural sediments and gas hydrate formation in order to quantify physical properties that are useful to predictive models.

Initial report of the IMAGES VIII/PAGE 127 gas hydrate and paleoclimate cruise on the RV Marion Dufresne in the Gulf of Mexico, 2-18 July 2002

USGS Publications Warehouse

Winters, William J.; Lorenson, T.D.; Paull, Charles K.

2007-01-01

The northern Gulf of Mexico contains many documented gas hydrate deposits near the sea floor. Although gas hydrate often is present in shallow subbottom sediment, the extent of hydrate occurrence deeper than 10 meters below sea floor in basins away from vents and other surface expressions is unknown. We obtained giant piston cores, box cores, and gravity cores and performed heat-flow analyses to study these shallow gas hydrate deposits aboard the RV Marion Dufresne in July 2002. This report presents measurements and interpretations from that cruise. Our results confirm the presence of gas hydrate in vent-related sediments near the sea bed. The presence of gas hydrate near the vents is governed by the complex interaction of regional and local factors, including heat flow, fluid flow, faults, pore-water salinity, gas concentrations, and sediment properties. However, conditions appropriate for extensive gas hydrate formation were not found away from the vents.

Monitoring early hydration of reinforced concrete structures using structural parameters identified by piezo sensors via electromechanical impedance technique

NASA Astrophysics Data System (ADS)

Talakokula, Visalakshi; Bhalla, Suresh; Gupta, Ashok

2018-01-01

Concrete is the most widely used material in civil engineering construction. Its life begins when the hydration process is activated after mixing the cement granulates with water. In this paper, a non-dimensional hydration parameter, obtained from piezoelectric ceramic (PZT) patches bonded to rebars embedded inside concrete, is employed to monitor the early age hydration of concrete. The non-dimensional hydration parameter is derived from the equivalent stiffness determined from the piezo-impedance transducers using the electro-mechanical impedance (EMI) technique. The focus of the study is to monitor the hydration process of cementitious materials commencing from the early hours and continue till 28 days using single non-dimensional parameter. The experimental results show that the proposed piezo-based non-dimensional hydration parameter is very effective in monitoring the early age hydration, as it has been derived from the refined structural impedance parameters, obtained by eliminating the PZT contribution, and using both the real and imaginary components of the admittance signature.

Glacial cycles influence marine methane hydrate formation

DOE PAGES

Malinverno, A.; Cook, A. E.; Daigle, H.; ...

2018-01-12

Methane hydrates in fine-grained continental slope sediments often occupy isolated depth intervals surrounded by hydrate-free sediments. As they are not connected to deep gas sources, these hydrate deposits have been interpreted as sourced by in situ microbial methane. We investigate here the hypothesis that these isolated hydrate accumulations form preferentially in sediments deposited during Pleistocene glacial lowstands that contain relatively large amounts of labile particulate organic carbon, leading to enhanced microbial methanogenesis. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent organic carbon deposition controlled by glacioeustatic sea level variations. In the model, hydrate forms in sedimentsmore » with greater organic carbon content deposited during the penultimate glacial cycle (~120-240 ka). As a result, the model predictions match hydrate-bearing intervals detected in three sites drilled on the northern Gulf of Mexico continental slope, supporting the hypothesis of hydrate formation driven by enhanced organic carbon burial during glacial lowstands.« less

Glacial cycles influence marine methane hydrate formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malinverno, A.; Cook, A. E.; Daigle, H.

Methane hydrates in fine-grained continental slope sediments often occupy isolated depth intervals surrounded by hydrate-free sediments. As they are not connected to deep gas sources, these hydrate deposits have been interpreted as sourced by in situ microbial methane. We investigate here the hypothesis that these isolated hydrate accumulations form preferentially in sediments deposited during Pleistocene glacial lowstands that contain relatively large amounts of labile particulate organic carbon, leading to enhanced microbial methanogenesis. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent organic carbon deposition controlled by glacioeustatic sea level variations. In the model, hydrate forms in sedimentsmore » with greater organic carbon content deposited during the penultimate glacial cycle (~120-240 ka). As a result, the model predictions match hydrate-bearing intervals detected in three sites drilled on the northern Gulf of Mexico continental slope, supporting the hypothesis of hydrate formation driven by enhanced organic carbon burial during glacial lowstands.« less

RH-temperature phase diagrams of hydrate forming deliquescent crystalline ingredients.

PubMed

Allan, Matthew; Mauer, Lisa J

2017-12-01

Several common deliquescent crystalline food ingredients (including glucose and citric acid) are capable of forming crystal hydrate structures. The propensity of such crystals to hydrate/dehydrate or deliquesce is dependent on the environmental temperature and relative humidity (RH). As an anhydrous crystal converts to a crystal hydrate, water molecules internalize into the crystal structure resulting in different physical properties. Deliquescence is a solid-to-solution phase transformation. RH-temperature phase diagrams of the food ingredients alpha-d-glucose and citric acid, along with sodium sulfate, were produced using established and newly developed methods. Each phase diagram included hydrate and anhydrate deliquescence boundaries, the anhydrate-hydrate phase boundary, and the peritectic temperature (above which the hydrate was no longer stable). This is the first report of RH-temperature phase diagrams of glucose and citric acid, information which is beneficial for selecting storage and processing conditions to promote or avoid hydrate formation or loss and/or deliquescence. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-situ visual observation for the formation and dissociation of methane hydrates in porous media by magnetic resonance imaging.

PubMed

Zhao, Jiafei; Lv, Qin; Li, Yanghui; Yang, Mingjun; Liu, Weiguo; Yao, Lei; Wang, Shenglong; Zhang, Yi; Song, Yongchen

2015-05-01

In this work, magnetic resonance imaging (MRI) was employed to observe the in-situ formation and dissociation of methane hydrates in porous media. Methane hydrate was formed in a high-pressure cell with controlled temperature, and then the hydrate was dissociated by thermal injection. The process was photographed by the MRI, and the pressure was recorded. The images confirmed that the direct visual observation was achieved; these were then employed to provide detailed information of the nucleation, growth, and decomposition of the hydrate. Moreover, the saturation of methane hydrate during the dissociation was obtained from the MRI intensity data. Our results showed that the hydrate saturation initially decreased rapidly, and then slowed down; this finding is in line with predictions based only on pressure. The study clearly showed that MRI is a useful technique to investigate the process of methane hydrate formation and dissociation in porous media. Copyright © 2015 Elsevier Inc. All rights reserved.

Elasticity and Stability of Clathrate Hydrate: Role of Guest Molecule Motions.

PubMed

Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

2017-05-02

Molecular dynamic simulations were performed to determine the elastic constants of carbon dioxide (CO 2 ) and methane (CH 4 ) hydrates at one hundred pressure-temperature data points, respectively. The conditions represent marine sediments and permafrost zones where gas hydrates occur. The shear modulus and Young's modulus of the CO 2 hydrate increase anomalously with increasing temperature, whereas those of the CH 4 hydrate decrease regularly with increase in temperature. We ascribe this anomaly to the kinetic behavior of the linear CO 2 molecule, especially those in the small cages. The cavity space of the cage limits free rotational motion of the CO 2 molecule at low temperature. With increase in temperature, the CO 2 molecule can rotate easily, and enhance the stability and rigidity of the CO 2 hydrate. Our work provides a key database for the elastic properties of gas hydrates, and molecular insights into stability changes of CO 2 hydrate from high temperature of ~5 °C to low decomposition temperature of ~-150 °C.

Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments

NASA Astrophysics Data System (ADS)

Shin, Donghoon; Cha, Minjun; Yang, Youjeong; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Ahn, Docheon; Im, Junhyuck; Lee, Yongjae; Han, Oc Hee; Yoon, Ji-Ho

2017-03-01

Understanding the stability of volatile species and their compounds under various surface and subsurface conditions is of great importance in gaining insights into the formation and evolution of planetary and satellite bodies. We report the experimental results of the temperature- and pressure-dependent structural transformation of methane hydrates in salt environments using in situ synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance, and Raman spectroscopy. We find that under pressurized and concentrated brine solutions methane hydrate forms a mixture of type I clathrate hydrate, ice, and hydrated salts. Under a low-pressure condition, however, the methane hydrates are decomposed through a rapid sublimation of water molecules from the surface of hydrate crystals, while NaCl · 2H2O undergoes a phase transition into a crystal growth of NaCl via the migration of salt ions. In ambient pressure conditions, the methane hydrate is fully decomposed in brine solutions at temperatures above 252 K, the eutectic point of NaCl · 2H2O.

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2005-01-01

The composition of methane hydrate, namely nW for CH 4??nWH2O, 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 nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O 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. ?? 2005 American Chemical Society.

Geologic implications of gas hydrates in the offshore of India: Krishna-Godavari Basin, Mahanadi Basin, Andaman Sea, Kerala-Konkan Basin

USGS Publications Warehouse

Kumar, Pushpendra; Collett, Timothy S.; Boswell, Ray; Cochran, James R.; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna; Yadav, U.S.

2014-01-01

NGHP-01 yielded evidence of gas hydrate from downhole log and core data obtained from all the sites in the Krishna–Godavari Basin, the Mahanadi Basin, and in the Andaman Sea. The site drilled in the Kerala–Konkan Basin during NGHP-01 did not yield any evidence of gas hydrate. Most of the downhole log-inferred gas hydrate and core-recovered gas hydrate were characterized as either fracture-filling in clay-dominated sediments or as pore-filling or grain-displacement particles disseminated in both fine- and coarse-grained sediments. Geochemical analyses of gases obtained from sediment cores recovered during NGHP-01 indicated that the gas in most all of the hydrates in the offshore of India is derived from microbial sources; only one site in the Andaman Sea exhibited limited evidence of a thermogenic gas source. The gas hydrate petroleum system concept has been used to effectively characterize the geologic controls on the occurrence of gas hydrates in the offshore of India.

Cyclic formation and dissociation of methane hydrate within partially water saturated sand

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Nakagawa, S.

2010-12-01

For partially water-saturated sediments, laboratory experiments have shown that methane hydrate forms heterogeneously within a sample at the core scale. The heterogeneous distribution of hydrate in combination with grain-scale hydrate location (eg. grain cementing, load bearing, and pore filling), determines the overall mechanical properties of hydrate-bearing sediments including shear strength and seismic properties. For this reason, understanding the heterogeneity of hydrate-bearing sample is essential when the bulk properties of the sample are examined in the laboratory. We present a series of laboratory methane hydrate formation and dissociation experiments with concurrent x-ray CT imaging and low-frequency (near 1 kHz) seismic measurements. The seismic measurements were conducted using a new acoustic resonant bar technique called the Split Hopkinson Resonant Bar method, which allows using a small sediment core (3.75 cm diameter, 7.5 cm length). The experiment was conducted using a jacketed, pre-compacted, fine-grain silica sand sample with a 40% distilled water saturation. Under isotropic confining stress of 6.9 MPa and a temperature 4 oC, the hydrate was formed in the sample by injecting pure methane gas at 5.6 MPa. Once the hydrate formed, it was dissociated by reducing the pore pressure to 2.8 MPa. This cycle was repeated by three times (dissociation test for the third cycle was not done) to examine the resulting changes in the hydrate distribution and seismic signatures. The repeated formation of hydrate resulted in significant changes in its distribution, which resulted in differences in the overall elastic properties of the sample, determined from the seismic measurements. Interestingly, the time intervals between the dissociation and subsequent formation of hydrate affected the rate of hydrate formation, shorter intervals resulting in faster formation. This memory effect, possibly caused by the presence of residual “seed crystals” in the pore water providing nucleation points for hydrate formation, did not result in rapid formation at all locations in the sample. In spite of heterogeneity, observed seismic properties were very similar for the two measurements during dissociation.

Methane Recovery from Hydrate-bearing Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Carlos Santamarina; Costas Tsouris

2011-04-30

Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations,more » and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with emphasis; (6) detailed study of CH4-CO2 exchange as a unique alternative to recover CH4 gas while sequestering CO2; (7) the relevance of fines in otherwise clean sand sediments on gas recovery and related phenomena such as fines migration and clogging, vuggy structure formation, and gas-driven fracture formation during gas production by depressurization.« less

Non-Destructive X-ray Computed Tomography (XCT) of Gas Hydrate Bearing Fractures in Marine Sediment

NASA Astrophysics Data System (ADS)

Oti, E.; Buchwalter, E.; Cook, A.; Crandall, D.

2017-12-01

Hydrate-filled fractures are found in many environments, both related to methane vents and constrained to lithologic layers; how hydrate filled fractures form in layered environments is not well understood. We focus on understanding hydrate origins and fracture formation by examining hydrate-bearing fractures in conventional cores taken from Gulf of Mexico sites from JIP Leg 1 and UT-GOM, Keathley Canyon 151. There are two main methane sources available for hydrate formation. The first is the hydrocarbon reservoir underlying the Gulf sediments. This reservoir formed when deeply buried organic matter of high molecular weight was exposed to high temperature and pressures and degraded. A second source is the biogenesis of organic material, which occurs when microbial activity breaks down organic materials. Biogenic methane is more enriched in lighter carbon isotopes as the reduction or fermentation reactions preferentially consume lighter carbon isotopes. As a result, we hypothesize that sediment surrounding biogenically derived methane will have heavier carbon isotopes when compared to non-host sediment, due to the consumption of the lighter carbon isotopes during methanogenesis. We use non-destructive X-ray Computed Tomography (XCT) scanning to visualize and identify hydrate-bearing fractures. The presence of hydrate fractures is further confirmed with a salinity analysis, as hydrate dissociation freshens the pore water and lowers the salinity. After hydrate fracture location is inferred, carbon isotope analysis is used to identify hydrocarbon source. XCT scans of Keathley Canyon core JIP-1 17H-4 revealed 10 total fractures, five of which XCT and salinity analysis indicated as formerly containing hydrate. All ten fractures, in addition to background sediment, underwent a carbon isotope analysis in which organic isotopes were measured. In the background sediment and the non hydrate-bearing fractures, DOC values were relatively light, with dC13 percentages ranging from -27.8% to -30.8%. In the five hydrate fracture regions, DOC was comparatively heavy, with DOC dC13 values ranging from -23.2% to -30.3%. These values suggest that biogenic methane was formed adjacent to the fracture and likely migrated into the hydrate filled fracture.

Origin Of Methane Gas And Migration Through The Gas Hydrate Stability Zone Beneath The Permafrost Zone

NASA Astrophysics Data System (ADS)

Uchida, T.; Waseda, A.; Namikawa, T.

2005-12-01

In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. Continuous downhole well log data as well as visible gas hydrates have confirmed pore-space hydrate as intergranular pore filling within sandy layers whose saturations are up to 80% in pore volume, but muddy sediments scarcely contain. Plenty of gas hydrate-bearing sand core samples have been obtained from the Mallik wells. According to grain size distributions pore-space hydrate is dominant in medium- to very fine-grained sandy strata. Methane gas accumulation and original pore space large enough to occur within host sediments may be required for forming highly saturated gas hydrate in pore system. The distribution of a porous and coarser-grained host rock should be one of the important factors to control the occurrence of gas hydrate, as well as physicochemical conditions. Subsequent analyses in sedimentology and geochemistry performed on gas hydrate-bearing sandy core samples also revealed important geologic and sedimentological controls on the formation and concentration of natural gas hydrate. This appears to be a similar mode for conventional oil and gas accumulations. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicate that highly saturated sands may have permeability of a few millidarcies. The isotopic data of methane show that hydrocarbon gas contained in gas hydrate is generated by thermogenic decomposition of kerogen in deep mature sediments. Based on geochemical and geological data, methane is inferred to migrate upward closely associated with pore water hundreds of meters into and through the hydrate stability zone partly up to the permafrost zone and the surface along faults and permeable sandy pathways. It should be remarked that there are many similar features in appearance and characteristics between the terrestrial and deep marine areas such as Nankai Trough with observations of well-interconnected and highly saturated pore-space hydrate.

Scientific objectives of the Gulf of Mexico gas hydrate JIP leg II drilling

USGS Publications Warehouse

Jones, Emrys; Latham, T.; McConnell, Daniel R.; Frye, Matthew; Hunt, J.H.; Shedd, William; Shelander, Dianna; Boswell, Ray; Rose, Kelly K.; Ruppel, Carolyn D.; Hutchinson, Deborah R.; Collett, Timothy S.; Dugan, Brandon; Wood, Warren T.

2008-01-01

The Gulf of Mexico Methane Hydrate Joint Industry Project (JIP) has been performing research on marine gas hydrates since 2001 and is sponsored by both the JIP members and the U.S. Department of Energy. In 2005, the JIP drilled the Atwater Valley and Keathley Canyon exploration blocks in the Gulf of Mexico to acquire downhole logs and recover cores in silt- and clay-dominated sediments interpreted to contain gas hydrate based on analysis of existing 3-D seismic data prior to drilling. The new 2007-2009 phase of logging and coring, which is described in this paper, will concentrate on gas hydrate-bearing sands in the Alaminos Canyon, Green Canyon, and Walker Ridge protraction areas. Locations were selected to target higher permeability, coarser-grained lithologies (e.g., sands) that have the potential for hosting high saturations of gas hydrate and to assist the U.S. Minerals Management Service with its assessment of gas hydrate resources in the Gulf of Mexico.This paper discusses the scientific objectives for drilling during the upcoming campaign and presents the results from analyzing existing seismic and well log data as part of the site selection process. Alaminos Canyon 818 has the most complete data set of the selected blocks, with both seismic data and comprehensive downhole log data consistent with the occurrence of gas hydrate-bearing sands. Preliminary analyses suggest that the Frio sandstone just above the base of the gas hydrate stability zone may have up to 80% of the available sediment pore space occupied by gas hydrate.The proposed sites in the Green Canyon and Walker Ridge areas are also interpreted to have gas hydrate-bearing sands near the base of the gas hydrate stability zone, but the choice of specific drill sites is not yet complete. The Green Canyon site coincides with a 4-way closure within a Pleistocene sand unit in an area of strong gas flux just south of the Sigsbee Escarpment. The Walker Ridge site is characterized by a sand-prone sedimentary section that rises stratigraphically across the base of the gas hydrate stability zone and that has seismic indicators of gas hydrate.

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with methane recycling, such as the formation of free gas zone, concentrated hydrate zone, bottom simulating reflector, and overpressured zone around the BHSZ, and gas venting at seafloor.

First determination of volume changes and enthalpies of the high-pressure decomposition reaction of the structure H methane hydrate to the cubic structure I methane hydrate and fluid methane.

PubMed

Ogienko, Andrey G; Tkacz, Marek; Manakov, Andrey Yu; Lipkowski, Janusz

2007-11-08

Pressure-temperature (P-T) conditions of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane were studied with a piston-cylinder apparatus at room temperature. For the first time, volume changes accompanying this reaction were determined. With the use of the Clausius-Clapeyron equation the enthalpies of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane have been calculated.

Theoretical study of gas hydrate decomposition kinetics: model predictions.

PubMed

Windmeier, Christoph; Oellrich, Lothar R

2013-11-27

In order to provide an estimate of intrinsic gas hydrate dissolution and dissociation kinetics, the Consecutive Desorption and Melting Model (CDM) was developed in a previous publication (Windmeier, C.; Oellrich, L. R. J. Phys. Chem. A 2013, 117, 10151-10161). In this work, an extensive summary of required model data is given. Obtained model predictions are discussed with respect to their temperature dependence as well as their significance for technically relevant areas of gas hydrate decomposition. As a result, an expression for determination of the intrinsic gas hydrate decomposition kinetics for various hydrate formers is given together with an estimate for the maximum possible rates of gas hydrate decomposition.

Potential role of gas hydrate decomposition in generating submarine slope failures: Chapter 12

USGS Publications Warehouse

Pauli, Charles K.; Ussler, William III; Dillon, William P.; Max, Michael D.

2003-01-01

Gas hydrate decomposition is hypothesized to be a factor in generating weakness in continental margin sediments that may help explain some of the observed patterns of continental margin sediment instability. The processes associated with formation and decomposition of gas hydrate can cause the strengthening of sediments in which gas hydrate grow and the weakening of sediments in which gas hydrate decomposes. The weakened sediments may form horizons along which the potential for sediment failure is increased. While a causal relationship between slope failures and gas hydrate decomposition has not been proven, a number of empirical observations support their potential connection.

Water dynamics in protein hydration shells: the molecular origins of the dynamical perturbation.

PubMed

Fogarty, Aoife C; Laage, Damien

2014-07-17

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra.

Water Dynamics in Protein Hydration Shells: The Molecular Origins of the Dynamical Perturbation

PubMed Central

2014-01-01

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra. PMID:24479585

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

PubMed

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-08-16

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

PubMed Central

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-01-01

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes. PMID:27526869

Gas hydrate characterization from a 3D seismic dataset in the deepwater eastern Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Daniel; Haneberg, William C.

Seismic stratigraphic features are delineated using principal component analysis of the band limited data at potential gas hydrate sands, and compared and calibrated with spectral decomposition thickness to constrain thickness in the absence of well control. Layers in the abyssal fan sediments are thinner than can be resolved with 50 Hz seismic and thus comprise composite thin-bed reflections. Amplitude vs frequency analysis are used to indicate gas and gas hydrate reflections. Synthetic seismic wedge models show that with 50Hz seismic data, a 40% saturation of a Plio Pleistocene GoM sand in the hydrate stability zone with no subjacent gas canmore » produce a phase change (negative to positive) with a strong correlation between amplitude and hydrate saturation. The synthetic seismic response is more complicated if the gas hydrate filled sediments overlie gassy sediments. Hydrate (or gas) saturation in thin beds enhances the amplitude response and can be used to estimate saturation. Gas hydrate saturation from rock physics, amplitude, and frequency analysis is compared to saturation derived from inversion at several interpreted gas hydrate accumulations in the eastern Gulf of Mexico.« less

Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

NASA Astrophysics Data System (ADS)

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

2016-08-01

Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

Gas hydrate prospecting using well cuttings and mud-gas geochemistry from 35 wells, North Slope, Alaska

USGS Publications Warehouse

Lorenson, T.D.; Collett, Timothy S.

2011-01-01

Gas hydrate deposits are common on the North Slope of Alaska around Prudhoe Bay; however, the extent of these deposits is unknown outside of this area. As part of a U.S. Geological Survey (USGS) and Bureau of Land Management gas hydrate research collaboration, well-cutting and mud-gas samples have been collected and analyzed from mainly industry-drilled wells on the North Slope for the purpose of prospecting for gas hydrate deposits. On the Alaska North Slope, gas hydrates are now recognized as an element within a petroleum systems approach or "total petroleum system." Since 1979, 35 wells have been sampled from as far west as Wainwright to Prudhoe Bay in the east. Regionally, the USGS has assessed the gas hydrate resources of the North Slope and determined that there is about 85.4 trillion cubic feet of technically recoverable hydrate-bound gas within three assessment units. The assessment units are defined mainly by three separate stratigraphic sections and constrained by the physical temperatures and pressures where gas hydrate can form. Geochemical studies of known gas hydrate occurrences on the North Slope have shown a link between gas hydrate and more deeply buried conventional oil and gas deposits. The link is established when hydrocarbon gases migrate from depth and charge the reservoir rock within the gas hydrate stability zone. It is likely gases migrated into conventional traps as free gas and were later converted to gas hydrate in response to climate cooling concurrent with permafrost formation. Results from this study indicate that some thermogenic gas is present in 31 of the wells, with limited evidence of thermogenic gas in four other wells and only one well with no thermogenic gas. Gas hydrate is known to occur in one of the sampled wells, likely present in 22 others on the basis of gas geochemistry, and inferred by equivocal gas geochemistry in 11 wells, and one well was without gas hydrate. Gas migration routes are common in the North Slope and include faults and widespread, continuous shallowly dipping permeable sand sections that are potentially in communication with deeper oil and gas sources. The application of the petroleum system model with the geochemical evidence suggests that gas hydrate deposits may be widespread across the North Slope of Alaska.

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

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.; Durham, W.B.; Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Ishii, Y.

2003-01-01

Structure I (sI) carbon dioxide (CO2) hydrate exhibits markedly different dissociation behavior from sI methane (CH4) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H2O melting point (273.15 K). The CO2 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 CO2 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 CO2??nH2O = CO2(g) + nH2O(1 to s) is measurably distinct from the pure H2O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH4 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 CO2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO2 hydrate was synthesized from CO2 liquid and H2O 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 ??m 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.

Growth of a Hydrate Mound in the Sea of Japan over 300 ka as Revealed by U-Th Ages of MDAC and by H2S Concentrations of Massive Hydrates

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Snyder, G. T.; Hiruta, A.; Kakizaki, Y.; Huang, C. Y.; Shen, C. C.

2017-12-01

The geological and geophysical exploration of gas hydrate in the Sea of Japan has revealed that hydrates occur as thick massive deposits within gas chimneys which often give rise to pingo-like hydrate mounds on the seafloor. We examine one case in which LWD has demonstrated anomalous profiles including both very low natural gamma ray (<10 API) and high acoustic velocities (2.5 to 3.5 km/s) extending down to 120mbsf, the base of gas hydrate stability (BGHS)[1]. Both conventional and pressure coring have confirmed thick, massive deposits of pure-gas hydrates. Hydrates in the shallow subsurface (< 20mbsf) are characterized by high H2S concentrations corresponding to AOM-induced production of HS-. The deeper hydrates generally have negligible amounts of H2S, with occasional exceptions in which H2S is moderately high. These observations lead us to conclude that both the re-equilibration and growth of hydrates in high CH4 and low to zero H2S conditions has continued during burial, and that this ongoing growth is an essential processes involved in the development of massive hydrates in the Sea of Japan.Regardless of depth, the Japan Sea gas hydrates are closely associated with 13-C depleted, methane-derived authigenic carbonates (MDACs). These MDACs are considered to have been formed at near-SMT depths as a response to increased alkalinity caused by AOM and, as such, MDACs are assumed to represent approximate paleo-seafloor at times of enhanced methane flux and intensive accumulation of gas hydrate in shallow subsurface. U-Th ages of MDACs collected from various depths in a mound-chimney system in central Joetsu Spur have revealed that the paleo-seafloor of 300 ka is presently situated at 30 to 55 mbsf within the gas chimney, in contrast to off-mound sites where it is situated at 100 mbsf. This suggests that at 300 ka the mound stood as a "hydrate-pingo" of 70 m high relative to the surrounding sea floor. At this time, the BGHS shoaled upwards 10m due to eustatic sea level fall, resulting in the dissociation of gas hydrates right above the BGHS and an enhancement of methane flux through the gas chimney. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI. Reference [1] Matsumoto et al. (2017), Fire in the Ice, 17, 1-6.

Hydration and Thermal Expansion in Anatase Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, He; Li, Qiang; Ren, Yang

A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

Cross Directorate Proposal: Nanostructured Materials for Munitions and Propellants-Production, Modeling, and Characterization

DTIC Science & Technology

2016-07-15

towards hydration and decomposition along with probing their hydration mechanisms, we are now exploring processing and deposition effects for this...oxidizer films and tested for their reactivity. Hydration Mechanism for HI3O8 → HIO3 Previous efforts by our group investigating the hydration ...mechanism of I2O5 → HI3O8 reflected that the hydration mechanism proceeded through a nucleation and growth process followed by a diffusion limited

Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manohara, G.V.; Vishnu Kamath, P., E-mail: vishnukamath8@hotmail.com; Milius, Wolfgang

2012-12-15

Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueousmore » exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.« less

Detection of gas hydrate with downhole logs and assessment of gas hydrate concentrations (saturations) and gas volumes on the Blake Ridge with electrical resistivity log data

USGS Publications Warehouse

Collett, T.S.; Ladd, J.

2000-01-01

Let 164 of the Ocean Drilling Program was designed to investigate the occurrence of gas hydrate in the sedimentary section beneath the Blake Ridge on the southeastern continental margin of North America. Site 994, and 997 were drilled on the Blake Ridge to refine our understanding of the in situ characteristics of natural gas hydrate. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas hydrate-bearing sediments. Downhole logging tool strings deployed on Leg 164 included the Schlumberger quad-combination tool (NGT, LSS/SDT, DIT, CNT-G, HLDT), the Formation MicroScanner (FMS), and the Geochemical Combination Tool (GST). Electrical resistivity (DIT) and acoustic transit-time (LSS/SDT) downhole logs from Sites 994, 995, and 997 indicate the presence of gas hydrate in the depth interval between 185 and 450 mbsf on the Blake Ridge. Electrical resistivity log calculations suggest that the gas hydrate-bearing sedimentary section on the Blake Ridge may contain between 2 and 11 percent bulk volume (vol%) gas hydrate. We have determined that the log-inferred gas hydrates and underlying free-gas accumulations on the Blake Ridge may contain as much as 57 trillion m3 of gas.

Gas hydrate volume estimations on the South Shetland continental margin, Antarctic Peninsula

USGS Publications Warehouse

Jin, Y.K.; Lee, M.W.; Kim, Y.; Nam, S.H.; Kim, K.J.

2003-01-01

Multi-channel seismic data acquired on the South Shetland margin, northern Antarctic Peninsula, show that Bottom Simulating Reflectors (BSRs) are widespread in the area, implying large volumes of gas hydrates. In order to estimate the volume of gas hydrate in the area, interval velocities were determined using a 1-D velocity inversion method and porosities were deduced from their relationship with sub-bottom depth for terrigenous sediments. Because data such as well logs are not available, we made two baseline models for the velocities and porosities of non-gas hydrate-bearing sediments in the area, considering the velocity jump observed at the shallow sub-bottom depth due to joint contributions of gas hydrate and a shallow unconformity. The difference between the results of the two models is not significant. The parameters used to estimate the total volume of gas hydrate in the study area were 145 km of total length of BSRs identified on seismic profiles, 350 m thickness and 15 km width of gas hydrate-bearing sediments, and 6.3% of the average volume gas hydrate concentration (based on the second baseline model). Assuming that gas hydrates exist only where BSRs are observed, the total volume of gas hydrates along the seismic profiles in the area is about 4.8 ?? 1010 m3 (7.7 ?? 1012 m3 volume of methane at standard temperature and pressure).

Morin hydrate augments phagocytosis mechanism and inhibits LPS induced autophagic signaling in murine macrophage.

PubMed

Jakhar, Rekha; Paul, Souren; Chauhan, Anil Kumar; Kang, Sun Chul

2014-10-01

Morin, a natural flavonoid that is the primary bioactive constituent of the family Moraceae, has been found to be associated with many therapeutic properties. In this study, we evaluated the immunomodulatory activities of increasing concentration of morin hydrate in vitro. Three different concentrations of morin hydrate (5, 10, and 15μM) were used to evaluate their effect on splenocyte proliferation, phagocytic activity of macrophages, cytokine secretion and complement inhibition. We also evaluated the role of morin hydrate on lipopolysaccharide (LPS) induced autophagy. Our study demonstrated that morin hydrate elicited a significant increase in splenocyte proliferation, phagocytic capacity and suppressed the production of cytokines and nitric oxide in activated macrophages. Humoral immunity measured by anti-complement activity showed an increase in inhibition of the complement system after the addition of morin hydrate, where morin hydrate at 15μM concentration induced a significant inhibition. Depending on our results, we can also conclude that morin hydrate protects macrophages from LPS induced autophagic cell death. Our findings suggest that morin hydrate represents a structurally diverse class of flavonoid and this structural variability can profoundly affect its cell-type specificity and its biological activities. Supplementation of immune cells with morin hydrate has an upregulating and immunoprotective effect that shows potential as a countermeasure to the immune dysfunction and suggests an interesting use in inflammation related diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer.

PubMed

Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S

2017-02-01

Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finley, P.D.; Krason, J.; Dominic, K.

Multichannel and selected single-channel seismic lines of the continental margin sediments of the Colombia basin display compelling evidence for large accumulations of natural gas hydrate. Seismic bottom simulating reflectors (BSRs), interpreted to mark the base of the hydrate stability zone, are pronounced and very widespread along the entire Panama-Colombia lower continental slope. BSRs have also been identified at two locations on the abyssal plain. Water depths for these suspected hydrate occurrences range from 900 to 4000 m. Although no gas hydrate samples have been recovered from this area, biogenic methane is abundant in Pliocene turbidites underlying the abyssal plain. Moremore » deeply buried rocks beneath the abyssal plain are thermally mature. Thermogenic gas from these rocks may migrate upward along structural pathways into the hydrate stability zone and form hydrate. Impermeable hydrate layers may form caps over large accumulations of free gas, accounting for the very well-defined BSRs in the area. The abyssal plain and the deformed continental margin hold the highest potential for major economic accumulations of gas hydrate in the basin. The extensive continuity of BSRs, relatively shallow water depths, and promixity to onshore production facilities render the marginal deformed belt sediments the most favorable target for future economic development of the gas hydrate resource within the Colombia basin. The widespread evidence of gas hydrates in the Colombia basin suggests a high potential for conventional hydrocarbon deposits offshore of Panama and Colombia.« less

High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer

NASA Astrophysics Data System (ADS)

Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S.

2017-02-01

Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

PubMed

Rayne, Sierra; Forest, Kaya

2016-01-01

The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds.

Raman studies of methane-ethane hydrate metastability.

PubMed

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-01

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

NASA Technical Reports Server (NTRS)

Blake, D. F.; Allamandola, L. J.; Sandford, S. A.; Freund, F.

1991-01-01

The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K.

Microscopic Origin of Strain Hardening in Methane Hydrate

PubMed Central

Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

2016-01-01

It has been reported for a long time that methane hydrate presents strain hardening, whereas the strength of normal ice weakens with increasing strain after an ultimate strength. However, the microscopic origin of these differences is not known. Here, we investigated the mechanical characteristics of methane hydrate and normal ice by compressive deformation test using molecular dynamics simulations. It is shown that methane hydrate exhibits strain hardening only if the hydrate is confined to a certain finite cross-sectional area that is normal to the compression direction. For normal ice, it does not present strain hardening under the same conditions. We show that hydrate guest methane molecules exhibit no long-distance diffusion when confined to a finite-size area. They appear to serve as non-deformable units that prevent hydrate structure failure, and thus are responsible for the strain-hardening phenomenon. PMID:27009239

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.

PubMed

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-06

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Oceanic methane hydrate: The character of the Blake Ridge hydrate stability zone, and the potential for methane extraction

USGS Publications Warehouse

Max, M.D.; Dillon, William P.

1998-01-01

Oceanic methane hydrates are mineral deposits formed from a crystalline 'ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by 'freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.Oceanic methane hydrates are mineral sits formed from a crystalline `ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by `freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.

A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2012-12-01

The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, nonaqueous liquid, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulations that predict the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. The phase equilibria for the ternary gas hydrate system within the gas hydrate stability range of composition, temperature and pressure, includes regions where the gas hydrate is in equilibrium with gas, nonaqueous liquid, or mixtures of gas and nonaqeuous liquid near the CO2-CH4-N2 mixture critical point. In these regions, solutions to cubic equations of state can be nonconvergent without accurate initial guesses. A hybrid tabular-cubic equation of state is described which avoids convergence issues, but conserves the characteristics and advantages of the cubic equation of state approaches to phase equilibria calculations. The application of interest will be the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

Electrical properties of methane hydrate + sediment mixtures: The σ of CH 4 Hydrate + Sediment

DOE PAGES

Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; ...

2015-07-30

Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. We built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EMmore » field surveys. We report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. Finally, these results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.« less

3-D basin-scale reconstruction of natural gas hydrate system of the Green Canyon, Gulf of Mexico

NASA Astrophysics Data System (ADS)

Burwicz, Ewa; Reichel, Thomas; Wallmann, Klaus; Rottke, Wolf; Haeckel, Matthias; Hensen, Christian

2017-05-01

Our study presents a basin-scale 3-D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin reconstruction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics, and associated multistage fault development. The resulting 3-D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (>80 vol %) at the base of the gas hydrate stability zone (GHSZ) is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intrasalt minibasins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upward to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ˜3256 Mt of gas hydrate, which is equivalent to ˜340 Mt of carbon (˜7 × 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Optical coherence tomography of the effects of stromal hydration on clear corneal incision architecture.

PubMed

Calladine, Daniel; Tanner, Vaughan

2009-08-01

To evaluate the effects of stromal hydration on clear corneal incision (CCI) architecture immediately after surgery using anterior segment optical coherence tomography (AS-OCT). Department of Ophthalmology, Royal Berkshire Hospital, Reading, United Kingdom. Clear corneal incisions in adult eyes were examined using a Visante AS-OCT imaging system within 1 hour of surgery. Half the CCIs had stromal hydration with a balanced salt solution and half did not. Incisions were made with a 2.75 mm steel keratome. Intraocular pressure (IOP) was measured within 90 minutes after surgery. The CCI length and corneal thickness at the CCI site were measured using software built into the AS-OCT system. Thirty CCIs were evaluated. Stromal hydration significantly increased the measured CCI length (P<.05, t test); this was the result of a trend toward increased corneal thickness at the CCI site with hydration (P<.1, t test). The mean CCI length was 1.69 mm +/- 0.27 (SD) (range 1.31 to 2.32 mm) with hydration and 1.51 +/- 0.23 mm (range 1.30 to 1.95 mm) without hydration. The mean IOP was 20.9 +/- 8.18 mm Hg and 15.8 +/- 8.20 mm Hg, respectively. The IOP tended to be higher with hydration (P<.1, t test). Local detachment of Descemet membrane was more likely with stromal hydration (63%) than without (25%). Stromal hydration significantly increased CCI length and tended to leave the eye with a higher early postoperative IOP, showing the importance of taking stromal hydration into account when designing similar OCT studies of CCI architecture.

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

USGS Publications Warehouse

Stern, L.A.; Hogenboom, D.L.; Durham, W.B.; Kirby, S.H.; Chou, I.-Ming

1998-01-01

We previously reported indirect but compelling evidence that fine-grained H2O ice under elevated CH4 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 H2O 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 H2O 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 CO2 as the hydrate-forming species demonstrated that this superheating effect is not unique to the CH4-H2O system.

Reflective terahertz (THz) imaging: system calibration using hydration phantoms

NASA Astrophysics Data System (ADS)

Bajwa, Neha; Garritano, James; Lee, Yoon Kyung; Tewari, Priyamvada; Sung, Shijun; Maccabi, Ashkan; Nowroozi, Bryan; Babakhanian, Meghedi; Sanghvi, Sajan; Singh, Rahul; Grundfest, Warren; Taylor, Zachary

2013-02-01

Terahertz (THz) hydration sensing continues to gain traction in the medical imaging community due to its unparalleled sensitivity to tissue water content. Rapid and accurate detection of fluid shifts following induction of thermal skin burns as well as remote corneal hydration sensing have been previously demonstrated in vivo using reflective, pulsed THz imaging. The hydration contrast sensing capabilities of this technology were recently confirmed in a parallel 7 Tesla Magnetic Resonance (MR) imaging study, in which burn areas are associated with increases in local mobile water content. Successful clinical translation of THz sensing, however, still requires quantitative assessments of system performance measurements, specifically hydration concentration sensitivity, with tissue substitutes. This research aims to calibrate the sensitivity of a novel, reflective THz system to tissue water content through the use of hydration phantoms for quantitative comparisons of THz hydration imagery.Gelatin phantoms were identified as an appropriate tissue-mimicking model for reflective THz applications, and gel composition, comprising mixtures of water and protein, was varied between 83% to 95% hydration, a physiologically relevant range. A comparison of four series of gelatin phantom studies demonstrated a positive linear relationship between THz reflectivity and water concentration, with statistically significant hydration sensitivities (p < .01) ranging between 0.0209 - 0.038% (reflectivity: %hydration). The THz-phantom interaction is simulated with a three-layer model using the Transfer Matrix Method with agreement in hydration trends. Having demonstrated the ability to accurately and noninvasively measure water content in tissue equivalent targets with high sensitivity, reflective THz imaging is explored as a potential tool for early detection and intervention of corneal pathologies.

Electrical properties of methane hydrate + sediment mixtures: The σ of CH 4 Hydrate + Sediment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven

Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. We built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EMmore » field surveys. We report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. Finally, these results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.« less

Widespread gas hydrate instability on the upper U.S. Beaufort margin

NASA Astrophysics Data System (ADS)

Phrampus, Benjamin J.; Hornbach, Matthew J.; Ruppel, Carolyn D.; Hart, Patrick E.

2014-12-01

The most climate-sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three-dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5-7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.

Archie's Saturation Exponent for Natural Gas Hydrate in Coarse-Grained Reservoirs

NASA Astrophysics Data System (ADS)

Cook, Ann E.; Waite, William F.

2018-03-01

Accurately quantifying the amount of naturally occurring gas hydrate in marine and permafrost environments is important for assessing its resource potential and understanding the role of gas hydrate in the global carbon cycle. Electrical resistivity well logs are often used to calculate gas hydrate saturations, Sh, using Archie's equation. Archie's equation, in turn, relies on an empirical saturation parameter, n. Though n = 1.9 has been measured for ice-bearing sands and is widely used within the hydrate community, it is highly questionable if this n value is appropriate for hydrate-bearing sands. In this work, we calibrate n for hydrate-bearing sands from the Canadian permafrost gas hydrate research well, Mallik 5L-38, by establishing an independent downhole Sh profile based on compressional-wave velocity log data. Using the independently determined Sh profile and colocated electrical resistivity and bulk density logs, Archie's saturation equation is solved for n, and uncertainty is tracked throughout the iterative process. In addition to the Mallik 5L-38 well, we also apply this method to two marine, coarse-grained reservoirs from the northern Gulf of Mexico Gas Hydrate Joint Industry Project: Walker Ridge 313-H and Green Canyon 955-H. All locations yield similar results, each suggesting n ≈ 2.5 ± 0.5. Thus, for the coarse-grained hydrate bearing (Sh > 0.4) of greatest interest as potential energy resources, we suggest that n = 2.5 ± 0.5 should be applied in Archie's equation for either marine or permafrost gas hydrate settings if independent estimates of n are not available.

Gas Hydrates as a CH4 Source and a CO2 Sink: New Approaches Based on Fundamental Research

NASA Astrophysics Data System (ADS)

Schicks, J. M.; Spangenberg, E.; Erzinger, J.

2007-12-01

The huge amount of methane, stored in the gas hydrate reservoirs of the world suggests that natural gas hydrates may be used in the future as a source of energy. A first production test was performed during the Mallik 2002 Gas Hydrate Production Research Well Program, showing that the thermal stimulation of natural gas hydrates successfully results in methane production (Dallimore et al. 2005). However, regarding the energy balance, the most efficient method for methane production from hydrates still needs to be developed. From another point of view, the sequestration of CO2 in form of gas hydrates in (marine) sediments is an interesting idea. A combination of methane production from natural gas hydrates on the one hand and CO2 - sequestration on the other hand seems to be an obvious and ideal solution. Different studies on possible methods - e.g. the exchange of CH4 with CO2 in gas hydrates (Lee et al, 2003, Graue and Kvamme, 2006) - have been published recently and demonstrated that this could be a possible way, in principle. Our own investigations on the exchange of CH4 with gaseous CO2 showed that this reaction is much too slow and inefficient to be a reasonable approach. The exchange of only 20 percent CH4 with CO2 could be detected in stable structure I hydrate crystals after 120 hours. In addition, multicomponent hydrates containing higher hydrocarbons beside methane tend to be more stable than pure methane hydrates (Schicks et al, 2006). Therefore, the application of an additional and controlled method for CH4 -hydrate destabilization seems to be necessary and might lead to an efficient release of CH4 from and CO2 inclusion into hydrates. In any case, the question of process optimization still remains. In this contribution the chances and challenges of a combination of these two processes based on experimental data will be examined. Different kinds of experiments have been performed on natural marine and permafrost gas hydrates and synthesized clathrate hydrates: Differential scanning calorimetric measurements for the determination of the specific enthalpy of dissociation, determination of stability fields for pure and multicomponent systems, CH4 - CO2 -exchange reaction in clathrate hydrates and CO2 -hydrate formation in sediments under different pressure and temperature conditions were studied. Based on these fundamental data, new concepts for methane production and combined CO2 - sequestration will be presented and discussed. Reference: S.R. Dallimore, T.S. Collet (Eds.), 2005. Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program, Mackenzie Delta, Northwest Territories, Canada, Geological Survey of Canada, WO H. Lee, Y. Seo, Y.-T. Seo, I.L. Moudrakovski, J.A. Ripmeester, 2003. Angewandte Chemie International Edition, 42, 5049-5051 A. Graue, B. Kvamme, 2006. Conference Paper presented at the Offshore Technology Conference in Houston, Texas, U.S.A., 1-4 May 2006 J.M. Schicks, R. Naumann, J. Erzinger, K.C. Hester, Caroly A. Koh, E.D. Sloan, 2006. Journal of Physical Chemistry, 110, 11468-11474

Using NMR to Probe the Regio- and Stereochemistry of the Hydration of 1-Hexene

ERIC Educational Resources Information Center

Saba, Shahrokh; Clarke, Donald D.; Iwanoski, Christa; Lobasso, Thomas

2010-01-01

This undergraduate organic laboratory experiment complements previously described and popular experiments on hydration of 1-hexene where students experimentally establish the Markovnikov regioselectivity of alkene hydration. In this experiment, students explore not only the regiochemistry but also the stereochemistry of 1-hexene hydration and…

21 CFR 522.380 - Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Chloral hydrate, pentobarbital, and magnesium... INJECTABLE DOSAGE FORM NEW ANIMAL DRUGS § 522.380 Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution. (a) [Reserved] (b)(1) Specifications. Chloral hydrate, pentobarbital, and...

21 CFR 522.380 - Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Chloral hydrate, pentobarbital, and magnesium... INJECTABLE DOSAGE FORM NEW ANIMAL DRUGS § 522.380 Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution. (a) [Reserved] (b)(1) Specifications. Chloral hydrate, pentobarbital, and...

21 CFR 522.380 - Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Chloral hydrate, pentobarbital, and magnesium... INJECTABLE DOSAGE FORM NEW ANIMAL DRUGS § 522.380 Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution. (a) [Reserved] (b)(1) Specifications. Chloral hydrate, pentobarbital, and...

21 CFR 522.380 - Chloral hydrate, pentobarbital, and magnesium sulfate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Chloral hydrate, pentobarbital, and magnesium... FORM NEW ANIMAL DRUGS § 522.380 Chloral hydrate, pentobarbital, and magnesium sulfate. (a) Specifications. Each milliliter of solution contains 42.5 milligrams (mg) of chloral hydrate, 8.86 mg of...

21 CFR 522.380 - Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Chloral hydrate, pentobarbital, and magnesium... INJECTABLE DOSAGE FORM NEW ANIMAL DRUGS § 522.380 Chloral hydrate, pentobarbital, and magnesium sulfate sterile aqueous solution. (a) [Reserved] (b)(1) Specifications. Chloral hydrate, pentobarbital, and...

Method for the photocatalytic conversion of gas hydrates

DOEpatents

Taylor, Charles E.; Noceti, Richard P.; Bockrath, Bradley C.

2001-01-01

A method for converting methane hydrates to methanol, as well as hydrogen, through exposure to light. The process includes conversion of methane hydrates by light where a radical initiator has been added, and may be modified to include the conversion of methane hydrates with light where a photocatalyst doped by a suitable metal and an electron transfer agent to produce methanol and hydrogen. The present invention operates at temperatures below 0.degree. C., and allows for the direct conversion of methane contained within the hydrate in situ.

Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

1995-01-01

Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

NASA Technical Reports Server (NTRS)

Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

1995-01-01

Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

Water Dynamics in the Hydration Shells of Biomolecules

PubMed Central

2017-01-01

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

Final Project Report - Revised Version

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, Manika; Carolyn, Koh

An over-arching goal of this research is to calibrate geophysical techniques for hydrate exploration, evaluation, and production monitoring. Extensive field data of hydrate-bearing sediments exist, but quantitative estimates of the amount and distribution of hydrates are difficult to determine. Thus, the primary project objectives were to relate seismic and acoustic velocities and attenuations to hydrate saturation and texture. The project aimed to collect seismic properties along with other measurements (e.g., complex resistivity, micro-focus x-ray computed tomography, etc.). The multiphysics dataset would enable researchers to understand not only the interaction between mineral surfaces and gas hydrates, but also how the hydratemore » formation method affects the hydrate-sediment system in terms of elastic properties.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

M. D. White; B. P. McGrail; S. K. Wurstner

Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to poremore » clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.« less

Influence of surfactants on gas-hydrate formation' kinetics in water-oil emulsion

NASA Astrophysics Data System (ADS)

Zemenkov, Yu D.; Shirshova, A. V.; Arinstein, E. A.; Shuvaev, A. N.

2018-05-01

The kinetics of gas hydrate formation of propane in a water-oil emulsion is experimentally studied when three types of surfactants (SAA (surface acting agent)) - anionic type emulsifiers - are added to the aqueous phase. It is shown that all three types of surfactants decelerate the growth of the gas-hydrate in the emulsion and can be considered as anti-agglutinating and kinetic low-dose inhibitors. The most effective inhibitor of hydrate formation in water-oil emulsion of SV-102 surfactant was revealed. For comparison, experimental studies of gas-hydrate formation under the same conditions for bulk water have been carried out. It is shown that in bulk water, all the surfactants investigated act as promoters (accelerators) of hydrate formation. A qualitative explanation of the action mechanisms of emulsifiers in the process of gas-hydrate formation in water-oil emulsion is given.

Downhole well log and core montages from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Collett, T.S.; Lewis, R.E.; Winters, W.J.; Lee, M.W.; Rose, K.K.; Boswell, R.M.

2011-01-01

The BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well was an integral part of an ongoing project to determine the future energy resource potential of gas hydrates on the Alaska North Slope. As part of this effort, the Mount Elbert well included an advanced downhole geophysical logging program. Because gas hydrate is unstable at ground surface pressure and temperature conditions, a major emphasis was placed on the downhole-logging program to determine the occurrence of gas hydrates and the in-situ physical properties of the sediments. In support of this effort, well-log and core data montages have been compiled which include downhole log and core-data obtained from the gas-hydrate-bearing sedimentary section in the Mount Elbert well. Also shown are numerous reservoir parameters, including gas-hydrate saturation and sediment porosity log traces calculated from available downhole well log and core data. ?? 2010.

Effect of hydration treatments on laryngeal nodules and polyps and related voice measures.

PubMed

Verdolini-Marston, K; Sandage, M; Titze, I R

1994-03-01

In this study, a double-blind, placebo-controlled approach was used in assessing the effectiveness of hydration treatments in the clinical management of selected voice disorders. Six adult female patients with laryngeal nodules or polyps each received 5 consecutive days of hydration treatment and 5 consecutive days of placebo/control treatment. The combined results indicated improvements in voice and in laryngeal appearance following both placebo/control and hydration treatments as compared with baseline. However, the greatest improvements were obtained following the hydration treatment. Although caution about generalization of the effects to the typical clinical situation is emphasized, the study provides preliminary evidence of a therapeutic benefit from hydration treatments in patients with nodules or polyps. Based on previous theoretical work, hydration effects may be related to reductions in the viscosity of vocal fold tissue, although other explanations are also possible.

Gas hydrate dissociation off Svalbard induced by isostatic rebound rather than global warming.

PubMed

Wallmann, Klaus; Riedel, M; Hong, W L; Patton, H; Hubbard, A; Pape, T; Hsu, C W; Schmidt, C; Johnson, J E; Torres, M E; Andreassen, K; Berndt, C; Bohrmann, G

2018-01-08

Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

Glacigenic sedimentation pulses triggered post-glacial gas hydrate dissociation.

PubMed

Karstens, Jens; Haflidason, Haflidi; Becker, Lukas W M; Berndt, Christian; Rüpke, Lars; Planke, Sverre; Liebetrau, Volker; Schmidt, Mark; Mienert, Jürgen

2018-02-12

Large amounts of methane are stored in continental margins as gas hydrates. They are stable under high pressure and low, but react sensitively to environmental changes. Bottom water temperature and sea level changes were considered as main contributors to gas hydrate dynamics after the last glaciation. However, here we show with numerical simulations that pulses of increased sedimentation dominantly controlled hydrate stability during the end of the last glaciation offshore mid-Norway. Sedimentation pulses triggered widespread gas hydrate dissociation and explains the formation of ubiquitous blowout pipes in water depths of 600 to 800 m. Maximum gas hydrate dissociation correlates spatially and temporally with the formation or reactivation of pockmarks, which is constrained by radiocarbon dating of Isorropodon nyeggaensis bivalve shells. Our results highlight that rapid changes of sedimentation can have a strong impact on gas hydrate systems affecting fluid flow and gas seepage activity, slope stability and the carbon cycle.

Rapid gas hydrate formation process

DOEpatents

Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

2013-01-15

The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

Fundamentals and applications of gas hydrates.

PubMed

Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

2011-01-01

Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties.

In situ thermal conductivity of gas-hydrate-bearing sediments of the Mallik 5L-38 well

NASA Astrophysics Data System (ADS)

Henninges, J.; Huenges, E.; Burkhardt, H.

2005-11-01

Detailed knowledge about thermal properties of rocks containing gas hydrate is required in order to quantify processes involving gas hydrate formation and decomposition in nature. In the framework of the Mallik 2002 program, three wells penetrating a continental gas hydrate occurrence under permafrost were successfully equipped with permanent fiber-optic distributed temperature sensing cables. Temperature data were collected over a 21-month period after completing the wells. Thermal conductivity profiles were calculated from the geothermal data as well as from a petrophysical model derived from the available logging data and application of mixing law models. Results indicate that thermal conductivity variations are mainly lithologically controlled with a minor influence from hydrate saturation. Average thermal conductivity values of the hydrate-bearing sediments range between 2.35 and 2.77 W m-1 K-1. Maximum gas hydrate saturations can reach up to about 90% at an average porosity of 0.3.

The effect of hydrate content on seismic attenuation: A case study for Mallik 2L-38 well data, Mackenzie delta, Canada

NASA Astrophysics Data System (ADS)

Chand, Shyam; Minshull, Tim A.

2004-07-01

Observations of velocities in sediments containing gas hydrates show that the strength of sediments increases with hydrate saturation. Hence it is expected that the attenuation of these sediments will decrease with increasing hydrate saturation. However, sonic log measurements in the Mallik 2L-38 well and cross hole tomography measurements in the Mallik field have shown that attenuation increases with hydrate saturation. We studied a range of mechanisms by which increasing hydrate saturation could cause increased attenuation. We found that a difference in permeability between the host sediment and the newly formed hydrate can produce the observed effect. We modelled attenuation in terms of Biot and squirt flow mechanisms in composite media. We have used our model to predict observed attenuations in the Mallik 2L-38 well, Mackenzie Delta, Canada.

Gas processing developments. Why not use methanol for hydrate control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nielsen, R.B.; Bucklin, R.W.

1983-04-01

Hydrate formation in turboexpander plants can be avoided more economically by using methanol than by using solid bed dehydration. Although the first turboexpander plant used methanol, most expander installations now have used solid bed dehydration. The reasons are obscure, since methanol often grants greater ease of operation as well as lower capital and operating costs, especially when the water in the feed gas is low or when recompression is required. Natural gas generally contains water before processing. High pressure, low temperature, or both favor the combination of water with light gases to form hydrates. Free water always must be presentmore » for hydrates to form. Hydrates cause problems by plugging pipelines, valves, and other process equipment. Therefore, proper equipment design requires accurate prediction of the limiting conditions at which hydrates are formed anytime a gas stream containing hydrate formers and free water is cooled below 80 F. (16 refs.)« less

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in sI methane hydrate

USGS Publications Warehouse

Waite, W.F.; Stern, L.A.; Kirby, S.H.; Winters, W.J.; Mason, D.H.

2007-01-01

Thermal conductivity, thermal diffusivity and specific heat of sI methane hydrate were measured as functions of temperature and pressure using a needle probe technique. The temperature dependence was measured between −20°C and 17°C at 31.5 MPa. The pressure dependence was measured between 31.5 and 102 MPa at 14.4°C. Only weak temperature and pressure dependencies were observed. Methane hydrate thermal conductivity differs from that of water by less than 10 per cent, too little to provide a sensitive measure of hydrate content in water-saturated systems. Thermal diffusivity of methane hydrate is more than twice that of water, however, and its specific heat is about half that of water. Thus, when drilling into or through hydrate-rich sediment, heat from the borehole can raise the formation temperature more than 20 per cent faster than if the formation's pore space contains only water. Thermal properties of methane hydrate should be considered in safety and economic assessments of hydrate-bearing sediment.

Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

USGS Publications Warehouse

Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

2014-01-01

One of the specific objectives of this expedition was to test gas hydrate formation models and constrain model parameters, especially those that account for the formation of concentrated gas hydrate accumulations. The necessary data for characterizing the occurrence of in situ gas hydrate, such as interstitial water chlorinities, core-derived gas chemistry, physical and sedimentological properties, thermal images of the recovered cores, and downhole measured logging data (LWD and/or conventional wireline log data), were obtained from most of the drill sites established during NGHP-01. Almost all of 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 drilled during NGHP-01 indicate that the occurrence of concentrated gas hydrate is mostly associated with the presence of fractures in the sediments, and in some limited cases, by coarser grained (mostly sand-rich) sediments.

Hydration kinetics of CA{sub 2} and CA-Investigations performed on a synthetic calcium aluminate cement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klaus, S.R., E-mail: klaus@geol.uni-erlangen.de; Neubauer, J., E-mail: juergen.neubauer@gzn.uni-erlangen.de; Goetz-Neunhoeffer, F., E-mail: friedlinde.goetz@gzn.uni-erlangen.de

2013-01-15

Much is already known about the hydration of monocalcium aluminate (CA) in calcium aluminate cements (CACs). CA{sub 2} is known to be weakly hydraulic. Therefore, the hydration kinetics of CA{sub 2} were not of as great interest as those of the hydration of CAC. We were able to show that the hydration of CA{sub 2} begins as soon as the hydration rate of CA has reached its maximum and the first precipitation of C{sub 2}AH{sub 8} has started. The hydration of different CA/CA{sub 2} ratios was analyzed by the G-factor quantification. The individual contributions of the phases CA and CA{submore » 2} to the heat flow were calculated based on the amounts dissolved by applying thermodynamic data. The heat flow as calculated from XRD data was then compared with the measured heat flow. It obtained a good consistency between the two. The very pronounced influence of CA{sub 2} during hydration of CAC can be clearly demonstrated.« less

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radha, S.; Milius, Wolfgang; Breu, Josef, E-mail: josef.breu@uni-bayreuth.de

2013-08-15

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacingmore » evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.« less

Controlled formation of cyclopentane hydrate suspensions via capillary-driven jet break-up

NASA Astrophysics Data System (ADS)

Geri, Michela; McKinley, Gareth

2017-11-01

Clathrate hydrates are crystalline compounds that form when a lattice of hydrogen-bonded water molecules is filled by guest molecules sequestered from an adjacent gas or liquid phase. Being able to rapidly produce and transport synthetic hydrates is of great interest given their significant potential as a clean energy source and safe option for hydrogen storage. We propose a new method to rapidly produce cyclopentane hydrate suspensions at ambient pressure with tunable particle size distribution by taking advantage of the Rayleigh-Plateau instability to form a mono-disperse stream of droplets during the controlled break-up of a water jet. The droplets are immediately frozen into ice particles through immersion in a subcooled reservoir and converted into hydrates with a dramatic reduction in the nucleation induction time. By measuring the evolution of the rheological properties with time, we monitor the process of hydrates formation via surface crystallization and agglomeration with different droplet size distributions. This new method enables us to gain new insights into hydrate formation and transport which was previously hindered by uncontrolled droplet formation and hydrate nucleation processes. MITei Chevron Fellowship.

Hydration rate of obsidian.

PubMed

Friedman, I; Long, W

1976-01-30

The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

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

USGS Publications Warehouse

Waite, W.F.; Kneafsey, T.J.; Winters, W.J.; Mason, D.H.

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X– ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

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

USGS Publications Warehouse

Waite, W.F.; Kneafsey, T.J.; Winters, W.J.; Mason, D.H.

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X-ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

Effect of a new moisturizing lotion on immediate and cumulative skin hydration: Two randomized, intra-individual, vehicle- and comparator-controlled studies.

PubMed

Nogueira, Alessandra; Sidou, Farzaneh; Brocard, Sylvie

2011-08-01

Moisturizers increase skin hydration and can serve as adjunctive care in dermatologic conditions such as xerosis, psoriasis vulgaris, atopic dermatitis and ichthyosis, in which dry skin is implicated. A non-irritating hydrating lotion (CDA lotion) was recently developed. We assessed the effect of CDA lotion on skin hydration in two randomized, evaluator-blind and intra-individual comparison studies. After a single application, CDA lotion induced significantly greater hydration than the non-treated control for at least 24 hours (p < 0.001). After 4 days of twice-daily application, compared with the non-treated control, CDA lotion induced significantly greater skin hydration up to 3 days after treatment cessation (p < 0.05) and significant improvement in the clinical skin dryness score up to 7 days after treatment cessation (p < 0.05). The immediate and cumulative hydration effects of CDA lotion were also compared to those of several currently available moisturizing products. In summary, application of CDA lotion increases skin hydration and alleviates the condition of skin dryness.

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Phase diagram and high-pressure boundary of hydrate formation in the ethane-water system.

PubMed

Kurnosov, Alexander V; Ogienko, Andrey G; Goryainov, Sergei V; Larionov, Eduard G; Manakov, Andrey Y; Lihacheva, Anna Y; Aladko, Eugeny Y; Zhurko, Fridrikh V; Voronin, Vladimir I; Berger, Ivan F; Ancharov, Aleksei I

2006-11-02

Dissociation temperatures of gas hydrate formed in the ethane-water system were studied at pressures up to 1500 MPa. In situ neutron diffraction analysis and X-ray diffraction analysis in a diamond anvil cell showed that the gas hydrate formed in the ethane-water system at 340, 700, and 1840 MPa and room temperature belongs to the cubic structure I (CS-I). Raman spectra of C-C vibrations of ethane molecules in the hydrate phase, as well as the spectra of solid and liquid ethane under high-pressure conditions were studied at pressures up to 6900 MPa. Within 170-3600 MPa Raman shift of the C-C vibration mode of ethane in the hydrate phase did not show any discontinuities, which could be evidence of possible phase transformations. The upper pressure boundary of high-pressure hydrate existence was discovered at the pressure of 3600 MPa. This boundary corresponds to decomposition of the hydrate to solid ethane and ice VII. The type of phase diagram of ethane-water system was proposed in the pressure range of hydrate formation (0-3600 MPa).

Traditional Portland cement and MgO-based cement: a promising combination?

NASA Astrophysics Data System (ADS)

Tonelli, Monica; Martini, Francesca; Calucci, Lucia; Geppi, Marco; Borsacchi, Silvia; Ridi, Francesca

2017-06-01

MgO/SiO2 cements are materials potentially very useful for radioactive waste disposal, but knowledge about their physico-chemical properties is still lacking. In this paper we investigated the hydration kinetics of cementitious formulations prepared by mixing MgO/SiO2 and Portland cement in different proportions and the structural properties of the hydrated phases formed in the first month of hydration. In particular, the hydration kinetics was investigated by measuring the free water index on pastes by means of differential scanning calorimetry, while the structural characterization was carried out by combining thermal (DTA), diffractometric (XRD), and spectroscopic (FTIR, 29Si solid state NMR) techniques. It was found that calcium silicate hydrate (C-S-H) and magnesium silicate hydrate (M-S-H) gels mainly form as separate phases, their relative amount and structural characteristics depending on the composition of the hydrated mixture. Moreover, the composition of the mixtures strongly affects the kinetics of hydration and the pH of the aqueous phase in contact with the cementitious materials. The results here reported show that suitable mixtures of Portland cement and MgO/SiO2 could be used to modify the properties of hydrated phases with potential application in the storage of nuclear waste in clayey disposal.

Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

PubMed

Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

2009-04-23

In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

Assessment of corneal hydration sensing in the terahertz band: in vivo results at 100 GHz

PubMed Central

Taylor, Zachary; Tewari, Pria; Sung, Shijun; Maccabi, Ashkan; Singh, Rahul; Culjat, Martin; Grundfest, Warren; Hubschman, Jean-Pierre; Brown, Elliott

2012-01-01

Abstract. Terahertz corneal hydration sensing has shown promise in ophthalmology applications and was recently shown to be capable of detecting water concentration changes of about two parts in a thousand in ex vivo corneal tissues. This technology may be effective in patient monitoring during refractive surgery and for early diagnosis and treatment monitoring in diseases of the cornea. In this work, Fuchs dystrophy, cornea transplant rejection, and keratoconus are discussed, and a hydration sensitivity of about one part in a hundred is predicted to be needed to successfully distinguish between diseased and healthy tissues in these applications. Stratified models of corneal tissue reflectivity are developed and validated using ex vivo spectroscopy of harvested porcine corneas that are hydrated using polyethylene glycol solutions. Simulation of the cornea’s depth-dependent hydration profile, from 0.01 to 100 THz, identifies a peak in intrinsic reflectivity contrast for sensing at 100 GHz. A 100 GHz hydration sensing system is evaluated alongside the current standard ultrasound pachymetry technique to measure corneal hydration in vivo in four rabbits. A hydration sensitivity, of three parts per thousand or better, was measured in all four rabbits under study. This work presents the first in vivo demonstration of remote corneal hydration sensing. PMID:23085925

Uniform manganese hexacyanoferrate hydrate nanocubes featuring superior performance for low-cost supercapacitors and nonenzymatic electrochemical sensors

NASA Astrophysics Data System (ADS)

Pang, Huan; Zhang, Yizhou; Cheng, Tao; Lai, Wen-Yong; Huang, Wei

2015-09-01

Uniform manganese hexacyanoferrate hydrate nanocubes are prepared via a simple chemical precipitation method at room temperature. Due to both micro/mesopores of the Prussian blue analogue and nanocubic structures, the manganese hexacyanoferrate hydrate nanocubes allow the efficient charge transfer and mass transport for electrolyte solution and chemical species. Thus, the manganese hexacyanoferrate hydrate nanocube electrode shows a good rate capability and cycling stability for electrochemical capacitors. Furthermore, electrodes modified with manganese hexacyanoferrate hydrate nanocubes demonstrate a sensitive electrochemical response to hydrogen peroxide (H2O2) in buffer solutions with a high selectivity.Uniform manganese hexacyanoferrate hydrate nanocubes are prepared via a simple chemical precipitation method at room temperature. Due to both micro/mesopores of the Prussian blue analogue and nanocubic structures, the manganese hexacyanoferrate hydrate nanocubes allow the efficient charge transfer and mass transport for electrolyte solution and chemical species. Thus, the manganese hexacyanoferrate hydrate nanocube electrode shows a good rate capability and cycling stability for electrochemical capacitors. Furthermore, electrodes modified with manganese hexacyanoferrate hydrate nanocubes demonstrate a sensitive electrochemical response to hydrogen peroxide (H2O2) in buffer solutions with a high selectivity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04322k

Sun-induced changes of stratum corneum hydration vary with age and gender in a normal Chinese population.

PubMed

Liu, Zhili; Song, Shunpeng; Luo, Wenhai; Elias, Peter M; Man, Mao-Qiang

2012-02-01

Previous studies have demonstrated that sun-induced alteration of epidermal permeability barrier function varies with gender and age. In the present study, we assess the stratum corneum (SC) hydration in sun-exposed males and females. A total of 168 subjects (84 males and 84 females) aged 19-75 years were enrolled. A multifunctional skin physiology monitor was used to measure SC hydration. In comparison with non-sun exposure, sun exposure does not cause a significant change in SC hydration in either young males or young females, whereas in aged females, a significant reduction of SC hydration is seen on the forehead and the dorsal hand of sun-exposed subjects. SC hydration on the canthus of both aged males and aged females is significantly lower than that of young subjects. Additionally, SC hydration on the dorsal hand of aged females is also significantly lower as compared with young females. Sun-induced reduction of SC hydration is more evident on the dorsal hand of aged females than that of males (P<0.001). Moreover, the SC rehydration capacity is significantly lower in sun-exposed aged females than in age-matched males. These results demonstrated that sun-induced changes of the SC hydration property vary with age and gender. © 2011 John Wiley & Sons A/S.

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Kinetics of methane hydrate replacement with carbon dioxide and nitrogen gas mixture using in situ NMR spectroscopy.

PubMed

Cha, Minjun; Shin, Kyuchul; Lee, Huen; Moudrakovski, Igor L; Ripmeester, John A; Seo, Yutaek

2015-02-03

In this study, the kinetics of methane replacement with carbon dioxide and nitrogen gas in methane gas hydrate prepared in porous silica gel matrices has been studied by in situ (1)H and (13)C NMR spectroscopy. The replacement process was monitored by in situ (1)H NMR spectra, where about 42 mol % of the methane in the hydrate cages was replaced in 65 h. Large amounts of free water were not observed during the replacement process, indicating a spontaneous replacement reaction upon exposing methane hydrate to carbon dioxide and nitrogen gas mixture. From in situ (13)C NMR spectra, we confirmed that the replacement ratio was slightly higher in small cages, but due to the composition of structure I hydrate, the amount of methane evolved from the large cages was larger than that of the small cages. Compositional analysis of vapor and hydrate phases was also carried out after the replacement reaction ceased. Notably, the composition changes in hydrate phases after the replacement reaction would be affected by the difference in the chemical potential between the vapor phase and hydrate surface rather than a pore size effect. These results suggest that the replacement technique provides methane recovery as well as stabilization of the resulting carbon dioxide hydrate phase without melting.

Inhibition of insulin amyloid fibrillation by Morin hydrate.

PubMed

Patel, Palak; Parmar, Krupali; Das, Mili

2018-03-01

We report here the inhibition of amyloid fibrillation of human insulin in vitro by Morin hydrate, a naturally occurring small molecule. Using spectroscopic assays and transmission electron microscopy, we found that Morin hydrate effectively inhibits insulin amyloid fibrillation in a dose dependent manner with more than 80% inhibition occurring even at only a 1:1 concentration. As suggested by fluorescence spectroscopic titration studies, Morin hydrate binds to insulin with a fairly strong affinity of -26.436kJmol -1 . Circular dichroism (CD) spectroscopy was used to analyse structural changes of insulin in the presence of Morin hydrate demonstrating the ability of Morin hydrate to bind with the native monomeric protein and/or its near native state, intermediate oligomeric species and amyloid fibrils. Based on computational docking and molecular dynamics study, we propose that Morin hydrate binds to residues having greater aggregation propensity and prevent structural and/or conformational changes leading to amyloid fibrillation. Morin hydrate should also bind to fibrils by hydrogen bonding and/or hydrophobic forces throughout the surface, stabilize them and inhibit the release of oligomeric species which could be nuclei or template for further fibrillation. Overall results provide an insight into the mechanism of inhibition of insulin amyloid fibrillation by Morin hydrate. Copyright © 2017 Elsevier B.V. All rights reserved.

Gas hydrate saturations estimated from pore-and fracture-filling gas hydrate reservoirs in the Qilian Mountain permafrost, China.

PubMed

Xiao, Kun; Zou, Changchun; Lu, Zhenquan; Deng, Juzhi

2017-11-24

Accurate calculation of gas hydrate saturation is an important aspect of gas hydrate resource evaluation. The effective medium theory (EMT model), the velocity model based on two-phase medium theory (TPT model), and the two component laminated media model (TCLM model), are adopted to investigate the characteristics of acoustic velocity and gas hydrate saturation of pore- and fracture-filling reservoirs in the Qilian Mountain permafrost, China. The compressional wave (P-wave) velocity simulated by the EMT model is more consistent with actual log data than the TPT model in the pore-filling reservoir. The range of the gas hydrate saturation of the typical pore-filling reservoir in hole DKXX-13 is 13.0~85.0%, and the average value of the gas hydrate saturation is 61.9%, which is in accordance with the results by the standard Archie equation and actual core test. The P-wave phase velocity simulated by the TCLM model can be transformed directly into the P-wave transverse velocity in a fracture-filling reservoir. The range of the gas hydrate saturation of the typical fracture-filling reservoir in hole DKXX-19 is 14.1~89.9%, and the average value of the gas hydrate saturation is 69.4%, which is in accordance with actual core test results.

Detailed evaluation of gas hydrate reservoir properties using JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well downhole well-log displays

USGS Publications Warehouse

Collett, T.S.

1999-01-01

The JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well project was designed to investigate the occurrence of in situ natural gas hydrate in the Mallik area of the Mackenzie Delta of Canada. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas-hydrate-bearing sediments. Downhole logging tool strings deployed in the Mallik 2L-38 well included the Schlumberger Platform Express with a high resolution laterolog, Array Induction Imager Tool, Dipole Shear Sonic Imager, and a Fullbore Formation Microlmager. The downhole log data obtained from the log- and core-inferred gas-hydrate-bearing sedimentary interval (897.25-1109.5 m log depth) in the Mallik 2L-38 well is depicted in a series of well displays. Also shown are numerous reservoir parameters, including gas hydrate saturation and sediment porosity log traces, calculated from available downhole well-log and core data. The gas hydrate accumulation delineated by the Mallik 2L-38 well has been determined to contain as much as 4.15109 m3 of gas in the 1 km2 area surrounding the drill site.

Structural Basis for the Inhibition of Gas Hydrates by α-Helical Antifreeze Proteins

PubMed Central

Sun, Tianjun; Davies, Peter L.; Walker, Virginia K.

2015-01-01

Kinetic hydrate inhibitors (KHIs) are used commercially to inhibit gas hydrate formation and growth in pipelines. However, improvement of these polymers has been constrained by the lack of verified molecular models. Since antifreeze proteins (AFPs) act as KHIs, we have used their solved x-ray crystallographic structures in molecular modeling to explore gas hydrate inhibition. The internal clathrate water network of the fish AFP Maxi, which extends to the protein’s outer surface, is remarkably similar to the {100} planes of structure type II (sII) gas hydrate. The crystal structure of this water web has facilitated the construction of in silico models for Maxi and type I AFP binding to sII hydrates. Here, we have substantiated our models with experimental evidence of Maxi binding to the tetrahydrofuran sII model hydrate. Both in silico and experimental evidence support the absorbance-inhibition mechanism proposed for KHI binding to gas hydrates. Based on the Maxi crystal structure we suggest that the inhibitor adsorbs to the gas hydrate lattice through the same anchored clathrate water mechanism used to bind ice. These results will facilitate the rational design of a next generation of effective green KHIs for the petroleum industry to ensure safe and efficient hydrocarbon flow. PMID:26488661

Assessment of corneal hydration sensing in the terahertz band: in vivo results at 100 GHz

NASA Astrophysics Data System (ADS)

Bennett, David; Taylor, Zachary; Tewari, Pria; Sung, Sijun; Maccabi, Ashkan; Singh, Rahul; Culjat, Martin; Grundfest, Warren; Hubschman, Jean-Pierre; Brown, Elliott

2012-09-01

Terahertz corneal hydration sensing has shown promise in ophthalmology applications and was recently shown to be capable of detecting water concentration changes of about two parts in a thousand in ex vivo corneal tissues. This technology may be effective in patient monitoring during refractive surgery and for early diagnosis and treatment monitoring in diseases of the cornea. In this work, Fuchs dystrophy, cornea transplant rejection, and keratoconus are discussed, and a hydration sensitivity of about one part in a hundred is predicted to be needed to successfully distinguish between diseased and healthy tissues in these applications. Stratified models of corneal tissue reflectivity are developed and validated using ex vivo spectroscopy of harvested porcine corneas that are hydrated using polyethylene glycol solutions. Simulation of the cornea's depth-dependent hydration profile, from 0.01 to 100 THz, identifies a peak in intrinsic reflectivity contrast for sensing at 100 GHz. A 100 GHz hydration sensing system is evaluated alongside the current standard ultrasound pachymetry technique to measure corneal hydration in vivo in four rabbits. A hydration sensitivity, of three parts per thousand or better, was measured in all four rabbits under study. This work presents the first in vivo demonstration of remote corneal hydration sensing.

Kinetic studies of methane-ethane mixed gas hydrates by neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Kuhs, Werner F

2009-04-16

In situ formations of CH(4)-C(2)H(6) mixed gas hydrates were made using high flux neutron diffraction at 270 K and 5 MPa. For this purpose, a feed gas composition of CH(4) and C(2)H(6) (95 mol% CH(4)) was employed. The rates of transformation of spherical grains of deuterated ice Ih into hydrates were measured by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. Phase fractions of the crystalline constituents were obtained from Rietveld refinements. A concomitant formation of structure type I (sI) and structure type II (sII) hydrates were observed soon after the gas pressure was applied. The initial fast formation of sII hydrate reached its maximum volume and started declining very slowly. The formation of sI hydrate followed a sigmoid growth kinetics that slowed down due to diffusion limitation. This observation has been interpreted in terms of a kinetically favored nucleation of the sII hydrate along with a slow transformation into sI. Both powder diffraction and Raman spectroscopic results suggest that a C(2)H(6)-rich sII hydrate was formed at the early part of the clathration, which slowly decreased to approximately 3% after a reaction of 158 days as confirmed by synchrotron XRD. The final persistence of a small portion of sII hydrate points to a miscibility gap between CH(4)-rich sI and C(2)H(6)-rich sII hydrates.

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

USGS Publications Warehouse

Booth, J.S.; Winters, W.J.; Dillon, William P.; Clennell, M.B.; Rowe, M.M.

1998-01-01

This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). 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 100m 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 concentratiion. 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.

Using Carbon Dioxide to Enhance Recovery of Methane from Gas Hydrate Reservoirs: Final Summary Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGrail, B. Peter; Schaef, Herbert T.; White, Mark D.

2007-09-01

Carbon dioxide sequestration coupled with hydrocarbon resource recovery is often economically attractive. Use of CO2 for enhanced recovery of oil, conventional natural gas, and coal-bed methane are in various stages of common practice. In this report, we discuss a new technique utilizing CO2 for enhanced recovery of an unconventional but potentially very important source of natural gas, gas hydrate. We have focused our attention on the Alaska North Slope where approximately 640 Tcf of natural gas reserves in the form of gas hydrate have been identified. Alaska is also unique in that potential future CO2 sources are nearby, and petroleummore » infrastructure exists or is being planned that could bring the produced gas to market or for use locally. The EGHR (Enhanced Gas Hydrate Recovery) concept takes advantage of the physical and thermodynamic properties of mixtures in the H2O-CO2 system combined with controlled multiphase flow, heat, and mass transport processes in hydrate-bearing porous media. A chemical-free method is used to deliver a LCO2-Lw microemulsion into the gas hydrate bearing porous medium. The microemulsion is injected at a temperature higher than the stability point of methane hydrate, which upon contacting the methane hydrate decomposes its crystalline lattice and releases the enclathrated gas. Small scale column experiments show injection of the emulsion into a CH4 hydrate rich sand results in the release of CH4 gas and the formation of CO2 hydrate« less

Methane Hydrate Concentrations at GC955 and WR313 Drilling Sites in the Gulf of Mexico Determined from Seismic Prestack Waveform Inversion

NASA Astrophysics Data System (ADS)

Fortin, W.; Goldberg, D.; Küçük, H. M.

2016-12-01

Gas hydrates are naturally occurring compounds, which, at a molecular scale, are lattice structures of ice embedded with various gas molecules in the lattice voids. Volumetric estimates of associated hydrocarbons vary greatly due to the difficulty in remotely estimating hydrate concentrations in marine sediments but embedded hydrocarbon stores are thought to represent a significant portion of global deposits. The unstable nature of methane hydrates has been linked to submarine landslides and the subsequent release of large quantities of methane can accelerate global climate change. Understanding the details of gas hydrate systems is important for potential economic production and assessing natural hazards risks. Seismic reflection techniques are uniquely capable of detecting gas hydrates. Often, hydrate layers appear as bottom simulating reflectors (BSRs); however, BSRs are not present everywhere gas hydrates are known to occur. Using recently reprocessed prestack time migrated data and prestack waveform inversion (PWI) techniques, we produce velocity models at high vertical and horizontal resolution in order to investigate the presence of gas hydrates in the Gulf of Mexico. Coupling our PWI results with known velocity-property relationships and data from nearby well controls, we determine the viability of recently collected high-resolution seismic data and outline small-scale heterogeneities at GC955 and WR313. We outline where PWI techniques are capable of identifying gas hydrates in seismic reflection data where BSRs are not present.

Prestack Waveform Inversion and Well Log Examination at GC955 and WR313 in the Gulf of Mexico for Estimation of Methane Hydrate Concentrations

NASA Astrophysics Data System (ADS)

Fortin, W.; Goldberg, D.; Kucuk, H. M.

2017-12-01

Gas hydrates are naturally occurring compounds, which, at a molecular scale, are lattice structures of ice embedded with various gas molecules in the lattice voids. Volumetric estimates of associated hydrocarbons vary greatly due to the difficulty in remotely estimating hydrate concentrations in marine sediments but embedded hydrocarbon stores are thought to represent a significant portion of global deposits. Inherent hydrate instabilities obscure our understanding of and complicates processes related to resource extraction and hydrate response to disturbances in the local environment. Understanding the spatial extent and variability of hydrate deposits have important implications for potential economic production, climate change, and assessing natural hazards risks. Seismic reflection techniques are capable of determining the extent of gas hydrate deposits, often through the observation of bottom simulating reflectors (BSRs). However, BSRs are not present everywhere gas hydrates exist. Using high resolution prestack time migrated seismic data and prestack waveform inversion (PWI) we produce highly resolved velocity models and compare them to co-located well logs. Coupling our PWI results with velocity-porosity relationships and nearby well control, we map hydrate properties at GC955 and WR313. Integrating small scale heterogeneities and variations along the velocity model with in-situ measurements, we develop a workflow aimed to quantify hydrate concentrations observed in seismic data over large areas in great detail regardless of the existence of a BSR.

Impact of welan gum on tricalcium aluminate-gypsum hydration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma Lei, E-mail: malei198713@163.com; Zhao Qinglin, E-mail: zhaoqinglin@whut.edu.cn; Yao Chukang

The retarding effect of welan gum on tricalcium aluminate-gypsum hydration, as a partial system of ordinary Portland cement (OPC) hydration, was investigated with several methods. The tricalcium aluminate-gypsum hydration behavior in the presence or absence of welan gum was researched by field emission gun scanning electron microscopy, X-ray diffraction and zeta potential analysis. Meanwhile, we studied the surface electrochemical properties and adsorption characteristics of welan gum by utilizing a zeta potential analyzer and UV-VIS absorption spectrophotometer. By adding welan gum, the morphology change of ettringite and retardation of hydration stages in tricalcium aluminate-gypsum system was observed. Moreover, we detected themore » adsorption behavior and zeta potential inversion of tricalcium aluminate and ettringite, as well as a rapid decrease in the zeta potential of tricalcium aluminate-gypsum system. The reduction on nucleation rate of ettringite and hydration activity of C{sub 3}A was also demonstrated. Thus, through the adsorption effect, welan gum induces a retarding behavior in tricalcium aluminate-gypsum hydration. Highlights: Black-Right-Pointing-Pointer Adsorption characteristics of welan gum on C{sub 3}A and ettringite have been studied. Black-Right-Pointing-Pointer C{sub 3}A-gypsum hydration behavior and the hydration products are examined in L/S = 3. Black-Right-Pointing-Pointer Welan gum retards the process of C{sub 3}A-gypsum hydration. Black-Right-Pointing-Pointer The addition of welan gum changes the nucleation growth of ettringite.« less

Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Stern, Laura A.; Lorenson, T.D.; Pinkston, John C.

2011-01-01

Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA–DOE–USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5 m to 760.1 m depth, and sections investigated here were retrieved from 619.9 m and 661.0 m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70–75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20–120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas.

Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Stern, L.A.; Lorenson, T.D.; Pinkston, J.C.

2011-01-01

Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5. m to 760.1. m depth, and sections investigated here were retrieved from 619.9. m and 661.0. m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70-75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20-120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas. ?? 2009.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone.

PubMed

Braun, Doris E; Griesser, Ulrich J

2018-01-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4'-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III ) differ only by ~1 kJ mol -1 . The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces.

PubMed

Smith, Benjamin J; Rawal, Aditya; Funkhouser, Gary P; Roberts, Lawrence R; Gupta, Vijay; Israelachvili, Jacob N; Chmelka, Bradley F

2011-05-31

Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state (1)H, (13)C, (29)Si, and (27)Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications.

Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

NASA Astrophysics Data System (ADS)

Malinverno, A.; Cook, A.; Daigle, H.

2016-12-01

Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction, solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.

A petroleum system model for gas hydrate deposits in northern Alaska

USGS Publications Warehouse

Lorenson, T.D.; Collett, Timothy S.; Wong, Florence L.

2011-01-01

Gas hydrate deposits are common on the North Slope of Alaska around Prudhoe Bay, however the extent of these deposits is unknown outside of this area. As part of a United States Geological Survey (USGS) and the Bureau of Land Management (BLM) gas hydrate research collaboration, well cutting and mud gas samples have been collected and analyzed from mainly industry-drilled wells on the Alaska North Slope for the purpose of prospecting for gas hydrate deposits. On the Alaska North Slope, gas hydrates are now recognized as an element within a petroleum systems approach or TPS (Total Petroleum System). Since 1979, 35 wells have been samples from as far west as Wainwright to Prudhoe Bay in the east. Geochemical studies of known gas hydrate occurrences on the North Slope have shown a link between gas hydrate and more deeply buried conventional oil and gas deposits. Hydrocarbon gases migrate from depth and charge the reservoir rock within the gas hydrate stability zone. It is likely gases migrated into conventional traps as free gas, and were later converted to gas hydrate in response to climate cooling concurrent with permafrost formation. Gas hydrate is known to occur in one of the sampled wells, likely present in 22 others based gas geochemistry and inferred by equivocal gas geochemistry in 11 wells, and absent in one well. Gas migration routes are common in the North Slope and include faults and widespread, continuous, shallowly dipping permeable sand sections that are potentially in communication with deeper oil and gas sources. The application of this model with the geochemical evidence suggests that gas hydrate deposits may be widespread across the North Slope of Alaska.

Assessing Gas-Hydrate Prospects on the North Slope of Alaska - Theoretical Considerations

USGS Publications Warehouse

Lee, Myung W.; Collett, Timothy S.; Agena, Warren F.

2008-01-01

Gas-hydrate resource assessment on the Alaska North Slope using 3-D and 2-D seismic data involved six important steps: (1) determining the top and base of the gas-hydrate stability zone, (2) 'tying' well log information to seismic data through synthetic seismograms, (3) differentiating ice from gas hydrate in the permafrost interval, (4) developing an acoustic model for the reservoir and seal, (5) developing a method to estimate gas-hydrate saturation and thickness from seismic attributes, and (6) assessing the potential gas-hydrate prospects from seismic data based on potential migration pathways, source, reservoir quality, and other relevant geological information. This report describes the first five steps in detail using well logs and provides theoretical backgrounds for resource assessments carried out by the U.S. Geological Survey. Measured and predicted P-wave velocities enabled us to tie synthetic seismograms to the seismic data. The calculated gas-hydrate stability zone from subsurface wellbore temperature data enabled us to focus our effort on the most promising depth intervals in the seismic data. A typical reservoir in this area is characterized by the P-wave velocity of 1.88 km/s, porosity of 42 percent, and clay volume content of 5 percent, whereas seal sediments encasing the reservoir are characterized by the P-wave velocity of 2.2 km/s, porosity of 32 percent, and clay volume content of 20 percent. Because the impedance of a reservoir without gas hydrate is less than that of the seal, a complex amplitude variation with respect to gas-hydrate saturation is predicted, namely polarity change, amplitude blanking, and high seismic amplitude (a bright spot). This amplitude variation with gas-hydrate saturation is the physical basis for the method used to quantify the resource potential of gas hydrates in this assessment.

Skin Hydration Assessment through Modern Non-Invasive Bioengineering Technologies

PubMed Central

CONSTANTIN, Maria-Magdalena; POENARU, Elena; POENARU, Calin; CONSTANTIN, Traian

2014-01-01

Non-invasive bioengineering technologies continuously discovered and developed in recent decades provide a significant input to research development and remarkably contribute to the improvement of medical education and care to our patients. Aim: Assessing skin hydration by using the capacitance method for a group of patients with allergic contact dermatitis versus healthy subjects, before and after applying a moisturiser (assessing the immediate and long-term effectiveness of hydration). Results: For both groups, but especially for the patients with dry skin, there was a clear improvement of hydration, statistically significant after applying the moisturiser. In the case of the patients with allergic contact dermatitis, hydration was at a maximum immediately after the first application, and then maintained an increased level after 7 and 28 days, respectively. In the healthy subjects, the increase in hydration was lower, but progressive. The moisturiser determined an increase in hydration for all age groups, but those who showed the most obvious effect were the young adults (18-29 years old) with an increase of 19.9%. The maintenance effect of hydration lasted for 28 days, while the improvement was important for allergic skin (17.1%) and significant for healthy skin (10.9%). Conclusion: The assessment of epidermal hydration performed by using the corneometer showed very good hydration of the stratum corneum for both groups studied, with immediate and long-term effect. This study also showed that the degree of skin hydration was inversely proportional with age. The corneometer is easy to use, efficient and widely utilised in international studies for measurements in healthy or pathological conditions, for quantitative assessment of the effectiveness of various preparations intended for application to the skin surface, under well-controlled and standardised conditions. PMID:25553123

Skin Membrane Electrical Impedance Properties under the Influence of a Varying Water Gradient

PubMed Central

Björklund, Sebastian; Ruzgas, Tautgirdas; Nowacka, Agnieszka; Dahi, Ihab; Topgaard, Daniel; Sparr, Emma; Engblom, Johan

2013-01-01

The stratum corneum (SC) is an effective permeability barrier. One strategy to increase drug delivery across skin is to increase the hydration. A detailed description of how hydration affects skin permeability requires characterization of both macroscopic and molecular properties and how they respond to hydration. We explore this issue by performing impedance experiments on excised skin membranes in the frequency range 1 Hz to 0.2 MHz under the influence of a varying gradient in water activity (aw). Hydration/dehydration induces reversible changes of membrane resistance and effective capacitance. On average, the membrane resistance is 14 times lower and the effective capacitance is 1.5 times higher when the outermost SC membrane is exposed to hydrating conditions (aw = 0.992), as compared to the case of more dehydrating conditions (aw = 0.826). Molecular insight into the hydration effects on the SC components is provided by natural-abundance 13C polarization transfer solid-state NMR and x-ray diffraction under similar hydration conditions. Hydration has a significant effect on the dynamics of the keratin filament terminals and increases the interchain spacing of the filaments. The SC lipids are organized into lamellar structures with ∼ 12.6 nm spacing and hexagonal hydrocarbon chain packing with mainly all-trans configuration of the acyl chains, irrespective of hydration state. Subtle changes in the dynamics of the lipids due to mobilization and incorporation of cholesterol and long-chain lipid species into the fluid lipid fraction is suggested to occur upon hydration, which can explain the changes of the impedance response. The results presented here provide information that is useful in explaining the effect of hydration on skin permeability. PMID:23790372

Skin Hydration Assessment through Modern Non-Invasive Bioengineering Technologies.

PubMed

Constantin, Maria-Magdalena; Poenaru, Elena; Poenaru, Calin; Constantin, Traian

2014-03-01

Non-invasive bioengineering technologies continuously discovered and developed in recent decades provide a significant input to research development and remarkably contribute to the improvement of medical education and care to our patients. Assessing skin hydration by using the capacitance method for a group of patients with allergic contact dermatitis versus healthy subjects, before and after applying a moisturiser (assessing the immediate and long-term effectiveness of hydration). For both groups, but especially for the patients with dry skin, there was a clear improvement of hydration, statistically significant after applying the moisturiser. In the case of the patients with allergic contact dermatitis, hydration was at a maximum immediately after the first application, and then maintained an increased level after 7 and 28 days, respectively. In the healthy subjects, the increase in hydration was lower, but progressive. The moisturiser determined an increase in hydration for all age groups, but those who showed the most obvious effect were the young adults (18-29 years old) with an increase of 19.9%.The maintenance effect of hydration lasted for 28 days, while the improvement was important for allergic skin (17.1%) and significant for healthy skin (10.9%). The assessment of epidermal hydration performed by using the corneometer showed very good hydration of the stratum corneum for both groups studied, with immediate and long-term effect. This study also showed that the degree of skin hydration was inversely proportional with age. The corneometer is easy to use, efficient and widely utilised in international studies for measurements in healthy or pathological conditions, for quantitative assessment of the effectiveness of various preparations intended for application to the skin surface, under well-controlled and standardised conditions.

Japan's Methane Hydrate R&D Program, Accomplishments and Future Challenges

NASA Astrophysics Data System (ADS)

Shimada, T.

2009-12-01

JOGMEC have been searching for methane hydrate offshore around Japan for use as a future energy resource as a member of the research consortium of methane hydrate resources in Japan (MH21 Research Consortium). The MH21 Research Consortium was established in 2002 to carry out "Japan's Methane Hydrate R&D Program" published by the Ministry of Economy, Trade and Industry (METI) in July 2001. The program has been extended over 18 years (until 2018) and is divided into three phases. During phase 1, the following key accomplishments had been achieved. Revealed and confirmed the occurrence of methane hydrate filling pore spaces of sand layers in the marine environment for the first time in the eastern Nankai Trough. Established methodology to delineate the thick methane hydrate concentrated zones composed of alternations of highly hydrate-saturated turbidite sand mainly by geophysical measures. Evaluated the amount of gas trapped in the eastern Nankai Trough, applied a probabilistic method based on the borehole data and seismic data, contained in methane hydrate-bearing layers. Tested and achieved substantial methane gas production through the wellbore from subsurface hydrate-bearing layers by dissociating hydrates in Canadian arctic area under international collaboration. Both depressurization method and hot water circulation method were successfully conducted to produce methane gas, and the depressurization method was proved to be effective as a production method that could be utilized in the future. We accumulated a significant amount of knowledge and experience during phase 1. However, many technical and economic challenges still remain for the development of methane hydrate. The research program proceeded to phase 2 in 2009. This time we would like to present summary of phase 1 and challenges during phase 2. The author would like to express sincere appreciation to MH21 Research Consortium and METI for permission for this presentation.

Gas hydrate saturation and distribution in the Kumano Forearc Basin of the Nankai Trough

NASA Astrophysics Data System (ADS)

Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi

2017-02-01

The Kumano Forearc Basin is located to the south-east of the Kii Peninsula, Japan, overlying the accretionary prism in the Nankai Trough. The presence of gas hydrate in submarine sediments of the forearc basin has resulted in the widespread occurrence of bottom simulating reflectors (BSRs) on seismic profiles, and has caused distinct anomalies in logging data in the region. We estimated the in situ gas hydrate saturation from logging data by using three methods: effective rock physics models, Archie's equation, and empirical relationships between acoustic impedance (AI) and water-filled porosity. The results derived from rock physics models demonstrate that gas hydrates are attached to the grain surfaces of the rock matrix and are not floating in pore space. By applying the empirical relationships to the AI distribution derived from model-based AI inversion of the three-dimensional (3D) seismic data, we mapped the spatial distribution of hydrate saturation within the Kumano Basin and characterised locally concentrated gas hydrates. Based on the results, we propose two different mechanisms of free gas supply to explain the process of gas hydrate formation in the basin: (1) migration along inclined strata that dip landwards, and (2) migration through the faults or cracks generated by intensive tectonic movements of the accretionary prism. The dipping strata with relatively low AI in the forearc basin could indicate the presence of hydrate formation due to gas migration along the dipping strata. However, high hydrate concentration is observed at fault zones with high pore pressures, thus the second mechanism likely plays an important role in the genesis of gas hydrates in the Kumano Basin. Therefore, the tectonic activities in the accretionary wedge significantly influence the hydrate saturation and distribution in the Kumano Forearc Basin.

Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

NASA Astrophysics Data System (ADS)

Park, T.; Kyung, D.; Lee, W.

2013-12-01

Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

Seismic character of gas hydrates on the Southeastern U.S. continental margin

USGS Publications Warehouse

Lee, M.W.; Hutchinson, D.R.; Agena, W.F.; Dillon, William P.; Miller, J.J.; Swift, B.A.

1994-01-01

Gas hydrates are stable at relatively low temperature and high pressure conditions; thus large amounts of hydrates can exist in sediments within the upper several hundred meters below the sea floor. The existence of gas hydrates has been recognized and mapped mostly on the basis of high amplitude Bottom Simulating Reflections (BSRs) which indicate only that an acoustic contrast exists at the lower boundary of the region of gas hydrate stability. Other factors such as amplitude blanking and change in reflection characteristics in sediments where a BSR would be expected, which have not been investigated in detail, are also associated with hydrated sediments and potentially disclose more information about the nature of hydratecemented sediments and the amount of hydrate present. Our research effort has focused on a detailed analysis of multichannel seismic profiles in terms of reflection character, inferred distribution of free gas underneath the BSR, estimation of elastic parameters, and spatial variation of blanking. This study indicates that continuous-looking BSRs in seismic profiles are highly segmented in detail and that the free gas underneath the hydrated sediment probably occurs as patches of gas-filled sediment having variable thickness. We also present an elastic model for various types of sediments based on seismic inversion results. The BSR from sediments of high ratio of shear to compressional velocity, estimated as about 0.52, encased in sediments whose ratios are less than 0.35 is consistent with the interpretation of gasfilled sediments underneath hydrated sediments. This model contrasts with recent results in which the BSR is explained by increased concentrations of hydrate near the base of the hydrate stability field and no underlying free gas is required. 

Seismic Characterization of a Gas Hydrate Chimney Associated with Acoustic Blanking: Pegasus Basin, New Zealand

NASA Astrophysics Data System (ADS)

Henrys, S. A.; Fraser, D. R. A.; Gorman, A. R.; Pecher, I. A.; Crutchley, G. J.

2016-12-01

The Pegasus Basin on the east coast of New Zealand's North Island in the southern part of the Hikurangi Margin is a frontier petroleum basin that is also expected to contain significant gas hydrate deposits. Extensive faulting in the basin has lead to the development of many interesting and unique focused accumulations of gas hydrates. A 2D seismic dataset acquired in 2009/2010 was reprocessed to examine the gas hydrate systems within the basin. Here, we present one of the more interesting hydrate features in the dataset: a presumed gas chimney within the regional gas hydrate stability zone at the centre of a roughly triangular (in 2D) region of low reflectivity, approximately 8 km wide, that is interpreted to be the result of acoustic blanking. Using automated high density velocity picking, the chimney structure is interpreted to be cored by a 200 m wide low-velocity zone which contains free gas and is flanked by high-velocity bands that are 200-400 m wide. The high-velocity zone is interpreted to correspond to concentrated hydrate deposits within the sedimentary pore spaces. Amplitude vs offset (AVO) and inversion techniques have been applied and the results of this work correspond well to the high-density velocity analyses. The analysis methods all indicate zones of free gas below the Bottom Simulating Reflection (BSR) and within the chimney. Areas of increased hydrate concentrations, including at the base of the gas hydrate stability zone, were also identified. A model for fluid flow and how free gas within the chimney at the centre of the blanking zone is converted to hydrate is discussed. The potential size of the gas hydrate resource present in this feature can be estimated based on the seismic velocities and physical properties determined by inversion.

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

Chloral hydrate, chloral hydrate--promethazine and chloral hydrate -hydroxyzine efficacy in electroencephalography sedation.

PubMed

Fallah, Razieh; Alaei, Ali; Akhavan Karbasi, Sedighah; Shajari, Ahmad

2014-06-01

To compare efficacy and safety of chloral hydrate (CH), chloral hydrate and promethazine (CH + P) and chloral hydrate and hydroxyzine (CH + H) in electroencephalography (EEG) sedation. In a parallel single-blinded randomized clinical trial, ninety 1-7 y-old uncooperative kids who were referred to Pediatric Neurology Clinic of Shahid Sadoughi University, Yazd, Iran from April through August 2012, were randomly assigned to receive 40 mg/kg of chloral hydrate or 40 mg/kg of chloral hydrate and 1 mg/kg of promethazine or 40 mg/kg of chloral hydrate and 2 mg/kg of hydroxyzine. The primary endpoint was efficacy in sufficient sedation (obtaining four Ramsay sedation score) and successful completion of EEG. Secondary endpoint was clinical adverse events. Thirty nine girls (43.3 %) and 51 boys (56.7 %) with mean age of 3.34 ± 1.47 y were assessed. Sufficient sedation and completion of EEG were achieved in 70 % (N = 21) of chloral hydrate group, in 83.3 % (N = 25) of CH + H group and in 96.7 % (N = 29) of CH + P group (p = 0.02). Mild clinical adverse events including vomiting [16.7 % (N = 5) in CH, 6.7 % (N = 2) in CH + P, 6.7 % (N = 2) in CH + H], agitation in 3.3 % of CH + P (N = 1) group and mild transient hypotension in 3.3 % of CH + H (N = 1) group occurred. Safety of these three sedation regimens was not statistically significant different (p = 0.14). Combination of chloral hydrate-antihistamines can be used as the most effective and safe sedation regimen in drug induced sleep electroencephalography of kids.

Widespread gas hydrate instability on the upper U.S. Beaufort margin

USGS Publications Warehouse

Phrampus, Benjamin J.; Hornbach, Matthew J.; Ruppel, Carolyn D.; Hart, Patrick E.

2014-01-01

The most climate-sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three-dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5–7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

DOE PAGES

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

2015-10-14

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

Determining the mechanism and parameters of hydrate formation and loss in glucose.

PubMed

Scholl, Sarah K; Schmidt, Shelly J

2014-11-01

Water-solid interactions are known to play a major role in the chemical and physical stability of food materials. Despite its extensive use throughout the food industry, the mechanism and parameters of hydrate formation and loss in glucose are not well characterized. Hydrate formation in alpha-anhydrous glucose (α-AG) and hydrate loss in glucose monohydrate (GM) were studied under equilibrium conditions at various relative humidity (RH) values using saturated salt slurries for 1 y. The mechanism of hydrate formation and hydrate loss were determined through mathematical modeling of Dynamic Vapor Sorption data and Raman spectroscopy was used to confirm the mechanisms. The critical temperature for hydrate loss in GM was determined using thermogravimetric analysis (TGA). The moisture sorption profiles of α-AG and GM were also studied under dynamic conditions using an AquaSorp Isotherm Generator. Hydrate formation was observed at and above 68% RH at 25 °C and the conversion of α-AG to GM can best be described as following a nucleation mechanism, however, diffusion and/or geometric contraction mechanisms were also observed by Raman spectroscopy subsequent to the coalescence of initial nucleation sites. Hydrate loss was observed to occur at and below 11% RH at 25 °C during RH storage and at 70 °C during TGA. The conversion of GM to α-AG follows nucleation and diffusion mechanisms. Hydrate formation was evident under dynamic conditions in α-AG and GM prior to deliquescence. This research is the first to report hydrate formation and loss parameters for crystalline α-AG and GM during extended storage at 25 ˚C. © 2014 Institute of Food Technologists®

Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction,more » solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.« less

THCM Coupled Model for Hydrate-Bearing Sediments: Data Analysis and Design of New Field Experiments (Marine and Permafrost Settings)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanchez, Marcelo J.; Santamarina, J. Carlos

Gas hydrates are solid compounds made of water molecules clustered around low molecular weight gas molecules such as methane, hydrogen, and carbon dioxide. Methane hydrates form under pressure (P) and temperature (T) conditions that are common in sub-permafrost layers and in deep marine sediments. Stability conditions constrain the occurrence of gas hydrates to submarine sediments and permafrost regions. The amount of technically recoverable methane trapped in gas hydrate may exceed 104tcf. Gas hydrates are a potential energy resource, can contribute to climate change, and can cause large-scale seafloor instabilities. In addition, hydrate formation can be used for CO2 sequestration (alsomore » through CO2-CH4 replacement), and efficient geological storage seals. The experimental study of hydrate bearing sediments has been hindered by the very low solubility of methane in water (lab testing), and inherent sampling difficulties associated with depressurization and thermal changes during core extraction. This situation has prompted more decisive developments in numerical modeling in order to advance the current understanding of hydrate bearing sediments, and to investigate/optimize production strategies and implications. The goals of this research has been to addresses the complex thermo-hydro-chemo-mechanical THCM coupled phenomena in hydrate-bearing sediments, using a truly coupled numerical model that incorporates sound and proven constitutive relations, satisfies fundamental conservation principles. Analytical solutions aimed at verifying the proposed code have been proposed as well. These tools will allow to better analyze available data and to further enhance the current understanding of hydrate bearing sediments in view of future field experiments and the development of production technology.« less

Geochemistry of a naturally occurring massive marine gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.; Threlkeld, C.N.; Dendy, Sloan E.

1984-01-01

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4??C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ???0.2% ethane, and ???0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 permil(( 0 00), relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift. ?? 1984.

India National Gas Hydrate Program Expedition 02 Technical Contributions

NASA Astrophysics Data System (ADS)

Collett, T. S.; Kumar, P.; Shukla, K. M.; Nagalingam, J.; Lall, M. V.; Yamada, Y.; Schultheiss, P. J.; Holland, M.; Waite, W. F.

2017-12-01

The National Gas Hydrate Program Expedition 02 (NGHP-02) was conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India. The primary objective of this expedition was the exploration and discovery of highly saturated gas hydrate occurrences in sand reservoirs that would be targets of future production testing. The first 2 months of the expedition were dedicated to logging while drilling (LWD) operations with a total of 25 holes being drilled and logged. The next 3 months were dedicated to coring operations at 10 of the most promising sites. NGHP-02 downhole logging, coring and formation pressure testing have confirmed the presence of large, highly saturated, gas hydrate accumulations in coarse-grained sand-rich depositional systems throughout the Krishna-Godavari Basin within the regions defined during NGHP-02 as Area-B, Area-C, and Area-E. The nature of the discovered gas hydrate occurrences closely matched pre-drill predictions, confirming the project developed depositional models for the sand-rich depositional facies in the Krishna-Godavari and Mahanadi Basins. The existence of a fully developed gas hydrate petroleum system was established in Area-C of the Krishna-Godavari Basin with the discovery of a large slope-basin interconnected depositional system, including a sand-rich, gas-hydrate-bearing channel-levee prospect at Sites NGHP-02-08 and -09. The acquisition of closely spaced LWD and core holes in the Area-B L1 Block gas hydrate accumulation have provided one of the most complete three-dimensional petrophysical-based views of any known gas hydrate reservoir system in the world. It was concluded that Area-B and Area-C in the area of the greater Krishna-Godavari Basin contain important world-class gas hydrate accumulations and represent ideal sites for consideration of future gas hydrate production testing.

Hydration in advanced cancer: can bioelectrical impedance analysis improve the evidence base? A systematic review of the literature.

PubMed

Nwosu, Amara Callistus; Mayland, Catriona R; Mason, Stephen R; Khodabukus, Andrew F; Varro, Andrea; Ellershaw, John E

2013-09-01

Decisions surrounding the administration of clinically assisted hydration to patients dying of cancer can be challenging because of the limited understanding of hydration in advanced cancer and a lack of evidence to guide health care professionals. Bioelectrical impedance analysis (BIA) has been used to assess hydration in various patient groupings, but evidence for its use in advanced cancer is limited. To critically appraise existing methods of hydration status assessment in advanced cancer and review the potential for BIA to assess hydration in advanced cancer. Searches were carried out in four electronic databases. A hand search of selected peer-reviewed journals and conference abstracts also was conducted. Studies reporting (de)hydration assessment (physical examination, biochemical measures, symptom assessment, and BIA) in patients with advanced cancer were included. The results highlight how clinical examination and biochemical tests are standard methods of assessing hydration, but limitations exist with these methods in advanced cancer. Furthermore, there is disagreement over the evidence for some commonly associated symptoms with dehydration in cancer. Although there are limitations with using BIA alone to assess hydration in advanced cancer, analysis of BIA raw measurements through the method of bioelectrical impedance vector analysis may have a role in this population. The benefits and burdens of providing clinically assisted hydration to patients dying of cancer are unclear. Bioelectrical impedance vector analysis shows promise as a hydration assessment tool but requires further study in advanced cancer. Innovative methodologies for research are required to add to the evidence base and ultimately improve the care for the dying. Copyright © 2013 U.S. Cancer Pain Relief Committee. Published by Elsevier Inc. All rights reserved.

X-ray Computed Tomography Observation of Methane Hydrate Dissociation

USGS Publications Warehouse

Tomutsa, L.; Freifeld, B.; Kneafsey, T.J.; Stern, L.A.

2002-01-01

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.

High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Sun, Y.; Goldberg, D.; Collett, T.; Hunter, R.

2011-01-01

A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis. ?? 2010 Elsevier Ltd.

Hydration and Fluid Replacement Knowledge, Attitudes, Barriers, and Behaviors of NCAA Division 1 American Football Players.

PubMed

Judge, Lawrence W; Kumley, Roberta F; Bellar, David M; Pike, Kim L; Pierson, Eric E; Weidner, Thomas; Pearson, David; Friesen, Carol A

2016-11-01

Judge, LW, Kumley, RF, Bellar, DM, Pike, KL, Pierson, EE, Weidner, T, Pearson, D, and Friesen, CA. Hydration and fluid replacement knowledge, attitudes, barriers, and behaviors of NCAA Division 1 American football players. J Strength Cond Res 30(11): 2972-2978, 2016-Hydration is an important part of athletic performance, and understanding athletes' hydration knowledge, attitudes, barriers, and behaviors is critical for sport practitioners. The aim of this study was to assess National Collegiate Athletic Association (NCAA) Division 1 (D1) American football players, with regard to hydration and fluid intake before, during, and after exercise, and to apply this assessment to their overall hydration practice. The sample consisted of 100 student-athletes from 2 different NCAA D1 universities, who participated in voluntary summer football conditioning. Participants completed a survey to identify the fluid and hydration knowledge, attitudes and behaviors, demographic data, primary football position, previous nutrition education, and barriers to adequate fluid consumption. The average Hydration Knowledge Score (HKS) for the participants in the present study was 11.8 ± 1.9 (69.4% correct), with scores ranging from 42 to 100% correct. Four key misunderstandings regarding hydration, specifically related to intervals of hydration habits among the study subjects, were revealed. Only 24% of the players reported drinking enough fluids before, during, immediately after, and 2 hours after practice. Generalized linear model analysis predicted the outcome variable HKS (χ = 28.001, p = 0.045), with nutrition education (Wald χ = 8.250, p = 0.041) and position on the football team (χ = 9.361, p = 0.025) being significant predictors. "Backs" (e.g., quarterbacks, running backs, and defensive backs) demonstrated significantly higher hydration knowledge than "Linemen" (p = 0.014). Findings indicated that if changes are not made to increase hydration awareness levels among football teams, serious health consequences, including potential fatalities, could occur on the field, especially among heavier linemen.

Evaluation of long-term gas hydrate production testing locations on the Alaska north slope

USGS Publications Warehouse

Collett, T.S.; Boswell, R.; Lee, M.W.; Anderson, B.J.; Rose, K.; Lewis, K.A.

2011-01-01

The results of short duration formation tests in northern Alaska and Canada have further documented the energy resource potential of gas hydrates and justified the need for long-term gas hydrate production testing. Additional data acquisition and long-term production testing could improve the understanding of the response of naturally-occurring gas hydrate to depressurization-induced or thermal-, chemical-, and/or mechanical-stimulated dissociation of gas hydrate into producible gas. The Eileen gas hydrate accumulation located in the Greater Prudhoe Bay area in northern Alaska has become a focal point for gas hydrate geologic and production studies. BP Exploration (Alaska) Incorporated and ConocoPhillips have each established research partnerships with U.S. Department of Energy to assess the production potential of gas hydrates in northern Alaska. A critical goal of these efforts is to identify the most suitable site for production testing. A total of seven potential locations in the Prudhoe Bay, Kuparuk, and Milne Point production units were identified and assessed relative to their suitability as a long-term gas hydrate production test site. The test site assessment criteria included the analysis of the geologic risk associated with encountering reservoirs for gas hydrate testing. The site selection process also dealt with the assessment of the operational/logistical risk associated with each of the potential test sites. From this review, a site in the Prudhoe Bay production unit was determined to be the best location for extended gas hydrate production testing. The work presented in this report identifies the key features of the potential test site in the Greater Prudhoe Bay area, and provides new information on the nature of gas hydrate occurrence and potential impact of production testing on existing infrastructure at the most favorable sites. These data were obtained from well log analysis, geological correlation and mapping, and numerical simulation. Copyright 2011, Offshore Technology Conference.

The Growth and Decay of Hydrate Anomalies in Marine Sediments

NASA Astrophysics Data System (ADS)

Irizarry, J. T.; Rempel, A. W.

2014-12-01

Natural gas hydrates, stored in huge quantities beneath permafrost, and in submarine sediments on the continental shelf, have the potential to become a vital clean-burning energy source. However, clear evidence is recorded in coastal sediments worldwide that past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. Arctic permafrost is thawing, and environmental changes can alter ocean circulation to warm the seafloor, causing hydrates to dissociate or dissolve in the sediments beneath. Decades of focused research provide a firm understanding of laboratory conditions under which hydrates become unstable and dissociate, and how hydrate reserves form when microbes convert organic material into methane, which can also dissolve and be carried by pore waters into the hydrate stability zone. Despite these advances, many key questions that concern both the resource potential of hydrates and their role in causing environmental geohazards, are intimately tied to the more poorly understood behavior of hydrate anomalies, which tend to be concentrated in the large pores of sand layers and form segregated lenses and nodules in muds. We present simple models designed to unravel the importance of the diverse physical interactions (i.e. flow focusing, free-gas infiltration, and pore-scale solubility effects) that help control how hydrate anomalies form. Predicted hydrate distributions are qualitatively different when accumulation in anomalies is supplied primarily by: 1. aqueous flow through sediments with enhanced permeability, 2. free-gas transport high above the three-phase stability boundary, or 3. diffusive transport along solubility gradients associated with pore-scale effects. We discuss examples that illustrate each of these distinct generation modes, in hopes of providing a framework for interpreting field observations of hydrate anomalies and their geomechanical properties in terms of the history of environmental forcing that led to their development.

Invasion of drilling mud into gas-hydrate-bearing sediments. Part I: effect of drilling mud properties

NASA Astrophysics Data System (ADS)

Ning, Fulong; Zhang, Keni; Wu, Nengyou; Zhang, Ling; Li, Gang; Jiang, Guosheng; Yu, Yibing; Liu, Li; Qin, Yinghong

2013-06-01

To our knowledge, this study is the first to perform a numerical simulation and analysis of the dynamic behaviour of drilling mud invasion into oceanic gas-hydrate-bearing sediment (GHBS) and to consider the effects of such an invasion on borehole stability and the reliability of well logging. As a case study, the simulation background sets up the conditions of mud temperature over hydrate equilibrium temperature and overbalanced drilling, considering the first Chinese expedition to drill gas hydrate (GMGS-1). The results show that dissociating gas may form secondary hydrates in the sediment around borehole by the combined effects of increased pore pressure (caused by mud invasion and flow resistance), endothermic cooling that accompanies hydrate dissociation compounded by the Joule-Thompson effect and the lagged effect of heat transfer in sediments. The secondary hydrate ring around the borehole may be more highly saturated than the in situ sediment. Mud invasion in GHBS is a dynamic process of thermal, fluid (mud invasion), chemical (hydrate dissociation and reformation) and mechanical couplings. All of these factors interact and influence the pore pressure, flow ability, saturation of fluid and hydrates, mechanical parameters and electrical properties of sediments around the borehole, thereby having a strong effect on borehole stability and the results of well logging. The effect is particularly clear in the borehole SH7 of GMGS-1 project. The borehole collapse and resistivity distortion were observed during practical drilling and wireline logging operations in borehole SH7 of the GMGS-1.mud density (i.e. the corresponding borehole pressure), temperature and salinity have a marked influence on the dynamics of mud invasion and on hydrate stability. Therefore, perhaps well-logging distortion caused by mud invasion, hydrate dissociation and reformation should be considered for identifying and evaluating gas hydrate reservoirs. And some suitable drilling measurements need to be adopted to reduce the risk of well-logging distortion and borehole instability.

Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

NASA Astrophysics Data System (ADS)

Daigle, H.; Nole, M.; Cook, A.; Malinverno, A.

2017-12-01

In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability ( 1 md in the absence of hydrate). Pore sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.

Hydration shell parameters of aqueous alcohols: THz excess absorption and packing density.

PubMed

Matvejev, V; Zizi, M; Stiens, J

2012-12-06

Solvation in water requires minimizing the perturbations in its hydrogen bonded network. Hence solutes distort water molecular motions in a surrounding domain, forming a molecule-specific hydration shell. The properties of those hydration shells impact the structure and function of the solubilized molecules, both at the single molecule and at higher order levels. The size of the hydration shell and the picoseconds time-scale water dynamics retardation are revealed by terahertz (THz) absorption coefficient measurements. Room-temperature absorption coefficient at f = 0.28 [THz] is measured as a function of alcohol concentration in aqueous methanol, ethanol, 1,2-propanol, and 1-butanol solutions. Highly diluted alcohol measurements and enhanced overall measurement accuracy are achieved with a THz absorption measurement technique of nL-volume liquids in a capillary tube. In the absorption analysis, bulk and interfacial molecular domains of water and alcohol are considered. THz ideal and excess absorption coefficients are defined in accordance with thermodynamics mixing formulations. The parameter extraction method is developed based on a THz excess absorption model and hydrated solute molecule packing density representation. First, the hydration shell size is deduced from the hydrated solute packing densities at two specific THz excess absorption nonlinearity points: at infinite alcohol dilution (IAD) and at the THz excess absorption extremum (EAE). Consequently, interfacial water and alcohol molecular domain absorptions are deduced from the THz excess absorption model. The hydration shell sizes obtained at the THz excess absorption extremum are in excellent agreement with other reports. The hydration shells of methanol, ethanol, 1- and 2-propanol consist of 13.97, 22.94, 22.99, and 31.10 water molecules, respectively. The hydration shell water absorption is on average 0.774 ± 0.028 times the bulk water absorption. The hydration shell parameters might shed light on hydration dynamics of biomolecules.

Geological controls on the occurrence of gas hydrate from core, downhole log, and seismic data in the Shenhu area, South China Sea

USGS Publications Warehouse

Xiujuan Wang,; ,; Collett, Timothy S.; Lee, Myung W.; Yang, Shengxiong; Guo, Yiqun; Wu, Shiguo

2014-01-01

Multi-channel seismic reflection data, well logs, and recovered sediment cores have been used in this study to characterize the geologic controls on the occurrence of gas hydrate in the Shenhu area of the South China Sea. The concept of the "gas hydrate petroleum system" has allowed for the systematic analysis of the impact of gas source, geologic controls on gas migration, and the role of the host sediment in the formation and stability of gas hydrates as encountered during the 2007 Guangzhou Marine Geological Survey Gas Hydrate Expedition (GMGS-1) in the Shenhu area. Analysis of seismic and bathymetric data identified seventeen sub-linear, near-parallel submarine canyons in this area. These canyons, formed in the Miocene, migrated in a northeasterly direction, and resulted in the burial and abandonment of canyons partially filled by coarse-grained sediments. Downhole wireline log (DWL) data were acquired from eight drill sites and sediment coring was conducted at five of these sites, which revealed the presence of suitable reservoirs for the occurrence of concentrated gas hydrate accumulations. Gas hydrate-bearing sediment layers were identified from well log and core data at three sites mainly within silt and silt clay sediments. Gas hydrate was also discovered in a sand reservoir at one site as inferred from the analysis of the DWL data. Seismic anomalies attributed to the presence of gas below the base of gas hydrate stability zone, provided direct evidence for the migration of gas into the overlying gas hydrate-bearing sedimentary sections. Geochemical analyses of gas samples collected from cores confirmed that the occurrence of gas hydrate in the Shenhu area is controlled by the presence thermogenic methane gas that has migrated into the gas hydrate stability zone from a more deeply buried source.

Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daigle, Hugh; Nole, Michael; Cook, Ann

In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability (~1 md in the absence of hydrate). Poremore » sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.« less

Evaluation of long-term gas hydrate production testing locations on the Alaska North Slope

USGS Publications Warehouse

Collett, Timothy; Boswell, Ray; Lee, Myung W.; Anderson, Brian J.; Rose, Kelly K.; Lewis, Kristen A.

2011-01-01

The results of short duration formation tests in northern Alaska and Canada have further documented the energy resource potential of gas hydrates and justified the need for long-term gas hydrate production testing. Additional data acquisition and long-term production testing could improve the understanding of the response of naturally-occurring gas hydrate to depressurization-induced or thermal-, chemical-, and/or mechanical-stimulated dissociation of gas hydrate into producible gas. The Eileen gas hydrate accumulation located in the Greater Prudhoe Bay area in northern Alaska has become a focal point for gas hydrate geologic and production studies. BP Exploration (Alaska) Incorporated and ConocoPhillips have each established research partnerships with U.S. Department of Energy to assess the production potential of gas hydrates in northern Alaska. A critical goal of these efforts is to identify the most suitable site for production testing. A total of seven potential locations in the Prudhoe Bay, Kuparuk, and Milne Point production units were identified and assessed relative to their suitability as a long-term gas hydrate production test site. The test site assessment criteria included the analysis of the geologic risk associated with encountering reservoirs for gas hydrate testing. The site selection process also dealt with the assessment of the operational/logistical risk associated with each of the potential test sites. From this review, a site in the Prudhoe Bay production unit was determined to be the best location for extended gas hydrate production testing. The work presented in this report identifies the key features of the potential test site in the Greater Prudhoe Bay area, and provides new information on the nature of gas hydrate occurrence and potential impact of production testing on existing infrastructure at the most favorable sites. These data were obtained from well log analysis, geological correlation and mapping, and numerical simulation.

A Systematic Review of Strategies to Prevent Cisplatin‐Induced Nephrotoxicity

PubMed Central

Crona, Daniel J.; Faso, Aimee; Nishijima, Tomohiro F.; McGraw, Kathleen A.; Galsky, Matthew D.

2017-01-01

Abstract Introduction. Cisplatin, a platinum‐based antineoplastic agent, is the cornerstone for the treatment of many malignancies. Nephrotoxicity is the primary dose‐limiting toxicity, and various hydration regimens and supplementation strategies are used to prevent cisplatin‐induced kidney injury. However, evidence‐based recommendations on specific hydration regimens are limited. A systematic review was performed to evaluate clinical studies that have examined hydration and supplementation strategies to prevent cisplatin‐induced nephrotoxicity. Materials and Methods. PubMed and Excerpta Medica databases were searched from 1966 through October 2015 for clinical trials and other studies focused on hydration regimens to prevent nephrotoxicity in cancer patients treated with cisplatin. The University of Oxford Centre for Evidence‐Based Medicine criteria were used to grade level of evidence. Results. Among the 1,407 identified studies, 24 were included in this systematic review. All studies differed on type, volume, and duration of hydration. Among the 24 studies, 5 evaluated short‐duration hydration, 4 evaluated low‐volume hydration, 4 investigated magnesium supplementation, and 7 reviewed forced diuresis with hydration. Short‐duration and lower‐volume hydration regimens are effective in preventing cisplatin‐induced nephrotoxicity. Magnesium supplementation may have a role as a nephroprotectant, and forced diuresis may be appropriate in some patients receiving cisplatin. Conclusion. Hydration is essential for all patients to prevent cisplatin‐induced nephrotoxicity. Specifically, short‐duration, low‐volume, outpatient hydration with magnesium supplementation and mannitol forced diuresis (in select patients) represent best practice principles for the safe use of cisplatin. The Oncologist 2017;22:609–619 Implications for Practice. The findings contained within this systematic review show that (a) hydration is essential for all patients to prevent cisplatin‐induced nephrotoxicity, (b) short‐duration, low‐volume, outpatient hydration regimens appear to be safe and feasible, even in patients receiving intermediate‐ to high‐dose cisplatin, (c) magnesium supplementation (8–16 milliequivalents) may limit cisplatin‐induced nephrotoxicity, and (d) mannitol may be considered for high‐dose cisplatin and/or patients with preexisting hypertension. These findings have broad implications for clinical practice and represent best practice principles for the prevention of cisplatin‐induced nephrotoxicity. PMID:28438887

Characterization of methane-hydrate formation inferred from insitu Vp-density relationship for hydrate-bearing sediment cores obtained off the eastern coast of India

NASA Astrophysics Data System (ADS)

Kinoshita, M.; Hamada, Y.; Hirose, T.; Yamada, Y.

2017-12-01

In 2015, the Indian National Gas Hydrate Program (NGHP) Drilling Expedition 02 was carried out off the eastern margin of the Indian Peninsula in order to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. One of the target areas (area B) is located on the axial and flank of an anticline, where the BSR is identified 100 m beneath the summit of anticline. 3 sites were drilled in the crest. The lower potential hydrate zone II was suggested by downhole logging (LWD) at 270-290 m below seafloor across the top of anticline. Core samples from this interval is characterized by a higher natural gamma radiation, gamma-ray-based higher bulk density and lower porosity, and higher electrical resistivity. All these features are in good agreement with LWD results. During this expedition, numerous special core sampling operations (PCAT) were carried out, keeping its insitu pressure in a pressure-tight vessel. They enabled acquiring insitu P-wave velocity and gamma-ray attenuation density measurements. In-situ X-CT images exhibit very clear hydrate distribution as lower density patches. Hydrate-bearing sediments exhibit a Vp-density trend that is clearly different from the ordinary formation. Vp values are significantly higher than 2 km/s whereas the density remains constant at 2-2.2 g/cm3 in hydrate zones. At some hydrate-bearing sediments, we noticed that Vp is negatively correlated to the density in the deeper portion (235-285 mbsf). On the other hand, in the shallower portion they are positively correlated. From lithostratigraphy the shallower portion consists of sand, whereas deeper portion are silty-clay dominant. We infer that the sand-dominant, shallower hydrate is a pore-filling type, and Vp is correlated positively to density. On the other hand, the clay-dominant, deeper hydrate is filled in vertical veins, and Vp is negatively correlated to density. Negative correlation may be explained by a (partial) replacement of pore water with hydrate because the density of hydrate is lower than the water.

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

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1998-01-01

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 CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (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 H2O 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, H2O 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, 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 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.

Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, Sabine; Nöthen, Kerstin; Hensen, Christian; Spieß, Volkhard; Blumenberg, Martin; Schneider, Ralph R.

2012-12-01

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Characterization of a stratigraphically constrained gas hydrate system along the western continental margin of Svalbard from ocean bottom seismometer data

NASA Astrophysics Data System (ADS)

Chabert, Anne; Minshull, Tim A.; Westbrook, Graham K.; Berndt, Christian; Thatcher, Kate E.; Sarkar, Sudipta

2011-12-01

The ongoing warming of bottom water in the Arctic region is anticipated to destabilize some of the gas hydrate present in shallow seafloor sediment, potentially causing the release of methane from dissociating hydrate into the ocean and the atmosphere. Ocean-bottom seismometer (OBS) experiments were conducted along the continental margin of western Svalbard to quantify the amount of methane present as hydrate or gas beneath the seabed. P- and S-wave velocities were modeled for five sites along the continental margin, using ray-trace forward modeling. Two southern sites were located in the vicinity of a 30 km long zone where methane gas bubbles escaping from the seafloor were observed during the cruise. The three remaining sites were located along an E-W orientated line in the north of the margin. At the deepest northern site, Vp anomalies indicate the presence of hydrate in the sediment immediately overlying a zone containing free gas up to 100-m thick. The acoustic impedance contrast between the two zones forms a bottom-simulating reflector (BSR) at approximately 195 m below the seabed. The two other sites within the gas hydrate stability zone (GHSZ) do not show the clear presence of a BSR or of gas hydrate. However, anomalously low Vp, indicating the presence of free gas, was modeled for both sites. The hydrate content was estimated from Vp and Vs, using effective-medium theory. At the deepest northern site, modeling suggests a pore-space hydrate concentration of 7-12%, if hydrate forms as part of a connected framework, and about 22% if it is pore-filling. At the two other northern sites, located between the deepest site and the landward limit of the GHSZ, we suggest that hydrate is present in the sediment as inclusions. Hydrate may be present in small quantities at these two sites (4-5%) of the pore space. The variation in lithology for the three sites indicated by high-resolution seismic profiles may control the distribution, concentration and formation of hydrate and free gas.

Time lapse survey plan on the first offshore methane hydrate production test in 2013 around the eastern Nankai Trough area by multi-component OBC seismic tool

NASA Astrophysics Data System (ADS)

Inamori, T.; Hayashi, T.; Asakawa, E.; Takahashi, H.; Saeki, T.

2011-12-01

We are planning to conduct the multi-component ocean bottom cable (hereafter OBC) seismic survey to monitor the methane hydrate dissociation zone at the 1st offshore methane hydrate production test site in the eastern Nankai Trough, Japan, in 2013. We conducted the first OBC survey in the methane hydrate concentrated zone around the eastern Nankai Trough area in 2006 by RSCS which we developed. We obtained to the good image of methane hydrate bearing layer by P-P section as similar as the conventional surface seismic survey. However, we could not obtain the good image from P-S section compared with P-P section. On the other hand, we studied the sonic velocity distribution at the Mallik 2nd production test before and after in 2007, by the sonic tool data. We could clearly delineate the decrease of S-wave velocity, however, we could not detect the decrease of P-wave velocity because of the presence of the dissociated methane gas from methane hydrate. From these reason we guess the S-wave data is more proper to delineate the condition of the methane hydrate zone at the methane hydrate production tests than P-wave data. We are now developing the new OBC system, which we call Deep-sea Seismic System (hereafter DSS). The sensor of the DSS will install three accelerometers and one hydrophone. A feasibility study to detect the methane hydrate dissociation with the DSS was carried out and we found that the methane hydrate dissociation could be detected with the DSS depending on the zone of the dissociation. And the baseline survey will be held at the 1st offshore methane hydrate production test site in summer 2012. Two monitoring surveys are planned after the methane hydrate production test in 2013. We believe that we will get the good images to delineate the methane hydrate dissociated zone from this time lapse survey. The Authors would like to thank METI, MH21 consortium and JOGMEC for permissions to publish this paper.

Dynamics of Permafrost Associated Methane Hydrate in Response to Climate Change

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2014-12-01

The formation and melting of methane hydrate and ice are intertwined in permafrost regions. A shortage of methane supply leads to formation of hydrate only at depth, below the base of permafrost. We consider a system with the ground surface initially at 0 oC with neither ice nor hydrate present. We abruptly decrease the temperature from 0 to -10 oC to simulate the effect of marine regression/ global cooling. A low methane supply rate of 0.005 kg m-2 yr-1 from depth leads to distinct ice and hydrate layers: a 100 m continuous hydrate layer is present beneath 850 m at 80 k.y.. However, a high methane supply rate of 0.1 kg m-2 yr-1 leads to 50 m ice-bonded methane hydrate at the base of permafrost, and the hydrate layer distributes between the depth of 350 and 700 m at 80 k.y.. We apply our model to illuminate future melting of hydrate at Mallik, a known Arctic hydrate accumulation. We assume a 600 m thick ice saturated (average 90%) layer extending downward from the ground surface. We increase the surface temperature linearly from -6 to 0 oC for 300 yr and then keep the surface temperature at 0 oC to reflect future climate warming caused by doubling of CO2. Hydrate melting is initiated at the base of the hydrate layer after 15 k.y.. Methane gas starts to vent to the atmosphere at 38 k.y. with an average flux of ~ 0.35 g m-2 yr-1. If the 600 m thick average ice saturation is decreased to half (45%) (or to zero), methane gas starts to vent to the atmosphere at 29 k.y. (or at 20 k.y.) with the same average flux. These results are found by a newly-developed fully-coupled multiphase multicomponent fluid flow and heat transport model. Our thermodynamic equilibrium-based model emphasizes the role of salinity in both ice and hydrate dynamics.

Clathrate hydrate tuning for technological purposes

NASA Astrophysics Data System (ADS)

di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

2010-05-01

Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006/000274 [2] Di Profio P., Arca S., Germani R., Savelli G., 2005, "Surfactant promoting effects on clathrate hydrate formation: are micelles really involved?", Chem. Eng. Sci., 60, pp. 4141-4145 [3] Di Profio P., Arca S., Germani R., Savelli G., 2006, "Novel Nanostructured Media for Gas Storage and Transport: Clathrate Hydrates of Methane and Hydrogen", J. Fuel Cell Sci. & Tech., February 2007, vol. 4. [4] Di Profio, P., Germani, R., Savelli, G., EP07010346.

Iodine and Bromine Distributions in Pore Waters: A Comparison Between Permafrost and Marine Gas Hydrate Fields

NASA Astrophysics Data System (ADS)

Tomaru, H.; Fehn, U.; Lu, Z.

2005-12-01

Iodine and, to a lesser degree, bromine are commonly enriched in waters associated with hydrocarbons. The concentrations of these halogens and their ratios can thus be used to identify potential source formations for hydrocarbons such as gas hydrates. While the largest reservoir of gas hydrates is found in marine sediments, permafrost locations are also an important source of gas hydrates. We measured iodine and bromine concentrations in pore waters associated with gas hydrates in the Mallik exploration well, a permafrost location in the Mackenzie delta, Northwest Territory, Canada and compared them to results from gas hydrates in marine sediments. Gas hydrates are found in the Mallik site in two horizons below the permafrost layer which reaches a depth of about 600 m in this location. We measured concentrations in samples collected from depths between 850 and 1150 m. Large sections of the test well have iodine concentrations around 1 μM, but the concentrations increase to values between 10 and 20 μM at the gas hydrate horizons. Bromine concentrations show a similar pattern, with maxima reaching values between 700 and 800 μM. Although iodine concentrations are considerably higher than in seawater (0.4 μM), they are much lower than in marine gas hydrate locations such as Nankai (200 μM); Blake Ridge (2 mM) or Hydrate Ridge (2.5 mM). Bromine concentrations at Mallik do not reach the seawater value (840 μM) in contrast to marine hydrate locations where Br is enriched by factors of four or more compared to seawater. Chlorine concentrations at Mallik are close to that of seawater, in this case similar to the marine hydrate locations. The comparison between marine hydrate locations and Mallik suggests that the organic sources responsible for the methane at Mallik are considerably different from those in marine situations. Since iodine concentrations are generally higher in marine organisms than in terrestrial organisms, the relatively low concentrations of iodine and bromine at Mallik suggest that the source material there is of more terrestrial character than in the marine locations, a observation supported by the presence of several coal seams at Mallik. The large volume of methane in this region suggests that terrestrial sources may play an important role in the accumulation of gas hydrates.

Formation of a Structure II Hydrate by 1,4-Thioxane in Sea Water

NASA Astrophysics Data System (ADS)

Hester, K. C.; Mancillas, O.; Walz, P. M.; Peltzer, E. T.; Brewer, P. G.

2007-12-01

We have show that a sII clathrate hydrate containing 1,4-thioxane (TO) will form under the appropriate pressure and temperature conditions. The molecular size of TO poised it at the boundary between sII hydrate formation either as the sole cage occupant, or where a second help gas molecule is required to stabilize the small hydrate cages. In addition to its size, TO is chemical similar to cyclic ethers, such as tetrahydrofuran, which readily form clathrate hydrates. For the experimental temperatures in this study (all above 273.15 K), a pure TO hydrate was not observed to form. However, binary hydrates of TO and either CH4 and N2 were readily formed under moderate pressure conditions (33-158 bar). Both Raman spectroscopy and visual observations were used to verify that a solid hydrate formed and that TO was trapped in the cages. For TO + CH4, a pressure-temperature phase equilibria diagram was created. This showed that the addition of TO increased hydrate stability versus a pure CH4 system by approximately 10 degC, indicating that should CH4 gas be present a TO hydrate would readily form at shallow depths under typical oceanic temperature regimes. TO is of environmental interest as a breakdown product of mustard gas (1,1'-thiobis[2-chloroethane] as a result of hydrolysis in sea water, and has been shown to occur in seafloor chemical weapon disposal sites. In the years after World War II large quantities of chemical weapons were disposed of in the ocean at sites off the US east and west coasts, off Japan, in the Baltic and Adriatic Seas, and in the Russian Arctic, until the signing of the London Convention in 1972. Mustard gas represents the largest tonnage of weapons materiel and while the general scheme of breakdown by hydrolysis is known there is little information on the actual behavior of these breakdown products in marine sediments. This work illuminates such gaps in knowledge, and formation of a hydrate profoundly alters molecular mobility and diffusion away from a site. Simple calculations show that other help gases, such as H2S, should also form a mixed hydrate with TO with remarkable ease; thus, extending the range of possible hydrate formation with TO in anoxic marine sediments to shallow depths, if a second hydrate former is present.

NMR Studies of Protein Hydration and Protein-Ligand Interactions

NASA Astrophysics Data System (ADS)

Chong, Yuan

Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be facilitated by hydration. On the other hand, alcohols can bind to many nonspecific sites on the protein. In dry proteins, this type of binding only occurs above a threshold of alcohol vapor pressure. Such a threshold is gradually reduced by increasing the hydration level and can be removed above a critical hydration level. Hydration also shifts the nonspecific alcohol binding from an entropy-driven to an enthalpy-driven process. This dissertation reveals the mechanism of protein hydration and the detailed roles of hydration in ligand binding, with important implications for the understanding of protein functions.

Gas-hydrate occurrence on the W-Svalbard margin at the gateway to the Arctic Ocean

NASA Astrophysics Data System (ADS)

Bünz, Stefan; Mienert, Jürgen

2010-05-01

Gas hydrates contain more carbon than does any other global reservoir and are abundant on continental margins worldwide. These two facts make gas hydrates important as a possible future energy resource, in submarine landsliding and in global climate change. With the ongoing global warming, there is a need for a better understanding of the distribution of gas hydrates and their sensitivity to environmental changes. Gas hydrate systems in polar latitudes may be of particular importance due to the fact that environmental changes will be felt here first and most likely are more extreme than elsewhere. The gas-hydrate systems offshore western Svalbard are far more extensive (~4000km^2) than previously assumed and include the whole Vestnesa Ridge, an elongated sediment drift north of the Molloy Transform and just east of the Molloy Ridge, one of the shortest segments of the slow spreading North-Atlantic Ridge system. However, in this peculiar setting gas hydrates also occur within few km of a mid-oceanic ridge and transform fault, which makes this gas hydrate system unique on Earth. The close proximity to the spreading centre and its hydrothermal circulation system affects the dynamics of the gas hydrate system. A strong cross-cutting BSR is visible, especially in areas of dipping seafloor. Other places show a weak almost subtle BSR. The base of gas-hydrate stability varies with distance from the ridge system, suggesting a strong temperature-controlled subsurface depth as the underlying young oceanic crust cools off eastward. High amplitude reflections over a depth range of up to 150m underneath the BSR indicate the presence of a considerable amount of free gas. The free gas is focused laterally upwards by the less-permeable hydrated sediments as the only fluid-escape features occur at the crest of the Vestnesa Ridge. The fluid migration system and its active plumbing system at the crest provide an efficient mechanism for gas escape from the base of the hydrate stability zone. The high heat flow together with the high tectonic activity of this region, a thick sedimentary cover, a shallow maturation window and an accelerated rate of biogenic and thermogenic gas production cause substantial disturbance to the gas hydrate system leading to high variability in gas hydrate build up and dissociation. This young and dynamic system allows studying gas hydrate formation in marine sediments, their governing parameters and their relationship with the fluid flow in great detail.

Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

NASA Astrophysics Data System (ADS)

Qorbani, Khadijeh; Kvamme, Bjørn

2016-04-01

Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated as non-equilibrium processes under local constraint of mass and heat fluxes. In this work, we have extended RCB by adding another route for dissociation or reformation of CH4-hydrate towards CH4 into the aqueous phase and water. CH4-hydrate formation and dissociation is resolved by looking at supersaturation and undersaturation with respect to thermodynamics variables. Hydrate instability due to undersaturation of CH4 in the contacting water phase is also considered. A complete non-equilibrium thermodynamic package, developed in-house, was combined with RCB to account for competing phase transitions by considering the minimization of Gibb's free energy. The energy differences were calculated from variations in chemical potentials of hydrate and hydrate formers. Mass transport, heat transport and non-equilibrium thermodynamic effects were implemented through classical nucleation theory to model the kinetic rate of hydrate phase transitions. To illustrate our implementations we ran simulations covering time-spans in the order of hundred years. CH4 production was modelled using the depressurization method, where we employed the Messoyakha field data. We discuss our implementations, as well as results obtained from simulations utilizing our modifications.

CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

NASA Astrophysics Data System (ADS)

Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

2013-04-01

In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with the reservoir is minimized. Our results clearly indicate that the formation of mixed CH4-CO2-hydrates is an important aspect in the conversion process. The experimental studies have shown that the injection of heated CO2 into the hydrate reservoir induces a variety of spatial and temporal processes which result in substantial bulk heterogeneity. Current numerical simulators are not able to predict these process dynamics and it is important to improve available transport-reaction models (e.g. to include the effect of bulk sediment permeability on the conversion dynamics). Our results confirm that experimental studies are important to better understand the mechanisms of hydrate dissociation and conversion at CO2-injection conditions as a basis towards the development of a suitable hydrate conversion technology. The application of non-invasive analytical methods such as Magnetic Resonance Imaging (MRI) and Raman microscopy are important tools, which were applied to resolve process dynamics on the pore scale. Additionally, the NESSI system is being modified to allow high-pressure flow-through experiments under triaxial loading to better simulate hydrate-sediment mechanics. This aspect is important for overall process development and evaluation of process safety issues.

Types and Evolution of Gas Hydrate System along the Tectonically Active Zones of the Western Pacific: Nankai Trough vs. Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Tomaru, H.; Takeuchi, L.; Hiruta, A.; Ishizaki, O.; Aoyama, C.; Machiyama, H.; Goto, T.

2007-12-01

A series of sea-going surveys of marine gas hydrates around Japan Islands for more than a decade has revealed characteristic and contrasting features and evolution of gas hydrate system between the Nankai subduction zone and the Joetsu Basin of Japan Sea. Gas hydrate of the Nankai trough largely occurs as pore-filling type, laterally extending in turbidites. Methane is depleted in C-13, mostly derived from microbial brake-down of organic matters. Strong and continuous BSRs occur at around 270 mbsf, corresponding to the base of gas hydrate stability (BGHS). Furthermore, double BSRs with weak reflector (BSR-2) 20-30 m below BSR appear in uplifting knolls. BSR-2 is explained as a relic BSR, which coincides with BGHS. Combination effects of uplifting of gas hydrate bearing sediments and sea-level fall are likely to have caused shoaling of BGHS and BSRs, dissociation of gas hydrate between old and new BRSs, and further accumulation of gas hydrates above BSR. Thus the recycling of methane at BGHS triggered by glacial sea level fall contributed for the development of subsurface gas hydrate deposits. Joetsu basin is located on a newly formed convergent boundary between Eurasia and Philippine Sea Plates. Well-defined circular pockmarks with ca.500 m in diameter develop on the folded and faulted Umitaka spur and Joetsu knoll in the basin. A number of circular swells and mounds, 200-500 m in diameter, have been also recognized nearby the pockmarks. Thus the Umitaka spur and perhaps Joetsu knoll are characterized by rough topography of pockmarks and mounds. Methane of plumes and gas hydrate originates in deep-seated thermogenic gases with relatively heavy carbon. 3D seismic profiles clearly depict gas chimney structures below pockmark-mound zones, and gigantic methane plumes stand on the mounds not in the pockmarks. Pockmarks are often considered as vent holes, however, those of the Joestu Basin are quite. BSRs occur at about 150 mbsr, corresponding to very high heat flow, and are widely distributed throughout the area, while no double BSRs are observed. BSRs within gas chimneys are very strong and often exhibit pull-up structure. A number of piston corers have recovered chunks of massive gas hydrate from the mounds. ROV dives observed gas hydrates exposed atop the mounds. Furthermore, electric ocean floor survey has revealed that sediments below the pockmark-mound zones were not conductive. These lines of evidence suggest that the mounds are more-or-less composed of or at least contain significant amounts of methane. Sea-level fall during the last glacial, 120 m in Japan Sea, should have caused instability of gas hydrate, in particular, those within pockmarks. Pull-up structures within the chimney seem to support the model that the mounds are gas hydrate dome and the pockmark, probably a relic hydrate mound. Glacial sea level fall should have caused massive dissociation of subsurface methane hydrate as in case of the Nankai trough. However the methane from the dissociation of massive hydrate in the chimney should escape to seawater to form a crater-like depression pockmarks. Considering active venting, gigantic plumes, inferred violent venting and perhaps floating of massive gas hydrates, gas hydrate deposits are to be formed during warmer, high-sea level periods, and episodic dissociation and massive emission of methane to ocean/atmosphere system.

Characterization of Methane Hydrate Growth from Aqueous Solution by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Chou, I.; Lu, W.; Yuan, S.; Li, J.; Burruss, R. C.

2009-12-01

We observed the growth of methane hydrate from aqueous solution in fused silica capillaries near room temperature (RT) in two different experiments. In the first, we sealed methane together with ~2 wt% Na2SO4 solution in a fused silica capillary (0.3x0.3 mm cross-section with 0.05x0.05 mm cavity, and ~6 cm long), using the method of Chou et al. (2008, Geochim. Cosmochim. Acta, 72, 2517). The hydrate, liquid, and vapor coexist at ~23 °C and ~36.5 MPa. The behavior of two methane bubbles, one of which was enclosed by a hydrate crystal and the other near a small hydrate crystal, was monitored. These two bubbles are the only methane sources near the hydrate crystals. The system was slowly cooled to RT (~21 °C), and images were recorded continuously for a period of ~1.5 hours, together with temperature and time information. The images show the exposed bubble decreased in size, while both of the hydrate crystals increased in size, which was caused by the transfer of methane in solution. According to our previous report (Fig. 8 of Lu et al., 2008, Geochim. Cosmochim. Acta, 72, 412), the concentrations of methane in the solution near the exposed bubble are higher than those near the hydrate crystals. Most of the dissolved methane, transferred down the concentration gradient, was consumed and encaged in the nearby crystal, with only a small fraction of methane being consumed by the more distant crystal. Eventually, the exposed vapor bubble was totally consumed, but the bubble shielded by the hydrate crystal remained. This shows hydrate can grow from dissolved methane in the solution far away from free gas. In the 2nd experiment, we sealed methane, together with pure H2O and glass beads (0.04 to 0.07 mm in dia.), in a fused silica capillary (0.3 mm OD, 0.1 mm ID, and ~6 cm long) using the method cited above. We separated the vapor phase from the solution and glass beads by centrifuging the sealed capsule, then imposed a T gradient to the sample by cooling the solution end of the capsule to ~0 °C. It is difficult to recognize the nucleation and growth of hydrate crystals under a microscope, but Raman spectroscopy was used to identify and map the distribution of hydrate crystals along the capsule. Near the original vapor-aqueous phase boundary (V-A B), Raman signals show 100% methane hydrate. However, the lack of dissolved methane in the solution further away from the V-A B limited the growth of hydrate, as indicated by the increase in water/hydrate ratio when the Raman spectrum, which combines signals from both water and hydrate, was collected further away from the V-A B. We are investigating other possible ways to map the distribution of hydrate crystals around the glass beads, including x-ray computed tomography, to understand the nature of methane hydrate crystals that grow around grains in marine sediments from pore water. These observations will improve our ability to interpret the geophysical responses (e.g., electric and acoustic signals) obtained from hydrate-bearing sediments in the field.

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

USGS Publications Warehouse

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-01-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°–225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests ~2 orders of magnitude higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60–150 °C, suggest that if sufficient hot water or steam is available, any rhyolite flow greater than ~5 m thick can develop the observed ~250-µm hydration rinds within the expected timescale of cooling (weeks–years). As the process of hydration involves shattering of 30- to 100-µm-thick slivers to expose unhydrated rhyolite glass, the time required for hydration may be even shorter. Rapid hydration and formation of relatively thick-walled glass shards allow perlites to provide a snapshot view of the meteoric water (and thus climate) at the time of initial alteration. Perlites retain their initial hydration D/H signal better than thin-walled ash, which in contrast hydrates over many thousands of years with time-averaged precipitation.

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

NASA Astrophysics Data System (ADS)

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-11-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant "onion-skin" fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2-3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched "hydration fronts" where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between 110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°-225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests 2 orders of magnitude higher rates of diffusion at 60-110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are -150 to -191 or 20-40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60-150 °C, suggest that if sufficient hot water or steam is available, any rhyolite flow greater than 5 m thick can develop the observed 250-µm hydration rinds within the expected timescale of cooling (weeks-years). As the process of hydration involves shattering of 30- to 100-µm-thick slivers to expose unhydrated rhyolite glass, the time required for hydration may be even shorter. Rapid hydration and formation of relatively thick-walled glass shards allow perlites to provide a snapshot view of the meteoric water (and thus climate) at the time of initial alteration. Perlites retain their initial hydration D/H signal better than thin-walled ash, which in contrast hydrates over many thousands of years with time-averaged precipitation.

Life Origination and Development Hydrate theory (LOH-Theory): new approaches to the problems of the optimal nutrition and life prolongation

NASA Astrophysics Data System (ADS)

Kadyshevich, E. A.; Ostrovskii, V. E.

2014-04-01

Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRHTheory), both grounded on the notion of honeycomb gas-hydrate structures formation/destruction as the physicochemical phenomenon governing the DNA origination and replication, allow new approaches to the optimal nutrition and life prolongation problems.

49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 2 2012-10-01 2012-10-01 false Chloric acid solution or chlorine dioxide hydrate... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When the.... Fiberboard boxes must be reinforced and insulated and sufficient dry ice must be used to maintain the hydrate...

49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false Chloric acid solution or chlorine dioxide hydrate... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When the.... Fiberboard boxes must be reinforced and insulated and sufficient dry ice must be used to maintain the hydrate...

49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false Chloric acid solution or chlorine dioxide hydrate... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When the.... Fiberboard boxes must be reinforced and insulated and sufficient dry ice must be used to maintain the hydrate...

49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false Chloric acid solution or chlorine dioxide hydrate... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When the.... Fiberboard boxes must be reinforced and insulated and sufficient dry ice must be used to maintain the hydrate...

49 CFR 173.229 - Chloric acid solution or chlorine dioxide hydrate, frozen.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false Chloric acid solution or chlorine dioxide hydrate... Than Class 1 and Class 7 § 173.229 Chloric acid solution or chlorine dioxide hydrate, frozen. When the.... Fiberboard boxes must be reinforced and insulated and sufficient dry ice must be used to maintain the hydrate...

Highly porous CO 2 hydrate generation aided by silica nanoparticles for potential secure storage of CO 2 and desalination

DOE PAGES

Kim, Ijung; Nole, Michael; Jang, Sunghyun; ...

2017-01-31

Here in this paper, we report a new way of storing CO 2 in a highly porous hydrate structure, stabilized by silica nanoparticles (NPs). Such a porous CO 2 hydrate structure was generated either by cooling down NP-stabilized CO 2-in-seawater foams, or by gently mixing CO 2 and seawater that contains silica NPs under CO 2 hydrate-generating conditions. With the highly porous structure, enhanced desalination was also achievable when the partial meltdown of CO 2 hydrate was allowed.

Method for controlling clathrate hydrates in fluid systems

DOEpatents

Sloan, Jr., Earle D.

1995-01-01

Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member and/or six member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone.

Highly porous CO 2 hydrate generation aided by silica nanoparticles for potential secure storage of CO 2 and desalination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Ijung; Nole, Michael; Jang, Sunghyun

Here in this paper, we report a new way of storing CO 2 in a highly porous hydrate structure, stabilized by silica nanoparticles (NPs). Such a porous CO 2 hydrate structure was generated either by cooling down NP-stabilized CO 2-in-seawater foams, or by gently mixing CO 2 and seawater that contains silica NPs under CO 2 hydrate-generating conditions. With the highly porous structure, enhanced desalination was also achievable when the partial meltdown of CO 2 hydrate was allowed.

Gas Hydrate Characterization from a 3D Seismic Dataset in the Eastern Deepwater Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Dan

The presence of a gas hydrate petroleum system and seismic attributes derived from 3D seismic data are used for the identification and characterization of gas hydrate deposits in the deepwater eastern Gulf of Mexico. In the central deepwater Gulf of Mexico (GoM), logging while drilling (LWD) data provided insight to the amplitude response of gas hydrate saturation in sands, which could be used to characterize complex gas hydrate deposits in other sandy deposits. In this study, a large 3D seismic data set from equivalent and distal Plio-Pleistocene sandy channel deposits in the deepwater eastern Gulf of Mexico is screened formore » direct hydrocarbon indicators for gas hydrate saturated sands.« less

Gas Hydrate Stability at Low Temperatures and High Pressures with Applications to Mars and Europa

NASA Technical Reports Server (NTRS)

Marion, G. M.; Kargel, J. S.; Catling, D. C.

2004-01-01

Gas hydrates are implicated in the geochemical evolution of both Mars and Europa [1- 3]. Most models developed for gas hydrate chemistry are based on the statistical thermodynamic model of van der Waals and Platteeuw [4] with subsequent modifications [5-8]. None of these models are, however, state-of-the-art with respect to gas hydrate/electrolyte interactions, which is particularly important for planetary applications where solution chemistry may be very different from terrestrial seawater. The objectives of this work were to add gas (carbon dioxide and methane) hydrate chemistries into an electrolyte model parameterized for low temperatures and high pressures (the FREZCHEM model) and use the model to examine controls on gas hydrate chemistries for Mars and Europa.

Testing a thermo-chemo-hydro-geomechanical model for gas hydrate-bearing sediments using triaxial compression laboratory experiments

NASA Astrophysics Data System (ADS)

Gupta, S.; Deusner, C.; Haeckel, M.; Helmig, R.; Wohlmuth, B.

2017-09-01

Natural gas hydrates are considered a potential resource for gas production on industrial scales. Gas hydrates contribute to the strength and stiffness of the hydrate-bearing sediments. During gas production, the geomechanical stability of the sediment is compromised. Due to the potential geotechnical risks and process management issues, the mechanical behavior of the gas hydrate-bearing sediments needs to be carefully considered. In this study, we describe a coupling concept that simplifies the mathematical description of the complex interactions occurring during gas production by isolating the effects of sediment deformation and hydrate phase changes. Central to this coupling concept is the assumption that the soil grains form the load-bearing solid skeleton, while the gas hydrate enhances the mechanical properties of this skeleton. We focus on testing this coupling concept in capturing the overall impact of geomechanics on gas production behavior though numerical simulation of a high-pressure isotropic compression experiment combined with methane hydrate formation and dissociation. We consider a linear-elastic stress-strain relationship because it is uniquely defined and easy to calibrate. Since, in reality, the geomechanical response of the hydrate-bearing sediment is typically inelastic and is characterized by a significant shear-volumetric coupling, we control the experiment very carefully in order to keep the sample deformations small and well within the assumptions of poroelasticity. The closely coordinated experimental and numerical procedures enable us to validate the proposed simplified geomechanics-to-flow coupling, and set an important precursor toward enhancing our coupled hydro-geomechanical hydrate reservoir simulator with more suitable elastoplastic constitutive models.

Examination of core samples from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Effects of retrieval and preservation

USGS Publications Warehouse

Kneafsey, T.J.; Lu, H.; Winters, W.; Boswell, R.; Hunter, R.; Collett, T.S.

2011-01-01

Collecting and preserving undamaged core samples containing gas hydrates from depth is difficult because of the pressure and temperature changes encountered upon retrieval. Hydrate-bearing core samples were collected at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well in February 2007. Coring was performed while using a custom oil-based drilling mud, and the cores were retrieved by a wireline. The samples were characterized and subsampled at the surface under ambient winter arctic conditions. Samples thought to be hydrate bearing were preserved either by immersion in liquid nitrogen (LN), or by storage under methane pressure at ambient arctic conditions, and later depressurized and immersed in LN. Eleven core samples from hydrate-bearing zones were scanned using x-ray computed tomography to examine core structure and homogeneity. Features observed include radial fractures, spalling-type fractures, and reduced density near the periphery. These features were induced during sample collection, handling, and preservation. Isotopic analysis of the methane from hydrate in an initially LN-preserved core and a pressure-preserved core indicate that secondary hydrate formation occurred throughout the pressurized core, whereas none occurred in the LN-preserved core, however no hydrate was found near the periphery of the LN-preserved core. To replicate some aspects of the preservation methods, natural and laboratory-made saturated porous media samples were frozen in a variety of ways, with radial fractures observed in some LN-frozen sands, and needle-like ice crystals forming in slowly frozen clay-rich sediments. Suggestions for hydrate-bearing core preservation are presented.

Hydration of calcium sulfoaluminate cements - Experimental findings and thermodynamic modelling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnefeld, Frank, E-mail: Frank.Winnefeld@empa.c; Lothenbach, Barbara

Calcium sulfoaluminate cements (CSA) are a promising low-CO{sub 2} alternative to ordinary Portland cements and are as well of interest concerning their use as binder for waste encapsulation. In this study, the hydration of two CSA cements has been investigated experimentally and by thermodynamic modelling between 1 h and 28 days at w/c ratios of 0.72 and 0.80, respectively. The main hydration product of CSA is ettringite, which precipitates together with amorphous Al(OH){sub 3} until the calcium sulfate is consumed after around 1-2 days of hydration. Afterwards, monosulfate is formed. In the presence of belite, straetlingite occurs as an additionalmore » hydration product. The pore solution analysis reveals that straetlingite can bind a part of the potassium ions, which are released by the clinker minerals. The microstructure of both cements is quite dense even after 16 h of hydration, with not much pore space available at a sample age of 28 days. The pore solution of both cements is dominated during the first hours of hydration by potassium, sodium, calcium, aluminium and sulfate; the pH is around 10-11. When the calcium sulfate is depleted, the sulfate concentration drops by a factor of 10. This increases pH to around 12.5-12.8. Based on the experimental data, a thermodynamic hydration model for CSA cements based on cement composition, hydration kinetics of clinker phases and calculations of thermodynamic equilibria by geochemical speciation has been established. The modelled phase development with ongoing hydration agrees well with the experimental findings.« less

Chloral hydrate for sedation of children with asthma during dental treatment.

PubMed

Abdulhamid, I; Tremblay, M; Stenger, J; Tutag Lehr, V

2016-06-01

We hypothesised that chloral hydrate is safe and effective for sedation during dental treatments for children with mild asthma. We evaluated the safety and efficacy of chloral hydrate by measuring changes in heart rate (HR), transcutaneous oxygen saturation, (SpO2), asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Children (<10 years old) with mild asthma undergoing dental treatments received a single 65 mg/kg oral dose of chloral hydrate liquid 1 hour prior to treatment in an open label trial. Heart rate (HR), SpO2, asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Asthma score was obtained before and after treatment. Thirty minutes after treatment, SpO2, HR, and level of consciousness was assessed. Twenty four children were enrolled and 92% (22/24) recovered from sedation without respiratory depression. Two experienced mild respiratory depression related to chloral hydrate. Asthma was not a contributing factor as they did not experience wheezing, cough, tachypnoea, or retractions. Inhaled nitrous oxide supplemented chloral hydrate sedation in 63% (15/24) children to achieve effective cooperation. Three children had a SpO2 <95% (2 during treatment, 1 during recovery). Chloral hydrate 65 mg/kg administered a as single oral dose appears to be safe with respect to disease exacerbation for children with mild asthma undergoing dental treatment. Due to ineffective sedation and mild respiratory depression associated with chloral hydrate, newer, easily titrated medications, such as midazolam, may offer advantages.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

PubMed Central

Braun, Doris E.; Griesser, Ulrich J.

2018-01-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

PubMed Central

Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

2013-01-01

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

Hydrate kinetics study in the presence of nonaqueous liquid by nuclear magnetic resonance spectroscopy and imaging.

PubMed

Susilo, Robin; Moudrakovski, Igor L; Ripmeester, John A; Englezos, Peter

2006-12-28

The dynamics of methane hydrate growth and decomposition were studied by nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI). Three well-known large molecule guest substances (LMGS) were used as structure H hydrate formers: 2,2-dimethylbutane (NH), methylcyclohexane (MCH), tert-butyl methyl ether (TBME). In addition, the impact of a non-hydrate former (n-heptane/nC7) was studied. The methane diffusion and hydrate growth were monitored by recording the 2H NMR spectra at 253 K and approximately 4.5 MPa for 20 h. The results revealed that methane diffuses faster in TBME and NH, slower in nC7, and slowest in MCH. The TBME system gives the fastest hydrate formation kinetics followed by NH, MCH, and nC7. The conversion of water into hydrate was also observed. The imaging study showed that TBME has a strong affinity toward ice, which is not the case for the NH and MCH systems. The degree of ice packing was also found to affect the LMGS distribution between ice particles. Highly packed ice increases the mass transfer resistance and hence limits the contact between LMGS and ice. It was also found that "temperature ramping" above the ice point improves the conversion significantly. Finally, hydrates were found to dissociate quickly within the first hour at atmospheric pressure and subsequently at a much slower rate. Methane dissolved in LMGS was also seen. The residual methane in hydrate phase and dissolved in LMGS phase explain the faster kinetics during hydrate re-formation.

Hydration status of Air Force military basic trainees after implementation of the back-mounted hydration system.

PubMed

Fogt, Donovan L; Brosch, Lorie C; Dacey, Danny C; Kalns, John E; Ketchum, Norma S; Rohrbeck, Patricia; Venuto, Margaret M; Tchandja, Juste B; Bunning, Mike L

2009-08-01

The Air Force makes an extraordinary effort to prevent heat-related illnesses associated with basic military training (BMT) in south Texas. However, inadequate hydration can still contribute to lost training time and qualified trainees leaving military service without completing BMT. The purpose of the present study was to determine whether equipping BMTs with back-mounted hydration systems (BM) is better than the standard-issue (SI) canteens with respect to hydration status. Male BMTs were randomly assigned to either BM (n = 40) or SI (n = 38) groups. Baseline values were assessed at week 0 before any physical readiness training (PRT). Subsequent data collection took place in the a.m. before PRT and in the p.m. before dinner the first 3 weeks, and during the 5 weeks of training. BMT total body water (TBW) and body composition were assessed by bioelectrical impedance. Saliva osmolality and total protein concentration were also determined. Hydration status increased daily in BM and SI and was well maintained over the duration of BMT. A significant hydration effect (p < 0.05) was observed for average daily increases in TBW and body weight with BM gaining more compared to SI. Average a.m. TBW was 0.3-0.8 L greater in SI versus BM (p < 0.05). Our findings demonstrate that adequate hydration status is maintained during Air Force BMT in a hot environment using either hydration mode and therefore do not support widespread issuance of the BM system on the premise of improved hydration during USAF BMT military training.

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

PubMed

Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

2013-05-21

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests.

Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

USGS Publications Warehouse

Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.; McFarlane, J.; Kirkwood, W.

1997-01-01

We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

Hydration behaviors of calcium silicate-based biomaterials.

PubMed

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

Racial/Ethnic and Socioeconomic Disparities in Hydration Status Among US Adults and the Role of Tap Water and Other Beverage Intake

PubMed Central

Gortmaker, Steven L.; Long, Michael W.; Cradock, Angie L.; Kenney, Erica L.

2017-01-01

Objectives. To evaluate whether differences in tap water and other beverage intake explain differences in inadequate hydration among US adults by race/ethnicity and income. Methods. We estimated the prevalence of inadequate hydration (urine osmolality ≥ 800 mOsm/kg) by race/ethnicity and income of 8258 participants aged 20 to 74 years in the 2009 to 2012 National Health and Nutrition Examination Survey. Using multivariable regression models, we estimated associations between demographic variables, tap water intake, and inadequate hydration. Results. The prevalence of inadequate hydration among US adults was 29.5%. Non-Hispanic Blacks (adjusted odds ratio [AOR] = 1.44; 95% confidence interval [CI] = 1.17, 1.76) and Hispanics (AOR = 1.42; 95% CI = 1.21, 1.67) had a higher risk of inadequate hydration than did non-Hispanic Whites. Lower-income adults had a higher risk of inadequate hydration than did higher-income adults (AOR = 1.23; 95% CI = 1.04, 1.45). Differences in tap water intake partially attenuated racial/ethnic differences in hydration status. Differences in total beverage and other fluid intake further attenuated sociodemographic disparities. Conclusions. Racial/ethnic and socioeconomic disparities in inadequate hydration among US adults are related to differences in tap water and other beverage intake. Policy action is needed to ensure equitable access to healthy beverages. PMID:28727528

Coupled numerical modeling of gas hydrates bearing sediments from laboratory to field-scale conditions

NASA Astrophysics Data System (ADS)

Sanchez, M. J.; Santamarina, C.; Gai, X., Sr.; Teymouri, M., Sr.

2017-12-01

Stability and behavior of Hydrate Bearing Sediments (HBS) are characterized by the metastable character of the gas hydrate structure which strongly depends on thermo-hydro-chemo-mechanical (THCM) actions. Hydrate formation, dissociation and methane production from hydrate bearing sediments are coupled THCM processes that involve, amongst other, exothermic formation and endothermic dissociation of hydrate and ice phases, mixed fluid flow and large changes in fluid pressure. The analysis of available data from past field and laboratory experiments, and the optimization of future field production studies require a formal and robust numerical framework able to capture the very complex behavior of this type of soil. A comprehensive fully coupled THCM formulation has been developed and implemented into a finite element code to tackle problems involving gas hydrates sediments. Special attention is paid to the geomechanical behavior of HBS, and particularly to their response upon hydrate dissociation under loading. The numerical framework has been validated against recent experiments conducted under controlled conditions in the laboratory that challenge the proposed approach and highlight the complex interaction among THCM processes in HBS. The performance of the models in these case studies is highly satisfactory. Finally, the numerical code is applied to analyze the behavior of gas hydrate soils under field-scale conditions exploring different features of material behavior under possible reservoir conditions.

Molecular and isotopic analyses of the hydrocarbon gases within gas hydrate-bearing rock units of the Prudhoe Bay-Kuparuk River area in northern Alaska

USGS Publications Warehouse

Valin, Zenon C.; Collett, Timothy S.

1992-01-01

Gas hydrates, which are crystalline substances of water molecules that encase gas molecules, have the potential for being a significant source of natural gas. World-wide estimates for the amount of gas contained in hydrates range from 1.1 x 105 to 2.7 x 108 trillion cubic feet. Gas hydrates exist in many Arctic regions, including the North Slope of Alaska. The two primary objectives of the U.S. Geological Survey Gas Hydrate Research Project are (1) to map the distribution of in-situ gas hydrates on the North Slope of Alaska, and (2) to evaluate the geologic parameters that control the distribution of these gas hydrates. To aid in this study, British Petroleum Exploration, ARCO Alaska, Exxon Company USA, and the Continental Oil Company allowed the U.S. Geological Survey to collect geochemical samples from drilling North Slope production wells. Molecular analysis of gaseous drill cutting and free-flowing gas samples from 10 production wells drilled in the Prudhoe Bay, Kuparuk River, and Milne Point oil fields indicates that methane is the primary hydrocarbon gas in the gas hydrate-bearing stratigraphic units. Isotopic data for several of these rock units indicate that the methane within the inferred gas hydrate occurences originated from both microbial and thermogenic processes.

Racial/Ethnic and Socioeconomic Disparities in Hydration Status Among US Adults and the Role of Tap Water and Other Beverage Intake.

PubMed

Brooks, Carolyn J; Gortmaker, Steven L; Long, Michael W; Cradock, Angie L; Kenney, Erica L

2017-09-01

To evaluate whether differences in tap water and other beverage intake explain differences in inadequate hydration among US adults by race/ethnicity and income. We estimated the prevalence of inadequate hydration (urine osmolality ≥ 800 mOsm/kg) by race/ethnicity and income of 8258 participants aged 20 to 74 years in the 2009 to 2012 National Health and Nutrition Examination Survey. Using multivariable regression models, we estimated associations between demographic variables, tap water intake, and inadequate hydration. The prevalence of inadequate hydration among US adults was 29.5%. Non-Hispanic Blacks (adjusted odds ratio [AOR] = 1.44; 95% confidence interval [CI] = 1.17, 1.76) and Hispanics (AOR = 1.42; 95% CI = 1.21, 1.67) had a higher risk of inadequate hydration than did non-Hispanic Whites. Lower-income adults had a higher risk of inadequate hydration than did higher-income adults (AOR = 1.23; 95% CI = 1.04, 1.45). Differences in tap water intake partially attenuated racial/ethnic differences in hydration status. Differences in total beverage and other fluid intake further attenuated sociodemographic disparities. Racial/ethnic and socioeconomic disparities in inadequate hydration among US adults are related to differences in tap water and other beverage intake. Policy action is needed to ensure equitable access to healthy beverages.

CO2 capture from simulated fuel gas mixtures using semiclathrate hydrates formed by quaternary ammonium salts.

PubMed

Park, Sungwon; Lee, Seungmin; Lee, Youngjun; Seo, Yongwon

2013-07-02

In order to investigate the feasibility of semiclathrate hydrate-based precombustion CO2 capture, thermodynamic, kinetic, and spectroscopic studies were undertaken on the semiclathrate hydrates formed from a fuel gas mixture of H2 (60%) + CO2 (40%) in the presence of quaternary ammonium salts (QASs) such as tetra-n-butylammonium bromide (TBAB) and fluoride (TBAF). The inclusion of QASs demonstrated significantly stabilized hydrate dissociation conditions. This effect was greater for TBAF than TBAB. However, due to the presence of dodecahedral cages that are partially filled with water molecules, TBAF showed a relatively lower gas uptake than TBAB. From the stability condition measurements and compositional analyses, it was found that with only one step of semiclathrate hydrate formation with the fuel gas mixture from the IGCC plants, 95% CO2 can be enriched in the semiclathrate hydrate phase at room temperature. The enclathration of both CO2 and H2 in the cages of the QAS semiclathrate hydrates and the structural transition that results from the inclusion of QASs were confirmed through Raman and (1)H NMR measurements. The experimental results obtained in this study provide the physicochemical background required for understanding selective partitioning and distributions of guest gases in the QAS semiclathrate hydrates and for investigating the feasibility of a semiclathrate hydrate-based precombustion CO2 capture process.

Influence of stromal refractive index and hydration on corneal laser refractive surgery.

PubMed

de Ortueta, Diego; von Rüden, Dennis; Magnago, Thomas; Arba Mosquera, Samuel

2014-06-01

To evaluate the influence of the stromal refractive index and hydration on postoperative outcomes in eyes that had corneal laser refractive surgery using the Amaris laser system. Augenzentrum Recklinghausen, Recklinghausen, Germany. Comparative case series. At the 6-month follow-up, right eyes were retrospectively analyzed. The effect of the stromal refractive index and hydration on refractive outcomes was assessed using univariate linear and multilinear correlations. Sixty eyes were analyzed. Univariate linear analyses showed that the stromal refractive index and hydration were correlated with the thickness of the preoperative exposed stroma and was statistically different for laser in situ keratomileusis and laser-assisted subepithelial keratectomy treatments. Univariate multilinear analyses showed that the spherical equivalent (SE) was correlated with the attempted SE and stromal refractive index (or hydration). Analyses suggest overcorrections for higher stromal refractive index values and for lower hydration values. The stromal refractive index and hydration affected postoperative outcomes in a subtle, yet significant manner. An adjustment toward greater attempted correction in highly hydrated corneas and less intended correction in low hydrated corneas might help optimize refractive outcomes. Mr. Magnago and Dr. Arba-Mosquera are employees of and Dr. Diego de Ortueta is a consultant to Schwind eye-tech-solutions GmbH & Co. KG. Mr. Rüden has no financial or proprietary interest in any material or method mentioned. Copyright © 2014 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

Permafrost-associated gas hydrate: is it really approximately 1% of the global system?

USGS Publications Warehouse

Ruppel, Carolyn

2015-01-01

Permafrost-associated gas hydrates are often assumed to contain ∼1 % of the global gas-in-place in gas hydrates based on a study26 published over three decades ago. As knowledge of permafrost-associated gas hydrates has grown, it has become clear that many permafrost-associated gas hydrates are inextricably linked to an associated conventional petroleum system, and that their formation history (trapping of migrated gas in situ during Pleistocene cooling) is consistent with having been sourced at least partially in nearby thermogenic gas deposits. Using modern data sets that constrain the distribution of continuous permafrost onshore5 and subsea permafrost on circum-Arctic Ocean continental shelves offshore and that estimate undiscovered conventional gas within arctic assessment units,16 the done here reveals where permafrost-associated gas hydrates are most likely to occur, concluding that Arctic Alaska and the West Siberian Basin are the best prospects. A conservative estimate is that 20 Gt C (2.7·1013 kg CH4) may be sequestered in permafrost-associated gas hydrates if methane were the only hydrate-former. This value is slightly more than 1 % of modern estimates (corresponding to 1600 Gt C to 1800 Gt C2,22) for global gas-in-place in methane hydrates and about double the absolute estimate (11.2 Gt C) made in 1981.26

Thermogenic methane injection via bubble transport into the upper Arctic Ocean from the hydrate-charged Vestnesa Ridge, Svalbard

NASA Astrophysics Data System (ADS)

Smith, Andrew J.; Mienert, Jürgen; Bünz, Stefan; Greinert, Jens

2014-05-01

We use new gas-hydrate geochemistry analyses, echosounder data, and three-dimensional P-Cable seismic data to study a gas-hydrate and free-gas system in 1200 m water depth at the Vestnesa Ridge offshore NW Svalbard. Geochemical measurements of gas from hydrates collected at the ridge revealed a thermogenic source. The presence of thermogenic gas and temperatures of ˜3.3°C result in a shallow top of the hydrate stability zone (THSZ) at ˜340 m below sea level (mbsl). Therefore, hydrate-skinned gas bubbles, which inhibit gas-dissolution processes, are thermodynamically stable to this shallow water depth. This was confirmed by hydroacoustic observations of flares in 2010 and 2012 reaching water depths between 210 and 480 mbsl. At the seafloor, bubbles are released from acoustically transparent zones in the seismic data, which we interpret as regions where free gas is migrating through the hydrate stability zone (HSZ). These intrusions result in vertical variations in the base of the HSZ (BHSZ) of up to ˜150 m, possibly making the shallow hydrate reservoir more susceptible to warming. Such Arctic gas-hydrate and free-gas systems are important because of their potential role in climate change and in fueling marine life, but remain largely understudied due to limited data coverage in seasonally ice-covered Arctic environments.

Shallow Methane Hydrates: Rates, Mechanisms of Formation and Environmental Significance.

NASA Astrophysics Data System (ADS)

Torres, M. E.; Trehu, A. M.

2005-05-01

Shallow gas hydrates have been identified at more than 20 locations worldwide, and are commonly associated with observations of bubble discharge at the seafloor. These deposits are host to active chemosynthetic communities and are likely to play a predominant role in energy, climate and carbon cycle issues associated with hydrate processes. Because seafloor gas hydrates are not in equilibrium with seawater, these deposits require a constant supply of methane to replace loss by continuous diffusion to bottom water. We will summarize evidence documenting that at the shallow deposits on Hydrate Ridge (OR) methane must be delivered in the free gas phase and present simple models used to infer formation rates, which are orders of magnitude higher than those for hydrates formed deeper in the sediment column (Torres et al., 2004). At Hydrate Ridge, methane gas is channeled from deep accretionary margin sequences to the gas hydrate stability zone (GHSZ) through a permeable layer that has been mapped seismically (Horizon A). High gas pressure in this horizon can drive gas through the GHSZ to the seafloor (Trehu et al., 2004). We will review current ideas that address mechanisms whereby gas migrates from Horizon A to the seafloor, including inhibition by capillary effects and the development of a high salinity front that can shift the hydrate stability field enough to allow for methane transport as a gas phase.

A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

2011-02-01

Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

Pore-Scale Determination of Gas Relative Permeability in Hydrate-Bearing Sediments Using X-Ray Computed Micro-Tomography and Lattice Boltzmann Method

NASA Astrophysics Data System (ADS)

Chen, Xiongyu; Verma, Rahul; Espinoza, D. Nicolas; Prodanović, Maša.

2018-01-01

This work uses X-ray computed micro-tomography (μCT) to monitor xenon hydrate growth in a sandpack under the excess gas condition. The μCT images give pore-scale hydrate distribution and pore habit in space and time. We use the lattice Boltzmann method to calculate gas relative permeability (krg) as a function of hydrate saturation (Shyd) in the pore structure of the experimental hydrate-bearing sand retrieved from μCT data. The results suggest the krg - Shyd data fit well a new model krg = (1-Shyd)·exp(-4.95·Shyd) rather than the simple Corey model. In addition, we calculate krg-Shyd curves using digital models of hydrate-bearing sand based on idealized grain-attaching, coarse pore-filling, and dispersed pore-filling hydrate habits. Our pore-scale measurements and modeling show that the krg-Shyd curves are similar regardless of whether hydrate crystals develop grain-attaching or coarse pore-filling habits. The dispersed pore filling habit exhibits much lower gas relative permeability than the other two, but it is not observed in the experiment and not compatible with Ostwald ripening mechanisms. We find that a single grain-shape factor can be used in the Carman-Kozeny equation to calculate krg-Shyd data with known porosity and average grain diameter, suggesting it is a useful model for hydrate-bearing sand.

Role of Polymeric Excipients in the Stabilization of Olanzapine when Exposed to Aqueous Environments.

PubMed

Paisana, Maria; Wahl, Martin; Pinto, João

2015-12-12

Hydrate formation is a phase transition which can occur during manufacturing processes involving water. This work considers the prevention of hydration of anhydrous olanzapine and hydrate conversions in the presence of water and polymers (polyethyleneglycol; hydroxypropylcellulose; polyvinylpyrrolidone) in forming pellets by wet extrusion and spheronisation. Anhydrous olanzapine was added to water with or without those polymers prior to extrusion with microcrystalline cellulose. Assessment of olanzapine conversion was made by XRP-Diffraction; FTIR spectroscopy; calorimetry (DSC) and microscopy (SEM for crystal size and shape). The addition of water converted the anhydrous form into dihydrate B and higher hydrate; whereas polyethyleneglycol promoted a selective hydrate conversion into the higher hydrate olanzapine form. Both polyvinylpyrrolidone and hydroxypropylcellulose prevented the hydrate transformations of the anhydrous drug; the latter even in the presence of hydrate seeds. This may be explained by the higher H-bond ability; higher network association and higher hydrophobicity of hydroxypropylcellulose by comparison with polyethyleneglycol and polyvinylpyrrolidone; which could contribute to its higher affinity to the crystal surfaces of the hydrate nuclei/initial crystals and promoting steric hindrance to the incorporation of other drug molecules into the crystal lattice; thus, preventing the crystal growth. The addition of microcrystalline cellulose needed for the pellets production (final product) did not eliminate the protector effect of both hydroxypropylcellulose and polyvinylpyrrolidone during pellets' processing and dissolution evaluation.

Effects of Systemic Hydration on Vocal Acoustics of 18- to 35-Year-Old Females

ERIC Educational Resources Information Center

Franca, Maria Claudia; Simpson, Kenneth O.

2012-01-01

The influence of body hydration and vocal acoustics was investigated in this study. Effects of two levels of hydration on objective measures of vocal acoustics were explored. In an attempt to reduce variability in the degree of systemic hydration and to induce a state of systemic dehydration, participants were instructed to refrain from ingestion…

Mechanosensitive ATP Release Maintains Proper Mucus Hydration of Airways

PubMed Central

Button, Brian; Okada, Seiko F.; Frederick, Charles Brandon; Thelin, William R.; Boucher, Richard C.

2013-01-01

The clearance of mucus from the airways protects the lungs from inhaled noxious and infectious materials. Proper hydration of the mucus layer enables efficient mucus clearance through beating of cilia on airway epithelial cells, and reduced clearance of excessively concentrated mucus occurs in patients with chronic obstructive pulmonary disease and cystic fibrosis. Key steps in the mucus transport process are airway epithelia sensing and responding to changes in mucus hydration. We reported that extracellular adenosine triphosphate (ATP) and adenosine were important luminal auto-crine and paracrine signals that regulated the hydration of the surface of human airway epithelial cultures through their action on apical membrane purinoceptors. Mucus hydration in human airway epithelial cultures was sensed by an interaction between cilia and the overlying mucus layer: Changes in mechanical strain, proportional to mucus hydration, regulated ATP release rates, adjusting fluid secretion to optimize mucus layer hydration. This system provided a feedback mechanism by which airways maintained mucus hydration in an optimum range for cilia propulsion. Understanding how airway epithelia can sense and respond to changes in mucus properties helps us to understand how the mucus clearance system protects the airways in health and how it fails in lung diseases such as cystic fibrosis. PMID:23757023

Evaluation of the stability of gas hydrates in Northern Alaska

USGS Publications Warehouse

Kamath, A.; Godbole, S.P.; Ostermann, R.D.; Collett, T.S.

1987-01-01

The factors which control the distribution of in situ gas hydrate deposits in colder regions such as Northern Alaska include; mean annual surface temperatures (MAST), geothermal gradients above and below the base of permafrost, subsurface pressures, gas composition, pore-fluid salinity and the soil condition. Currently existing data on the above parameters for the forty-six wells located in Northern Alaska were critically examined and used in calculations of depths and thicknesses of gas hydrate stability zones. To illustrate the effect of gas hydrate stability zones, calculations were done for a variable gas composition using the thermodynamic model of Holder and John (1982). The hydrostatic pressure gradient of 9.84 kPa/m (0.435 lbf/in2ft), the salinity of 10 parts per thousand (ppt) and the coarse-grained soil conditions were assumed. An error analysis was performed for the above parameters and the effect of these parameters on hydrate stability zone calculations were determined. After projecting the hydrate stability zones for the forty-six wells, well logs were used to identify and to obtain values for the depth and thickness of hydrate zones. Of the forty-six wells, only ten wells showed definite evidence of the presence of gas hydrates. ?? 1987.